CN100509994C - Light emitting film, luminescent device, method for manufacturing light emitting film and method for manufacturing luminescent device - Google Patents

Abstract

The present invention provides a reliable, long-life phosphor, or the like, which is prevented from darkening due to aging. A light emitting apparatus has a light emitting element and a phosphor layer. The phosphor layer has a phosphor excited by light from the light emitting element, and a binder which binds the phosphor. The binder is hydroxide oxide gel obtained by curing sol of a hydroxide oxide mixed with sol containing at least one metallic element selected from the group consisting of Al, Y, Gd, Lu, Sc, Ga, In, and B. Transmittance of hydroxide oxide in a gel state is higher than the transmittance in the polycrystal state where the sol-gel reaction is proceeded. In addition, the content of hydroxyl group or water of crystallization in the hydroxide oxide is 10% or less by weight.

Description

Light-emitting film, light-emitting device, manufacturing method of light-emitting film, and manufacturing method of light-emitting device

technical field

The present invention relates to a luminescent film, a luminescent device, and a method for manufacturing the luminescent film and luminescent device, which can be used in light sources for illumination, LED displays, backlight sources, signal machines, illuminated switches, various sensors, and various indicators.

Background technique

People have developed such a light-emitting device, which converts a part of the light of the light-emitting element by means of a phosphor, and mixes the wavelength-converted light and the light of the light-emitting element that has not undergone wavelength conversion. It is emitted, thereby emitting light with a color different from that of the light-emitting element (for example, Japanese Patent Application Laid-Open No. 2002-198573). For example, a white LED light-emitting device has been put into practical use. This device uses a blue light-emitting diode (hereinafter also referred to as "LED") using an InGaN-based material as a light-emitting element, and a fluorescent member is coated on the surface of the light-emitting element. The fluorescent member is made of a translucent material such as epoxy resin containing yttrium aluminum garnet (hereinafter also referred to as "YAG")-based phosphor that can be represented by the composition formula (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ constitute. The luminous color of the white LED light emitting device can be obtained through the principle of light mixing. After the blue light emitted from the LED enters the fluorescent member, it is repeatedly absorbed and scattered in the layer, and then emitted outward. On the other hand, the blue light absorbed by the phosphor acts as an excitation source to emit yellow fluorescence. By mixing the yellow light of the phosphor with the blue light of the LED, the human eye can see white light.

An LED light-emitting device using such an LED is characterized in that it is compact, has high power efficiency, and emits brightly colored light. In addition, because the LED is a semiconductor element, there is no need to worry about burning out (burn out). Furthermore, the LED light-emitting device also has the characteristics of excellent initial excitation characteristics, strong vibration and repeatability of on-off lighting. Because of such excellent characteristics, LED lighting devices can be utilized as various light sources.

However, conventional white light-emitting devices use a large amount of resin, so when used in a light-emitting element with high output power and short wavelength, there is a problem that the resin degrades. In addition, in the case of using an inorganic binder, especially in the case of using a cured film formed of silica gel, when exposed to an environment of high output power and ultraviolet rays, there is coloring degradation and blackening The problem. Although the reason for this is unclear, it is generally considered that the organic groups contained in the silica sol remain after curing, and these organic groups are reduced by strong photoexcitation.

In addition, in order to improve the light extraction efficiency of the light-emitting device, it is conceivable to increase the transmittance of the light-emitting film. The transmittance of the luminescent film depends on the transmittance of the binder carrying the phosphor on the luminescent film. When using a gel formed by thermally curing the sol in a binder, as shown in Figure 1, it can generally be considered that as the sol-gel reaction proceeds, the closer it is to polycrystalline, the transmittance of the luminescent film is like As shown in A in the figure, it rises further.

However, if the gel is made close to polycrystalline, the sol-gel reaction will be a reaction at high temperature, requiring more time and energy. Furthermore, due to the high temperature, there is a problem of adverse effects on semiconductor light emitting elements and phosphors. For example, lead wires connecting LED chips are damaged due to heat, or phosphors are degraded. In order to improve the light extraction efficiency, inorganic vitrification of polycrystals occurs as the sol-gel reaction progresses, which is accompanied by difficulties in terms of reaction temperature.

Furthermore, even if inorganic vitrification occurs as the sol-gel reaction progresses, various problems arise at the interface between the light-emitting film and the light-emitting element. For example, total reflection occurs at the vitrified interface, resulting in low light extraction efficiency, or the following problems occur, that is, curing occurs to form a space layer at the interface of the light emitting element and the interface of the phosphor, and the space layer becomes a blocking layer to prevent light from being released. It becomes difficult to take out.

In addition, in a structure in which a light-emitting element such as an LED is used to excite the light-emitting layer, there is also a problem that the light-emitting layer is degraded due to exposure to the powerful energy of the excitation light of the LED. The degraded light-emitting layer is colored black, which impairs the original light transmittance and degrades the light extraction efficiency. The cause of such blackened color degradation is not clear, but it is generally considered to be caused by silica used as a binder of the light-emitting layer.

Even if a general resin is used as a sealing material for sealing the phosphor on the light-emitting layer, it is difficult to use the resin as a sealing material because it is significantly degraded by exposure to strong light. For this purpose, a light-transmitting binder such as silicon dioxide (SiO ₂ ) is used. Silica gel, which is gel-like silica, is easy to be used because of its good cohesiveness, excellent light transmittance, high light extraction efficiency, and industrial cheapness.

However, when exposed to the intense light of LEDs for a long time, the silica adhesive layer degrades in coloration. Especially in high output light emitting devices, the silica binder layer is degraded due to high optical density and heat, and is colored black or dark brown. As a result of research conducted by the present inventors, it is presumed that the cause is that SiO ₂ , that is, silicon dioxide, forms SiO _x (x<2) due to oxygen deficiency. The silica binder is in the state of silica gel in which some hydroxyl groups and organic groups remain in the _SiO2 skeleton at a thermal curing temperature of 250°C or lower. In such a silica gel state, when high-density light enters from the LED, oxygen deficiency occurs, and SiO ₂ becomes SiO _X (x<2). In this way, since Si is prone to oxidation and reduction, it is generally considered that the loss of oxygen in the silica gel is the cause of coloring deterioration. Once the coloring degradation occurs, there arises a problem that the light output power from the light emitting element decreases.

In recent years, development of a light-emitting device using a high-output light-emitting element has been progressing, but light generated by the light-emitting element tends to accelerate resin degradation. In addition, while development of short-wavelength light-emitting elements ranging from blue to visible light to short-wavelength regions and further to ultraviolet light regions is ongoing, coating films that can withstand these ultraviolet rays and the like for a long period of time have not yet been found. Even if you try to use a general resin, it is difficult to use the resin as a coating film because it is significantly degraded by exposure to strong light.

Contents of the invention

The present invention has been made to solve such problems. The main object of the present invention is to provide a light-emitting film, a light-emitting device, a method of manufacturing a light-emitting film, and a method of manufacturing a light-emitting device with improved light extraction efficiency and excellent reliability, and to provide such a highly reliable A light-emitting device and a method of manufacturing the same, wherein the light-emitting device has a coating film that is hardly degraded by light from a light-emitting element such as ultraviolet rays.

The luminescent film of the present invention is a luminescent film for covering a light-emitting element, and it is at least composed of a filler member containing a luminescent material and a binder member, wherein the binder member contains at least a hydrated oxide of a metal element (also called an oxide- hydroxide). This luminescent film can also be used as a diffusion layer not containing phosphor.

In addition, another luminescent film of the present invention is characterized in that the luminescent material is an inorganic phosphor, the filler member is an inorganic filler, and the binder member is an inorganic binder mainly composed of a hydrated oxide of a metal element with a constant valence.

Since the luminescent film is formed mainly of inorganic substances, and the metal elements constituting the hydrated oxide have a constant valence, the oxidation-reduction reaction of the compound after film formation is suppressed, and the luminescent film becomes stable. Therefore, high optical density, A luminescent film that does not degrade even under high temperature excitation.

In addition, another luminescent film of the present invention is characterized in that: the luminescent material is an inorganic phosphor, the filler component is an inorganic filler, the binder component is an inorganic binder mainly composed of a hydrated oxide of a metal element, and the hydration of the metal element is an inorganic binder. The oxides are at least hydrous oxides of Group IIIA or Group IIIB elements.

By using a trivalent metal element, it has a greater inhibitory effect on oxidation-reduction reactions, and a more stable luminescent film can be obtained.

In addition, still another luminescent film of the present invention is characterized in that the Group IIIA or Group IIIB element contains Sc, Y, Gd, Lu, or at least one of B, Al, Ga, and In.

The hydrated oxides of these elements are highly transparent and stable, and are relatively easy to obtain.

In addition, still another luminescent film of the present invention is characterized in that the hydrous oxide of the metal element contained in the binder member is a hydrous oxide of Al having at least a boehmite structure or a pseudo-boehmite structure.

In addition, still another luminescent film of the present invention is characterized in that the binder member contains: a hydrated oxide of aluminum and a Group IIIA element other than aluminum in an amount of 0.5% by weight to 50% by weight relative to the binder member. Or hydrated oxides of group IIIB elements.

In addition, still another luminescent film of the present invention is characterized in that the adhesive member contains boron oxide or boric acid in an amount of 0.5% by weight to 50% by weight relative to the adhesive member.

In addition, still another luminescent film of the present invention is characterized in that the hydrous oxide of the metal element contained in the binder member is a hydrous oxide of yttrium.

In addition, still another luminescent film of the present invention is characterized in that the binder member contains a hydrated oxide of yttrium and a group IIIA element different from yttrium in an amount of 0.5% by weight to 50% by weight relative to the binder member. Or hydrated oxides of group IIIB elements.

In addition, still another luminescent film of the present invention is characterized in that the adhesive member contains boron oxide or boric acid in an amount of 0.5% by weight to 50% by weight relative to the adhesive member.

In addition, still another luminescent film of the present invention is characterized in that the binder member is a porous body having a crosslinked structure, a network structure, or a polymer structure formed of an aggregate of particles containing a hydrous oxide.

The dehydration and curing of the binder member of the luminescent film does not completely progress to the state of an oxide, so that the luminescent film is in an amorphous state compared to a crystalline substance, and can form a material with increased adhesive force and good light extraction efficiency. Glowing film.

In addition, still another luminescent film of the present invention is characterized in that the binder member is in the form of a gel filled with inorganic particles containing hydrated oxides.

Further, still another luminescent film of the present invention is characterized in that the light transmittance of the luminescent film is higher than the transmittance of polycrystalline or amorphous in the case of sintering after the sol-gel reaction.

In addition, still another luminescent film of the present invention is characterized in that the adhesive member contains 10% by weight or less of hydroxyl groups or crystal water relative to the adhesive member.

In addition, still another luminescent film of the present invention is characterized in that the weight ratio of the filler member and the binder member constituting the luminescent film is 0.05 to 30 in terms of filler/binder.

In addition, the light-emitting device of the present invention has a light-emitting element and a light-emitting layer that absorbs at least part of the light emitted by the light-emitting element to emit light. The light-emitting device is characterized in that the light-emitting layer is the above-mentioned light-emitting film.

Furthermore, another light-emitting device of the present invention is characterized in that the light-emitting layer directly covers the light-emitting element.

In addition, still another light-emitting device of the present invention includes a light-emitting element and a light-emitting layer that absorbs at least part of the light emitted from the light-emitting element and emits light of a different wavelength. This light-emitting device is characterized in that the light-emitting layer has phosphor particles excited by light from the light-emitting element, and a binder member in which the phosphor particles are dispersed and supported in the layer.

Still another light-emitting device according to the present invention is characterized in that the light-emitting device includes a semiconductor light-emitting element having a light-emitting wavelength of 550 nm or less, and a phosphor that is excited to emit light with light of the wavelength.

Further, still another light-emitting device of the present invention is characterized in that the light-emitting device includes a semiconductor light-emitting element having a light-emitting wavelength of 410 nm or less, and a phosphor that is excited to emit light by light of the wavelength.

In addition, still another light-emitting device of the present invention is characterized in that the light-emitting layer emits light at a temperature of 50° C. or higher.

The reason for the degradation of the binder of the light-emitting layer is generally considered to be light, heat or the interaction between them. The light-emitting device having the above-mentioned structure hardly degrades the binder even under high-power excitation of visible light, ultraviolet light, high-temperature excitation, etc., and thus is particularly effective in excitation with high excitation density.

In addition, still another light-emitting device of the present invention is characterized in that the light-emitting layer is bonded and formed on the semiconductor light-emitting element, and the input power when the semiconductor light-emitting element is excited is 0.1 W/cm ² or more. It is especially effective at input powers up to 1 W/cm ² or more.

In addition, still another light-emitting device of the present invention is characterized in that: the light-emitting wavelength of the semiconductor light-emitting element is 410 nm or less, and the luminance of the light-emitting layer after 1000 hours when the semiconductor light-emitting element is excited at an input power of ¹ W/cm The maintenance rate is 80% or above.

In addition, still another light-emitting device of the present invention is characterized in that the phosphor contained in the filler of the light-emitting layer of the light-emitting device has blue light-emitting phosphors, blue-green light-emitting phosphors, green light-emitting phosphors, yellow-green light-emitting phosphors, At least one of the yellow light-emitting phosphor, the yellow-red light-emitting phosphor, the orange light-emitting phosphor, and the red light-emitting phosphor emits white or intermediate color light.

In addition, another light-emitting device of the present invention is characterized in that the phosphor contained in the filler of the light-emitting layer has a light emission from green to yellow-red with a peak wavelength between 510nm and 600nm, and is a rare-earth aluminate activated by at least Ce. Phosphor.

In addition, another light-emitting device of the present invention is characterized in that the phosphor contained in the filler of the light-emitting layer of the light-emitting device has a light emission from yellow-red to red with a peak wavelength between 580nm and 650nm, and is an alkaline earth material activated at least with Eu. Silicon nitride-like phosphors.

In addition, still another light-emitting device of the present invention is characterized in that the phosphor contained in the filler of the light-emitting layer has light emission from blue-green to yellow-red with a peak wavelength between 500nm and 600nm, and is an alkaline-earth oxygen activated at least with Eu. silicon nitride phosphor.

In addition, another light-emitting device of the present invention is characterized in that it is a semiconductor light-emitting element that emits light at a light-emitting wavelength of 410 nm or less, and that the phosphor contained in the filler of the light-emitting layer has blue light, and includes at least Eu-activated alkaline-earth halogen apatite phosphor, at least Eu-activated alkaline-earth halogen boric acid phosphor, and at least Eu-activated alkaline-earth alumina phosphor, and has a light emission from green to yellow-red The mixture of rare earth alumina phosphors activated by at least Ce shows white light emission.

In addition, another light-emitting device of the present invention is characterized in that it is a semiconductor light-emitting element that emits light at a light-emitting wavelength of 410 nm or less, and that the phosphor contained in the filler of the light-emitting layer has blue light, and includes at least Eu-activated alkaline-earth halogen apatite phosphor, at least Eu-activated alkaline-earth halogen boric acid phosphor, and at least Eu-activated alkaline-earth alumina phosphor, and has a light emission from green to yellow-red The rare-earth alumina phosphor activated by at least Ce and the alkaline-earth silicon nitride phosphor activated by at least Eu with yellow-red to red luminescence exhibit white-based luminescence.

In addition, another light-emitting device of the present invention is characterized in that it is a semiconductor light-emitting element that emits light in the blue region of the light-emitting wavelength of 440nm to 480nm, and the phosphor contained in the filler of the light-emitting layer is activated with at least Ce Rare-earth alumina phosphors are mixed to display white light emission.

In addition, another light-emitting device of the present invention is characterized in that it is a semiconductor light-emitting element that emits light in the blue region of the light-emitting wavelength of 440nm to 480nm, and the phosphor contained in the filler of the light-emitting layer has a color ranging from green to 480nm. A mixture of a rare-earth alumina phosphor activated with at least Ce that emits yellow-red light and an alkaline-earth silicon nitride phosphor activated with at least Eu that emits yellow-red to red light emits white light.

In addition, the method for producing a light-emitting film of the present invention is a method for producing a light-emitting film for covering a light-emitting element, which is composed of at least a filler member containing a light-emitting material and an adhesive member, and is characterized in that it includes the following steps: A step of preparing a slurry by mixing a metalloxane sol containing a metal element of the binder member and a filler member, a step of forming the slurry into a film, and thermally curing the slurry formed into a film to make the slurry containing the metal element The particles of the hydrated oxide are aggregated, and the filler member is attached to the binder member composed of the structure of the aggregated particles.

In addition, another method for producing a luminescent film according to the present invention is characterized in that the metalloxane sol is at least aluminoxane sol or yttriumoxane sol.

In addition, still another method of manufacturing a light-emitting device of the present invention is a method of manufacturing a light-emitting device having a light-emitting element and a light-emitting film obtained by covering at least a part of the light-emitting element according to the above-mentioned manufacturing method, and is characterized in that: In the process, the slurry is used to cover the light-emitting element and/or the area separated from the light-emitting element under heat treatment conditions, thereby forming a film.

According to the present invention, a light-emitting film, a light-emitting device, a method for manufacturing a light-emitting film, and a method for manufacturing a light-emitting device with high light extraction efficiency can be obtained. This is because: By using a hydrous oxide in the luminescent film, even in the gel state that does not reach the polycrystalline state, the transmittance of the luminescent film is less inhibited, resulting in a higher light extraction efficiency . Furthermore, according to the present invention, since a hydrated oxide of a metal element having a constant valence is used, it is possible to obtain a luminescent film, a luminescent device, and a luminescent film with less coloring degradation due to use, good durability, and excellent reliability. A manufacturing method and a manufacturing method of a light-emitting device. This is because: as the binder of the phosphor, the present invention does not use metal elements such as silicon dioxide that can take a variety of valences, so that oxygen deficiency will not occur, and the bonding layer produced by oxygen deficiency Color degradation can also be avoided. This avoids a drop in light output due to the coloring of the adhesive layer and achieves long-term stable performance. Even if a dynamic light-emitting element is used, excellent reliability and long life can be achieved. In addition, a light-emitting film, a light-emitting device, a method for manufacturing a light-emitting film, and a method for manufacturing a light-emitting device can be obtained that are excellent in heat resistance, have improved durability of the phosphor, and are extremely reliable.

In addition, the present invention relates to a light-emitting device, which has a light-emitting element and a substrate carrying the light-emitting element. The light-emitting device is characterized in that: the light-emitting element is covered with an inorganic binder, and the inorganic binder is covered with a resin. covered, the inorganic binder is impregnated with the resin, and the inorganic binder is formed with an inorganic binder layer covering at least a part of the light emitting element and the base.

The inorganic binder is preferably capable of filling voids in the inorganic binder layer with a resin.

In addition, the inorganic binder is preferably capable of filling about 95% or more of voids in the inorganic binder layer with the resin.

Covering the inorganic binder with resin is preferably done by pouring or spraying, so that the inorganic binder is impregnated with resin.

Furthermore, the inorganic binder preferably contains a phosphor.

The resin is preferably capable of forming a resin layer covering at least a part of the inorganic binder.

The surface of the resin layer is preferably a smooth surface.

The resin preferably contains at least any one of oil, gel and rubber.

The resin is preferably a silicone resin having a dialkylsiloxane skeleton both before and after molding. The following chemical formula 1 represents a dialkylsiloxane skeleton, wherein R represents an alkyl group.

化学式1

chemical formula 1

The resin preferably has dimethylsiloxane on the main chain before molding. Dimethylsiloxane is one form of dialkylsiloxane skeleton. The following Chemical Formula 2 represents dimethylsiloxane.

化学式2

chemical formula 2

In the bond absorption intensity of the resin in the infrared spectrum, it is preferable that the intensity ratio of the C—Si—O bond and the Si—O—Si bond in the resin composition is 1.2/1 or more.

The invention relates to a method for manufacturing a light-emitting device, which comprises: a first step of carrying a light-emitting element on a substrate; a second step of covering the light-emitting element with an inorganic binder; covering the inorganic binder with a resin The third process, wherein the third process uses pouring means or spraying means to cover the resin with the inorganic binder.

In the third step, it is preferable to impregnate in a vacuum.

Because of the configuration described above, the present invention produces the following effects.

The invention relates to a light-emitting device, which has a light-emitting element and a substrate carrying the light-emitting element. In the light-emitting device, the light-emitting element is covered by an inorganic binder, and the inorganic binder is covered by a resin, so that In the step of covering the inorganic binder with the resin, the resin is impregnated with the inorganic binder by pouring or spraying. Thereby, even in the case of using a high-output light-emitting element or a light-emitting element emitting ultraviolet light, it is possible to provide a coating film that is resistant to ultraviolet rays or the like for a long period of time while the promotion of resin degradation is suppressed. In addition, the light extraction efficiency can be improved without causing degradation of the inorganic binder covering the light emitting element. Furthermore, since the entire inorganic binder is impregnated with resin, the inorganic binder does not generate cracks and defects, and an impact-resistant coating film can be formed.

This is determined by the following effects.

When the inorganic binder is cured, there are portions where voids are formed. In the prior art, light extraction was suppressed due to the effect of the void, but in the present invention, the light extraction efficiency can be improved by filling the void with a resin.

As a means of filling this void with resin, pouring means or spraying means is used. For methods other than pouring and spraying, such as the method of injecting resin into the entire inorganic binder at one time, the gas to be exhausted either remains in the inorganic adhesive layer or infiltrates into the resin to preserve the gas. The gas present in the inorganic adhesive layer is enclosed in the layer, and the gas stored in the layer expands due to heat generated by the light-emitting element when the light-emitting device is activated. As a result, light extraction efficiency tends to decrease. In contrast, in the pouring method and the spraying spray method, the resin penetrates into the inorganic binder while extruding the gas contained in the voids of the inorganic binder to the outside, so the voids of the inorganic binder are almost Without residual gas, the resin can almost completely fill the voids that the inorganic binder has. Therefore, even when the light-emitting device is excited, the reflection at the interface between the void and the inorganic adhesive layer is suppressed, the light extraction efficiency does not decrease, and the coating film itself is stable.

Since the soft organic resin penetrates into the voids of the inorganic binder, the occurrence of cracks due to the volume expansion of the gas due to heat can be suppressed.

The inorganic adhesive is preferably formed with an inorganic adhesive layer covering at least a part of the light-emitting element and the substrate. This is because it is possible to easily use the resin-impregnated voids that the inorganic binder has by forming a layer structure. In addition, from the viewpoint of light extraction, light from the light emitting element can be emitted to the outside almost uniformly.

As the inorganic binder, it is preferable to fill voids in the inorganic binder layer with a resin. Thereby, voids in the inorganic adhesive layer disappear, and light extraction efficiency can be improved. Therefore, the amount of resin used is only enough to fill the voids of the inorganic adhesive layer.

In addition, the inorganic binder is preferably capable of filling 95% or more of voids in the inorganic binder layer with the resin. This is because if only a part of the voids of the inorganic adhesive layer is filled with the resin, the voids will suppress the extraction of light. When the inorganic adhesive layer is separated from the light-emitting element, since heat conduction is not directly performed from the light-emitting element, degradation due to heat is not particularly considered, and the resin does not need to fill the gap. However, if it is necessary to consider the light from the light-emitting element, it is preferable to fill the void almost completely with a resin.

The inorganic binder preferably contains a phosphor therein. Accordingly, the phosphor absorbs part of the light from the light-emitting element and converts the wavelength to emit light different from the light from the light-emitting element to the outside, and the part of the light from the light-emitting element and the light from the phosphor A part of the mixture can thereby provide a light-emitting device with a desired color tone. In addition, by designing an inorganic adhesive layer containing a phosphor, color tone adjustment can be facilitated, and a light-emitting device that emits uniform light and has a high yield can be provided.

The resin is preferably capable of forming a resin layer covering at least a part of the inorganic binder. By forming a layer structure, a coating film with a uniform film thickness can be formed, and the light extraction efficiency can be improved.

The surface of the resin layer is preferably a smooth surface. When the inorganic binder is cured, there are unevenness on its surface. Therefore, when the light emitted from the light-emitting element passes through the inorganic binder and is emitted to the outside, the directivity of the light is deviated due to the effect of the concave-convex portion. On the other hand, when the inorganic binder is impregnated with a resin, the surface of the coating film becomes smooth, and variations in light directivity can be reduced.

The resin preferably contains at least any one of oil, gel and rubber. This is to impregnate the resin into the inorganic binder. In particular, when the resin is impregnated into the inorganic binder using a resin in an oil state, gelation occurs due to heating or the like, whereby a light-emitting device with high light extraction efficiency can be improved. In addition, in a gel-like or rubber-like form, the hardness of the resin can be easily controlled. Furthermore, the lead wires electrically connected to the electrodes provided on the light emitting element and the external electrodes are not cut even if the resin is cured. In the prior art, when the epoxy resin is cured, the lead wire is cut due to the difference in thermal expansion coefficient between the lead wire and the epoxy resin. However, in the present invention, since the resin is oily, or gelatinous, or rubbery, the lead wire will not be cut. In addition, the impact resistance of the inorganic binder alone is weak, and by filling it with a resin such as rubber, the coating film can be given flexibility and a coating film with strong impact resistance can be formed.

The resin is preferably a silicone resin having a dialkylsiloxane skeleton both before and after molding. By using this resin, it is possible to provide a light-emitting device in which degradation of the resin is further suppressed, and a coating film that is resistant to ultraviolet rays or the like for a long period of time can be used.

The resin preferably has dimethylsiloxane on the main chain before molding. Accordingly, it is possible to provide a light-emitting device in which degradation of the resin is further suppressed, and a coating film that is resistant to ultraviolet rays or the like for a long period of time can be used.

In the bond absorption intensity of the resin in the infrared spectrum, it is preferable that the intensity ratio of the C—Si—O bond and the Si—O—Si bond in the resin composition is 1.2/1 or more. By setting it at 1.2/1 or more, since the resin remains in an oily, gel-like, or rubber-like state, stress can be relaxed and a coating film in which cracks or defects hardly occur can be formed.

The invention relates to a method for manufacturing a light-emitting device, which comprises: a first step of carrying a light-emitting element on a substrate; a second step of covering the light-emitting element with an inorganic binder; covering the inorganic binder with a resin The third process, wherein the third process uses the means of pouring the resin or spraying the resin to cover the inorganic binder. Voids in the inorganic binder can be filled by pouring the resin or spraying the resin. In addition, it is possible to prevent the gas present in the void from intruding into the resin. Furthermore, the resin covering the adhesive can be stably and uniformly applied. In particular, the light extraction efficiency can be improved by using a gel of hydrated oxides such as Al and Y elements whose oxidation states are stable without valence change during the sol-gel reaction process.

The third step may also be impregnated in a vacuum. Thereby, the resin can be easily impregnated into the voids in the inorganic adhesive layer. Although the cause thereof is not clear, it is generally considered to be caused by capillarity. Here, the so-called "gel" refers to a colloidal system composed of a solid and a liquid that have lost fluidity of the sol.

Description of drawings

FIG. 1 shows the relationship between the progress of the sol-gel reaction and the change in the light transmittance of the luminescent film.

Fig. 2 is a schematic diagram showing a light-emitting device according to Embodiment 1 of the present invention.

Fig. 3 is a plan view schematically showing a light emitting device according to Embodiment 2 of the present invention.

FIG. 4 is a cross-sectional view of the light emitting device of FIG. 3 .

Fig. 5 is a schematic cross-sectional view of a light emitting device according to still another embodiment of the present invention.

Fig. 6 schematically shows the process of forming a light emitting device according to an embodiment of the present invention.

Fig. 7 schematically shows a device for forming a light emitting device according to an embodiment of the present invention.

Fig. 8 is a plan view schematically showing a light emitting device according to Embodiment 3 of the present invention.

Fig. 9 is a cross-sectional view of the light emitting device of Fig. 8 along the line A-A'.

Fig. 10 is a cross-sectional view schematically showing a light emitting device according to Embodiment 4 of the present invention.

Fig. 11 is a cross-sectional view schematically showing a manufacturing process of a light-emitting device according to Embodiment 5 of the present invention.

Fig. 12 is a cross-sectional view schematically showing a manufacturing process of a light-emitting device according to Embodiment 5 of the present invention.

Fig. 13 is a cross-sectional view schematically showing a manufacturing process of a light-emitting device according to Embodiment 5 of the present invention.

Fig. 14 is a cross-sectional view schematically showing a manufacturing process of a light-emitting device according to Embodiment 5 of the present invention.

Fig. 15 is a cross-sectional view schematically showing a manufacturing process of a light-emitting device according to Embodiment 5 of the present invention.

Fig. 16 is a cross-sectional view schematically showing a manufacturing process of a light-emitting device according to Embodiment 5 of the present invention.

Fig. 17 is a cross-sectional view schematically showing a manufacturing process of a light-emitting device according to Embodiment 5 of the present invention.

Fig. 18 is a cross-sectional view schematically showing a manufacturing process of a light-emitting device according to Embodiment 5 of the present invention.

Fig. 19 is a cross-sectional view schematically showing a light emitting device according to Embodiment 5 of the present invention.

Fig. 20 is a plan view schematically showing another light-emitting device according to Embodiment 5 of the present invention.

Fig. 21 is a cross-sectional view of the light emitting device of Fig. 20 taken along line BB'.

Fig. 22 is an enlarged cross-sectional view of a main part of the light emitting device of Fig. 21 .

23 is a chromaticity diagram showing the chromaticity of phosphors in Examples 15 to 23 of the present invention.

Fig. 24 is a spectrum diagram of the three-wavelength white phosphor of Example 23 of the present invention excited by an LED with a wavelength of 365 nm.

Fig. 25 is a spectrum diagram of the three-wavelength white phosphor of Example 19 of the present invention excited by an LED with a wavelength of 400 nm.

Fig. 26 shows the results of a reliability test of phosphors according to examples of the present invention.

Fig. 27 shows the results of a reliability test of phosphors according to examples of the present invention.

Fig. 28 shows the results of a reliability test of phosphors according to examples of the present invention.

Fig. 29 shows the results of a reliability test of phosphors according to examples of the present invention.

Fig. 30 shows the results of a reliability test of phosphors according to examples of the present invention.

Fig. 31 is a schematic plan view showing a light emitting device according to Embodiment 6 of the present invention.

Fig. 32(a) is a schematic cross-sectional view showing a light-emitting device according to an embodiment of the present invention, and Fig. 32(b) is a schematic cross-sectional view showing an enlarged concave portion of a substrate.

Fig. 33 is a schematic diagram showing a part of the manufacturing process of the light-emitting device according to the embodiment of the present invention.

Fig. 34 is a schematic view showing part of another manufacturing process of the light-emitting device according to the embodiment of the present invention.

Fig. 35 is a schematic diagram showing part of yet another manufacturing process of the light-emitting device according to the embodiment of the present invention.

Fig. 36(a) is an enlarged schematic cross-sectional view of a concave portion of a substrate of a light-emitting device according to Embodiment 7 of the present invention, and Fig. 36(b) is a perspective view showing the light-emitting device.

Fig. 37(a) is an enlarged schematic cross-sectional view of a concave portion of a substrate of a light emitting device according to Embodiment 8 of the present invention, and Fig. 37(b) is a perspective view showing the light emitting device.

Fig. 38 is a schematic cross-sectional view showing part of a light-emitting device according to Embodiment 9 of the present invention.

Fig. 39 shows the results of the durability test of the light-emitting device of the example.

FIG. 40 shows the results of the light extraction efficiency of the light emitting device of the example.

Fig. 41 is an infrared spectrogram showing coating films of Examples.

Fig. 42 is a schematic cross-sectional view showing a light emitting device of a comparative example.

Fig. 43 is an infrared spectrum chart showing a coating film of a comparative example.

Fig. 44 is a schematic configuration diagram showing a light-emitting device according to Embodiment 10 of the present invention.

Detailed ways

Embodiments of the present invention will be described below on the basis of the drawings. However, the embodiments shown below are only for actualizing the technical idea of the present invention, and are illustrations of a light emitting film, a light emitting device, a method of manufacturing a light emitting film, and a method of manufacturing a light emitting device, and do not describe the light emitting film of the present invention. , a light-emitting device, a method for manufacturing a light-emitting film, and a method for manufacturing a light-emitting device are specified as follows. In addition, the means shown in the claims are by no means specified as the means of the embodiment. In addition, the size, positional relationship, and the like of members shown in the drawings are sometimes exaggerated for clarity of description. Furthermore, each element constituting the present invention may be configured in such a manner that a plurality of elements are constituted by the same member, or a plurality of elements are used in combination by one member.

In an embodiment of the invention, gels of hydrous oxides are used as binders. Figure 1 shows that as the sol-gel reaction proceeds, from the sol state through the gel containing crystal water, or hydrated oxides and oxides to amorphous or polycrystalline oxides, the luminescent film Changes in light transmittance and light extraction efficiency. As shown in Figure 1, in the case of using gel as a binder, it can generally be considered that as the sol-gel reaction progresses, the closer to the polycrystalline structure, the transmittance of the luminescent film is as shown in A in the figure. As shown, it will rise more and more. However, considerable energy is required in obtaining polycrystals using sol-gel reactions. The process of separating the hydroxyl groups and organic groups contained in the structure of the gel state requires a relatively high temperature, so it is not so easy.

As a result of intensive studies, the present inventors have found that, among specific metal elements, high light extraction efficiency can be obtained in a gel state without improving the crystallinity, thereby achieving the present invention. In particular, if a gel of hydrated oxides such as Al and Y elements whose oxidation state is stable without valence change during the sol-gel reaction is used, as shown in B in FIG. 1, it is found that The light extraction efficiency in the gel state tends to be higher than that in the polycrystalline state where the sol-gel reaction is progressing. For example, in amorphous materials such as yttrium, it is generally believed that one of the causes is the scattering of light. That is to say, in the stage of crystallization by high-temperature heating, in the crystallization process from a to b that forms multimolecules from the perspective of chemical structure, it is generally considered that the partially crystallized part and the part that is in the condensed phase are microscopically The part in the gel state undergoes phase separation to form a multiphase structure. Therefore, from a microscopic point of view, there is inhomogeneity between phases, so light scattering occurs at the interface of the phases, and the transmittance decreases as a whole. As another reason, it is generally considered to be caused by the crystal structure. That is, in the state from a to b, due to the formation of crystalline regions and amorphous regions based on the formation of spherulites, the density and refractive index of each region are different. Even if it is microscopically uniform, it will form a multi-molecular structure optically, thus lowering the transmittance as a whole. Therefore, by forming a luminescent film in a gel state even without forming polycrystals, the sol-gel reaction does not continue, and a luminescent film with high light extraction efficiency can be easily obtained in a short time and with low energy.

In addition, the gel state is a state containing hydroxyl groups in hydrous oxides or water of crystallization, and it is presumed that the light extraction efficiency changes depending on the content thereof. As a result of repeated experiments by the present inventors, it was confirmed that higher light extraction efficiency can be obtained when the content of hydroxyl groups or water of crystallization is 10% by weight or less of the hydrous oxide. In this way, by setting the gel state containing crystal water, a dense film can be obtained, and the light extraction efficiency is better than that of a film that has been completely cured and crystallized. This is generally considered to be because in the gel state, the hydrous oxide has a cross-linked structure including some oxides, which improves the adhesion between the phosphor and the device.

In addition, the quality of the formed luminescent film and luminescent layer can be improved by using the gel of the hydrated oxide to constitute the binder member. A binder member containing a hydrated oxide has particulate matter aggregated by a sol-gel method to form a porous body having a crosslinked structure, a network structure, or a polymer structure.

If the skeleton structure of the particle assembly of the hydrous oxide is a network structure having pores, the flexibility of the luminescent film can be improved because it is a porous structure. In addition, even if filler members such as phosphor particles are attached during film formation of the luminescent layer, and the object to be coated has a complex shape, the film can be formed accordingly, and a luminescent film with high adhesion can be obtained. Furthermore, since it is a hydrous oxide, a film that is stable against heat and light and does not deteriorate can be obtained.

Since the formed light-emitting film is exposed to light from the light-emitting element, it is degraded by use of the light-emitting device. It is generally considered that the cause of this degradation is the occurrence of a reaction due to either or both of light output power and heat generation from the light-emitting element. Therefore, when ultraviolet rays with high light energy are used for large components that generate heat and have high thermal resistance values, degradation is likely to occur. As will be described later, samples of examples of the present invention were prepared and subjected to durability tests, and as a result, it was confirmed that they had extremely high durability. Although the reason for this is not clear, it is generally believed that the reason is that such a structure is selected that a hydrated oxide having a constant valence is less likely to undergo redox reactions under the action of thermal energy and light energy. Therefore, it is preferable to use a metal element whose valence does not change in the hydrous oxide. For example, in the case of using Si, etc., which can obtain various ion valence states, as a gel or a cured film, it is presumed that the change in valence is likely to occur due to optical density and heat conduction due to heat generation of the element, thereby causing coloring deterioration. produce. In contrast, in the light-emitting layer using the trivalent hydrated oxide obtained in the embodiment of the present invention as a binder, oxidation-reduction reactions hardly occur. Therefore, the light-emitting device of the present invention can have sufficient resistance even when it is in contact with or close to a high-output semiconductor light-emitting element with a light irradiation density of, for example, 0.1 W/cm ² to 1000 W/cm ² .

(binder)

Silica (SiO ₂ ) is used as a binder for attaching phosphors used under high temperature or ultraviolet excitation. As the silica binder continues to be used, the fluorescent member in which the fluorescent substance that converts the light emission of the light-emitting element and the light-transmitting material are mixed gradually blackens. The inventors of the present invention studied the cause of such deterioration of coloration, and as a result, found that the cause is generation of SiO _X (x<2) due to oxygen deficiency in the silica adhesive layer.

The silica binder is in the form of silica gel at a thermal curing temperature of 250°C or below, and a part of hydroxyl groups and organic groups remain in the _SiO2 skeleton. In the state of such a silica gel, when high-density light is incident from the LED, oxygen vacancies are generated by light energy or thermal energy, thereby generating SiO _X from SiO ₂ (x<2: x is 1.4 to 1.9 about). It is generally considered that the SiO _X is colored to cause blackening. In this way, silica gel is generally considered to be because Si, the main metal element, can take various valences, and Si tends to change in valence to cause oxidation and reduction, thereby causing coloring degradation. Therefore, in an embodiment of the present invention, a binder containing a hydrated oxide or an oxide in which a metal element does not change in valence is used. An example using alumina and yttrium oxide will be described below.

(alumina)

Amorphous alumina or microparticle hydrated alumina is uniformly dispersed in water, and the alumina sol thus formed is used as a binder, in this case, the alumina sol is heated and solidified to form a stable boehmite Before the structure of the hydrated alumina, it undergoes a stage of pseudo-boehmite structure. The boehmite crystal structure of hydrated alumina and the pseudo-boehmite structure of hydrated alumina can be represented by the chemical formula AlOOH or Al ₂ O ₃ ·H ₂ O and (AlOOH)·xH ₂ O or Al ₂ O ₃ ·2H ₂ O wait to express. Specifically, Al ₂ O ₃ ·2H ₂ O, Al ₂ O ₃ ·xCH ₃ COOH ·yH ₂ O, Al ₂ O ₃ ·xHCl·yH ₂ O, Al ₂ O ₃ ·xHNO ₃ ·yH ₂ O and other forms, finally forming a stable boehmite structure. If the crystallinity of the boehmite structure is further improved, it becomes γ-alumina (Al ₂ O ₃ ) or α-alumina (Al ₂ O ₃ ). An alumina sol having such properties is used as a binder, thereby forming a light emitting film.

As the specific main material of the luminescent film, a sol solution prepared by the following method can be used, that is, a small amount of inorganic acid, organic acid and alkali are used as stabilizers, and amorphous metal oxides, ultrafine metal hydrated oxides and ultrafine particles Oxides, etc. are uniformly dispersed in water or organic solvents. As the starting materials for the synthesis of amorphous metal oxides, ultrafine metal hydrated oxides, and ultrafine particle oxides, metal alkoxides, metal diketonates, metal halides, or metal oxides can be used. Hydrolyzed products of carboxylate and metal alkyl compounds, and hydrolyzed products after mixing them. In addition, a colloid (sol) solution prepared by uniformly dispersing metal hydroxides, metal chlorides, metal nitrates, and metal oxide fine particles in water and an organic solvent, or a mixed solvent of water and a water-soluble organic solvent can also be used. . They are collectively referred to as aluminoxanes. Aluminoxane has a repeating unit of [AlO] _X in its skeleton.

As the metal alkoxide, there are: aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, aluminum isopropoxide , tert-butoxy aluminum, methoxy yttrium, ethoxy yttrium, n-propoxy yttrium, isopropoxy yttrium, n-butoxy yttrium, sec-butoxy yttrium, isopropoxy yttrium, tert-butoxy Yttrium etc.

As bis-diketonate metals, available are: aluminum triethylacetoacetate, diisopropoxyaluminum alkylacetoacetate, diisopropoxyaluminum ethylacetoacetate, diethylacetylacetonate monoacetylacetonate Aluminum acetate, aluminum triacetylacetonate, yttrium triacetylacetonate, and yttrium triethylacetoacetate.

Usable metal carboxylates include aluminum acetate, aluminum propionate, aluminum 2-ethylhexanoate, yttrium acetate, yttrium propionate, and yttrium 2-ethylhexanoate.

In addition, as metal halides, aluminum chloride, aluminum bromide, aluminum iodide, yttrium chloride, yttrium bromide, yttrium iodide, and the like can be used.

As an organic solvent, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, tetrahydrofuran, dioxane, acetone, ethylene glycol, methyl ethyl ketone, N, N -Dimethylformamide and N,N-dimethylacetamide, etc.

In addition to these used as a binder for forming the light emitting layer, phosphors and diffusing particles as fillers may be mixed. Furthermore, as a composite of these, the coefficients of linear expansion of the substrate and the light-emitting element can also be made the same. As a filler, it is not only necessary to mix phosphors to produce light emission, but also to create fine channels for moisture evaporation during curing, which has the effect of accelerating the curing and drying of the adhesive. In addition, it also has the function of diffusing the luminescence of the phosphor and increasing the bonding strength and physical strength of the luminescent layer. In addition, a light emitting layer and a light emitting film can also be used as a diffusion layer not containing a phosphor. In addition, the composite material used as a binder may contain a small amount of elements having various valences in addition to trivalent metal elements. Furthermore, the binder member may contain a hydrated oxide as a main compound, and may function even if it contains a part of metal oxide and metal hydroxide and combinations thereof.

(filler)

Fillers are fillers, which can be used: barium titanate, titanium oxide, aluminum oxide (aluminum oxide), yttrium oxide (yttrium oxide), silicon dioxide, calcium carbonate, and other hydrated oxides. For example, there may also be a colorless hydrated oxide containing at least one or more elements selected from Al, Ga, Ti, Gc, P, B, Zr, Y, or alkaline earth metals, or at least containing one or more elements selected from Oxides of one or more elements among Si, Al, Ga, Ti, Ge, P, B, Zr, Y or alkaline earth metals have higher thermal conductivity fillers. By adding such fillers, the heat removal effect of the light emitting device can be improved. Examples of such fillers include metal powders such as alumina and Ag when forming an adhesive layer using the above-mentioned inorganic binder and performing die bonding on an LED chip.

In the sol of the binder, besides the phosphor and the lower alcohol, by mixing the dispersant in advance, a dense coating film can be formed at low temperature by means of azeotropic dehydration with the lower alcohol during curing. In addition, photostabilizers, colorants, ultraviolet absorbers, and the like may be contained.

Furthermore, boric acid and boron oxide may be added when forming the luminescent film. Due to the addition of boric acid and boron oxide, the elasticity of the luminescent film is reduced, so the quality of the film is improved. For example, it is possible to suppress the occurrence of cracks in the luminescent film and form a dense film. Boric acid and boron oxide are preferably contained in an amount of 0.5% by weight to 50% by weight relative to the binder member. In addition, a tackifier other than boric acid and boron oxide may be added to the luminescent film. In this way, the binder member may contain additives for controlling the viscosity of the slurry in addition to hydrated oxides such as aluminum. Therefore, by controlling viscosity and improving thixotropy during film formation, films with complex shapes can be formed. In addition, after the film is formed, since the binder is a hydrous oxide, the tolerance to additives can be improved, and it can also play a role in controlling the structure of the binder structure.

The light emitting layer is formed using a slurry solution. The slurry solution is prepared by using amorphous metal hydrated oxide, fine particle metal hydrated oxide, and metal hydroxide as the main components, and the main components are further mixed with amorphous metal oxide and fine particle metal oxide. Dispersed in water, thereby preparing a sol solution, and then mixing the phosphor and the filler in the sol solution. The weight ratio of the effective solid component in the sol solution to the phosphor, or the weight ratio of the effective solid component in the sol solution to the phosphor and the filler mixture is preferably 0.05-30. For example, the ratio can be adjusted within a range from 90 g of phosphor to 20 g of a sol solution with an effective solid concentration of 15% to 4.5 g of phosphor to 600 g of a sol solution with an effective solid concentration of 15%.

(yttrium oxide)

In the case where amorphous yttrium oxide or fine particle yttrium oxide is uniformly dispersed in water, and the yttrium oxide sol thus formed is used as a binder, even if the yttrium oxide sol is heat-cured, the main body of the crystalline structure is amorphous. Hydrated yttrium oxide and yttrium oxide can be represented by chemical formulas such as YOOH·xH ₂ O and Y ₂ O ₃ ·xH ₂ O, respectively. Specifically, as an intermediate, it passes through the form of YOOH·xCH ₃ COOH·yH ₂ O or Y ₂ O ₃ ·xCH ₃ COOH·yH ₂ O, and finally becomes a form partially containing hydrated yttrium oxide or yttrium oxide. Yttrium oxide can form a stable film even in such a gel state. The reason for this is considered to be that each component has a cross-linked structure, which enables stabilization.

Yttrium oxide has a property that it is difficult to form a crystal structure compared with alumina. In this way, even an amorphous non-crystalline structure having no crystallinity can be a stable compound, and the valency of Y remains unchanged without changing the valence number. That is, it has the advantage that oxidation-reduction reaction hardly occurs and there is no color degradation.

For the rest, the light-emitting layer is formed in the same manner as the above-mentioned alumina. As described above, commercially available inorganic binders, ceramic binders, and the like can be used as the sol in which the phosphor is used as a binder. In addition, among the materials that can be used as binders, they are not limited to hydrated oxides containing Al and Y elements such as alumina and yttrium oxide, and hydrated oxides of other IIIA group elements and IIIB group elements can also be used. compounds, oxides, and hydroxides. The selected metal element preferably does not change in valence. In particular, trivalent and stable metal elements are preferable. In addition, it is also preferably colorless and transparent. For example, in addition to Al and Y, metal compounds containing metal elements such as Gd, Lu, Sc, Ga, and In can also be used, preferably Sc and Lu can be used. Alternatively, composite oxides and composite hydrated oxides in which multiple types of these elements are combined can also be used. Not only aluminum and yttrium, but also various properties such as optical properties such as the refractive index of the luminescent film and physical properties of the film such as film flexibility and adhesiveness can be controlled by hydrated oxides containing other group III elements. desired value. In this way, by having an inorganic binder containing a hydrated oxide gel having a constant valence, preferably trivalent, obtained by the embodiment of the present invention, the formed light-emitting layer can be designed to be stable and have a high light extraction efficiency. layer. In addition, since it is composed of inorganic materials, it is possible to produce stable light-emitting layers and light-emitting films that do not change over time.

Implementation 1

Next, a light-emitting device according to Embodiment 1 of the present invention will be described with reference to FIG. 2 . The light-emitting device according to Embodiment 1 includes a light-emitting element 10, and a fluorescent member 11 composed of a phosphor 11a and a translucent adhesive 11b containing the phosphor 11a.

A light-emitting element 10 made of a cannonball-shaped LED is soldered to and carried by a substantially central portion of a cup, wherein the cup is disposed on an upper portion of a mount lead 13a. Electrodes formed on the light emitting element 10 are electrically connected to pin leads 13 a of a leadframe 13 and inner leads 13 b through conductive leads 14 . Phosphor 11 a includes a YAG-based phosphor and a nitride-based phosphor that absorb at least part of the light emitted from the light-emitting element 10 and emit light having a wavelength different from that of the absorbed light. Furthermore, the nitride-based phosphor can be covered with a covering material such as microcapsules. The fluorescent member 11 containing the fluorescent substance 11a in the adhesive 11b is placed on the cover on which the light emitting element 10 is placed. In this way, in order to protect the LED chips and phosphors from external stress, moisture, and dirt, and to improve light extraction efficiency, the lead frame 13 configuring the light emitting element 10 and the fluorescent member 11 is molded in the mold member 15, thereby forming light emitting device. In this way, after forming the light-emitting layer containing the binder made of hydrous oxide, it is also possible to form a lens or the like in the form of a resin mold.

(light emitting element)

In this specification, the light-emitting element includes, in addition to semiconductor light-emitting elements, elements for obtaining light emission by vacuum discharge and light emission by thermoluminescence. For example, an element that generates ultraviolet rays or the like by vacuum discharge can also be used as a light emitting element. In an embodiment of the present invention, the light-emitting element used has a wavelength of 550 nm or less, preferably 460 nm or less, more preferably 410 nm or less. For example, an ultraviolet light LED which emits light with a wavelength of 250 nm to 365 nm as ultraviolet light and a high-pressure mercury lamp with a wavelength of 253.7 nm can be used. In particular, as will be described later, the embodiments of the present invention have advantages in that they are excellent in durability and can be applied to dynamic light-emitting elements with high output power.

An example in which a Group III nitride-based semiconductor light-emitting element is used as the light-emitting element 10 will be described below. The light-emitting element 10 is, for example, a stacked structure formed by sequentially stacking the following layers on a sapphire substrate with a GaN buffer layer interposed therebetween: the first n-type GaN layer with undoped Si or a low Si concentration; An n-type contact layer composed of n-type GaN with a higher Si concentration than the first n-type GaN layer; a second GaN layer with an undoped or lower Si concentration than the n-type contact layer; a light-emitting layer with a multiple quantum well structure (GaN barrier layer /InGaN well layer quantum well structure); a p-cladding layer composed of P-type GaN, wherein P-type GaN is composed of Mg-doped P-type GaN; a P-type contact layer composed of Mg-doped P-type GaN. And the electrodes were formed as follows. Of course, a light emitting element having a configuration different from this may also be used.

The p-ohmic electrode is formed on almost the entire surface of the p-type contact layer, and a p-pad electrode (pad electrode) is formed on a part of the p-ohmic electrode.

In addition, the first GaN layer is removed from the p-type contact layer by etching to expose a part of the n-type contact layer, and the n-electrode is formed on the exposed part.

In addition, this embodiment uses a light-emitting layer with a multiple quantum well structure, but the present invention is not limited thereto. For example, both a single quantum well structure and a multiple quantum well structure of InGaN can be used, and GaN doped with Si and Zn can also be used.

In addition, by changing the In content of the light-emitting layer of the light-emitting element 10, the main light-emitting peak can be changed within the range of 420 nm to 490 nm. Furthermore, the emission wavelength is not limited to the above-mentioned range, and a light emitting element having an emission wavelength of 360 nm to 550 nm can be used. In particular, when the light-emitting device according to the embodiment of the present invention is applied to an ultraviolet LED light-emitting device, the absorption and conversion efficiency of excitation light can be improved, and the transmission of ultraviolet light can be reduced.

(phosphor)

The phosphor converts visible light and ultraviolet light emitted from the light emitting element into light emission of other wavelengths. For example, excitation is performed with light emitted from the semiconductor light emitting layer of the LED to generate light emission at other wavelengths. Usable phosphors include YAG-based, nitride-based phosphors such as alkaline-earth silicon nitride phosphors, and oxynitride-based phosphors such as alkaline-earth silicon oxynitride phosphors. In the present embodiment, a phosphor that is excited by ultraviolet light to generate light of a predetermined color is used as the phosphor. Specifically, examples of phosphors that can be used are as follows:

(1) Ca ₁₀ (PO ₄ ) ₆ FCl:Sb, Mn

(2) M ₅ (PO ₄ ) ₃ Cl:Eu (wherein: M is at least one selected from Sr, Ca, Ba and Mg)

(3) BaMg ₂ Al ₁₆ O ₂₇ :Eu

(4) BaMg ₂ Al ₁₆ O ₂₇ :Eu, Mn

(5) 3.5MgO·0.5MgF ₂ ·GeO ₂ : Mn

(6)Y ₂ O ₂ S:Eu

(7)Mg ₆ As ₂ O ₁₁ :Mn

(8) Sr ₄ Al ₁₄ O ₂₅ :Eu

(9)(Zr,Cd)S:Cu

(10)SrAl ₂ O ₄ :Eu

(11) Ca ₁₀ (PO ₄ ) ₆ ClBr:Mn, Eu

(12)Zn ₂ GeO ₄ :Mn

(13)Gd ₂ O ₂ S:Eu

(14) La ₂ O ₂ S:Eu

(15)Ca ₂ Si ₅ N ₈ :Eu

(16)Sr ₂ Si ₅ N ₈ :Eu

(17)SrSi ₂ O ₂ N ₂ :Eu

(18) BaSi ₂ O ₂ N ₂ :Eu

In addition to the above-mentioned phosphors, YAG-based rare-earth aluminates represented by (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce, etc., which emit light in the yellow region, can of course also be used. Phosphor.

When the light emitted by the LED chip and the light emitted by the phosphor have a complementary color relationship, white light can be emitted by mixing the respective lights. Specifically, the light emitted by the LED chip and the light of the phosphor excited by the light correspond to the three primary colors (red, green, and blue) and the blue light emitted by the LED chip. and the yellow light of the fluorescent substance excited by this light. Especially in the case of using ultraviolet light, because the emission color of the phosphor excited by ultraviolet light can be used alone, various intermediate color light-emitting devices such as blue-green, yellow-red, red, etc. and light colors for signals can be obtained. It is also possible.

By adjusting the ratio of various resins and inorganic bonding members such as glass and fillers, the sedimentation time of phosphors, the shape of phosphors, etc., which function as a binder between phosphors, and By selecting the light emission wavelength of the LED chip, the light emission color of the light emitting device can provide any white tone such as electric bulb color. On the outside of the light-emitting device, it is preferable that the light emitted from the LED chip and the light emitted from the phosphor efficiently pass through the mold member.

Typical phosphors include copper-activated cadmium zinc sulfide and cerium-activated YAG-based phosphors. Especially for high luminance and long-term use, (Re _1-x Sm _X ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ :Ce(0≤x<1, 0≤y≤1, where : Re is at least one element selected from Y, Gd, La and Lu.

(Re _1-x Sm _X ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ : Ce phosphor has a garnet structure, so it has strong resistance to heat, light and moisture, and the excitation peak can reach about 470nm . In addition, it may also have a broad emission spectrum, the emission peak of which is around 530nm, and the end of the peak extends to 720nm.

In the light-emitting device according to the embodiment of the present invention, the phosphor may be a mixture of two or more phosphors. That is, two or more (Re _1-x Sm _X ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ :Ce phosphors with different contents of Al, Ga, Y, La, Lu, and Gd and Sm can be used Mixing is performed to increase the wavelength components of RGB. In addition, by using a red-increasing component such as a nitride phosphor having yellow to red light emission, it is also possible to obtain lighting or bulb-colored LEDs with a high average color rendering index. Specifically, by mixing and matching the light-emitting wavelengths of light-emitting elements, adjusting the content of phosphors with different chromaticity points on the CIE chromaticity diagram, it is possible to emit light at any point on the chromaticity diagram, where the chromaticity diagram uses light-emitting elements to The phosphors are connected together.

In this way, the phosphor can be dispersed in the gas phase and the liquid phase and emit light uniformly. Phosphors dispersed in the gas phase and liquid phase drop by their own weight. Especially in the liquid phase, by allowing the suspension to stand still, it is possible to form a film having a more uniform phosphor. By repeating as many times as required, the desired amount of phosphor can be formed.

On the surface of the light-emitting device, two or more kinds of phosphors formed as above may exist in a single-layer light-emitting layer, or one or two kinds may exist in two-layer light-emitting layers. or more. In this way, white light can be obtained by color mixing of lights originating from different phosphors. At this time, in order to better mix colors of light emitted by each phosphor and reduce color unevenness, it is preferable that each phosphor has a similar average particle size and shape. In addition, the light emitting layer may be formed in consideration of the sedimentation characteristics influenced by the shape. As a method of forming a light-emitting layer that is not easily affected by sedimentation characteristics, a spray coating method, a screen printing method, a pouring method, and the like can be mentioned. In this embodiment, the inorganic binder can have an effective solid content of 1% to 80%, can adjust the viscosity in a wide range of 1cps to 5000cps, and can also adjust thixotropy, so it can be used with these light-emitting layers. Compatible with the forming method. As described above, the weight ratio of the filler to the inorganic binder is preferably set in the range of 0.05 to 30, and the binding force is enhanced by adjusting the compounding amount and particle size of the filler.

The phosphor used in this embodiment may be a combination of a YAG-based phosphor, a phosphor that may emit red light, and particularly a nitride phosphor such as an alkaline-earth silicon nitride phosphor. These YAG-based phosphors and phosphors may be mixed and included in the light-emitting layer, or may be separately included in a multi-layered light-emitting layer. The respective phosphors will be described in detail below.

(YAG-based phosphor)

The so-called YAG-based phosphor used in this embodiment is a phosphor activated by rare earth elements such as cerium or Pr, which contains Y and Al, and contains a phosphor selected from Lu, Sc, La, Gd, Tb, Eu, and Sm. At least one element and one element selected from Ga and In are phosphors that emit light when excited by visible light or ultraviolet light emitted by the LED chip. Particularly in this embodiment, two or more kinds of yttrium/aluminum oxide-based phosphors activated with cerium or Pr and having different compositions can also be used. If the blue-based light emitted by a light-emitting element using a nitride-based compound semiconductor as a light-emitting layer, and the green-based and red-based light emitted by a phosphor whose body color is yellow due to absorption of blue light, or The yellow-based light but the green-based light and the red-based light are mixed and displayed, and the desired white-based luminous color can be displayed. Since color mixing occurs in the light-emitting device, powders and lumps of phosphors may be contained in various resins such as epoxy resins, acrylic resins, or silicone resins, and light-transmitting inorganic substances such as the inorganic binder of this embodiment. In this way, the light-emitting layer containing phosphor can be used in various ways depending on the application of the phosphor in point form or layer form, and the light-emitting layer is formed thin enough to transmit light emitted from the LED chip. By adjusting the ratio of phosphors and translucent inorganic substances, coating and filling amounts, and by selecting the emission wavelength of the light-emitting element, it is possible to provide arbitrary color tones such as bulb colors including white.

In addition, a light-emitting device capable of emitting light efficiently can be obtained by arranging two or more kinds of phosphors in sequence with respect to incident light from the light-emitting element. That is, on a light-emitting element having a reflective member, a color conversion member containing a phosphor having an absorption wavelength on the long-wavelength side and capable of emitting long-wavelength light, that is, a light-emitting layer containing a phosphor as a filler, is arranged in a stacked manner, and There is a color conversion member that absorbs wavelengths longer than the light-emitting layer and can emit longer-wavelength light, whereby reflected light can be effectively used.

If a YAG-based phosphor is used, even if an LED chip having a radiant optical density of 0.1 W·cm ^-2 to 1000 W·cm ^-2 is placed in contact with or close to, a highly efficient light-emitting device with sufficient light resistance can be obtained.

The yttrium-aluminum oxide-based phosphor activated with cerium used in this embodiment, that is, the YAG-based phosphor that can emit green light, has a garnet structure, so it has strong resistance to heat, light, and moisture, and the excitation absorption spectrum The wavelength of the peak may be around 420nm to 470nm. In addition, it has a broad luminescence spectrum, and its luminescence peak peak wavelength λp is around 510nm, and the end of the peak extends to around 700nm. On the other hand, the yttrium-aluminum oxide-based phosphor activated by cerium, that is, the YAG-based phosphor that emits red light, also has a garnet structure, so it has strong resistance to heat, light, and moisture, and the excitation absorption spectrum The wavelength of the peak may be around 420nm to 470nm. In addition, it has a broad luminescence spectrum, and its luminescence peak peak wavelength λp is around 600nm, and the end of the peak extends to around 750nm.

In the composition of the YAG-based phosphor having a garnet structure, a part of Al is substituted with Ga, thereby shifting the emission spectrum to the short wavelength side, and a part of Y in the composition is substituted with Gd and/or La, thereby making The emission spectrum shifts to the long wavelength side. In this way, by changing the composition, the emission color can be continuously tuned. Therefore, the nitride semiconductor can continuously change the intensity on the long-wavelength side according to the composition ratio of Gd, and blue light emission using such a nitride semiconductor has ideal conditions for switching to white light emission. When the substitution of Y is less than 20%, the green component increases and the red component decreases, and when it is 80% or more, the luminance drops sharply although the red component increases. In addition, the same applies to the excitation absorption spectrum. In the composition of the YAG-based phosphor having a garnet structure, a part of Al is substituted with Ga, thereby shifting the excitation absorption spectrum to the short-wavelength side, and replacing it with Gd and/or La. A part of Y in the composition shifts the excitation absorption spectrum to the long-wavelength side. The peak wavelength of the excitation absorption spectrum of the YAG-based phosphor is preferably on the shorter wavelength side than the peak wavelength of the emission spectrum of the light emitting element. With such a structure, when the current supplied to the light-emitting element increases, the peak wavelength of the excitation absorption spectrum is basically the same as the peak wavelength of the emission spectrum of the light-emitting element, so that the excitation efficiency of the phosphor will not be reduced, and the chromaticity will be shifted. A light-emitting device in which migration is suppressed.

Such phosphors use oxides of Y, Gd, Ce, La, Lu, Al, Sm, and Ga or compounds that tend to become oxides at high temperatures as raw materials, and the raw materials are obtained by sufficiently mixing them in a stoichiometric ratio. Or dissolve the rare earth elements of Y, Gd, Ce, La, Lu, Al, Sm in the acid according to the stoichiometric ratio, then use oxalic acid to make the solution obtained in this way co-deposit, and then carry out the co-deposition product obtained in this way The co-deposition oxide is obtained by sintering, and then the co-deposition oxide is mixed with aluminum oxide and gallium oxide to obtain a mixed raw material. Add an appropriate amount of fluoride such as ammonium fluoride to the mixed raw material as a flux and put it into a crucible, and then sinter in air at a temperature range of 1350°C to 1450°C for 2 hours to 5 hours to obtain a sintered product, Next, the sintered product is ball-milled in water, washed, separated, dried, and finally sieved to obtain the phosphor. In addition, the manufacturing method of the phosphor in other embodiments is preferably sintered in two stages, and the two stages are composed of a first sintering process and a second sintering process, wherein the first sintering process will be composed of mixed raw materials mixed with phosphor raw materials and The flux composition mixture is sintered in the air or in a weakly reducing atmosphere, and the second sintering process is sintered in a reducing atmosphere. Here, the so-called weak reducing atmosphere refers to a weak reducing atmosphere that contains at least a necessary amount of oxygen during the reaction process of forming the required phosphor from the mixed raw materials. In this weak reducing atmosphere, the first step is performed. A sintering process is performed until the formation of the desired structure of the phosphor is completed, thereby preventing blackening of the phosphor and reducing light absorption efficiency. In addition, the reducing atmosphere in the second sintering step refers to a stronger reducing atmosphere than a weak reducing atmosphere. By performing sintering in two steps in this way, a phosphor having high absorption efficiency of the excitation wavelength can be obtained. Therefore, when a light-emitting device is formed using the phosphor formed in this way, the amount of phosphor required to obtain a desired color tone can be reduced, and a light-emitting device with high light extraction efficiency can be formed.

Two or more cerium-activated yttrium-aluminum oxide-based phosphors having different compositions may be used in combination, or may be arranged independently of each other. When disposing the phosphors independently, it is preferable to dispose them in the following order, first disposing the phosphors that are easy to absorb light from the light-emitting element on the short-wavelength side and emit light, and then disposing on the relatively long-wavelength side that is easy to absorb light from the light source. The light-emitting element emits light and emits phosphor. Accordingly, the phosphor can efficiently absorb light emitted from the light-emitting element and emit light.

(nitride phosphor)

As the phosphor used in this embodiment, in addition to the above-mentioned yttrium-aluminum-oxide-based phosphor activated by cerium, an alkaline-earth nitride-based phosphor activated by Eu or rare earths having a yellow-red to red emission wavelength is also suitable. . This phosphor is excited to emit light by absorbing visible light and ultraviolet light emitted from the LED chip and light emitted from the YAG-based phosphor. The phosphors of the embodiments of the present invention are particularly: Sr-Ca-Si-N:R, Ca-Si-N:R, Sr-Si-N:R, Sr-Ca-Si-ON:R, Ca-Si -ON:R and Sr-Si-ON:R-based silicon nitride. The basic constituent elements of these phosphors can be represented by the general formula L _X Si _Y N _(2/3X+4/3Y) : R or L _X Si _Y O _Z N _{(2/3X+4/3Y-2/3Z)} : R (L is any group among Sr, Ca, and Sr and Ca). In the general formula, X and Y are preferably X=2, Y=5 or X=1, Y=7, but may be arbitrary values. In addition, R is a rare earth element that must contain Eu, N is nitrogen, and O is oxygen. Specifically, it is preferable to use basic constituent elements such as (Sr _X Ca _1-X ) ₂ Si ₅ N ₈ :Eu, Sr ₂ Si ₅ N ₈ :Eu, Ca ₂ Si ₅ N ₈ :Eu, Sr _X Ca _1- Phosphors represented by _X Si ₇ N ₁₀ :Eu, SrSi ₇ N ₁₀ :Eu, CaSi ₇ N ₁₀ :Eu, but in the composition of the phosphors, may also contain Mg, B, Al, Cu, Mn, At least one or more of Cr and Ni. However, the present invention is not limited to the embodiments and examples.

L is any one group among Sr, Ca, and Sr and Ca. The ratio of Sr and Ca can be changed according to requirements.

As the luminescent center, europium Eu, which is a rare earth element, is mainly used. Europium mainly has divalent and trivalent energy levels. The phosphor according to the embodiment of the present invention uses Eu ²⁺ as an activator for alkaline earth metal-based silicon nitride as a matrix. In addition, Mn can also be used as an additive.

The method for producing the phosphor ((Sr _X Ca _1-X ) ₂ Si ₅ N ₈ :Eu) used in the embodiment of the present invention will be described below, but the present invention is not limited to this production method. Mn and O are contained in the above-mentioned phosphor.

Sr and Ca as raw materials are pulverized. It is preferable to use simple substances of Sr and Ca as raw materials, but compounds such as imide compounds and amide compounds may also be used. Sr and Ca obtained by pulverization preferably have an average particle diameter of about 0.1 μm to 15 μm, but the present invention is not limited to this range. The purity of Sr and Ca is preferably 2N or higher, but the present invention is not limited thereto.

Si as a raw material is pulverized. Si as a raw material is preferably used as a simple substance, but a nitride compound, an imide compound, an amide compound, or the like may also be used. The purity of raw material Si is preferably 3N or more. Si is also pulverized, and the average particle size of the preferred Si compound is about 0.1 μm to 15 μm.

Next, Sr and Ca, which are raw materials, are nitrided in a nitrogen atmosphere. The reaction formulas are shown in Chemical Formulas 3 and 4, respectively.

3Sr+N ₂ →Sr ₃ N ₂ chemical formula 3

3Ca+N ₂ →Ca ₃ N ₂ chemical formula 4

Nitriding Sr and Ca at a temperature of 600° C. to 900° C. for about 5 hours in a nitrogen atmosphere. The nitrides of Sr and Ca are preferably of high purity, and commercially available nitrides of Sr and Ca can also be used.

Si as a raw material is nitrided in a nitrogen atmosphere. The reaction formula is shown in Chemical Formula 5.

3Si+2N ₂ →Si ₃ N ₄ chemical formula 5

Silicon Si is also nitrided for about 5 hours at a temperature of 800° C. to 1200° C. in a nitrogen atmosphere. Silicon nitride is preferably of high purity, and commercially available silicon nitride can also be used.

Sr, Ca or Sr-Ca nitrides are pulverized. Similarly, nitrides of Si were pulverized. In addition, Eu ₂ O ₃ , a compound of Eu, was also pulverized in the same manner. As the Eu compound, europium oxide is used, but metal europium, europium nitride, and the like can also be used. In addition, as Eu as a raw material, imide compounds and amide compounds can also be used. Europium oxide is preferably of high purity, and commercially available europium oxide can also be used. The average particle size of the ground alkaline earth metal nitride, silicon nitride, and europium oxide is preferably about 0.1 μm to 15 μm.

Among the above raw materials, at least one or more selected from Mg, B, Al, Cu, Mn, Cr, O and Ni may be contained. In addition, in the following mixing step, the mixing ratio of the above-mentioned elements such as Mg, Mn, and B may be adjusted and mixed.

After the pulverization is completed, Sr, Ca, nitrides of Sr—Ca, nitrides of Si, and Eu ₂ O ₃ , a compound of Eu, are mixed, and Mn is added and mixed.

Finally, in an ammonia atmosphere, the mixture of Sr, Ca, nitrides of Sr—Ca, nitrides of Si and Eu compound Eu ₂ O ₃ is sintered. By sintering, a Mn-added phosphor represented by (Sr _X Ca _1-X ) ₂ Si ₅ N ₈ :Eu can be obtained. The reaction formula of the basic constituent elements obtained by this sintering is shown in Chemical Formula 6 below.

              化学式6

chemical formula 6

Wherein, by changing the proportion of each raw material, the composition of the target phosphor can be changed.

Regarding the sintering temperature, the sintering can be performed within the range of 1200°C to 1700°C, but a sintering temperature of 1400°C to 1700°C is preferable. The raw material of the phosphor is preferably sintered in a crucible or a boat made of boron nitride (BN). A crucible made of alumina (Al ₂ O ₃ ) may be used instead of a crucible made of boron nitride.

By using the above production method, the target phosphor can be obtained.

In the examples of the present invention, a nitride-based phosphor is particularly used as a phosphor emitting reddish light, but in this embodiment, a phosphor having the above-mentioned YAG-based phosphor and a phosphor that may emit reddish light can also be obtained. light emitting device. Such a phosphor that may emit red light is a phosphor that emits light when excited by light having a wavelength of 250 nm to 600 nm, for example, Y ₂ O ₂ S:Eu, La ₂ O ₂ S:Eu, CaS:Eu, SrS:Eu, ZnS:Mn, ZnCdS:Ag, Al and ZnCdS:Cu, Al, etc. Thus, by using a phosphor capable of emitting red light together with a YAG-based phosphor, the color rendering of the light-emitting device can be improved.

In the light-emitting device according to each embodiment of the present invention, various phosphors can be used as the phosphor. For example, there can be mentioned: a barium magnesium aluminate phosphor that produces light in the blue region, represented by BaMgAl ₁₀ O ₁₇ :Eu, activated with europium, and that produces light in the blue region, represented by (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl:Eu, activated by europium halogen calcium phosphate-based phosphor, which emits light in the blue region, represented by (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Alkaline-earth chloroborate-based phosphors represented by Eu, activated by europium, emitting light in the blue-green region, (Sr, Ca, Ba)Al ₂ O ₄ :Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : represented by Eu, an alkaline earth aluminate phosphor activated by europium, which emits light in the green region, represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu, represented by Europium-activated alkaline-earth silicon oxynitride-based phosphors that emit light in the green region, expressed as (Ba, Ca, Sr) ₂ SiO ₄ :Eu, alkaline-earth magnesium silicate-based phosphors activated with europium, that produce Rare earth aluminates, ie, YAG-based phosphors that emit light in the yellow region and are represented by (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ :Ce, and phosphors that emit light in the red region and are represented by (Y, La, Gd , Lu) ₂ O ₂ S: Eu, activated rare earth oxysulfide phosphors with europium, etc., but the present invention is not limited to these, the aforementioned phosphors and other phosphors can also be used in the implementation of the present invention scheme used in the luminescent layer. Furthermore, it is also possible to use a phosphor having a fractured surface on which a countermeasure against degradation of the coating is taken.

The above phosphors are, for example, alkaline earth chloroborate phosphors activated with europium, alkaline earth aluminate phosphors activated with europium, alkaline earth silicon oxynitride phosphors activated with europium, YAG phosphors, and The alkaline earth silicon nitride-based phosphor activated with europium preferably contains B to improve crystallinity, increase particle size, or adjust crystal shape. Thereby, the luminous brightness can be improved. These phosphors are also effective as fillers for the phosphors of this embodiment.

Regarding the crystal structure, for example, Ca ₂ Si ₅ N ₈ is monoclinic, Sr ₂ Si ₅ N ₈ and (Sr _0.5 Ca _0.5 ) ₂ Sr ₅ N ₈ are orthorhombic, and Ba ₂ Si ₅ N ₈ is monoclinic.

Furthermore, the present phosphor is a quasicrystal in which crystals account for 60% or more, preferably 80% or more of the composition. Generally speaking, X=2, Y=5 or X=1, Y=7 are preferable, but any numerical value may be used.

Among trace additives, B and the like can improve the crystallinity without lowering the luminescence characteristics, and Mn, Cu and the like also exhibit the same effect. In addition, La, Pr, and the like also have an effect of improving luminescent characteristics. In addition, Mg, Al, Cr, Ni, etc. have the effect of shortening afterglow, and can be used suitably. In addition, even if it is an element which is not clearly indicated in this specification, it can be added as long as it is about 10-1000 ppm, and does not significantly reduce brightness.

The rare earth elements contained in R preferably include one or more of Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu, but may also include Sc, Sm, Tm, and Yb. In addition, in addition to the above-mentioned elements, elements having an effect of improving luminance, such as B and Mn, may be contained. In addition to simple substances, these rare earth elements are also mixed in the raw materials in the form of oxides, imides, amides and other states. Rare earth elements mainly have a stable trivalent electron arrangement, but Yb, Sm, etc. also have a divalent electron arrangement, and Ce, Pr, Tb, etc. also have a tetravalent electron arrangement. In the case of using an oxide rare earth element, the participation of oxygen affects the emission characteristics of the phosphor. That is, the reduction in luminance may occur due to the oxygen contained therein. However, when Mn is used, the particle size can be increased due to the effect of Mn and O as a flux, thereby improving the luminance of light emission.

As the luminescent center, europium Eu, which is a rare earth element, is suitably used. Specific examples of basic constituent elements include: Ca ₂ Si ₅ O _0.1 N _7.9 :Eu to which Mn and B are added, Sr ₂ Si ₅ O _0.1 N _7.9 :Eu, (Ca _X Sr _1-X ) ₂ Si ₅ O _0.1 N _7.9 : Eu, CaSi ₇ O _0.5 N _9.5 : Eu, Ca ₂ Si ₅ O _0.1 N _7.9 : Eu, Sr ₂ Si ₅ O _0.5 N _7.7 : Eu, (Ca _X Sr _1-X ) ₂ Si ₅ O _0.1 N _7.9 : Eu, etc.

The nitride-based phosphors described above absorb part of the blue light emitted by the light-emitting element and emit light in a range from yellow to red. By using this phosphor in a light-emitting device having the above configuration, it is possible to provide a light-emitting device in which blue light emitted from a light-emitting element and red light from the phosphor are mixed to emit warm-colored white light. Especially in a white light emitting device, it is preferable to contain a nitride-based phosphor and a rare-earth aluminate phosphor, that is, a cerium-activated yttrium-aluminum oxide phosphor. This is because desired chromaticity can be adjusted by containing the above-mentioned yttrium/aluminum oxide phosphor. The yttrium-aluminum oxide phosphor activated with cerium can absorb part of the blue light emitted by the light-emitting element and emit light in the yellow region. Here, the blue light emitted from the light-emitting element and the chromatic light emitted by the yttrium-aluminum oxide phosphor can be mixed to emit blue-white white light. Therefore, a warm-color white light-emitting device can be provided by combining the phosphor obtained by mixing the yttrium-aluminum oxide phosphor and the nitride phosphor with a binder and blue light emitted from the light-emitting element. The warm color white light emitting device has an average color rendering evaluation index Ra of 75-95, and a color temperature of 2000K-8000K. Particularly preferred is a white light-emitting device having a high average color rendering index Ra and a color temperature on the locus of black body radiation on a chromaticity diagram. However, in order to provide a light-emitting device having a desired color temperature and average color rendering index, the compounding amounts of the yttrium-aluminum oxide phosphor and the phosphor and the composition ratio of each phosphor may be appropriately changed. In particular, this warm-color white light-emitting device seeks to improve the special color rendering index R9. A conventional light-emitting device that emits white light by combining a blue light-emitting element with a cerium-activated yttrium-aluminum oxide phosphor has a low special color rendering index R9 and insufficient red components. Therefore, improving the special color rendering evaluation index R9 has become a problem to be solved, and the alkaline earth silicon nitride-based phosphor activated by Eu is included in the yttrium-aluminum oxide phosphor activated by cerium, so that the special color rendering can be improved. Evaluation index R9 increased to 40-90. In addition, LED lighting devices that emit the color of light bulbs can also be made.

(light emitting device)

The light emitting element (LED chip) 10 is preferably carried by the housing by being soldered to the substantially central portion of the housing, wherein the housing is disposed on the upper portion of the pin leads 13a. The lead frame 13 is made of, for example, copper-iron alloys. The electrodes formed on the light emitting element 10 are electrically connected to the lead frame through conductive leads 14 . The conductive lead 14 is made of gold, and Ni plating is suitably plated on a bump for electrically connecting the electrode and the conductive lead 14 .

The fluorescent member 11 obtained by sufficiently mixing the fluorescent substance 11 a and the binder 11 b to form a slurry is poured into the case carrying the light emitting element 10 . Then, the gel containing the phosphor 11a is heated to be cured. The thermal curing of the slurry is preferably from 50°C to 500°C. The thermal curing temperature of Al and Y is about 100°C to 500°C. Here, thermal curing is performed at 150°C or below. Ultraviolet rays may be irradiated for thermal curing of the gel. For example, a mercury lamp, a VUV, or the like can be used, and a plurality of light sources and heat sources can also be used in combination. By irradiating strong light such as VUV, the bonding of organic groups such as carboxylic acid can be effectively broken, and the curing reaction can be stabilized. When VUV is used to irradiate the slurry-like fluorescent member, the mixed gas of _O2 and _N2 flows through, and under the irradiation of VUV, a part of oxygen reacts with isolated hydroxyl groups and organic groups to become _CO2 and _H2O , which can also facilitate the removal of these hydroxyl groups, organic groups, etc. In this embodiment, by combining vacuum ultraviolet irradiation of 254nm or more and heating, in the film formation stage of film curing, the adhesion of the binder to the phosphor and filler interface, and the adhesion to light-emitting elements such as LEDs become Good, and a film with few micropores can be formed. In this way, the fluorescent member 11 made of an adhesive containing fluorescent substance is formed on the LED chip to fix the LED chip. Thereafter, in order to protect the LED chips and phosphors from external stress, moisture, and dirt, the translucent epoxy resin is further appropriately molded in the form of a mold member 15 . The lead frame 13 on which the color conversion member is formed is inserted into a cannonball-shaped mold frame, and a light-transmitting epoxy resin is mixed and cured.

In addition, the fluorescent member 11 may be directly in contact with the LED chip to cover the LED chip, or may be provided with a translucent resin or the like interposed therebetween. Needless to say, at this time, it is preferable to use a translucent resin having high light resistance.

The phosphor according to the embodiment of the present invention can delay a sharp decrease in luminous efficiency even when the light-emitting device is exposed to high temperature to cause reflow. In particular, the phosphor according to the embodiment of the present invention is also useful for a light-emitting element in which a lead wire is in contact with or close to a fluorescent member, and heat is easily transferred to the phosphor through the lead wire.

Embodiment 2

Next, as an example of the light-emitting device according to Embodiment 2 of the present invention, FIGS. 3 and 4 are a schematic plan view and a schematic cross-sectional view, respectively, showing a state in which an LED as a light-emitting element is mounted on a metal case.

The housing 105 is made of metal and has a recess a at its center. In addition, two through-holes penetrating in the thickness direction are formed around the recessed portion, that is, the base portion b, and the respective through-holes are provided facing each other with the recessed portion a interposed therebetween. Positive and negative lead electrodes 102 are respectively inserted into the through holes via hard glass as an insulating member 103 . In addition, the main surface side of the metal case 105 has a light-transmitting window portion 107 and a lead wire 106 made of a metal part, and by welding the contact surface of the metal part and the metal case 105, the light-emitting element and the like are airtight together with nitrogen gas. inside the shell. The LED chip 101 housed in the recess a is a light-emitting element that emits blue light or ultraviolet light, and the bonding between the LED chip 101 and the metal casing 105 is performed through an adhesive layer 110, wherein the adhesive layer 110 is made of ethyl silicate obtained by drying and sintering the hydrolyzed solution.

Furthermore, as shown in FIG. 4 , in the concave portion a insulated from the lead electrode 102, CCA-Blue (chemical formula is Ca ₁₀ (PO ₄ ) ₆ ClBr, active material is Mn, Eu) is formed on the light-emitting element. ) phosphor bonded luminescent layer 109, and on the luminescent layer 109, a luminescent layer 108 made of AlOOH, YOOH or the like bonded YAG-based phosphor is formed. The constituent members of the embodiment of the present invention will be described in detail below with reference to the drawings.

(light emitting layers 108, 109)

In addition to the mold member, the luminescent layer is provided in the cover of the pin lead, the opening of the case, etc., and contains a phosphor that converts the light emitted by the LED chip 101 and a material layer that bonds the phosphor. In addition, as shown in FIG. 5 , the light-emitting layer according to the embodiment of the present invention has the same thickness as that of the light-emitting layer 109A provided on the top, side and corners of the LED chip 101 and that provided on a support other than the LED chip 101. The thicknesses of the light-emitting layers 108A are approximately equal. In addition, there is no discontinuity in the light emitting layer even at the corners of the LED chip 101 , and the light emitting layer is continuous.

High-energy light or the like emitted from the LED chip becomes high-density in the light-emitting layer due to reflection by the case or the like. Furthermore, diffuse reflection is also produced by the phosphor, and the light-emitting layer is sometimes exposed to high-density high-energy light. Therefore, when a nitride-based semiconductor that emits strong light and can emit high-energy light is used as an LED chip, it is preferable to use a semiconductor that has light resistance to these high-energy lights and contains Al, Y, Gd, Lu, Sc, Ga, In, and B. A hydrous oxide of any one of the metal elements is used as a binder or a binder.

As one of specific main materials of the light-emitting layer, a material containing a phosphor in a light-transmitting inorganic member such as Al(OH) ₃ and Y(OH) ₃ is suitably used. Phosphors are bonded to each other by means of a light-transmitting inorganic member, and the phosphors are deposited in layers on the LED chip and the support and bonded thereto. In this embodiment, the hydrous oxide is formed from a compound mainly composed of the following hydrous oxide, wherein the main hydrous oxide is any one of Al, Y, Gd, Lu, Sc, Ga, In, B Formed by organometallic compounds. Here, the so-called organometallic compound includes an alkyl group and an aryl group bonded to a metal via an oxygen atom. As such an organometallic compound, an alkyl metal, an alkoxy metal, a bis-diketonate metal, a complex compound of a bis-diketonate metal, a metal carboxylate, etc. are mentioned, for example. Among such organometallic compounds, if an organometallic compound that is liquid at normal temperature is used in particular, by adding an organic solvent, the viscosity can be easily adjusted from the viewpoint of manufacturability and the generation of coagulated matter such as the organometallic compound can be prevented, thereby Manufacturability can be improved. In addition, since such an organometallic compound easily undergoes chemical reactions such as hydrolysis, it is easy to scatter, and can form a light-emitting layer in which phosphors are bonded. Therefore, the method of using an organometallic compound can be easily applied to an LED without degrading the performance as an LED light-emitting element, unlike other methods of forming a light-emitting layer on an LED at a temperature of 350° C. or higher or in a state where static electricity is applied. A light-emitting layer is formed on the chip, so that the production yield can be improved.

In addition, although the light-emitting layer is composed mainly of inorganic substances, it may contain a part of organic substances mainly composed of carboxylic acid. The content of organic matter is preferably set to 1% by weight or less. In addition, the light-emitting layer preferably has a light transmittance of at least 50% or more in the wavelength region of 250 nm to 800 nm.

As a specific host material contained in the light emitting layer, AlOOH will be described below as an example.

(Emitting layer 109 made of AlOOH bonded phosphor)

The light-emitting layer formed by bonding phosphors with AlOOH is formed by hydrolyzing an aluminum alkoxide or an aluminum alkoxide in an organic solvent at a predetermined ratio, and then oxidizing the aluminoxane sol obtained by the hydrolysis. In the aluminum sol solution, the phosphor (powder) is uniformly dispersed to obtain a coating liquid, and the coating liquid is adjusted and coated with the alumina sol solution in which the phosphor is dispersed, so that it covers the entire The light-emitting element is then heated and cured, so that the phosphors are fixed to each other and to the surface of the light-emitting element by the AlOOH component.

Aluminum alkoxide or aluminum alkoxide is an organoaluminum compound used as a tackifier, gelling agent, curing agent, polymerization catalyst, and dispersant for pigments in paints.

Aluminum isopropoxide, aluminum ethoxide and aluminum butoxide, which are one of aluminum alkoxide or aluminum alkoxide, are very reactive, and form aluminum hydroxide or alkyl aluminate with the help of moisture in the air. A hydrated alumina with a boehmite structure is produced. For example, aluminum isopropoxide is easily reacted with water as shown in the following chemical formula 7, and finally becomes a cross-linked structure composed of hydrated alumina as the main component and cross-linked with aluminum hydroxide or alumina (alumina). mixture.

       化学式7

chemical formula 7

Therefore, after reacting aluminum isopropoxide with moisture in the air, the AlOOH generated by heating is used to bind the phosphor, so that the light-emitting layer formed by binding the phosphor to the AlOOH containing the phosphor can be formed on the light-emitting element as a light-emitting layer. On the surface of the light-emitting element and on the support other than the surface of the light-emitting element.

The above light-emitting layer made of AlOOH bonded phosphor can also be combined with a light-emitting layer made of Y, Gd, Lu, Sc, Ga, In, B and other hydrated oxides bonded with phosphor and AlOOH bonded phosphor A light-emitting layer made of a bulk, so that two or more layers are formed on the same light-emitting element. According to the method of forming a light-emitting layer by spray coating of this embodiment, since the film thicknesses of the two layers can also be controlled, it is easy to form light-emitting layers of the same shape. For example, on the same light-emitting element, a Y ₂ O ₃ light-emitting layer is formed first, and then an Al ₂ O ₃ light-emitting layer is formed thereon. Here, the phosphor may be contained in both layers, may be contained in only one layer, and may not be contained in both layers. According to such a configuration, there is an effect of improving light extraction efficiency depending on the magnitude of the refractive index of the fluorescent layer. When a light-emitting layer composed of one layer is formed, a sharp change in the refractive index occurs at the interface between the light-emitting layer and the external atmosphere or the nitride semiconductor light-emitting element, and part of the light extracted from the light-emitting element may be reflected at the interface. This leads to a decrease in light extraction efficiency. In addition, the coefficient of linear expansion and the refractive index can also be adjusted by forming, for example, a light emitting layer in which AlOOH and YOOH are mixed.

The light-emitting layer made of AlOOH bonded with phosphors formed in this way is an inorganic substance different from conventional resins, so compared with resins, the degradation caused by ultraviolet rays is extremely small, and light-emitting elements that emit ultraviolet light can also be used in combination And high output power dynamic LED and so on.

(LED chip 101)

In this embodiment, the LED chip 101 used as a light-emitting element can excite phosphors. The LED chip 101 as a light-emitting element is formed on a substrate by methods such as MOCVD, such as GaAs, InP, GaAlAs, InGaAlP, InN, AlN, GaN, InGaN, AlGaN, InGaAlN and other semiconductors as a light-emitting layer. Examples of semiconductor structures include homojunction structures, heterojunction structures, and double heterojunction structures having MIS junctions, PIN junctions, and PN junctions. The emission wavelength can be selected variously according to the material of the semiconductor layer and its degree of mixing. In addition, a single quantum well structure or a multiple quantum well structure in which a semiconductor active layer is formed on a thin film that produces a quantum effect may also be used. Nitride-based compound semiconductors (general formula In _i Ga _j Al _k N where 0≤i, 0≤j, 0≤k, and i+j+k=1).

In the case of using a gallium nitride-based compound semiconductor, materials suitable for the semiconductor substrate include sapphire, spinel, SiC, Si, ZnO, GaN, and the like. In order to form gallium nitride with good crystallinity, it is more preferable to use a sapphire substrate. When growing a semiconductor film on a sapphire substrate, it is preferable to form a buffer layer such as GaN, AlN, and then form a gallium nitride semiconductor having a PN junction on the buffer layer. In addition, GaN single crystal itself, which is selectively grown on a sapphire substrate with _SiO2 as a mask, can also be used as the substrate. In this case, after each semiconductor layer is formed, the light emitting element can be separated from the sapphire substrate by etching and removing SiO ₂ . Gallium nitride-based compound semiconductors exhibit n-type conductivity without doping. In the case of forming an n-type gallium nitride semiconductor that requires improvement of luminous efficiency, etc., it is preferable to appropriately introduce elements such as Si, Ge, Se, Te, and C as n-type dopants. On the other hand, when forming a p-type gallium nitride semiconductor, it is doped with Zn, Mg, Be, Ca, Sr, Ba, etc. as p-type dopants.

If the gallium nitride-based compound semiconductor is only doped with a p-type dopant, it is difficult to achieve p-type, so after introducing the p-type dopant, it is preferable to use furnace heating, low-speed electron beam irradiation, and plasma irradiation for annealing. , thereby realizing p-type. As a specific layer configuration of a light-emitting element, a suitable example can be given in which layers are laminated on a sapphire substrate or silicon carbide having a buffer layer formed at low temperature such as gallium nitride or aluminum nitride. , laminated as the n-type contact layer of gallium nitride semiconductor, as the n-type cladding layer of aluminum nitride gallium semiconductor, as the active layer of indium gallium nitride semiconductor doped with Zn and Si, as the active layer of aluminum gallium nitride semiconductor A p-type cladding layer and a p-type contact layer as gallium nitride semiconductor. In order to form the LED chip 101, in the case of the LED chip 101 having a sapphire substrate, after forming the exposed surfaces of the p-type semiconductor and the n-type semiconductor by etching, etc., the sputtering method and the vacuum evaporation method are used to form on the semiconductor layer. Each electrode having the desired shape. In the case of a SiC substrate, a pair of electrodes can also be formed by utilizing the conductivity of the substrate itself.

Then the formed semiconductor wafer etc. are scribed, scribing or a direct full cut (full cut) using a diamond wheel dicing machine, wherein the blade of the diamond wheel dicing machine has a diamond blade, and the blade rotates during cutting; Or after cutting a groove wider than the blade width (half cut), use external force to separate the semiconductor wafer. Or use a diamond wheel dicing machine with a diamond needle at the top to make a reciprocating linear motion to draw a very fine scribe line (warp line) on the semiconductor wafer, for example, into a textured pattern, and then use external force to separate the wafer, thereby cutting the semiconductor wafer. into chips. In this way, the LED chip 101 that is a nitride-based compound semiconductor can be formed.

In the light-emitting device of this embodiment, when emitting light, the main light-emitting wavelength of the LED chip 101 is preferably 350 nm to 530 nm in consideration of complementarity with the light-emitting color of the phosphor.

(metal shell 105)

The metal case 105 used in the light-emitting device according to one embodiment of the present invention is composed of a concave portion a for accommodating a light-emitting element and a base portion b on which a lead electrode is arranged, and the metal case 105 functions as a support for the light-emitting element. A bottom surface of the concave portion is substantially flush with a bottom surface of the lead electrode.

In light-emitting devices, the case is preferably formed of a thin film in consideration of heat dissipation and miniaturization. On the other hand, the insulating member is provided at the interface with the lead electrodes, and in order to alleviate differences such as thermal expansion coefficients with the insulating member and improve reliability, it is necessary to increase the respective contact surfaces. Therefore, the present inventors differentiated the portion where the light-emitting element is arranged and the portion where the lead electrodes are fixed in the metal case, and set the shape and film thickness according to the respective regions, thereby improving reliability.

(lead electrode 102)

The light-emitting device according to the embodiment of the present invention has positive and negative lead electrodes 102 , and the lead electrodes 102 are inserted into through holes provided in the base portion of the metal case through insulating members. A tip portion of the lead electrode protrudes from a surface of the base portion, and a bottom surface of the lead electrode is substantially flush with a bottom surface on the mounting surface side of the concave portion.

(lead 106)

A light-emitting device according to an embodiment of the present invention has a light-transmitting window portion 107 and a lead wire 106 made of a metal portion on the main surface side of a metal case 105 . The window portion 107 is preferably the light emitting surface of the light emitting device and is arranged at the center of the light emitting device.

In this embodiment, the window portion is located above the light-emitting element disposed in the concave portion of the metal casing, and intersects the extension line of the inner wall of the concave portion. The light emitted from the end of the light emitting element is diffusely reflected on the side surface of the concave portion and taken out in the front direction. It is generally considered that the existence range of these diffusely reflected lights is approximately within the extension line of the side surface of the concave portion. Then, by adjusting the area of the window portion as the light-emitting surface as described above, the diffusely reflected light can be efficiently focused on the window portion, and a light-emitting device capable of emitting high-intensity light can be obtained.

(housing 114)

As shown in FIG. 5 , the case 114 used in still another embodiment of the present invention functions as a support that fixes and protects the LED chip 101 in the concave portion. In addition, it also has an external electrode 102A capable of making electrical contact with the outside. Adapted to the quantity and size of the LED chips 101, the housing 114 can also be designed to have a plurality of openings. In order to have a suitable light-shielding function, the housing 114 is colored in a dark color system such as black or gray, or the side of the housing 114 that emits light to observe the surface is colored in a dark color system. In order to further protect the LED chip 101 from the external environment, in addition to the coatings 111 and 112, a mold member 113 as a translucent protector may be provided. The casing 114 preferably has good adhesion to the coatings 111 , 112 and the molded member 113 and strong rigidity. In order to electrically insulate the LED chip 101 from the outside, the casing 114 preferably has insulation properties. Furthermore, when the housing 114 is affected by heat from the LED chip 101 and the like, it is preferable to have a small coefficient of thermal expansion in consideration of adhesion to the mold member 113 .

The bonding between the LED chip 101 and the casing 114 can also be performed by using thermosetting resin or the like. Specifically, epoxy resin, acrylic resin, imide resin, etc. are mentioned. In the case where the light-emitting device uses an LED chip that emits light containing ultraviolet rays and is used at a high output power, the bonding portion between the LED chip 101 and the case 114 is also used as a sealing member due to ultraviolet rays emitted by the LED chip. The light is reflected by the resin or the phosphor contained therein, and the light becomes highly dense especially in the case, so the resin at the bonding part is degraded by ultraviolet rays, so it is considered that the luminous efficiency is lowered due to yellowing of the resin, etc. And the lifespan of the light-emitting device is shortened due to the reduction of the bonding strength. In order to prevent such degradation of the adhesive portion due to ultraviolet rays, a resin containing an ultraviolet absorber may be used, more preferably an inorganic substance of an embodiment of the present invention, etc. may be used. In particular, when a metal material is used for the case, the bonding between the LED chip 101 and the case 114 may use eutectic solder such as Au—Sn or the like in addition to the inorganic substance according to the embodiment of the present invention. Therefore, unlike the case where resin is used for bonding, the present invention does not degrade the bonded portion even when the light emitting device uses an LED chip emitting light containing ultraviolet rays and is used at high output.

In addition, Ag paste, carbon paste, ITO paste, metal flange, etc. are suitably used for electrical contact with external electrode 102A in case 114 while arranging and fixing LED chip 101 .

(External electrode 102A)

External electrode 102A shown in FIG. 5 is an electrode for supplying electric power from the outside of case 114 to LED chip 101 arranged inside. Therefore, various electrodes using conductive patterns and lead frames provided on the case 114 can be mentioned. In addition, the external electrode 102A may be formed in various sizes in consideration of heat dissipation and electrical conductivity of the external electrode 102A, characteristics of the LED chip 101 , and the like. The external electrodes 102A preferably have good thermal conductivity in order to transfer the heat emitted by the LED chips 101 to the outside while arranging the respective LED chips 101 . The specific resistance of the external electrode 102A is preferably 300 μΩ·cm or less, and more preferably 3 μΩ·cm or less. In addition, the specific thermal conductivity is preferably 0.01 cal/(s) (cm ² ) (°C/cm) or more, more preferably 0.5 cal/(s) (cm ² ) (°C/cm) or more.

As such an external electrode 102A, a copper or phosphor bronze plate whose surface is plated with a metal such as palladium or gold or subjected to soldering plating is suitably used. When a lead frame is used as the external electrode 102A, it can be used in various ways depending on the electric conductivity and thermal conductivity, but the plate thickness is preferably 0.1 mm to 2 mm from the viewpoint of workability. Copper foil and a tungsten layer can be formed as the external electrode 102A provided on a support such as glass epoxy resin or ceramics. When using metal foil on a printed wiring board, it is preferable to set it as thickness of copper foil etc. to 18 micrometers - 70 micrometers. In addition, gold plating or solder plating may be performed on the upper surface of copper foil or the like.

(conductive lead 104)

The conductive leads 104 are required to have low contact resistance with the electrodes of the LED chip 101 and have good mechanical connectivity, electrical conductivity and thermal conductivity. The thermal conductivity is preferably 0.01 cal/(s)(cm ² )(°C/cm) or more, more preferably 0.5 cal/(s)(cm ² )(°C/cm) or more. In addition, in the case of forming a high-output light emitting device, the diameter of the conductive lead 104 is preferably φ10 μm to φ70 μm in consideration of manufacturability and the like. Specific examples of such conductive leads 104 include conductive leads using metals such as gold, copper, platinum, and aluminum, and alloys thereof. Such conductive leads 104 can easily connect electrodes, internal leads, pin leads, etc. of each LED chip 101 by wire bonding equipment.

(mold member 113)

The molding member 113 can be provided according to the application of the light emitting device to protect the LED chip 101, the conductive lead 104, and the phosphor-containing coatings 111, 112 from the outside or to improve light extraction efficiency. The mold member 113 can be formed of various resins and glass. As specific materials for the mold member 113, transparent resins excellent in weather resistance such as epoxy resins, urea resins, silicone resins, and fluororesins, glass, and the like are mainly used suitably. In addition, the directivity of light from the LED chip 101 can be relaxed and the viewing angle can be increased by including a diffusing agent in the mold member. Such a mold member 113 may use the same material as the coating adhesive or the adhesive, or may use a different material.

In addition, when using a metal case and making the LED chip 101 airtight together with nitrogen gas, the mold member 113 is not an essential configuration of the present invention.

(spraying device 300)

As shown in Figures 6 and 7, the present embodiment uses a spray coating device 300, which uses conveying pipes 307, 308, and 309 to connect a container 301 for accommodating the coating liquid, a valve 302 for adjusting the flow rate of the coating liquid, and a handle The circulation pump 303 that sends the coating liquid to the nozzle 201 and then sends it to the container 301 from the nozzle 201 and the nozzle 201 that sprays the coating liquid 203 in a spiral form are connected.

(container 301)

A stirrer 304 is installed in the container 301 for storing the coating liquid, and the coating liquid is constantly stirred during the coating operation. The coating liquid 203 accommodated in the container 301 is constantly stirred by the stirrer 304, so that the phosphor 202 contained in the coating liquid 203 is always uniformly dispersed in the solution.

(valve 302)

The valve 302 adjusts the flow rate of the coating liquid delivered from the container 301 through the delivery pipe 309 by opening and closing the valve.

(circulation pump 303)

The circulating pump 303 delivers the coating liquid from the container 301 to the top end of the nozzle 201 through the delivery pipe 309 through the valve 302 and the compressor 305, after which, the remaining coating liquid that is not ejected from the nozzle 201 passes through the delivery pipe 308 Transported to container 301. The coating solution is delivered to the top end of the nozzle 201 from the container 301 through the valve 302 through the delivery pipe 309 by means of the circulation pump 303, and thereafter, is delivered to the container 301 through the delivery pipe 308, so the coating solution is often in the spraying device. The state of the inner loop. Therefore, since the coating liquid is stirred or circulated throughout the coating apparatus, the phosphor contained in the coating liquid is always in a uniformly distributed state during the coating operation.

(compressor 305)

The compressor 305 is installed in the device through the delivery pipe 307 or 309 , compresses the air sent through the delivery pipe 307 , and adjusts the pressure of the coating liquid sent through the delivery pipe 309 . By means of the compressor 305, the compressed air and the pressure-regulated coating liquid are delivered to the nozzle 201, respectively. Here, the pressure of the compressed air is monitored by a pressure gauge 306 . Using the spraying device 300 above, the coating liquid is sprayed together with the high-pressure gas at high speed, and sprayed on the top, side and corners of the light emitting element.

(Nozzle 201)

In the present embodiment, the device used is characterized in that the coating liquid and gas (here, air) are ejected in a helical form through the nozzle 201 . A number of gas ejection ports are arranged around the nozzle of the device, and the ejection directions of the gases ejected from these ejection ports each form a certain angle with respect to the surface to be coated. Therefore, when gas is simultaneously fed into these gas outlets that rotate around the outlet of the coating liquid, the flow of the entire gas that collects the gases ejected from the respective outlets becomes an upside-down volute. A spiral flow, a spiral flow, or the flow of air in a tornado. In addition, the center of the nozzle of the device is provided with a spray port for the coating liquid. When the coating liquid is sprayed out simultaneously with the gas, the mist-like coating liquid takes advantage of the upside-down volute flow, spiral spread out in the shape of the flow or the flow of air in a tornado.

The diameter of the entire spray spread in a helical shape starts from the spray starting point above the light-emitting element, and becomes larger as it approaches the surface of the light-emitting element. In addition, the rotation speed of the mist of the coating liquid becomes smaller as the spray starting point above the light-emitting element is closer to the surface of the light-emitting element. That is to say, when the mist-like coating liquid is sprayed from the nozzle and spreads in the air, the spray spreads out in a conical shape near the spray starting point, that is, the nozzle, and the spray spreads in a cylindrical shape at the place where it leaves the nozzle. Spread out. Therefore, in this embodiment, it is preferable to adjust and set the distance between the upper surface of the light-emitting element and the lower end of the nozzle so that the surface of the light-emitting element appears at the place where the spray spreads out in a cylindrical shape. At this time, the spray rotates in a helical shape, and the speed is relatively slow. Therefore, the spray can reach the surface of the light-emitting element under the shadow of the conductive lead wire, and can be fully sprayed not only on the entire light-emitting element, but also on the entire side. Thereby, work can be performed with the light emitting element or the nozzle fixed. In addition, because the spray speed is relatively slow where the spray spreads out in a cylindrical shape, when the spray is sprayed on the surface of the light-emitting element, the surface of the light-emitting element will not be affected by the phosphor particles contained in the spray. shock. In addition, deformation and disconnection of the conductive lead wires will not occur, thereby improving the product yield and manufacturability.

(heater 205)

As shown in FIG. 6 , the coated light-emitting element of this embodiment is in a heated state at a temperature of 50° C. to 500° C. on the heater 205 . As a method of heating the light-emitting element in this way, a method of heating the light-emitting element in a heating device such as an oven may also be used. By heating, ethanol, a small amount of water contained in the hydrolyzed solution in the gel state, and the solvent are evaporated, and amorphous Al(OH) ₃ and AlOOH can be obtained from the coating liquid 203 in the gel state. Furthermore, since the viscosity of the coating liquid 203 of this embodiment is adjusted, it is sprayed on the top, side, and corners of the light-emitting element, and even after the surface of the support 204, it does not flow out from the place where it is sprayed. In these places, heating is performed shortly after coating, so that the coating formed by bonding the phosphor with AlOOH can cover the top, side and corner parts of the light-emitting element.

In this embodiment, the bonding liquid is heated at a temperature of 50° C. to 500° C., so that the light emitting element can be soldered on the support 204 . As a method of heating in this way, the light emitting element may be installed on a heater, or a method of heating the light emitting element in a heating device such as an oven may be used. When heating, ethanol, a small amount of water contained in the hydrolyzed solution in the gel state, and the solvent are evaporated, an adhesive layer can be obtained from the adhesive liquid in the gel state, and the adhesive layer is mainly composed of AlOOH , formed densely by many particles with a diameter of several nanometers. The bonding layer is formed by densely packed particles with a particle size of several nanometers mainly composed of inorganic substances, and there are gaps between the particles. If the temperature applied to the adhesive layer changes sharply, the volume of the respective particles expands or contracts due to thermal stress. Therefore, unlike the case where the light-emitting element is bonded by molten glass or resin whose thermal expansion coefficient is greatly different from that of the support material in the absence of the above-mentioned particles, the bonding layer of the present embodiment as a whole does not suffer too much from thermal stress. Large impact, peeling and cracking of the adhesive layer will not occur. Therefore, even if the light emitting device is used in a state where the applied temperature changes rapidly, the light emitting device of the present embodiment can maintain its reliability.

Furthermore, in this embodiment, since the adhesive liquid is adjusted to a high viscosity, the adhesive liquid is interposed between the substrate surface of the light-emitting element and the surface of the support body, and does not generate from the place where it spreads to the side of the light-emitting element. flow. After die bonding is performed at these places, the bonding liquid is heated to cure. As a result, the light-emitting device can be formed by AlOOH soldering on the support without deviating from the position where the light-emitting element was originally placed.

(shielding baffle 206)

In this embodiment, in the case of arranging a plurality of cases, the light-emitting elements are respectively soldered in the cases, the electrodes of the light-emitting elements are wire-bonded to the external electrodes, and then the coating liquid 203 is sprayed from above the light-emitting elements. However, the side surface of the recessed part of the case is designed in a conical shape. When the side face of the recessed part of the case is used as a reflection part to improve the light extraction efficiency in the front direction of the case, if the coating liquid 203 adheres to the side face of the recessed part, light will be emitted. Light emitted from the element is diffusely emitted on the side surface, so it is difficult to improve the light extraction efficiency in the front direction of the case. Therefore, in this embodiment, in order to prevent the coating liquid 203 from adhering to the side of the concave portion of the case and the external electrodes, the coating liquid 203 is sprayed on the surface of the light emitting element from above the shield baffle 206 . The shielding baffle 206 is a plate that completely covers the side of the concave portion of the housing and the external electrodes, and is provided with a through hole of a size that allows the coating liquid 203 to be sprayed on the top, side and corners of the light-emitting element. It has a metal shielding baffle, Reinforced plastic shielding baffles, etc.

(adhesive layer 110)

The adhesive layer 110 used in this embodiment is an amorphous inorganic material layer formed by pasting the light-emitting element and the support with an organic material in a gel state, followed by heating and drying. Furthermore, the adhesive layer of this embodiment is a continuous colorless transparent layer existing between the upper surface of the support and the base surface of the light-emitting element, and extends to the upper surface of the light-emitting element.

High-energy light or the like emitted from the LED chip becomes high-density in the adhesive layer due to reflection by the case or the like. When a nitride-based semiconductor with high luminous intensity and capable of emitting high-energy light is used as an LED chip, it is preferable to use a nitride-based semiconductor that has light resistance to these high-energy lights and contains Si, Al, Ga, Ti, Ge, P, B, Zr, Y And oxides of one kind, two or more kinds of alkaline earth metals are used as a bonding solution between the light-emitting element and the support. In addition, the above-mentioned hydrated oxides may also be used as an adhesive layer.

As one of the specific main materials of the bonding layer, SiO ₂ , Al ₂ O ₃ , ZrO ₂ , Y ₂ O ₃ , MSiO ₃ (wherein, as M, Zn, Ca, Mg, Ba and Sr, etc.) and other light-transmitting inorganic members. With these light-transmitting inorganic members, the light-emitting element is fixed to the support so that the base surface of the light-emitting element and the surface of the support face each other. In this embodiment, oxides containing at least one or more elements selected from Si, Al, Ga, Ti, Ge, P, B, Zr, Y, or alkaline earth metals, and the material forming the coating Similarly, organometallic compounds are used to form. Using such an organometallic compound that is liquid at normal temperature can easily adjust the viscosity from the viewpoint of manufacturability and prevent the generation of coagulation of the organometallic compound and the like by adding an organic solvent, thereby improving manufacturability. In addition, such organometallic compounds are prone to chemical reactions such as hydrolysis to produce inorganic substances such as oxides and hydroxides, so by containing at least Si, Al, Ga, Ti, Ge, P, B, Zr, Y Alternatively, oxides of one or more elements among alkaline earth metals can easily form an adhesive layer without deteriorating the performance of the LED as a light-emitting element. However, since these elements also contain substances that are not easily colored, it is necessary to select them appropriately according to the application. In addition, the binders that are hydrous oxides of this embodiment also have light resistance and heat resistance, so they can also be used as an adhesive layer.

Furthermore, in the case where the adhesive layer extends to the side of the light-emitting element, if the light-emitting element is soldered with metal solder, a metal that absorbs light from near ultraviolet to blue emitted by the light-emitting element is often contained in the metal solder. For example, when soldering light-emitting elements with Au-Sn eutectic solder, since Au absorbs the light from near-ultraviolet to blue emitted by the light-emitting elements, there is a problem that the output power of the light-emitting device will decrease, but based on this The adhesive layer of the embodiment does not absorb light from near ultraviolet to blue emitted by the light emitting element, and thus can form a light emitting device with high luminous efficiency.

Embodiment 3

Next, a light-emitting device according to Embodiment 3 of the present invention will be described using FIGS. 8 and 9 . 8 and 9 respectively show a plan view of the light emitting device and a cross-sectional view taken along line A-A' of FIG. 8 . In the light-emitting device of Embodiment 3, the fluorescent member used may be the same fluorescent member as that of Embodiment 1. Here, a light-emitting element 401 having an InGaN-based semiconductor layer having a light-emitting peak in the blue region and a light-emitting wavelength of 460 nm as a light-emitting layer was used. A p-type semiconductor layer and an n-type semiconductor layer (not shown in the figure) are formed on the light emitting element 401, and a conductive lead 404 connected to the lead electrode 402 is formed on the p-type semiconductor layer and the n-type semiconductor layer. In addition, the insulating sealing material 403 is formed so as to cover the outer periphery of the lead electrode 402, thereby preventing a short circuit. Above the light emitting element 401, a translucent window portion 407 extending from the lead wire 406 on the upper portion of the housing 405 is provided. Adhesive 410 uniformly containing phosphor 408 is applied to substantially the entire inner surface of translucent window portion 407 .

In this way, in the light-emitting device of FIGS. 8 and 9 , the light-emitting film 409 containing phosphor is disposed above the LED chip and at a distance from the LED chip. This point is different from the structures of the above-mentioned light-emitting devices in FIG. 3 and FIG. 4 , but other parts are roughly the same, and the same materials can be used for the phosphor and the adhesive. The luminescent film is a multi-layer structure, and each layer can be mixed with different phosphors, or a film that is not mixed with phosphors can also be combined. The luminescent film in Fig. 8 and Fig. 9 can be detached from the light emitting device and can be replaced, so that it is also possible to change the luminous color or replace the degraded luminescent film.

Embodiment 4

Furthermore, Fig. 10 shows a light-emitting device according to Embodiment 4 of the present invention. The light-emitting device shown in this figure is contrary to the above-mentioned light-emitting device. LEDs are arranged on the upper side as light-emitting elements 501, and a curved concave portion is formed on the lower case 505, and a light-emitting layer 509 is provided on the surface. In this configuration, a multilayer structure composed of the above-mentioned phosphor and binder can also be used. In addition, the layer configuration can also be designed as a multilayer structure similarly to the above.

Embodiment 5

11 to 22 show a light emitting device according to Embodiment 5 of the present invention. The light-emitting devices shown in these figures are arranged such that the side on which the electrodes of the light-emitting elements are provided faces the substrate as shown in FIG. 19 . The manufacturing method of the light emitting device shown in FIG. 19 will be described below on the basis of FIGS. 11 to 18 .

First, as shown in FIG. 11 , a conductive member 602 is disposed on the surface of a sub-mount substrate 601 . Next, as shown in FIG. 12 , a conductive pattern is provided on the surface of the substrate 601 with an insulating portion 603 used to separate the conductive member 602 connecting the positive electrode and the negative electrode of the light emitting element 600 .

The material of the base substrate 601 is preferably a material having a thermal expansion coefficient substantially equal to that of the semiconductor light emitting element, such as aluminum nitride or the like. By using such a material, thermal stress generated between the base substrate 601 and the light emitting element 600 can be relaxed. The material of the susceptor substrate 601 may be preferably inexpensive silicon that can form a protective element. In addition, it is preferable to use silver and gold with high reflectivity as the conductive member 602 .

In order to improve the reliability of the light emitting device, an underfill 604 is filled in the gap formed between the positive and negative electrodes of the light emitting element 600 and the insulating portion 603 . As shown in FIG. 13 , an underfill 604 is disposed around the insulating portion 603 of the susceptor substrate 601 . The material of the underfill 604 is, for example, thermosetting resin such as epoxy resin. In order to alleviate the thermal stress of the underfill 604, aluminum nitride, aluminum oxide, and their composite mixture may be further mixed into the epoxy resin. The amount of the underfill 604 is such that the gap between the positive and negative electrodes of the light emitting element 600 and the base substrate 601 can be filled across the insulating portion 603 .

Next, as shown in FIG. 14 , the positive and negative electrodes of a light-emitting element 600 such as an LED chip produced by another method are fixed so as to face the positive and negative electrodes of the above-mentioned conductive pattern. First, the conductive material 605 is attached to the positive and negative electrodes of the light emitting element 600 . The material of the conductive material 605 includes, for example, Au, eutectic solder (Au—Sn), Pb—Sn, lead-free solder, and the like. When the underfill 604 is in a softened state, the positive and negative electrodes of the light-emitting element 600 are made to face the positive and negative electrodes of the above-mentioned conductive pattern through the conductive material 605, and then the positive and negative electrodes of the light-emitting element 600, The conductive material 605 and the above-mentioned conductive pattern are bonded together by thermocompression. At this time, the conductive material and the underfill 604 between the positive and negative electrodes of the conductive pattern are excluded.

Furthermore, as shown in FIG. 15 , the sieve plate 606 is arranged from the substrate side of the light emitting element 600 . In addition, instead of the sieve plate, a metal mask may be placed at a position where it is not desired to form a phosphor layer, such as a ball bonding position of a conductive lead or a parting line formation position.

Next, as shown in FIG. 16 , a phosphor layer forming material 607 in which phosphor is contained in thixotropic alumina sol is adjusted, and screen printing is performed using a squeegee (squeegee).

Furthermore, as shown in FIG. 17, the sieve plate is removed, and the phosphor layer forming material 607 is cured. Then, as shown in FIG. 18 , each light emitting element is cut along the parting line 609 to obtain a light emitting device 610 with a phosphor layer as shown in FIG. 19 .

Furthermore, a light-emitting device in which such a light-emitting device with a phosphor layer 610 is fixed on a support or the like can also be manufactured. 20 to 22 illustrate a light-emitting device in which a light-emitting device 610 with a phosphor layer is fixed to a support 611 having a concave portion 612 . Fig. 20 is a plan view of the light emitting device, Fig. 21 is a cross-sectional view taken along line BB' of Fig. 20 , and Fig. 22 is an enlarged view of Fig. 21 . The light-emitting devices shown in these figures are formed by fixing the light-emitting device 610 with a phosphor layer on the bottom surface of the recess 612 with an adhesive such as Ag paste, wherein the recess 612 is arranged on the metal base of a support 611 such as a casing. 615 on. Furthermore, the exposed lead electrodes 613 are connected to the conductive patterns provided on the base substrate 601 with conductive leads 614 .

In the light-emitting device described above, phosphors coated or coated with a coating material may also be used. A light-emitting device having a light-emitting layer composed of an inorganic binder mainly composed of the above-mentioned hydrated oxide and a filler does not limit the structure of the light-emitting device. For example, in addition to the example in which the light emitting element is mounted downward and the light emitting layer is formed on a sapphire substrate or the like, the example in which the light emitting layer is formed on the tube surface of a high pressure mercury lamp can also be applied.

Examples 1-29

Embodiments of the present invention will be described below. First, the phosphor slurry is formulated with alumina sol and yttrium sol to produce phosphor/sol slurry.

(Example 1)

10 g of commercially available alumina sol (Nissan Chemical A1520) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the alumina sol and mixed. 10 g of fluorescent substance YAG was added to the mixed solution, and after stirring and mixing well, a phosphor/sol slurry was obtained.

(Example 2)

10 g of commercially available alumina sol (Nissan Chemical A1200) was placed in a 100 ml beaker, and then 70% by weight of ethanol was added to the alumina sol and mixed. 10 g of fluorescent substance YAG was added to the mixed solution, and after stirring and mixing well, a phosphor/sol slurry was obtained.

(Example 3)

10 g of commercially available alumina sol (Catalyst AS3 manufactured by Catalyst Chemical Industry Co., Ltd.) was placed in a 100 ml beaker, and then 50% by weight of ethanol was added to the alumina sol and mixed. 10 g of fluorescent substance YAG was added to the mixed solution, and after stirring and mixing well, a phosphor/sol slurry was obtained.

(Example 4)

10 g of a commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol and mixed. 10 g of fluorescent substance YAG was added to the mixed solution, and after stirring and mixing well, a phosphor/sol slurry was obtained.

(Example 5)

10 g of commercially available alumina sol (Nissan Chemical A1520) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the alumina sol and mixed. 10 g of fluorescent substance SAE was added to this mixed solution, and after stirring and mixing well, a slurry of phosphor/sol was obtained.

(Example 6)

10 g of commercially available alumina sol (Nissan Chemical A1200) was placed in a 100 ml beaker, and then 70% by weight of ethanol was added to the alumina sol and mixed. 10 g of fluorescent substance SAE was added to this mixed solution, and after stirring and mixing well, a slurry of phosphor/sol was obtained.

(Example 7)

10 g of commercially available alumina sol (Catalyst AS3 manufactured by Catalyst Chemical Industry Co., Ltd.) was placed in a 100 ml beaker, and then 50% by weight of ethanol was added to the alumina sol and mixed. 10 g of fluorescent substance SAE was added to this mixed solution, and after stirring and mixing well, a slurry of phosphor/sol was obtained.

(Embodiment 8)

10 g of commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was put in a 100 ml beaker, and 70% by weight of ethanol was added to the yttrium oxide sol and mixed. 10 g of fluorescent substance SAE was added to this mixed solution, and after stirring and mixing well, a slurry of phosphor/sol was obtained.

(Example 9)

10 g of commercially available alumina sol (Nissan Chemical A1200) was placed in a 100 ml beaker, and then 50% by weight of ethanol was added to the alumina sol and mixed. 10 g of fluorescent substance BAM was added to this mixed solution, and after stirring and mixing sufficiently, a slurry of fluorescent substance/sol was obtained.

(Example 10)

10 g of a commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol and mixed. 10 g of fluorescent substance CCA-1 was added to this mixed liquid, and after stirring and mixing well, the slurry of fluorescent substance/sol was obtained.

(Example 11)

10 g of a commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol and mixed. 10 g of fluorescent substance CCA-2 was added to this mixed liquid, and after stirring and mixing well, the slurry of fluorescent substance/sol was obtained.

(Example 12)

10 g of a commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol and mixed. 10 g of fluorescent substance CCBE was added to this mixed solution, and after stirring and mixing sufficiently, a slurry of phosphor/sol was obtained.

(Example 13)

10 g of a commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol and mixed. 10 g of fluorescent substance SAE was added to this mixed solution, and after stirring and mixing well, a slurry of phosphor/sol was obtained.

(Example 14)

10 g of a commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol and mixed. 10 g of fluorescent substance CESN was added to this mixed solution, and after stirring and mixing well, a slurry of phosphor/sol was obtained.

In addition, as Examples 15 to 23, examples of producing LEDs under various conditions are shown below.

(Example 15-1)

A commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol, followed by mixing. Phosphor substance/sol slurry is obtained by adding fluorescent substance YAG to the mixed solution in a predetermined ratio, stirring and mixing sufficiently. Thus, combined with a semiconductor light-emitting element with a wavelength of 460nm, an LED that emits white light can be obtained.

(Example 15-2)

A commercially available alumina sol (Nissan Chemical Alumina Sol 200) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the alumina sol and mixed. Phosphor substance/sol slurry is obtained by adding fluorescent substance YAG to the mixed solution in a predetermined ratio, stirring and mixing sufficiently. Combining the phosphor/sol slurry with a semiconductor light-emitting element with a wavelength of 460 nm, an LED emitting white light is obtained.

(Example 16)

A commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol, followed by mixing. Fluorescent substance YAG and calcium silicon nitride activated with europium are added to the mixed solution in a predetermined ratio, and after being thoroughly stirred and mixed, a phosphor/sol slurry is obtained. Combining this phosphor/sol slurry with a semiconductor light-emitting element with a wavelength of 460 nm, an LED emitting light in the color of a light bulb was manufactured.

(Example 17-1)

A commercially available alumina sol (Nissan Chemical Alumina Sol 200) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the alumina sol and mixed. Fluorescent substance YAG and calcium chloroapatite activated with europium and manganese are added to the mixed liquid in a predetermined ratio, and after being fully stirred and mixed, a slurry of phosphor/sol is obtained. Combining the phosphor/sol slurry with a semiconductor light-emitting element with a wavelength of 400 nm, an LED emitting white light is produced.

(Example 17-2)

A commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol, followed by mixing. Fluorescent substance YAG and calcium chloroapatite activated with europium and manganese are added to the mixed liquid in a predetermined ratio, and after being fully stirred and mixed, a slurry of phosphor/sol is obtained. Combining the phosphor/sol slurry with a semiconductor light-emitting element with a wavelength of 400 nm, an LED emitting white light is produced.

(Example 18)

A commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol, followed by mixing. Add fluorescent substance YAG, calcium chloroapatite activated with europium and manganese, and calcium silicon nitride activated with europium in a predetermined ratio to the mixed solution, and stir and mix thoroughly to obtain a slurry of phosphor/sol . Combining this phosphor/sol slurry with a semiconductor light-emitting element with a wavelength of 400 nm, an LED that emits light in the color of a light bulb is fabricated.

(Example 19)

A commercially available alumina sol (Nissan Chemical Alumina Sol 200) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the alumina sol and mixed. Fluorescent substances, namely calcium chloroapatite activated with europium, barium magnesium aluminate activated with europium and manganese, and strontium silicon nitride activated with europium are added to the mixture in a predetermined ratio, and after being fully stirred and mixed, the A phosphor/sol slurry is obtained. Combining the phosphor/sol slurry with a semiconductor light-emitting element with a wavelength of 400 nm, an LED emitting white light is produced.

(Example 20)

A commercially available alumina sol (Nissan Chemical Alumina Sol 200) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the alumina sol and mixed. Fluorescent material, that is, strontium aluminate activated with europium, is added to the mixed liquid in a predetermined ratio, and after being thoroughly stirred and mixed, a slurry of fluorescent material/sol is obtained. Combining this phosphor/sol slurry with a semiconductor light-emitting element with a wavelength of 365 nm, an LED that emits blue-green light for signaling is manufactured.

(Example 21)

A commercially available alumina sol (Nissan Chemical Alumina Sol 200) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the alumina sol and mixed. Fluorescent substance, that is, barium silicon nitride activated with europium, is added in a predetermined ratio to the mixed liquid, and after being thoroughly stirred and mixed, a slurry of phosphor/sol is obtained. Combining the phosphor/sol slurry with a semiconductor light-emitting element with a wavelength of 365 nm, an LED that emits yellow light for signaling is fabricated.

(Example 22)

A commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol, followed by mixing. Fluorescent substance YAG, barium magnesium aluminate activated with europium and calcium strontium silicon nitride activated with europium are added to the mixed solution in a predetermined ratio, and after being fully stirred and mixed, a slurry of phosphor/sol is obtained. Combining this phosphor/sol slurry with a semiconductor light-emitting element with a wavelength of 365 nm, an LED that emits light in the color of a light bulb is manufactured.

(Example 23)

A commercially available yttrium oxide sol (manufactured by Tagi Chemical Co., Ltd.) was placed in a 100 ml beaker, and 50% by weight of ethanol was added to the yttrium oxide sol, followed by mixing. Add fluorescent substances to the mixture in a predetermined ratio, that is, calcium chloroapatite activated with europium, barium magnesium aluminate activated with europium and manganese, and calcium silicon nitride activated with europium. After fully stirring and mixing, the A phosphor/sol slurry is obtained. Combining the phosphor/sol slurry with a semiconductor light-emitting element with a wavelength of 365 nm, an LED emitting white light is produced.

Table 1 shows examples of combining phosphors, adhesives, and LEDs of Examples 15-1 to 23 described above. In addition, the emission color is shown on the chromaticity diagram of FIG. 23 . The luminescent colors of the LEDs in these embodiments are respectively: Examples 15-1 and 15-2 are white, Example 16 is the color of the bulb, Examples 17-1 and 17-2 are high color rendering white, and Examples 18 and 22 are As for the color of the light bulb, Examples 19 and 23 are three-wavelength white, Example 20 is blue-green for signals, and Example 21 is yellow for signals.

Table 1

Furthermore, as a preferred embodiment of the present invention, a high-output light-emitting element can also be fabricated. A high-output light-emitting element is suitable for, for example, lighting applications. Examples of combining phosphors, binders, and LEDs for producing LEDs having practically preferable characteristics are shown in Table 2 below as Examples 24 to 29. The luminescent colors (tones) of the LEDs of these embodiments are respectively: embodiment 24 is white, embodiments 25, 26, and 27 are bulb colors, and embodiment 28 is three-wavelength white.

In addition, the three-wavelength white phosphor spectrum data used in Example 19 and Example 23 are shown in FIGS. 24 and 25 . FIG. 24 and FIG. 25 show the spectrum excited by the LED with a wavelength of 365 nm used in Example 23 and the spectrum excited by the LED with a wavelength of 400 nm used in Example 19, respectively.

Table 2

(comparative example 1)

As Comparative Example 1, a sample using silica sol was produced to obtain comparative data. Get 10g of commercially available silica sol (Collo Cot-manufactured HAS10) and fill it in a 100ml beaker, then add 10g CESN therein as a fluorescent substance, stir and mix thoroughly to obtain a slurry of fluorescent substance/sol.

(comparative example 2)

As Comparative Example 2, a sample not using a phosphor was produced to obtain comparative data. Here, only 400nm LEDs are used.

(Formation of Phosphor Layer)

The method of forming the phosphor layer using the phosphor/sol slurry of Examples 1 to 14 obtained above is shown as follows: first, the phosphor/sol slurry of Examples 1 to 5 are respectively filled in a spraying device (manufactured by ノ-ドゾン) in a spray can. Below the nozzle, an LED (9φ stem package, 0.35 mm chip) having a wavelength of 400 nm was disposed as a light emitting element. Here, the LED chip is masked in advance in order to coat the phosphor/sol slurry only on the LED chip. Then, from the bottom of the LED chip, heat it to about 90°C with a hot plate. After spraying and forming, the phosphor is bonded to the LED chip by means of the mixed sol, so that the light-emitting layer can be formed.

Next, in order to fully proceed the curing, the main curing was carried out for 30 minutes in a nitrogen atmosphere at a temperature of 240°C. Finally, the LED chip is covered in a glow box by adopting a nitrogen gas-tight sealing technology, so that an LED with a light-emitting layer containing a phosphor is obtained.

Table 3 is a list of phosphors used in Examples.

table 3

Abbreviation official name composition Average particle size (μm) Central particle size (μm) Luminous color (excited at 400nm) YAG Yttrium aluminum garnet activated with cerium (Y_0.79Gd_0.2Ce_0.01)₃Al₅O₁₂ 3.8 6.4 yellow SAE Strontium aluminate activated with europium (Sr_0.9Eu_0.1)₄Al₁₄O₂₅ 9 14 blue-green CCA-1 Calcium chloroapatite activated with europium (Ca_0.95Eu_0.05)(PO₄)₃Cl 15.9 18 blue CCA-2 Calcium chloroapatite activated with europium and manganese (Ca_0.94Eu_0.05Mn_0.01)(PO₄)₃Cl twenty two 25 blue CCBE Calcium chloroborate activated with europium (Ca_0.9Eu_0.1)₂B₅O₉Cl 12 19.1 blue BAM Barium magnesium aluminate activated with europium (Ba_0.45Eu_0.25Sr_0.3) MgO₅Al₂O₃ 3.9 8.7 blue CESN Calcium silicon nitride activated with europium (Ca_0.97Eu_0.03)₂Si₅N₈ 4.7 7.5 red ~ orange

(Durability Test)

Next, an endurance test was performed to confirm the reliability of the produced light-emitting device. In the durability test, an LED chip with a wavelength of 400nm, an output power of 14.5mW, and a size of 350μm on one side was used to operate at a current of 60mA at room temperature to confirm durability. At this time, the light irradiation density injected into the light-emitting layer of the light-emitting device is about 86.3 W/cm ^-2 assuming that half of the light is output from the side surface of the chip. In addition, the junction temperature is about 80°C, and the thermal resistance of the entire case is 230°C/W. The light irradiation density of sunlight is about 0.1W/cm ^-2 at 14 o'clock in Tokyo, so by calculation, the energy density of the irradiated light is about 863 times that of sunlight. The results of this durability test are shown in FIGS. 26 to 28 .

FIG. 26 shows the results of durability tests of Examples 1 to 4 using YAG-based phosphors. Regarding the phosphors/sols prepared in Examples 1 to 4 coated with the above-mentioned adjusted phosphors/sols, the output powers before putting into the lighting test and after 1000 hours of lighting were compared, and no output power was found at all. of degradation. On the other hand, in Comparative Example 1, the output of the LED using the phosphor of silica sol gradually decreased, and the output decreased to 85% after 1000 hours of lighting. In addition, in each figure, since Comparative Example 2 is only a 400-nm LED and no phosphor is applied, it cannot be confirmed that degradation has occurred.

FIG. 27 shows the results of durability tests of Examples 5 to 8 using strontium aluminate phosphors. The phosphor/LED that is coated with the phosphor/sol of embodiment 5～8 allotment, its output power after 1000 hours just as shown in Figure 27, embodiment 5 is 88%, embodiment 6 is 89%, implement Example 7 is 92%, and Example 8 is 93%. The phosphor/LED coated with the phosphor/sol prepared in Example 5, as shown in FIG. Thereafter, no reduction in output power was seen, and 88% of output power was still maintained at 1000 hours.

Furthermore, FIG. 28 shows the durability test results of Examples 9 to 12 of the three-wavelength white, wherein the three-wavelength white is a combination of LEDs in which luminescent layers containing RGB phosphors are formed with yttrium oxide sol. At the same time, FIG. 29 and FIG. 30 show the durability test results of Example 13 and Example 14, respectively. In these examples, the output power of the phosphor/LED coated with the formulated phosphor/sol after 1000 hours is just as shown in Figure 28. Example 9 is 94%, and Example 10 is 88%. Example 11 was 94%, and Example 12 was 94%. In addition, Example 13 shown in FIG. 29 was 94%, and Example 14 shown in FIG. 30 was 96%. In addition, the output power of the phosphor/LED coated with the phosphor/sol formulated in Example 13 of FIG. 29 was maintained at 94% after 1000 hours.

In this way, it has been found that the phosphor/sol prepared and formulated in the above-described examples can achieve extremely high durability compared to conventional phosphors using silica or the like. And it has been confirmed that it is particularly effective as a light-emitting film and a light-emitting layer used in a wavelength region of 410 nm or less. In addition, when a semiconductor light-emitting element that emits ultraviolet rays is used as a light-emitting element, the inorganic binder used in the above embodiment is effective because the conditions are more severe. On the other hand, conventional LEDs using resins and phosphors using silica in the light-emitting layer have degraded phenomena even at a relatively long wavelength of about 520 nm. By using the inorganic binder of the above-mentioned embodiment, it is possible to obtain A light-emitting device that is relatively stable and highly reliable even when used for a long time. In addition, the above-mentioned embodiment can be effectively utilized in a combination of a semiconductor light emitting element and a phosphor formed by pasting on the element, and a light emitting element having a large input power. In a light-emitting device with a large input power, energy such as heat generation and light irradiation density acting on the light-emitting layer is large, so the conventional resin adhesive layer and silica gel degrade very quickly. In contrast, as described above, in this embodiment, even if it is used for a long period of time, almost no deterioration is observed, and a highly reliable light-emitting device can be obtained while maintaining a high output.

Embodiment 6

Next, a light-emitting device according to Embodiment 6 of the present invention will be described based on FIGS. 31 to 32 . 31 is a schematic plan view showing a light-emitting device of Embodiment 6, FIG. 32(a) is a schematic cross-sectional view showing the light-emitting device of Embodiment 6, and FIG. 32(b) is a schematic cross-sectional view showing an enlarged concave portion of a substrate. The light emitting device 1 according to Embodiment 6 of the present invention includes a light emitting element 60 , a base 20 carrying the light emitting element 60 , and a cover 26 formed on the base 20 . Taking the side on which the light-emitting element 60 is placed as the main surface, the opposite side is referred to as the back side.

The base 20 is made of metal and has a recess 20a at its center. In addition, two through-holes penetrating the thickness direction are provided on the periphery of the recessed portion 20a, that is, at the base portion, and the respective through-holes are provided facing each other with the recessed portion 20a interposed therebetween. Metal positive and negative lead electrodes 22 are respectively inserted into the through holes via hard glass as an insulating member 23 . In addition, the main surface side of the metal base 20 has a cover 26 including a light-transmitting window portion 25 and a lead 24 made of a metal portion, and the contact surfaces of the metal lead 24 and the metal base 20 are welded together. . By welding the base body 20 and the cover body 26, the light emitting element 60 is airtight. Inert gas such as nitrogen can be used for airtightness. The light emitting element 60 accommodated in the recess 20 a is a light emitting element emitting blue light or ultraviolet light, and the light emitting element 60 is bonded in the recess 20 a of the base body 20 . As an example of the binder, a material obtained by drying and sintering a hydrolyzed solution of ethyl silicate can be used. The light emitting element 60 placed in the concave portion 20a of the base body 20 is covered with the inorganic binder 30 containing phosphor. The surface of the inorganic binder 30 is covered with a resin 40 .

For the light-emitting device 601, even if the crystallinity of a specific metal element is not improved, the reduction in light extraction efficiency will not be incurred in the gel state, and by impregnating the resin 40 in the inorganic binder 30, a light can be provided. Take out the light emitting device with high efficiency. In particular, if a gel of hydrated oxides such as Al and Y elements whose oxidation state is stable without valence change during the sol-gel reaction is used, even if a part of the coating film is in the gel state, the By further impregnating the resin to form a luminescent film, a coating film with high light extraction efficiency can be easily obtained in a short time and with low energy without continuing the sol-gel reaction.

In addition, by constituting the inorganic binder 30 using a hydrous oxide gel, the quality of the formed coating film can be improved. In the inorganic binder member containing a hydrated oxide, its particulate matter is aggregated by a sol-gel method to form a porous body having a cross-linked structure, a network structure, or a polymer structure. If the skeleton structure of the particle assembly of the hydrous oxide is a network structure having pores, the flexibility of the coating film can be improved because it is a porous structure. In addition, when the inorganic binder 30 is formed into a film, even if filler members such as phosphor particles are attached and the shape of the object to be coated is complicated, the film can be formed accordingly, and a coating film with high adhesion can be obtained. . Furthermore, since it is a hydrous oxide, a film that is stable against heat and light and does not deteriorate can be obtained.

The coating film formed in the conventional light-emitting device is exposed to light from the light-emitting element, so it is degraded by use of the light-emitting device. It is generally considered that the cause of this degradation is the occurrence of a reaction due to either or both of light output power and heat generation from the light-emitting element. Therefore, when ultraviolet rays with high light energy are used for large components that generate heat and have high thermal resistance values, degradation is likely to occur. On the other hand, as will be described later, samples of examples of the present invention were fabricated and subjected to durability tests, and as a result, it was confirmed that they had extremely high durability. A light-emitting device according to Embodiment 6 of the present invention has the following configuration, and the constituent members of this embodiment will be described in detail below with reference to the drawings.

(inorganic binder)

The light emitting element 20 provided on the substrate 20 is covered with an inorganic binder 30 . The inorganic binder 30 in a sol state enters the concave portion 20a of the base body 20 by means of pouring, pouring, spraying, etc., so as to cover the surface of the light emitting element 60 and the concave portion 20a. Phosphor 50 is contained in this inorganic binder 30 .

The inorganic binder 30 is cured by gelation after spraying, pouring, or screen printing. This curing results in the creation of voids 31 in the inorganic binder 30 . Due to the presence of the voids, the inorganic binder 30 becomes brittle and generates cracks and defects.

In addition to the mold member, the inorganic adhesive 30 is provided in the cover of the pin lead and the opening of the base body, etc., and contains a phosphor that converts the light emitted by the light emitting element 60, a material that binds the phosphor, and the like. layer. Regarding the layer of inorganic binder 30, the thickness of the layer of inorganic binder 30 provided on the top and side surfaces of light-emitting element 60 is substantially equal to the thickness of the layer of inorganic binder 30 provided on the inner surface of recess 20a. In addition, the inorganic binder 30 has no discontinuity even at the corners of the light emitting element 60 , and the layer of the inorganic binder 30 is continuous.

High-energy light or the like emitted from the light emitting element 60 becomes high-density in the inorganic binder 30 due to reflection by the substrate 20 and the lead 21 or the like. Furthermore, diffuse reflection is also generated by the phosphor 50, and the inorganic binder 30 may be exposed to high-density high-energy light. Therefore, when using a nitride-based semiconductor that has a high luminous intensity and can emit high-energy light as the light-emitting element 60, it is preferable to use a nitride-based semiconductor that has light resistance to these high-energy lights and contains Al, Y, Gd, Lu, Sc, Ga, In, A hydrated oxide of any metal element among B is used as the inorganic binder 30 .

As one of specific main materials of the inorganic binder 30, a material containing a phosphor in a light-transmitting inorganic member such as Al(OH) ₃ and Y(OH) ₃ is suitably used. Phosphors 50 are bonded to each other via these light-transmitting inorganic members, and phosphors 50 are deposited in layers on the light-emitting element 60 and the support and bonded thereto. In this embodiment, the hydrous oxide is formed from a compound mainly composed of the following hydrous oxide, wherein the main hydrous oxide is any one of Al, Y, Gd, Lu, Sc, Ga, In, B Formed by organometallic compounds. Here, the so-called organometallic compound includes an alkyl group and an aryl group bonded to a metal via an oxygen atom. Examples of such organometallic compounds include metal alkyls, metal alkoxides, didiketonate metals, and metal carboxylates. Among such organometallic compounds, those highly soluble in organic solvents tend to become uniform sol solutions after hydrolysis. In addition, since such an organometallic compound easily undergoes a chemical reaction such as hydrolysis, it is easy to scatter, and can form the inorganic binder 30 that binds the phosphor 50 . Therefore, unlike other methods of forming the inorganic binder 30 on the light-emitting element 60 at a temperature of 350° C. or higher or in a state where static electricity is applied, the method of using an organometallic compound can The inorganic binder 30 is easily formed on the light emitting element 60, so that the production yield can be improved.

The inorganic binder 30 is preferably formed into a layered structure in a thin film state. This is because phosphor 50 contained in inorganic binder 30 can emit light uniformly by being formed into a layered structure. In addition, since it is in a thin film state, the resin 40 easily permeates the inorganic binder 30 . As means for forming the layer of the inorganic binder 30, pouring means or spraying means can be used. However, the inorganic binder 30 may be in a form other than a thin film state.

As the inorganic binder 30, alumina, yttrium oxide, silica, or a composite thereof can be used. They are also dispersed in water or the like from a solid state to form a sol-gel state, whereby various shapes can be formed. In addition, the phosphor may be uniformly dispersed in the inorganic binder 30 . Hereinafter, alumina and yttrium oxide will be described as examples of the inorganic binder 30, but the present invention is not limited thereto.

In addition, conventionally, inorganic binders have been used for coating films. In the case of using this inorganic binder, especially in the case of using a cured film formed of silica gel (SiO ₂ ), there is coloring deterioration when exposed to high output and ultraviolet rays And produce the problem of blackening. Especially in high output light emitting devices, the silica binder layer is degraded due to high optical density and heat, and is colored black or dark brown. As a result of research conducted by the present inventors, it is presumed that the cause is that SiO ₂ , that is, silicon dioxide, forms SiO _x (x<2) due to oxygen deficiency. The silica binder is in the state of silica gel in which some hydroxyl groups and organic groups remain in the _SiO2 skeleton at a thermal curing temperature of 250°C or lower. In such a silica gel state, when high-density light enters from the LED, oxygen deficiency occurs, and SiO ₂ becomes SiO _X (x<2). In this way, since Si is prone to oxidation and reduction, it is generally considered that the loss of oxygen in the silica gel is the cause of coloring deterioration. Once the coloring degradation occurs, there arises a problem that the light output power from the light emitting element decreases. In addition, inorganic binders have the problems of being prone to cracks and defects due to the presence of voids, and having weak impact resistance. This is considered to be due to the lack of impact resistance of inorganic binders unlike resins.

(alumina)

Amorphous alumina or microparticle hydrated alumina is uniformly dispersed in water, and the alumina sol thus formed is used as a binder, in this case, the alumina sol is heated and solidified to form a stable boehmite Before the structure of the hydrated alumina, it undergoes a stage of pseudo-boehmite structure. The boehmite crystal structure of hydrated alumina and the pseudo-boehmite structure of hydrated alumina can be represented by the chemical formula AlOOH or Al ₂ O ₃ ·H ₂ O and (AlOOH)·xH ₂ O or Al ₂ O ₃ ·2H ₂ O wait to express. Specifically, Al ₂ O ₃ ·2H ₂ O, Al ₂ O ₃ ·xCH ₃ COOH ·yH ₂ O, Al ₂ O ₃ ·xHCl·yH ₂ O, Al ₂ O ₃ ·xHNO ₃ ·yH ₂ O and other forms, finally forming a stable boehmite structure. If the crystallinity of the boehmite structure is further improved, it becomes γ-alumina (Al ₂ O ₃ ) or α-alumina (Al ₂ O ₃ ). An alumina sol having such properties is used as a binder, thereby forming a light emitting film.

As the specific main material of the inorganic binder 30, a sol solution prepared by the following method can be used, that is, a small amount of inorganic acid, organic acid and alkali are used as stabilizers, and an amorphous metal oxide, an ultrafine particle metal hydrated oxide And ultrafine particle oxides are evenly dispersed in water or organic solvents. As the initial raw materials for the synthesis of amorphous metal oxides, ultrafine metal hydrated oxides and ultrafine particle oxides, metal alkoxides, diketone metals, metal halides, or metal carboxylates, Hydrolyzed products of metal alkyl compounds and products hydrolyzed after mixing them. In addition, a colloid (sol) solution prepared by uniformly dispersing metal hydroxides, metal chlorides, metal nitrates, and metal oxide fine particles in water and an organic solvent, or a mixed solvent of water and a water-soluble organic solvent can also be used. . They are collectively referred to as aluminoxanes. Aluminoxane has a repeating unit of [AlO]x in its skeleton.

As the metal alkoxide, there are: aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, aluminum isopropoxide , tert-butoxy aluminum, methoxy yttrium, ethoxy yttrium, n-propoxy yttrium, isopropoxy yttrium, n-butoxy yttrium, sec-butoxy yttrium, isopropoxy yttrium, tert-butoxy Yttrium etc.

As bis-diketonate metals, available are: aluminum triethylacetoacetate, diisopropoxyaluminum alkylacetoacetate, diisopropoxyaluminum ethylacetoacetate, diethylacetylacetonate monoacetylacetonate Aluminum acetate, aluminum triacetylacetonate, yttrium triacetylacetonate, and yttrium triethylacetoacetate.

Usable metal carboxylates include aluminum acetate, aluminum propionate, aluminum 2-ethylhexanoate, yttrium acetate, yttrium propionate, and yttrium 2-ethylhexanoate.

In addition, as metal halides, aluminum chloride, aluminum bromide, aluminum iodide, yttrium chloride, yttrium bromide, yttrium iodide, and the like can be used.

As an organic solvent, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, tetrahydrofuran, dioxane, acetone, ethylene glycol, methyl ethyl ketone, N, N -Dimethylformamide and N,N-dimethylacetamide, etc.

In the inorganic binder 30 , fillers and diffusion particles may be mixed instead of the phosphor 50 , or fillers and diffusion particles may be mixed in addition to the phosphor 50 . Furthermore, as a composite material of these, the linear expansion coefficients of the coating substrate and the light emitting element can also be kept the same. As a filler, the fluorescent material 50 is mixed to produce light emission, and at the same time, it also creates fine channels for moisture evaporation during curing, and has the effect of accelerating the curing and drying of the adhesive. In addition, it also has the function of diffusing the light emitted by the phosphor 50 and increasing the bonding strength and physical strength of the inorganic binder 30 . In addition, the layer of the inorganic binder 30 and the film of the inorganic binder 30 can also be used as a diffusion layer not containing phosphor. In addition, the composite material used as a binder may contain a small amount of elements having various valences in addition to trivalent metal elements. Furthermore, in the present embodiment, the binder member may contain a hydrated oxide as a main compound, and it may function even if it contains a part of metal oxides and metal hydroxides and combinations thereof.

As a specific main material contained in the inorganic binder 30, AlOOH of alumina will be described below as an example.

(AlOOH)

The inorganic binder 30 formed by bonding the phosphor 50 with AlOOH is formed by hydrolyzing an aluminum alkoxide or an aluminum alkoxide at a predetermined ratio in an organic solvent, and the aluminum oxide obtained by the hydrolysis The phosphor 50 (powder) is uniformly dispersed in an alkane sol or alumina sol solution to obtain a coating solution, and the coating solution is adjusted to coat the alumina in which the phosphor 50 is dispersed by pouring, spraying or spreading. The sol solution is used to cover the entire light emitting element 60 , and then heated and cured to fix the phosphors to each other and to the surface of the light emitting element 60 by the AlOOH component.

Aluminum alkoxide or aluminum alkoxide is an organoaluminum compound used as a tackifier, gelling agent, curing agent, polymerization catalyst, and dispersant for pigments in paints.

Aluminum isopropoxide, aluminum ethoxide and aluminum butoxide, which are one of aluminum alkoxide or aluminum alkoxide, are very reactive, and form aluminum hydroxide or alkyl aluminate with the help of moisture in the air. A hydrated alumina with a boehmite structure is produced. For example, aluminum isopropoxide is easily reacted with water as shown in the following chemical formula 8, and finally becomes a cross-linked structure composed of hydrated alumina as the main component and cross-linked with aluminum hydroxide or alumina (alumina). mixture.

       化学式8

chemical formula 8

Therefore, after reacting aluminum isopropoxide with moisture in the air, the phosphor 50 is bonded with AlOOH generated by heating, so that the inorganic binder 30 formed by bonding the phosphor 50 with AlOOH containing the phosphor 50 can be used as The inorganic binder 30 is formed on the surface of the light emitting element 60 and on a support other than the surface of the light emitting element 60 .

The above inorganic binder 30 formed by bonding the phosphor 50 with AlOOH may also be combined with an inorganic bond formed by bonding the phosphor 50 with other hydrated oxides such as Y, Gd, Lu, Sc, Ga, In, and B. Agent 30 and inorganic binder 30 formed by bonding phosphor 50 with AlOOH are used to form two or more layers on the same light-emitting element 60 . According to the method of forming the inorganic binder 30 using the spraying method of the present embodiment, since the film thicknesses of the two layers can also be controlled, the inorganic binder 30 of the same shape can be easily formed. For example, on the same light-emitting element 60, the Y ₂ O ₃ inorganic binder 30 is formed first, and then the Al ₂ O ₃ inorganic binder 30 is formed thereon. Here, the phosphor 50 may be included in both layers, may be included in only one layer, and may not be included in both layers. According to such a configuration, there is an effect of improving the light extraction efficiency depending on the magnitude of the refractive index of the inorganic binder 30 . When the inorganic binder 30 composed of one layer is formed, a sharp change in the refractive index occurs at the interface between the inorganic binder 30 and the external atmosphere or the nitride semiconductor light-emitting element, and part of the light extracted from the light-emitting element 60 may Reflection occurs at this interface, resulting in a decrease in light extraction efficiency. In addition, by forming the inorganic binder 30 mixed with AlOOH and YOOH, for example, the coefficient of linear expansion and the refractive index can also be adjusted.

The inorganic adhesive 30 formed by bonding the phosphor 50 with AlOOH formed in this way is an inorganic substance unlike the case where only epoxy resin is used for sealing in the past, so compared with epoxy resin, the degradation caused by ultraviolet rays It is extremely small, and it is also possible to use a combination of a light-emitting element that emits ultraviolet light and a high-output power-type light-emitting element.

(yttrium oxide)

In the case where amorphous yttrium oxide or fine particle yttrium oxide is uniformly dispersed in water, and the yttrium oxide sol thus formed is used as the inorganic binder 30, even if the yttrium oxide sol is heat-cured, the main body of the crystalline structure is amorphous . Hydrated yttrium oxide and yttrium oxide can be represented by chemical formulas such as YOOH·xH ₂ O and Y ₂ O ₃ ·xH ₂ O, respectively. Specifically, as an intermediate, it passes through the form of YOOH·xCH ₃ COOH·yH ₂ O or Y ₂ O ₃ ·xCH ₃ COOH·yH ₂ O, and finally becomes a form partially containing hydrated yttrium oxide or yttrium oxide. Yttrium oxide can form a stable film even in such a gel state. The reason for this is considered to be that each component has a cross-linked structure, which enables stabilization.

Yttrium oxide has a property that it is difficult to form a crystal structure compared with alumina. In this way, even an amorphous non-crystalline structure having no crystallinity can be a stable compound, and the valency of Y remains unchanged without changing the valence number. That is, it has the advantage that oxidation-reduction reaction hardly occurs and there is no color degradation.

Regarding the others, the inorganic binder 30 is formed in the same manner as the above-mentioned alumina. As described above, commercially available inorganic binders, ceramic binders, and the like can be used as the sol in which the phosphor is used as a binder. In addition, among the materials that can be used as binders, they are not limited to hydrated oxides containing Al and Y elements such as alumina and yttrium oxide, and hydrated oxides of other IIIA group elements and IIIB group elements can also be used. compounds, oxides, and hydroxides. The selected metal element preferably does not change in valence. In particular, trivalent and stable metal elements are preferable. In addition, it is also preferably colorless and transparent. For example, in addition to Al and Y, metal compounds containing metal elements such as Gd, Lu, Sc, Ga, and In can also be used, preferably Sc and Lu can be used. Alternatively, composite oxides and composite hydrated oxides in which multiple types of these elements are combined can also be used. Not only aluminum and yttrium, but also other optical properties such as the refractive index of the layer of the inorganic binder 30 and physical properties of the film such as flexibility and adhesiveness of the film can be adjusted by hydrated oxides containing other Group III elements. Various properties are controlled to desired values. In this way, with the inorganic binder 30 obtained from the embodiment of the present invention containing a hydrated oxide gel having a constant valence, preferably trivalent, it is possible to design a stable inorganic binder 30 with high light extraction efficiency. In addition, since it is composed of an inorganic material, it is possible to form a stable inorganic adhesive layer and an inorganic adhesive film that do not change over time.

(resin)

The resin covers the surface of the inorganic binder 30 . This coating film forms a layer of resin 40 on the surface of the layer of inorganic binder 30 . However, it is also possible to have the resin 40 filled in the base body 20 having the concave portion 20 a and covered with the inorganic binder 30 . In addition, although various methods may be employed, it is preferable to impregnate the inorganic binder 30 with the resin 40 . The so-called impregnation means that the inorganic binder 30 is immersed in and contains the resin 40 .

When the viscosity of the resin 40 before curing is too high, the resin will not flow and a uniform coating film will not be formed. On the other hand, when the viscosity of the resin 40 before curing is too low, the resin stays in the depressions, the protrusions do not have resin residues, and a uniform coating film cannot be formed. Therefore, it is preferable to use a resin having a predetermined viscosity.

The resin 40 is preferably a layered structure. By adopting a layered structure, it is possible to improve the extraction efficiency of light emitted from the light emitting element 60 and to control the directivity. In addition, the heat generated by the light emitting element 60 can be discharged to the outside without being accumulated in the resin 40 .

The resin 40 is preferably gel-like. Stress due to thermal expansion can be relieved by the gel, so that cutting of the lead wire 21 extending from the light emitting element 60 can be prevented. In addition, the resin 40 may be oily.

The surface of the resin 40 covering the inorganic binder 30 is smooth. When only the inorganic binder 30 is cured, many granular irregularities can be seen when the surface is observed with an electron microscope. For this reason, light emitted from the light emitting element 60 is reflected or scattered by the granular unevenness, thereby suppressing extraction of light. Therefore, by covering the surface of the inorganic binder 30 with the resin 40 , the surface of the resin 40 can be smoothed. Thereby, the light emitted from the light emitting element 60 can be efficiently emitted to the outside, and the light extraction efficiency can be improved. In addition, since the surface of the inorganic binder 30 is formed with granular irregularities, the surface area with the resin 40 is increased, thereby increasing the adhesion force at the interface between the resin 40 and the inorganic binder 30 .

The gas content of the resin 40 is 3% by volume or less under normal pressure. It is preferably 1% by volume or less, more preferably 0.01% by volume or less. Gases such as air are contained in the voids 31 of the inorganic binder 30 . This gas is discharged to the outside when the resin 40 is impregnated. At this time, since the surface of the inorganic binder 30 is covered with the resin 40 , the gas in the void 31 may also be dissolved in the resin 40 , and since the gas is dissolved in the resin 40 , the resin 40 contains gas. The gas contained in the resin 40 generates heat when the light-emitting element 60 is excited, and thermal expansion occurs due to the heat generation, and bubbles may be generated in the resin 40 due to the thermal expansion. The light emitted from the light emitting element 60 may be reflected due to the effect of the air bubbles, resulting in a decrease in light extraction efficiency. Therefore, the amount of gas contained in the resin 40 is preferably as small as possible. The material of the resin 40 is a material that penetrates into the inorganic binder 30, and preferably has excellent heat resistance, light resistance, and weather resistance. Since the light-emitting element 60 generates heat of 120° C. or higher, the temperature is extremely high, so the resin 40 must be a heat-resistant resin that can withstand this temperature. In addition, the resin 40 needs to be a light-resistant resin because it is irradiated with and passes high-intensity light such as blue light or ultraviolet rays. On the other hand, resins with low water absorption and low moisture absorption are preferable. In the case of using a resin with high water absorption and moisture absorption, the moisture in the resin explodes with the heat generated by the light-emitting element 60, and peeling occurs at the interface between the light-emitting element 60 and the inorganic binder 30 or the resin 40, This leads to a decrease in light extraction efficiency. Therefore, it is preferable to use a resin with low water absorption and low moisture absorption, and not to contain moisture in the resin 40 .

Examples of the organic resin material impregnated into the layer of the inorganic binder 30 to which the phosphor 50 is bonded include silicone resin, acrylic resin, and epoxy resin. As a material of the resin 40, a silicone resin is preferable.

Silicone resin has stable chemical properties such as heat resistance, weather resistance, and light resistance. Silicone resin is composed of Si-O-Si framework. Because the bonding energy of the siloxane bond of Si-O is large, it is stable and has excellent transparency to light from visible to ultraviolet. Therefore, it is generally considered that since the resin 40 itself does not absorb such light, it is difficult to cause degradation. In addition, the silicone resin has low surface tension, low viscosity, excellent permeability, and can uniformly permeate into minute parts of the inorganic binder 30 . Silicone resins include addition curing type, UV curing type, condensation reaction type, and UV cationic polymerization type, among which addition curing type is preferable. This is because the addition curing type has almost no volatile components in the resin, and there is almost no volume shrinkage after heat curing. Since volume shrinkage does not occur, cracks due to volume shrinkage do not occur. In addition, peeling does not occur at the interface between the resin 40 and the inorganic binder 30 . Since the resin 40 has almost no volatile components, when used as an airtight substrate, there is no fear of damage to the substrate due to an increase in internal pressure accompanying heat generation of the light emitting element 60 . The resin 40 is preferably a soft gel or a rubber with a lower hardness in a cured resin state than in a hard state. Since the resin 40 exists in a soft state, the stress and external pressure acting on the resin 40 due to heat, impact, etc. can be alleviated, and the flexibility of the resin 40 can be improved. For example, a silicone resin having a dialkylsiloxane skeleton can be used for the resin 40 either before or after molding. After cross-linking, the silicone resin has a structure such as gel and rubber. In particular, the resin 40 preferably has a main chain of dimethylsiloxane before molding. However, it is not limited to dimethylsiloxane, and phenylmethylsiloxane can also be used.

The inorganic binder 30 is not completely oxide crystallized or polycrystalline, but is stored in a porous gel state. In particular, in the reflow process, etc., since it is necessary to apply stress to the inorganic binder 30 by thermal shock, when the silicone resin 40 and the like are impregnated, cracks and cracks are caused due to the difference in thermal expansion coefficient between the silicone resin 40 and the inorganic binder 30 . peel off.

Since the porous gel is formed into a cross-linked structure, a network structure, or a polymer structure, the thermal expansion coefficient is larger than that of the crystalline and polycrystalline states, and since it is close to the thermal expansion coefficient of silicone resin, cracking and peeling will not occur.

When the condensation type resin 40 is used for curing, small molecular components will be produced. At this time, the resin 40 shrinks in volume, cracks occur in the inorganic binder 30 , and peeling occurs at the contact surface between the inorganic binder 30 and the phosphor 50 .

Since the UV curable resin 40 has an organic functional group that absorbs ultraviolet rays introduced, the resin 40 absorbs excitation light and generated light, resulting in a decrease in light extraction efficiency.

(filler)

The filler (not shown in the figure) is the filler, which can be used: barium titanate, titanium oxide, aluminum oxide (two aluminum oxide), yttrium oxide (two yttrium oxide), silicon oxide, calcium carbonate and other hydrated oxides, etc. For example, there may also be a colorless hydrated oxide containing at least one or more elements selected from Al, Ga, Ti, Ge, P, B, Zr, Y, or alkaline earth metals, or at least containing one or more elements selected from Oxides of one or more elements among Si, Al, Ga, Ti, Ge, P, B, Zr, Y or alkaline earth metals have higher thermal conductivity fillers. By adding such fillers, the heat dissipation effect of the light emitting device 601 can be improved. Examples of such a filler include metal powders such as alumina and Ag when the above-mentioned inorganic binder 30 is used to form an adhesive layer and the light-emitting element 60 is die-bonded.

In the sol of the inorganic binder 30, in addition to the phosphor 50 and the lower alcohol, by mixing a dispersant in advance, a dense coating film can be formed at low temperature by azeotropic dehydration with the lower alcohol during curing. In addition, a photostabilizing material, a colorant, an ultraviolet absorber, and the like may be contained in the inorganic binder 30 .

The inorganic binder 30 is formed using a slurry solution. The slurry solution is prepared by using amorphous metal hydrated oxide, fine particle metal hydrated oxide, and metal hydroxide as the main components, and the main components are further mixed with amorphous metal oxide and fine particle metal oxide. Dispersed in water, thereby preparing a sol solution, and then mixing the phosphor 50 and the filler in the sol solution. The weight ratio of the effective solid content in the sol solution to the phosphor 50 or the weight ratio of the effective solid content in the sol solution to the phosphor 50 and the filler mixture is preferably 0.05-30. For example, the ratio can be adjusted within a range from 90 g of a sol solution having an effective solid concentration of 15% and a phosphor to 600 g of a sol solution having an effective solid concentration of 15% and a phosphor of 4.5 g.

(light emitting element)

The light emitting element 60 is not limited to a light emitting element capable of emitting visible light, and a light emitting element capable of emitting ultraviolet light may also be used. In addition, the light emitting element 60 may be used in combination with the phosphor 50 . That is, by irradiating the phosphor 50 with light emitted from the light emitting element 60 and exciting the phosphor 50 , it is possible to emit light different from that of the light emitting element 60 . The light-emitting element 60 adopts methods such as MOCVD to form semiconductors such as GaAs, InP, GaAlAs, InGaAlP, InN, AlN, GaN, InGaN, AlGaN, and InGaAlN on a substrate as a light-emitting layer. Examples of semiconductor structures include homojunction structures, heterojunction structures, and double heterojunction structures having MIS junctions, PIN junctions, and PN junctions. The emission wavelength can be selected variously according to the material of the semiconductor layer and its degree of mixing. In addition, a single quantum well structure or a multiple quantum well structure in which a semiconductor active layer is formed on a thin film that produces a quantum effect may also be used. Nitride-based compound semiconductors (general formula In _i Ga _j Al _k N where 0≤i, 0≤j, 0≤k, and i+j+k=1).

When a gallium nitride-based compound semiconductor is used as the light-emitting element 60 , materials suitable for the semiconductor substrate include sapphire, spinel, SiC, Si, ZnO, GaN, and the like. In order to form gallium nitride with good crystallinity, it is more preferable to use a sapphire substrate. When growing a semiconductor film on a sapphire substrate, it is preferable to form a buffer layer such as GaN, AlN, and then form a gallium nitride semiconductor having a PN junction on the buffer layer. In addition, GaN single crystal itself, which is selectively grown on a sapphire substrate with _SiO2 as a mask, can also be used as the substrate. In this case, after each semiconductor layer is formed, the light emitting element can be separated from the sapphire substrate by etching and removing SiO ₂ . Gallium nitride-based compound semiconductors exhibit n-type conductivity without doping. In the case of forming an n-type gallium nitride semiconductor that requires improvement of luminous efficiency, etc., it is preferable to appropriately introduce elements such as Si, Ge, Se, Te, and C as n-type dopants. On the other hand, when forming a p-type gallium nitride semiconductor, it is doped with Zn, Mg, Be, Ca, Sr, Ba, etc. as p-type dopants.

If the gallium nitride-based compound semiconductor is only doped with a p-type dopant, it is difficult to achieve p-type, so after introducing the p-type dopant, it is preferable to use furnace heating, low-speed electron beam irradiation, and plasma irradiation for annealing. , thereby realizing p-type. As a specific layer configuration of a light-emitting element, a suitable example can be given in which layers are laminated on a sapphire substrate or silicon carbide with a buffer layer formed at low temperature such as gallium nitride or aluminum nitride. , laminated as the n-type contact layer of gallium nitride semiconductor, as the n-type cladding layer of aluminum nitride gallium semiconductor, as the active layer of indium gallium nitride semiconductor doped with Zn and Si, as the active layer of aluminum gallium nitride semiconductor A p-type cladding layer and a p-type contact layer as gallium nitride semiconductor. In order to form the light-emitting element 60, in the case of the light-emitting element 60 having a sapphire substrate, after forming the exposed surfaces of the p-type semiconductor and the n-type semiconductor by etching or the like, they are formed on the semiconductor layer using sputtering or vacuum evaporation. Each electrode having the desired shape. In the case of a SiC substrate, a pair of electrodes can also be formed by utilizing the conductivity of the substrate itself.

Then the formed semiconductor wafer etc. are diced, diced or directly completely cut by using a diamond wheel dicing machine, wherein the blade of the diamond wheel dicing machine has a diamond blade, and the blade rotates during cutting; After making a groove wider than the blade width, the semiconductor wafer is separated by external force. Or use a diamond wheel dicing machine with a diamond needle at the top to make a reciprocating linear motion to draw a very fine scribe line (warp line) on the semiconductor wafer, for example, into a textured pattern, and then use external force to separate the wafer, thereby cutting the semiconductor wafer. into chips. In this way, the light-emitting element 60 that is a nitride-based compound semiconductor can be formed.

In the light-emitting device 601 of this embodiment, when emitting light, the main emission wavelength of the light-emitting element 60 is preferably 350 nm to 530 nm in consideration of complementarity with the emission color of the phosphor.

In addition, the light-emitting element includes, in addition to semiconductor light-emitting elements, elements for obtaining light emission by vacuum discharge and light emission by thermoluminescence. For example, an element that generates ultraviolet rays or the like by vacuum discharge can also be used as a light emitting element. In the embodiment of the present invention, the wavelength of the light-emitting element used is 550 nm or less, preferably 460 nm or less, more preferably 410 nm or less, but the present invention is not limited thereto. In particular, as will be described later, the embodiments of the present invention have advantages in that they are excellent in durability and can be applied to dynamic light-emitting elements with high output power.

An example in which a Group III nitride-based semiconductor light-emitting element is used as the light-emitting element 60 will be described below. The light-emitting element 60 is, for example, a laminated structure formed by sequentially stacking the following layers on a sapphire substrate with a GaN buffer layer interposed therebetween: the first n-type GaN layer with undoped Si or a low Si concentration; An n-type contact layer composed of n-type GaN with a higher Si concentration than the first n-type GaN layer; a second GaN layer with an undoped or lower Si concentration than the n-type contact layer; a light-emitting layer with a multiple quantum well structure (GaN barrier layer /InGaN well layer quantum well structure); a p-cladding layer composed of P-type GaN, wherein P-type GaN is composed of Mg-doped P-type GaN; a P-type contact layer composed of Mg-doped P-type GaN. And the electrodes were formed as follows. Of course, a light emitting element having a configuration different from this may also be used.

The p-ohmic electrode is formed substantially on the entire surface of the p-type contact layer, and a p-pad electrode is formed on a part of the p-ohmic electrode.

In addition, the first GaN layer is removed from the p-type contact layer by etching to expose a part of the n-type contact layer, and an n-electrode is formed on the exposed part.

In addition, this embodiment uses a light-emitting layer with a multiple quantum well structure, but the present invention is not limited thereto. For example, both a single quantum well structure and a multiple quantum well structure of InGaN can be used, and GaN doped with Si and Zn can also be used.

In addition, by changing the In content of the light-emitting layer of the light-emitting element 60, the main light-emitting peak can be changed within the range of 420 nm to 490 nm. Furthermore, the emission wavelength is not limited to the above-mentioned range, and a light emitting element having an emission wavelength of 360 nm to 550 nm can be used. In particular, when the light-emitting device of the present invention is applied to an ultraviolet LED light-emitting device, the absorption and conversion efficiency of excitation light can be improved, and the transmission of ultraviolet light can be reduced.

(phosphor)

Phosphor 50 converts visible light and ultraviolet light emitted from light emitting element 60 into light having a wavelength different from that of light emitting element 60 . For example, it is excited by light emitted from the semiconductor light emitting layer of the light emitting element 60 to emit light. As preferable phosphors, there are: rare earth garnet-based phosphors activated by at least Ce such as yttrium-aluminum-garnet (hereinafter referred to as "YAG"), nitride-based phosphors such as alkaline-earth silicon nitride phosphors, Oxynitride systems such as alkaline earth silicon oxide nitride phosphors. In the present embodiment, as the phosphor 50, a phosphor that is excited by ultraviolet light to generate light of a predetermined color is used. Specifically, examples of phosphors that can be used are as follows:

(1) Ca ₁₀ (PO ₄ ) ₆ FCl:Sb, Mn

(2) M ₅ (PO ₄ ) ₃ Cl:Eu (where: M has at least one alkaline earth metal selected from Sr, Ca, Ba, and Mg)

(3) BaMg ₂ Al ₁₆ O ₂₇ :Eu

(4) BaMg ₂ Al ₁₆ O ₂₇ :Eu, Mn

(5) 3.5MgO·0.5MgF ₂ ·GeO ₂ :Mn

(6)Y ₂ O ₂ S:Eu

(7)Mg ₆ As ₂ O ₁₁ :Mn

(8) Sr ₄ Al ₁₄ O ₂₅ :Eu

(9)(Zr,Cd)S:Cu

(10)SrAl ₂ O ₄ :Eu

(11) Ca ₁₀ (PO ₄ ) ₆ ClBr:Mn, Eu

(12)Zn ₂ GeO ₄ :Mn

(13)Gd ₂ O ₂ S:Eu

(14) La ₂ O ₂ S:Eu

(15)Ca ₂ Si ₅ N ₈ :Eu

(16)Sr ₂ Si ₅ N ₈ :Eu

(17)SrSi ₂ O ₂ N ₂ :Eu

(18) BaSi ₂ O ₂ N ₂ :Eu

(19) M ₂ SiO ₄ :Eu (where: M has at least one alkaline earth metal selected from Sr, Ca, Ba, and Mg)

In addition to the above-mentioned phosphors, YAG-based phosphors that are rare-earth aluminates represented by (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ :Ce and the like that emit light in the yellow region can also be used.

When the light emitted by the light emitting element 60 and the light emitted by the phosphor 50 have a complementary color relationship, white light can be emitted by mixing the respective lights. As a combination of the light-emitting element 60 emitting white light and the phosphor 50, specifically, the light emitted by the light-emitting element 60 and the light emitted by the phosphor 50 excited by the light correspond to the three primary colors (red, red, etc.). green-based, blue-based), and the blue light emitted by the light-emitting element 60 and the yellow light of the phosphor excited by the light and emitting light. Especially when ultraviolet light is used for the light-emitting element 60, since the light-emitting color is determined only by the light-emitting color of the phosphor 50, various intermediate colors such as blue-green, yellow-red, red, etc., and light colors for signals are obtained. devices are also possible.

Various resins and inorganic binders such as glass that function as a binder between the phosphors 50 and the phosphors 50, ratios to fillers, etc., settling time of the phosphors 50, shapes of the phosphors, etc. Various adjustments and selection of the light emission wavelength of the LED chip, the light emission color of the light emitting device 601 can provide any white tone such as the color of the light bulb. Outside the light emitting device 601, it is preferable that the light emitted from the light emitting element 60 and the light emitted from the phosphor 50 efficiently pass through the mold member.

Typical phosphors 50 include copper-activated cadmium zinc sulfide and cerium-activated YAG-based phosphors. Especially for high luminance and long-term use, (Re _1-x Sm _X ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ :Ce(0≤x<1, 0≤y≤l, where : Re is at least one element selected from Y, Gd, La, Lu, Tb and Pr =.

(Re _1-x Sm _X ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ : Ce phosphor has a garnet structure, so it has strong resistance to heat, light and moisture, and the excitation peak can reach about 470nm . In addition, it may also have a broad emission spectrum, the emission peak of which is around 530nm, and the end of the peak extends to 720nm.

In the light-emitting device 601 of this embodiment, the phosphor 50 may also be a mixture of two or more phosphors. That is, two or more kinds of (Re _1-x Sm _X ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ with different contents of Al, Ga, Y, La, Lu, Tb, Pr, and Gd and Sm can be combined :Ce phosphor is mixed to increase the wavelength components of RGB. In addition, by using a red-increasing component such as a nitride phosphor having yellow to red light emission, it is also possible to obtain a light-emitting device with a high average color rendering index or a light bulb color. Specifically, by mixing and matching the light-emitting wavelengths of light-emitting elements, adjusting the content of phosphors with different chromaticity points on the CIE chromaticity diagram, it is possible to emit light at any point on the chromaticity diagram, where the chromaticity diagram uses light-emitting elements to The phosphors are connected together.

In this way, the phosphor 50 can be uniformly dispersed in the inorganic binder 30 and emit light uniformly. The phosphor in the inorganic binder 30 settles or floats due to its own weight.

On the surface of the light-emitting device 601, the phosphor 50 formed as above may have two or more types in the inorganic binder 30 composed of one layer, or may exist in the inorganic binder 30 composed of two layers. There are one, two or more of them respectively. Furthermore, one, two or more phosphors may also exist in the resin 40 . In this way, white light can be obtained by color mixing of lights originating from different phosphors 50 . At this time, in order to better mix the colors of the light emitted by each phosphor 50 and reduce color unevenness, it is preferable that each phosphor has a similar average particle size and shape. In addition, the inorganic binder 30 may be formed in consideration of the sedimentation characteristics influenced by the shape. Examples of methods for forming the adhesive 30 that are not easily affected by sedimentation characteristics include a spray coating method, a screen printing method, and a pouring method. In this embodiment, the inorganic binder can have an effective solid content of 1% to 80%, can adjust the viscosity in a wide range of 1cps to 5000cps, and can also adjust thixotropy, so it can bond with these inorganic binders. Compatible with the formulation method of the agent. As described above, the weight ratio of the filler to the inorganic binder is preferably set in the range of 0.05 to 30, and the binding force is enhanced by adjusting the compounding amount and particle size of the filler.

The phosphor used in this embodiment may be a combination of a YAG-based phosphor, a phosphor that may emit red light, and particularly a nitride phosphor such as an alkaline-earth silicon nitride phosphor. These YAG-based phosphors and phosphors may be mixed and contained in the light-emitting layer, or may be contained separately in an inorganic binder composed of multiple layers.

The respective phosphors will be described in detail below.

(YAG-based phosphor)

The so-called YAG-based phosphor used in this embodiment is a phosphor activated by rare earth elements such as cerium or Pr, which contains Y and Al, and contains a phosphor selected from Lu, Sc, La, Gd, Tb, Pr, Eu, and Sm. At least one element in and one element selected from Ga and In are phosphors that emit light when excited by visible light or ultraviolet light emitted by the LED chip. Particularly in this embodiment, two or more types of yttrium/aluminum oxide-based phosphors activated with cerium, Tb, or Pr and having different compositions can also be used. If the blue-based light emitted by a light-emitting element using a nitride-based compound semiconductor as a light-emitting layer, and the green-based and red-based light emitted by a phosphor whose body color is yellow due to absorption of blue light, or The yellow-based light but the green-based light and the red-based light are mixed and displayed, and the desired white-based luminous color can be displayed. Since color mixing occurs in the light-emitting device, powders and lumps of phosphors may be contained in various resins such as epoxy resins, acrylic resins, or silicone resins, and light-transmitting inorganic substances such as the inorganic binder of this embodiment. In this way, the light-emitting layer containing phosphor can be used in various ways depending on the use of the phosphor in point form or layer form. The light-emitting layer is formed thin enough to transmit light emitted from the light-emitting element. By adjusting the ratio of phosphors and translucent inorganic substances, coating and filling amounts, and by selecting the emission wavelength of the light-emitting element, it is possible to provide arbitrary color tones such as bulb colors including white.

In addition, a light-emitting device capable of emitting light efficiently can be obtained by arranging two or more kinds of phosphors in sequence with respect to incident light from the light-emitting element. That is, on a light-emitting element having a reflective member, a color conversion member containing a phosphor having an absorption wavelength on the long-wavelength side and capable of emitting long-wavelength light, that is, a light-emitting layer containing a phosphor as a filler, is arranged in a stacked manner, and There is a color conversion member that absorbs wavelengths longer than the light-emitting layer and can emit longer-wavelength light, whereby reflected light can be effectively used.

The yttrium-aluminum oxide-based phosphor activated with cerium used in this embodiment, that is, the YAG-based phosphor that can emit green light, has a garnet structure, so it has strong resistance to heat, light, and moisture, and the excitation absorption spectrum The wavelength of the peak may be around 420nm to 470nm. In addition, it has a broad luminescence spectrum, and its luminescence peak peak wavelength λp is around 510nm, and the end of the peak extends to around 700nm. On the other hand, the yttrium-aluminum oxide-based phosphor activated by cerium, that is, the YAG-based phosphor that emits red light, also has a garnet structure, so it has strong resistance to heat, light, and moisture, and the excitation absorption spectrum The wavelength of the peak may be around 420nm to 470nm. In addition, it has a broad luminescence spectrum, and its luminescence peak peak wavelength λp is around 600nm, and the end of the peak extends to around 750nm.

In the composition of the YAG-based phosphor having a garnet structure, a part of Al is substituted with Ga, thereby shifting the emission spectrum to the short wavelength side, and a part of Y in the composition is substituted with Gd and/or La, thereby making The emission spectrum shifts to the long wavelength side. In this way, by changing the composition, the emission color can be continuously tuned. Therefore, the nitride semiconductor can continuously change the intensity on the long-wavelength side according to the composition ratio of Gd, and blue light emission using such a nitride semiconductor has ideal conditions for switching to white light emission. When the substitution of Y is less than 20%, the green component increases and the red component decreases, and when it is 80% or more, the luminance drops sharply although the red component increases. In addition, the same applies to the excitation absorption spectrum. In the composition of the YAG-based phosphor having a garnet structure, a part of Al is substituted with Ga, thereby shifting the excitation absorption spectrum to the short-wavelength side, and replacing it with Gd and/or La. A part of Y in the composition shifts the excitation absorption spectrum to the long-wavelength side. The peak wavelength of the excitation absorption spectrum of the YAG-based phosphor is preferably on the shorter wavelength side than the peak wavelength of the emission spectrum of the light emitting element. With such a structure, when the current supplied to the light-emitting element increases, the peak wavelength of the excitation absorption spectrum is basically the same as the peak wavelength of the emission spectrum of the light-emitting element, so that the excitation efficiency of the phosphor will not be reduced, and the chromaticity will be shifted. A light-emitting device in which migration is suppressed.

Such phosphors use oxides of Y, Gd, Tb, Pr, Ce, La, Lu, Al, Sm, and Ga or compounds that tend to become oxides at high temperatures as raw materials, and they are fully mixed in a stoichiometric ratio. Get the ingredients. Or dissolve the rare earth elements of Y, Gd, Ce, La, Lu, Al, Sm in the acid according to the stoichiometric ratio, then use oxalic acid to make the solution obtained in this way co-deposit, and then carry out the co-deposition product obtained in this way The co-deposition oxide is obtained by sintering, and then the co-deposition oxide is mixed with aluminum oxide and gallium oxide to obtain a mixed raw material. Add an appropriate amount of fluoride such as ammonium fluoride to the mixed raw material as a flux and put it into a crucible, and then sinter in air at a temperature range of 1350°C to 1450°C for 2 hours to 5 hours to obtain a sintered product, Next, the sintered product is ball-milled in water, washed, separated, dried, and finally sieved to obtain the phosphor. In addition, the manufacturing method of the phosphor in other embodiments is preferably sintered in two stages, and the two stages are composed of a first sintering process and a second sintering process, wherein the first sintering process will be composed of mixed raw materials mixed with phosphor raw materials and The flux composition mixture is sintered in the air or in a weakly reducing atmosphere, and the second sintering process is sintered in a reducing atmosphere. Here, the so-called weak reducing atmosphere refers to a weak reducing atmosphere that contains at least a necessary amount of oxygen during the reaction process of forming the required phosphor from the mixed raw materials. In this weak reducing atmosphere, the first step is performed. A sintering process is performed until the formation of the desired structure of the phosphor is completed, thereby preventing blackening of the phosphor and reducing light absorption efficiency. In addition, the reducing atmosphere in the second sintering step refers to a stronger reducing atmosphere than a weak reducing atmosphere. By performing sintering in two steps in this way, a phosphor having high absorption efficiency of the excitation wavelength can be obtained. Therefore, when a light-emitting device is formed using the phosphor formed in this way, the amount of phosphor required to obtain a desired color tone can be reduced, and a light-emitting device with high light extraction efficiency can be formed.

Two or more cerium-activated yttrium-aluminum oxide-based phosphors having different compositions may be used in combination, or may be arranged independently of each other. When disposing the phosphors independently, it is preferable to dispose them in the following order, first disposing the phosphors that are easy to absorb light from the light-emitting element on the short-wavelength side and emit light, and then disposing on the relatively long-wavelength side that is easy to absorb light from the light source. The light-emitting element emits light and emits phosphor. Accordingly, the phosphor can efficiently absorb light emitted from the light-emitting element and emit light.

(nitride phosphor)

As the phosphor used in this embodiment, in addition to the above-mentioned yttrium-aluminum-oxide-based phosphor activated by cerium, an alkaline-earth nitride-based phosphor activated by Eu or rare earths having a yellow-red to red emission wavelength is also suitable. . This phosphor is excited to emit light by absorbing visible light and ultraviolet light emitted from the LED chip and light emitted from the YAG-based phosphor. The phosphors of the embodiments of the present invention are particularly: Sr-Ca-Si-N:R, Ca-Si-N:R, Sr-Si-N:R, Sr-Ca-Si-ON:R, Ca-Si -ON:R and Sr-Si-ON:R-based silicon nitride. The basic constituent elements of these phosphors can be represented by the general formula L _X Si _Y N _(2/3X+4/3Y) : R or L _X Si _Y O _Z N _{(2/3X+4/3Y-2/3Z)} : R (L is any group among Sr, Ca, and Sr and Ca). In the general formula, X and Y are preferably X=2, Y=5 or X=1, Y=7, but may be arbitrary values. In addition, R is a rare earth element that must contain Eu, N is nitrogen, and O is oxygen. Specifically, it is preferable to use basic constituent elements such as (Sr _X Ca _1-X ) ₂ Si ₅ N ₈ :Eu, Sr ₂ Si ₅ N ₈ :Eu, Ca ₂ Si ₅ N ₈ :Eu, Sr _X Ca _1- Phosphors represented by _X Si ₇ N ₁₀ :Eu, SrSi ₇ N ₁₀ :Eu, CaSi ₇ N ₁₀ :Eu, but in the composition of the phosphors, may also contain Mg, B, Al, Cu, Mn, At least one or more of Cr and Ni. However, the present invention is not limited to the embodiments and examples.

L is any one group among Sr, Ca, and Sr and Ca. The ratio of Sr and Ca can be changed according to requirements.

As the luminescent center, europium Eu, which is a rare earth element, is mainly used. Europium mainly has divalent and trivalent energy levels. The phosphor according to the embodiment of the present invention uses Eu ²⁺ as an activator for alkaline earth metal-based silicon nitride as a matrix. In addition, Mn can also be used as an additive.

The method for producing the phosphor ((Sr _X Ca _1-X ) ₂ Si ₅ N ₈ :Eu) used in the embodiment of the present invention will be described below, but the present invention is not limited to this production method. Mn and O are contained in the above-mentioned phosphor.

In the examples of the present invention, a nitride-based phosphor is particularly used as a phosphor emitting reddish light, but in this embodiment, a phosphor having the above-mentioned YAG-based phosphor and a phosphor that may emit reddish light can also be obtained. light emitting device. Such a phosphor that may emit red light is a phosphor that emits light when excited by light having a wavelength of 250 nm to 600 nm, for example, Y ₂ O ₂ S:Eu, La ₂ O ₂ S:Eu, CaS:Eu, SrS:Eu, ZnS:Mn, ZnCdS:Ag, Al and ZnCdS:Cu, Al, etc. Thus, by using a phosphor capable of emitting red light together with a YAG-based phosphor, the color rendering of the light-emitting device can be improved.

In the light-emitting device according to each embodiment of the present invention, various phosphors can be used as the phosphor. For example, there can be mentioned: a barium magnesium aluminate phosphor that produces light in the blue region, represented by BaMgAl ₁₀ O ₁₇ :Eu, activated with europium, and that produces light in the blue region, represented by (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl:Eu, activated by europium halogen calcium phosphate-based phosphor, which emits light in the blue region, represented by (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Alkaline-earth chloroborate-based phosphors represented by Eu, activated by europium, emitting light in the blue-green region, (Sr, Ca, Ba)Al ₂ O ₄ :Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : represented by Eu, an alkaline earth aluminate phosphor activated by europium, which emits light in the green region, represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu, represented by Europium-activated alkaline-earth silicon oxynitride-based phosphors that emit light in the green region, expressed as (Ba, Ca, Sr) ₂ SiO ₄ :Eu, alkaline-earth magnesium silicate-based phosphors activated with europium, that produce Rare earth aluminates that emit light in the yellow region, represented by (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce, etc., that is, YAG-based phosphors, and those that emit light in the red region, represented by (Y, La, Gd, Lu) ₂ O ₂ S:Eu represented, activated rare earth oxysulfide phosphors with europium, etc., but the present invention is not limited to these, the aforementioned phosphors and other phosphors can also be used in the present invention It is used in the inorganic binder of the embodiment. Furthermore, it is also possible to use a phosphor having a fractured surface on which a countermeasure against degradation of the coating is taken.

The above phosphors are, for example, alkaline earth chloroborate phosphors activated with europium, alkaline earth aluminate phosphors activated with europium, alkaline earth silicon oxynitride phosphors activated with europium, YAG phosphors, and The alkaline-earth silicon nitride-based phosphor activated with europium preferably contains element B to improve crystallinity, increase particle size, or adjust crystal shape. Thereby, the luminous brightness can be improved. These phosphors are also effective as fillers for the phosphors of this embodiment.

Regarding the crystal structure, for example, Ca ₂ Si ₅ N ₈ is monoclinic, Sr ₂ Si ₅ N ₈ and (Sr _0.5 Ca _0.5 ) ₂ Sr ₅ N ₈ are orthorhombic, and Ba ₂ Si ₅ N ₈ is monoclinic.

Furthermore, the present phosphor is a quasicrystal in which crystals account for 60% or more, preferably 80% or more of the composition. Generally speaking, x=2, y=5 or x=1, y=7 are preferable, but any numerical value may be used.

Among trace additives, B and the like can improve the crystallinity without lowering the luminescence characteristics, and Mn, Cu and the like also exhibit the same effect. In addition, La, Pr, and the like also have an effect of improving luminescent characteristics. In addition, Mg, Al, Cr, Ni, etc. have the effect of shortening afterglow, and can be used suitably. In addition, even if it is an element which is not clearly indicated in this specification, it can be added as long as it is about 10-1000 ppm, and does not significantly reduce brightness.

The rare earth elements contained in R preferably include one or more of Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu, but may also include Sc, Sm, Tm, and Yb. In addition, in addition to the above-mentioned elements, elements having an effect of improving luminance, such as B and Mn, may be contained. In addition to simple substances, these rare earth elements are also mixed in the raw materials in the form of oxides, imides, amides and other states. Rare earth elements mainly have a stable trivalent electron arrangement, but Yb, Sm, etc. also have a divalent electron arrangement, and Ce, Pr, Tb, etc. also have a tetravalent electron arrangement. In the case of using an oxide rare earth element, the participation of oxygen affects the emission characteristics of the phosphor. That is, the reduction in luminance may occur due to the oxygen contained therein. However, when Mn is used, the particle size can be increased due to the effect of Mn and O as a flux, thereby improving the luminance of light emission.

As the luminescent center, europium Eu, which is a rare earth element, is used. Specific examples of basic constituent elements include: Ca ₂ Si ₅ O _0.1 N _7.9 :Eu to which Mn and B are added, Sr ₂ Si ₅ O _0.1 N _7.9 :Eu, (Ca _X Sr _1-X ) ₂ Si ₅ O _0.1 N _7.9 :Eu, CaSi ₇ O _0.5 N _9.5 :Eu, Ca ₂ Si ₅ O _0.5 N _7.9 :Eu, Sr ₂ Si ₅ O _0.5 N _7.7 :Eu, (Ca _X Sr _1-X ) ₂ Si ₅ O _0.1 N _7.9 : Eu, etc.

The nitride-based phosphors described above absorb part of the blue light emitted by the light-emitting element and emit light in a range from yellow to red. By using this phosphor in a light-emitting device having the above configuration, it is possible to provide a light-emitting device in which blue light emitted from a light-emitting element and red light from the phosphor are mixed to emit warm-colored white light. Especially in a white light emitting device, it is preferable to contain a nitride-based phosphor and a rare-earth aluminate phosphor, that is, a cerium-activated yttrium-aluminum oxide phosphor. This is because desired chromaticity can be adjusted by containing the above-mentioned yttrium/aluminum oxide phosphor. The yttrium-aluminum oxide phosphor activated with cerium can absorb part of the blue light emitted by the light-emitting element and emit light in the yellow region. Here, the blue light emitted from the light-emitting element and the chromatic light emitted by the yttrium-aluminum oxide phosphor can be mixed to emit blue-white white light. Therefore, a warm-color white light-emitting device can be provided by combining the phosphor obtained by mixing the yttrium-aluminum oxide phosphor and the nitride phosphor with a binder and blue light emitted from the light-emitting element. The warm-color white light emitting device has an average color rendering index Ra of 75-95, and a color temperature of 2000K-8000K. Particularly preferred is a white light-emitting device having a high average color rendering index Ra and a color temperature on the locus of black body radiation on a chromaticity diagram. However, in order to provide a light-emitting device having a desired color temperature and average color rendering index, the compounding amounts of the yttrium-aluminum oxide phosphor and the phosphor and the composition ratio of each phosphor may be appropriately changed. In particular, this warm-color white light-emitting device seeks to improve the special color rendering index R9. A conventional light-emitting device that emits white light by combining a blue light-emitting element with a cerium-activated yttrium-aluminum oxide phosphor has a low special color rendering index R9 and insufficient red components. Therefore, improving the special color rendering evaluation index R9 has become a problem to be solved, and the alkaline earth silicon nitride-based phosphor activated by Eu is included in the yttrium-aluminum oxide phosphor activated by cerium, so that the special color rendering can be improved. Evaluation index R9 increased to 40-90. In addition, LED lighting devices that emit the color of light bulbs can also be made.

(substrate)

The base body 20 is composed of a concave portion 20 a for accommodating the light emitting element 60 and a base portion on which the lead electrode 22 is disposed, and functions as a support for the light emitting element 60 . The bottom surface of the concave portion 20a is preferably substantially flush with the bottom surface of the lead electrode.

The base body 20 is preferably made of metal, but may be made of resin from the viewpoints of workability and productivity. The base body 20 can be formed in various shapes such as approximately square, approximately rectangular, approximately circular, approximately elliptical, etc. when viewed from the side of the light extraction surface. The portion carrying the light emitting element 60 preferably forms a concave portion 20a. This is because, by accommodating the light emitting element 60 in the recess 20a, the light emitted from the light emitting element 60 can be emitted from the opening side of the recess 20a, thereby improving the light output.

In the light-emitting device 601, the substrate 20 is preferably formed of a thin film in consideration of heat dissipation and miniaturization.

Adapting to the quantity and size of the light emitting elements 60, the base body can also be designed to have a plurality of openings. In order to have a proper light-shielding function, the base body 20 is colored in a dark color such as black or gray, or the side of the light-emitting observation surface of the base body 20 is colored in a dark color. In order to further protect the light-emitting element 60 from the external environment, in addition to the coating, a molding member as a light-transmitting protective body may also be provided. Also, when the base body 20 is affected by heat originating from the light emitting element 60, it is preferable that the base body 20 has a small coefficient of thermal expansion in consideration of adhesion with the mold member.

The bonding between the light emitting element 60 and the base body 20 can also be performed by using thermosetting resin or the like. Specifically, epoxy resin, acrylic resin, imide resin, etc. are mentioned. In the case where the light-emitting device 601 uses the light-emitting element 60 that emits light containing ultraviolet rays and is used at a high output power, since the ultraviolet rays emitted by the light-emitting element 60 and the like are also used as The inorganic adhesive 30 of the sealing member or the fluorescent substance 50 contained therein etc., the light becomes high density especially in the matrix 20, therefore, the resin of the bonding part is degraded by ultraviolet rays, so it can be considered that the yellow color of the resin Variations lead to a decrease in luminous efficiency and a decrease in the life of the light-emitting device due to a decrease in bonding strength. In order to prevent such degradation of the adhesive portion due to ultraviolet rays, a resin containing an ultraviolet absorber may be used, more preferably the inorganic substance of the present invention or the like may be used. In particular, when a metal material is used for the base, eutectic solder such as Au—Sn or the like may be used for bonding between the light emitting element 60 and the base 20 other than the inorganic substance of the present invention. Therefore, unlike the case where resin is used for bonding, the present invention does not degrade the bonded portion even when the light emitting device 601 uses the light emitting element 60 emitting light including ultraviolet rays and is used at high output.

In addition, Ag paste, carbon paste, ITO paste, metal flange, etc. are suitably used for electrical contact with external electrodes in base body 20 while arranging and fixing light emitting element 60 .

(lead electrode)

The light emitting device 601 has positive and negative lead electrodes 22 , and the lead electrodes 22 are inserted into through holes provided in the base portion of the metal base 20 through the insulating member 23 . The top end of the lead electrode 22 protrudes from the surface of the base, and the bottom surface of the lead electrode 22 is substantially flush with the bottom surface on the mounting surface side of the concave portion.

(cover body)

The light emitting device 601 has a cover body 26 including a translucent window portion 25 and a lead wire 24 made of a metal portion on the main surface side of the base body 20 . The window portion 25 is the light emitting surface of the light emitting device 601 and is preferably arranged in the center.

The window portion 25 is located on the upper surface of the light emitting element 60 arranged in the recess 20a of the base 20, and intersects the extension line of the inner wall of the recess 20a. The light emitted from the end of the light emitting element 60 is diffusely reflected on the side surface of the recessed portion 20 a and taken out in the front direction. It is generally considered that the range in which these diffusely reflected lights exist is approximately within the extension of the side surfaces of the concave portion 20a. Then, by adjusting the area of the window portion 25 as the light-emitting surface as described above, the diffusely reflected light can be effectively focused on the window portion 25, and a light-emitting device 601 capable of emitting high-intensity light can be obtained.

The window portion 25 has translucency. In the window portion 25, the phosphor 50 may be contained, and a film of the phosphor 50 may be pasted.

Various materials such as glass, epoxy resin, and polypropylene can be used for the window portion 25, but glass is preferable from the viewpoint of heat resistance.

The cover body 26 is arranged on the base body 20 in an airtight manner. Since it is airtight, it is possible to prevent moisture from entering the light emitting device 601 .

(lead)

The lead wire 21 is required to have good ohmic properties, mechanical connectivity, electrical conductivity, and thermal conductivity with the electrodes of the light emitting element 60 . Specific examples of the lead 21 include conductive leads using metals such as gold, copper, platinum, and aluminum, and alloys thereof. Such leads 21 can easily connect electrodes, internal leads, pin leads, etc. of each light emitting device 60 by wire bonding equipment.

(Manufacturing method of light-emitting device)

Next, a method of manufacturing the light-emitting device will be described based on FIGS. 31 to 35 . As described above, Fig. 31 is a schematic plan view of a light-emitting device according to Embodiment 6 of the present invention, Fig. 32(a) is a schematic cross-sectional view of the same light-emitting device, and Fig. 32(b) is a schematic cross-sectional view showing an enlarged concave portion of the substrate. Furthermore, FIG. 33 is a schematic diagram showing part of the manufacturing process of the light-emitting device according to the embodiment of the present invention, FIG. 34 is a schematic diagram showing part of another manufacturing process of the light-emitting device according to the embodiment, and FIG. 35 is a schematic diagram showing part of the manufacturing process of the light-emitting device according to the embodiment. A schematic diagram of part of another manufacturing process. Specifically, Fig. 34 is a schematic view showing the formation method of the layer of the inorganic binder 30 or the resin 40 adopting the spray spraying means, and Fig. 35 shows the formation of the layer of the inorganic binder 30 or the resin 40 of the screen printing means method. Hereinafter, a method of manufacturing a light emitting device will be described based on these figures. However, the following steps are just one embodiment, and the present invention is not limited thereto.

(first process)

The light emitting element 60 is carried on the base body 20 . The base body 20 is formed with a concave portion 20 a on which the light emitting element 60 is carried. The light emitting element 60 is soldered using an adhesive such as epoxy resin. After the process of carrying the light emitting element 60 is completed, the electrode of the light emitting element 60 is electrically connected to the lead electrode 22 through the lead 21 .

(second process)

The light emitting element 60 is covered with the inorganic adhesive 30 . Inorganic binder 30 preferably contains phosphor 50 in advance. The phosphor 50 is mixed and uniformly dispersed in the inorganic binder 30 in advance. The inorganic binder 30 can be poured, sprayed, screen printed, poured, etc., but is preferably poured or sprayed. The inorganic adhesive 30 covers the entire upper surface and the entire side of the light emitting element 60 . Furthermore, the bottom surface and the side surfaces of the recessed portion 20a on which the light emitting element 60 is placed are covered. The inorganic binder 30 forms a film-like layer structure. The third step is performed after the inorganic binder 30 is cured, but the third step may be performed before curing, and the resin 40 and the inorganic binder 30 may be cured simultaneously.

For example, the light emitting element 60 is covered with the inorganic adhesive 30 by means of screen printing. With respect to the light emitting element 60, the sieve plate 97 having a pattern is processed into a desired shape such as a belt shape, a lattice shape, a concentric circle shape, a scroll shape, a triangle shape, or a dot shape. The conductive member 91 is arranged on the upper surface of the base substrate 92 , and the light emitting element 60 is mounted face down on the conductive member 91 . At this time, predetermined grooves are provided in advance on the base substrate 92 so that the positive electrode and the negative electrode are not short-circuited. In addition, between the electrodes of the light emitting element 60 , an insulating member 94 is provided on the side of the base substrate 92 in advance, and then the light emitting element 60 is soldered to the upper surface of the base substrate 92 via the flange 96 . Screen printing is then performed with the phosphor-containing inorganic binder material using a squeegee. Thereby, the light emitting element 60 coated with the inorganic binder 30 often having a constant thickness can be formed. Thereafter, the base substrate 92 is cut along the parting line 93 . This step is preferably performed in a vacuum, but may also be performed in an inert gas atmosphere.

(third process)

The inorganic binder 30 is covered with a resin 40 . Phosphor 50 may be contained in resin 40 in advance. The resin 40 can be poured, sprayed, screen printed, poured, etc., but is preferably poured or sprayed. The resin 40 covers the surface of the inorganic binder 30 . The resin 40 preferably forms a film-like layer structure. The resin 40 penetrates into the inorganic binder 30 , and the voids of the inorganic binder 30 are filled by the resin 40 . Thus, the light emitting device 61 can be manufactured. This step is preferably performed in a vacuum, but may also be performed in an inert gas atmosphere.

(watering means, spraying spray means)

Fig. 33 is a schematic diagram showing a part of the manufacturing process of the light-emitting device according to the embodiment of the present invention. As the watering means, known watering means can be used. In FIG. 33(a), a method of coating the resin 40 on the inorganic binder 30 by pouring is illustrated. The resin 40 to be coated is injected into a pouring tool 66 mounted on a pouring device (not shown). The material, temperature and pouring speed of the resin 40 are adjusted according to factors such as viscosity, wettability, permeability to the inorganic binder 30 and adhesion. The sol of the resin 40 is poured from the tip of the nozzle 67 of the pouring tool 66 onto the target inorganic binder 30 . At this time, the potting resin 40 is preferably not in contact with the lead wire 21 .

In FIG. 33( b ), the resin 40 is poured from above the light emitting element 60 , and the resin 40 penetrates into the inorganic binder 30 from the poured place. At this time, the resin 40 is impregnated in the voids of the inorganic binder 30 , and the gas present in the voids is pulled out from the side surfaces of the resin 40 which are easily discharged to the outside. The resin 40 gradually flows toward the periphery of the light emitting element 60 . At this time, the resin is made to flow into the space while expelling the gas existing in the space of the inorganic binder 30 around the light emitting element 60 to the outside.

In FIG. 33( c ), the resin 40 continues to climb up from the peripheral portion of the light emitting element 60 along the side surface of the recessed portion 20 a. This is due to capillarity. At this time, the resin 40 also squeezes out the matrix in the gap 31 , which can prevent gas from intruding into the resin 40 .

In FIG. 33( d ), a resin 40 layer covering the inorganic binder 30 layer may be formed. The film thickness of the resin 40 layer is substantially uniform. In addition, the surface of the resin layer 40 is smooth.

The method of covering the inorganic binder 30 on the inorganic binder 30 by pouring instead of the resin 40 is the same as that described above.

Fig. 34 is a schematic view showing part of another manufacturing process of the light-emitting device of the present invention. As the spray spraying means, known spray spraying means can be used. The present invention uses the following spraying device (not shown in the figure), and the spraying device uses a delivery pipe (not shown in the figure) to transfer the container (not shown in the figure) that contains the coating liquid, that is, the resin 40, to adjust the coating The valve (not shown) of the flow rate of the liquid, the circulating pump (not shown) that sends the coating liquid to the nozzle 70 and then from the nozzle 70 to the container, and the coating liquid is sprayed in a spiral form. Out nozzle 70 is connected.

A stirrer (not shown in the figure) is installed in the container for storing the coating liquid, and the coating liquid is constantly stirred during the coating operation. The coating liquid contained in the container is constantly stirred with a stirrer, so that when the phosphor is contained in the coating liquid, the phosphor contained in the coating liquid is always uniformly dispersed in the solution. The valve adjusts the flow rate of the coating liquid delivered from the container through the delivery pipe by means of opening and closing of the valve. The circulation pump sends the coating liquid from the container to the tip of the nozzle 70 via the valve and the compressor through the delivery pipe, and thereafter, the remaining coating liquid that has not been sprayed from the nozzle 70 is sent to the container through the delivery pipe. Since the coating liquid is sent from the container to the tip of the nozzle through the valve through the delivery pipe by the circulation pump, and then sent to the container through the delivery pipe, the coating liquid is often in a state of circulating in the spraying device. Therefore, since the coating liquid is stirred or circulated throughout the coating apparatus, the phosphor contained in the coating liquid is always in a uniformly distributed state during the coating operation. The compressor is installed in the device through the delivery tube, compresses the air delivered through the delivery tube, and adjusts the pressure of the coating liquid delivered through the delivery tube. Compressed air and pressure-regulated coating liquid are delivered to nozzles 70 by means of compressors, respectively. Here, the pressure of the compressed air is monitored with a manometer. Using the above spraying device, the coating liquid is sprayed together with the high-pressure gas at a high speed, and sprayed on the upper surface, the side surface and the inner surface of the concave portion of the light emitting element.

The coating liquid and gas (air in this embodiment) are sprayed out in a spiral form through the nozzle 70 . A number of gas ejection ports are arranged around the nozzle of the device, and the ejection directions of the gases ejected from these ejection ports each form a certain angle with respect to the surface to be coated. Therefore, when gas is simultaneously fed into these gas outlets that rotate around the outlet of the coating liquid, the flow of the entire gas that collects the gases ejected from the respective outlets becomes an upside-down volute. A spiral flow, a spiral flow, or the flow of air in a tornado. In addition, the center of the nozzle of the device is provided with a spray port for the coating liquid. When the coating liquid is sprayed out simultaneously with the gas, the mist-like coating liquid takes advantage of the upside-down volute flow, spiral spread out in the shape of the flow or the flow of air in a tornado.

The diameter of the entire spray spread in a helical shape starts from the spray starting point above the light-emitting element, and becomes larger as it approaches the surface of the light-emitting element. In addition, the rotation speed of the mist of the coating liquid becomes smaller as the spray starting point above the light-emitting element is closer to the surface of the light-emitting element. That is to say, when the mist-like coating liquid is sprayed from the nozzle and spreads in the air, the spray spreads out in a conical shape near the spray starting point, that is, the nozzle, and the spray spreads in a cylindrical shape at the place where it leaves the nozzle. Spread out. Therefore, in this embodiment, it is preferable to adjust and set the distance between the upper surface of the light-emitting element and the lower end of the nozzle so that the surface of the light-emitting element appears at the place where the spray spreads out in a cylindrical shape. At this time, the spray rotates in a helical shape, and the speed is relatively slow. Therefore, the spray can reach the surface of the light-emitting element under the shadow of the conductive lead wire, and can be fully sprayed not only on the entire light-emitting element, but also on the entire side. Thereby, work can be performed with the light emitting element or the nozzle fixed. In addition, because the spray speed is relatively slow where the spray spreads out in a cylindrical shape, when the spray is sprayed on the surface of the light-emitting element, the surface of the light-emitting element will not be affected by the phosphor particles contained in the spray. shock. In addition, deformation and disconnection of the conductive lead wires will not occur, thereby improving the product yield and manufacturability.

The coated light-emitting device is in a heating state at a temperature of 50° C. to 500° C. on the heater. As a method of heating the light-emitting element in this way, a method of heating the light-emitting element in a heating device such as an oven may also be used. By heating, ethanol, a small amount of water contained in the hydrolyzed liquid in the gel state, and the solvent are evaporated, and amorphous Al(OH) ₃ and AlOOH can be obtained from the coating liquid in the gel state. Furthermore, since the viscosity of the coating solution of this embodiment is adjusted, it is sprayed on the top, side, and corners of the light-emitting element, and after the surface of the support, it does not flow out from the place where it is sprayed. In these places, heating is performed shortly after coating, so that the coating formed by bonding the phosphor with AlOOH can cover the top, side and corner parts of the light-emitting element.

In this embodiment, in the state where a plurality of substrates 20 are arranged, the light-emitting elements 60 are respectively soldered in the substrates 20, and the electrodes of the light-emitting elements 60 and the lead electrodes 22 are wire-bonded, and then covered with an inorganic adhesive 30. The light emitting element 60 is sprayed with the resin 40 from above the inorganic binder 30 . The resin 40 is sprayed on the surface of the inorganic adhesive 30 from above the shield baffle 80 in order to prevent the resin 40 from adhering to other than the inner surface of the concave portion 20a, for example, at a predetermined place. The shielding baffle 80 is a plate that completely covers the outside of the concave portion 20a of the base 20 and is provided with a through hole of a size that allows the resin 40 to be sprayed on the surface of the inorganic adhesive 30. It has metal shielding baffles and reinforced plastic shielding baffles. board etc.

When spraying means is used, since the resin 40 is sprayed in a granular form, the gas existing in the gap 31 is discharged to the outside from the gap between the particles. As a result, the amount of gas dissolved in the resin 40 can be reduced, and the gas content in the resin 40 can be reduced.

Embodiment 7

Next, a light-emitting device according to Embodiment 7 of the present invention will be described based on FIG. 36 . Fig. 36(a) is an enlarged schematic cross-sectional view of a concave portion of a substrate of a light-emitting device according to Embodiment 7, and Fig. 36(b) is a perspective view showing the light-emitting device. The light emitting device shown in these figures is specifically a cannonball type light emitting device. The light-emitting device 700 has: a light-emitting element 710, a lead frame (substrate) 720 carrying the light-emitting element 710, an inorganic adhesive 730 covering the light-emitting element 710, a phosphor 750 contained in the inorganic adhesive 730, and a cover inorganic adhesive. The resin 740 of 730 and the molding member 760. In addition, voids 731 are generated due to curing of the inorganic binder 730 . In the case of having the same function as the above-mentioned part, its description is omitted.

The light-emitting element 710 constituted by the cannonball-shaped light-emitting device 700 is soldered to and carried by the substantially central portion of the recess 720a disposed above the pin lead serving as the substrate. The electrodes formed on the light emitting element 710 are electrically connected to the pin leads 720 a and the internal leads 720 b of the lead frame 720 through the leads 721 . Phosphor 750 includes a YAG-based phosphor and a nitride-based phosphor that absorb at least part of the light emitted from light-emitting element 710 and emit light having a wavelength different from that of the absorbed light. Furthermore, the nitride-based phosphor can be covered with a covering material such as microcapsules. The phosphor 750 is uniformly dispersed in the inorganic binder 730 . The inorganic binder 730 containing the phosphor 750 is arranged in the concave portion carrying the light emitting element 710 . In this way, in order to protect the light-emitting element 710 and the phosphor 750 from external stress, moisture, and dirt, and to improve light extraction efficiency, the lead frame 720 configuring the light-emitting element 710 and the phosphor 750 is molded in the mold member 760, Thus, the light emitting device 700 is formed. It is also possible to form lenses and the like in the form of molded members.

The resin 740 covers the inorganic binder 730 and the light emitting element 710 by spraying or pouring. The resin 740 is filled in the concave portion 720 a of the lead frame 720 . By making the surface of the resin 740 flat, the directivity can be controlled and the light extraction efficiency can be improved.

(molding components)

The molding member 760 can be provided according to the usage of the light-emitting device 700 to protect the light-emitting element 710, the conductive lead 721, the layer of the inorganic binder 730 containing the phosphor 750, and the resin 740 from outside Improve light extraction efficiency. The molding member 760 may be formed of various resins and glasses. Specific materials for the mold member 760 are mainly transparent resins excellent in weather resistance such as epoxy resins, urea resins, silicone resins, and fluororesins, and glass. In addition, by containing a diffusing agent in the mold member, it is also possible to relax the directivity of light from the light emitting element 710 and to increase the viewing angle. Such a mold member 760 may use the same material as the resin 740 or may use a different material.

Embodiment 8

Furthermore, a light-emitting device according to Embodiment 8 of the present invention will be described based on FIG. 37 . Fig. 37(a) is an enlarged schematic cross-sectional view of a concave portion of a substrate of a light-emitting device, and Fig. 37(b) is a perspective view showing the light-emitting device. In this example, the light emitting device is also specifically the cannonball type light emitting device 800 . The light-emitting device 800 has: a light-emitting element 810, a lead frame (substrate) 820 carrying the light-emitting element 810, an inorganic binder 830 covering the light-emitting element 810, a phosphor 850 contained in the inorganic binder 830, and an inorganic binder covering the light-emitting element 810. Resin 840 of 830 and cover 826 . In addition, voids 831 are generated due to the curing of the inorganic binder 830 . Moreover, the electrodes are electrically connected to the lead frame 820 through the lead wires 821 . In the case where each part has the same function as that of the seventh embodiment described above, the description thereof will be omitted.

In the light-emitting device 800 , the lead frame 820 carrying the light-emitting element 810 is sealed with a cover 826 . The seal is preferably airtight. The upper surface of the cover 826 is provided with a window portion 825 through which light from the light emitting element 810 passes. The lead wire 824 supports the window portion 825 .

Embodiment 9

In addition, a light-emitting device according to Embodiment 9 of the present invention will be described based on FIG. 38 . Fig. 38 is a schematic cross-sectional view showing a part of the light emitting device. In particular, it relates to a schematic sectional view in the vicinity of a light emitting element 60 coated with an inorganic binder 30 and a resin 40 by screen printing as shown in FIG. 35 . On the base substrate 92, the light emitting element 60 is mounted downward, and the inorganic adhesive 30 is provided on the surface of the light emitting element 60 by screen printing. Afterwards, the base substrate 92 carrying the light-emitting element 60 is installed on the light-emitting device, and the lead wire 21 is soldered to the conductive member 91 . Then, the resin 40 is impregnated in the inorganic binder 30 by means of pouring or the like. Accordingly, it is possible to provide a light-emitting device in which the surface of the inorganic binder 30 is impregnated with the resin 40 . Wherein, the lead wire 21 may also be welded after the resin 40 is coated on the inorganic binder 30 by means of pouring or the like.

Examples 30-32

(Example 30 and 31)

The results obtained in Examples 30 to 32 will be described below as Examples corresponding to Embodiments 6 to 9 above. Embodiments 30 and 31 are cannonball-type light emitting devices. 33 is a schematic diagram showing a part of the manufacturing process of the light-emitting device of Examples 30 and 31, and FIG. 34 is a schematic diagram showing a part of the manufacturing process of the light-emitting device of Examples 30 and 31. 37( a ) is an enlarged schematic cross-sectional view of the concave portion of the base body of Examples 30 and 31, and FIG. 37( b ) is a perspective view showing the light emitting device 800 of Examples 30 and 31. FIG. 42 is a schematic cross-sectional view showing a light emitting device of Comparative Example 3. FIG.

Examples 30 and 31 have a configuration in which a □0.35 mm square die is used for the light emitting element 810 having a dominant emission wavelength at 400 nm. The lead wire 821 uses Au as a main component material. As the inorganic binder 830, yttrium oxide sol (Yttrium oxide sol manufactured by Tagi Chemical Co., Ltd.) was used. The phosphor 850 uses (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ :Ce YAG phosphor. Regarding the resin 840, Example 30 is a silicone resin for impregnation (trade name: KJF816, manufactured by Shin-Etsu Silicone Co., Ltd.), and Example 31 is a silicone resin for impregnation (trade name: KJF816L, manufactured by Shin-Etsu Silicone Co., Ltd.). The basic physical properties of the silicone resin for impregnation in Example 30 are: viscosity 100 (mm ² /sec), specific gravity (25°C) 0.97, volatile component (105°C/3 hours) 0.5, cured state is a rubbery film, The hardness (Shore C hardness) was 60. The basic physical properties of the silicone resin for impregnation in Example 31 are: viscosity is 60 (mm ² /sec), specific gravity (25°C) is 0.97, volatile component (105°C/3 hours) is 0.5, and the cured state is a rubbery film. The hardness (Shore C hardness) was 60.

Examples 30 and 31 were produced according to the following production methods. First, let the light emitting element 810 be carried on the lead frame (substrate) 820 . The lead frame 820 is formed with a recess 820a including a wide opening, and the light emitting element 810 is placed on the bottom surface of the recess 820a. Soldering is performed so that the substrate side of the light emitting element 810 is in contact with the bottom surface of the concave portion 820a. The light emitting element 810 is soldered using an adhesive such as eutectic solder such as Au—Sn. After the process of carrying the light emitting element 810 is completed, the electrodes of the light emitting element 810 and the lead electrodes are electrically connected through the lead wires 821 .

Next, after the phosphor 850 is weighed, a predetermined amount of the phosphor 850 is put into a predetermined amount of the inorganic binder 830 and mixed uniformly. In detail, 10 g of the yttrium oxide sol and the YAG phosphor are each taken in a 100 ml beaker, and then 50% by weight of ethanol is added to the yttrium oxide sol, and after being fully stirred and mixed, the phosphor/sol material is obtained. pulp.

Next, the inorganic adhesive 830 is sprayed onto the light-emitting element 810 carried by the lead frame 820 by means of spraying, so that the inorganic adhesive 830 is fixed. By fixing the inorganic adhesive 830 by spraying, it is possible to form a layer of the inorganic adhesive 830 with a substantially uniform thickness on the top and side surfaces of the light emitting element 810 and the bottom and side surfaces of the recess 820 a of the lead frame 820 . In order to prevent the inorganic binder 830 from being fixed except in predetermined places, a shielding baffle 80 is provided for spraying and spraying. After the inorganic adhesive 830 is sprayed and fixed, thermal curing is performed at a temperature of about 240° C. for 30 minutes.

Next, the resin 840 is poured on the surface of the inorganic binder 830 layer using a pouring tool. The resin 840 is poured by dripping directly above the light emitting element 810 and approximately in the center of the layer of the inorganic binder 830 . The resin 840 penetrates rapidly from the central part of the layer surface of the inorganic binder 830 and spreads toward the outer periphery, so that the voids inside the inorganic binder 830 can be filled and cover the surface until the entire surface of the inorganic binder 830 The surface of the layer glows with resin 840 . It is considered that the resin 840 climbs up the layer surface of the inorganic adhesive 830 on the side of the concave portion of the lead frame 820 due to a capillary phenomenon. As a result, a uniform film-like resin 840 layer is formed on the surface of the inorganic binder 830 layer. After pouring, the light-emitting element 810 is covered by the layer of inorganic adhesive 830 and the layer of resin 840, and then the lead frame 820 carrying the light-emitting element 810 is heated at a temperature of about 150° C. for about 3 hours, thereby The resin 840 is allowed to cure.

Finally, the lead frame 820 is sealed with a cover 826 in a nitrogen atmosphere. The inside of the cover 826 is filled with nitrogen gas. Under the window portion 825 of the cover 826, the recessed portion 820a of the lead frame 820 is disposed. In this way, the light-emitting devices 800 of Examples 30 and 31 were manufactured.

(Measurement result of durability test)

Durability tests were performed on the light-emitting devices of Examples 30 and 31. FIG. 39 shows the durability test results of the light emitting devices of Examples 30 and 31 and Comparative Example 3. FIG. Comparative Example 3 is not covered with the inorganic adhesive 830 and the resin 840 , but only the light emitting element 810 is carried in the concave portion 820 a of the lead frame 820 . Other than that, it is the same as in Example 30.

The light-emitting devices of Examples 30 and 31 were put into an excitation test of 100 mA at room temperature. The output power at 0 hours immediately after the introduction was set to 100%, and the output powers were measured after 100 hours, 200 hours, 350 hours, 500 hours, and 700 hours. As a result, the light-emitting devices of Examples 30 and 31 and Comparative Example 3 maintained a high output after 700 hours.

(Measurement results of light extraction efficiency)

The light extraction efficiency of the light-emitting devices of Examples 30 and 31 was measured. FIG. 40 shows the results of the light extraction efficiency of the light-emitting devices of Examples 30 and 31, and Comparative Example 4. FIG.

42 is a schematic cross-sectional view showing a light emitting device of Comparative Example 4. FIG. Comparative Example 4 does not cover the inorganic binder with resin, but uses only the inorganic binder 330 . In the inorganic binder 330 of Comparative Example 4, the same YAG phosphor 850 as in Example 30 was used. In the light-emitting device of Comparative Example 4, an inorganic adhesive 330 is used to cover the upper surface of the light-emitting element 310 . In this inorganic binder 330, many voids 331 are included.

In the light-emitting devices of Examples 30 and 31 and Comparative Example 4, a predetermined current was supplied, and the light output thereof was measured. As a result, it can be seen that Example 30 is 1.91 times that of Comparative Example 4, and the light extraction efficiency is improved, and Example 31 is 1.75 times that of Comparative Example 4, and the light extraction efficiency is also improved. This is considered to be because the voids 331 included in the layer of the inorganic binder 330 of Comparative Example 4 reflect light from the light emitting element 310 . That is, this is because air such as nitrogen is contained in the void 331 , and since the inorganic binder 330 and air have a difference in refractive index, reflection occurs at the interface between the air and the inorganic binder 330 . Therefore, the light-emitting devices provided by Examples 30 and 31 are durable and have high light extraction efficiency.

(Measurement result of infrared spectrum)

Infrared spectra were measured on the impregnating silicone resin of Example 30. Moreover, the infrared spectrum was measured about the silicone resin of the comparative example 5 as a comparison. FIG. 41 is an infrared spectrum chart showing the coating film of Example 30. FIG. FIG. 43 is an infrared spectrum chart showing the coating film of Comparative Example 5. FIG. This infrared spectrum is a result of measurement by Fourier transform infrared spectroscopy (FT-IR). As a measurement device for Fourier transform infrared spectroscopy, Nexus 870 <main body> and Continuum <microscope> (both manufactured by Nireko Japan Corporation) were used.

The light-emitting device using the silicone resin for impregnation of Example 30 has excellent light extraction efficiency, heat resistance, durability, and the like, compared with the light-emitting device using the silicone resin of Comparative Example 5. In addition, promotion of resin degradation is also suppressed. It is generally believed that the reason is that the ratio of C-Si-O bonds is lower than that of Si-O-Si bonds. That is to say, it is generally believed that the reason is that if the ratio of C-Si-O bonds is small, a ternary network structure with low crosslink density will be formed, thereby forming a rubber-like or gel-like material with relatively high flexibility. Resin coating. Formation into a rubbery film or a gel form can promote relaxation of internal stress and prevent peeling due to thermal expansion.

In the coating film of Comparative Example 5, the strength ratio of the C—Si—O bond to the Si—O—Si bond was 1.16/1 in the resin composition. In contrast, the intensity ratio of the coating film of Example 30 was 2.21/1. In addition, the silicone resin of Comparative Example 5 is a general silicone resin.

(Example 32)

Example 32 is a cannonball type light emitting device. FIG. 35 is a schematic view showing a part of the manufacturing process of the light-emitting device of Example 32. FIG. Fig. 38 is a schematic cross-sectional view showing part of a light-emitting device according to Embodiment 9 of the present invention. In particular, FIG. 35 is a schematic cross-sectional view showing the step of covering the light-emitting element 60 with the inorganic adhesive material 99 containing phosphor by screen printing. In addition, as shown in FIG. 38 , it is a schematic cross-sectional view showing the vicinity of the light-emitting element 60 when the inorganic adhesive 30 is covered on the light-emitting element 60 and the surface of the inorganic adhesive 30 is impregnated with a resin 40 . Example 32 adopts substantially the same configuration as that of Example 30 and Example 31, except that the loading state of the light-emitting element 810 is different. 37( a ) and ( b ) are perspective views showing light-emitting devices of Examples 30 and 31, and although there are differences in symbols from Example 32, they show substantially the same configuration as Example 32. The main differences between Embodiment 32 and Embodiments 30 and 31 will be described below.

Alumina sol (manufactured by Nissan Chemical Corporation, trade name: A1-520) was used as the inorganic binder 30 . By treating this alumina sol with an ion exchange resin, the concentration of nitrate ions serving as a stabilizer can be reduced. To 10 g of this alumina sol, 20 g of (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ :Ce YAG phosphor was added, mixed well and stirred. Using the thus-prepared phosphor paste, a phosphor layer is formed on a die wafer by screen printing by means of screen printing. As the resin 40, a silicone resin for impregnation (trade name: KJF816, manufactured by Shin-Etsu Silicone Co., Ltd.) or a silicone resin for impregnation (trade name: KJF816L, manufactured by Shin-Etsu Silicone Corporation) can be used.

The light emitting element 60 of Example 32 is mounted downward on the base substrate 92 . The inorganic adhesive 30 is provided on the surface of the light emitting element 60 mounted downward by screen printing. The base substrate 92 carrying the light emitting element 60 is electrically connected through the conductive member 91 and the flange 96 , and is soldered to the lead wire 21 through the base substrate 92 . The surface of the inorganic binder 30 is impregnated with a resin 40 . The surface of the inorganic binder 30 impregnated with the resin 40 is glossy.

The method for forming the inorganic binder 30 in the method for manufacturing a light-emitting device in Example 32 will be described in detail below. First, the conductive member 91 is disposed on the surface of the base substrate 92 , and then a conductive pattern having an insulating portion 94 isolating the positive electrode and the negative electrode is provided.

The material of the base substrate 92 is preferably a material having a thermal expansion coefficient substantially equal to that of the semiconductor light emitting element, for example, aluminum nitride for a nitride semiconductor light emitting element. By using such a material, thermal stress generated between the base substrate 92 and the light emitting element 60 can be relieved. The material of the susceptor substrate 92 is sometimes preferably silicon, which can form a protective element having a p-type semiconductor region and an n-type semiconductor region, has relatively good heat dissipation, and is also inexpensive. In addition, it is preferable to use silver, gold, and aluminum with high reflectivity as the conductive member 91 .

In order to improve the reliability of the light emitting device, an underfill material 95 is filled in the gap formed between the positive and negative electrodes of the light emitting element 60 and the insulating portion 94 . First, an underfill material 95 is arranged around the insulating portion 94 of the above-mentioned base substrate 92 . The underfill material 95 is, for example, a thermosetting resin such as silicone resin or epoxy resin. In order to relieve the thermal stress of the underfill material 95, aluminum nitride, aluminum oxide, and their composite mixtures may be further mixed into the epoxy resin. The amount of the underfill is an amount capable of filling the gap between the positive and negative electrodes of the light emitting element and the base substrate 92 .

The positive and negative electrodes of the light emitting element 60 are bonded and fixed by flanges 96 so as to face the positive and negative electrodes of the conductive pattern provided on the base substrate 92 , respectively. In addition, when the base is used as the protection element, the anode and cathode of the light emitting element are respectively connected to the n-type semiconductor region and the p-type semiconductor region of the protection element. First, a bump 96 as a conductive member is formed with respect to both positive and negative electrodes of the light emitting element 60 . In addition, the bumps 96 may be formed with respect to both positive and negative electrodes of the conductive pattern of the base substrate 92 . When the underfill material 95 disposed near the insulating portion 94 of the base substrate 92 softens, the positive and negative electrodes of the light emitting element 60 face the positive and negative electrodes of the conductive pattern through the flange 96 . Next, the positive and negative electrodes of the light-emitting element, the flange 96, and the above-mentioned conductive pattern are thermocompressed together by means of load, heat, and ultrasonic waves. At this time, the underfill between the flange 96 and the positive and negative electrodes of the above-mentioned conductive pattern is removed, and the conduction between the electrodes of the light-emitting element and the above-mentioned conductive pattern can be achieved. Examples of the material of the conductive material flange 96 include Au, eutectic solder (Au—Sn), Pb—Sn, lead-free solder, and the like.

The sieve plate 97 is disposed from the substrate side of the light emitting element 60 . In addition, a metal mask may be placed instead of the sieve plate 97 at a position where it is not desired to form an inorganic binder containing phosphor, such as a ball bonding position of a conductive lead or a parting line formation position.

A material containing a phosphor in thixotropic alumina sol was adjusted, and screen printing was performed using a squeegee (round-tip squeegee) 98 .

The sieve plate 97 is removed, the phosphor-containing material is cured, and then each light-emitting element is cut along the parting line to obtain the light-emitting device 60 with the phosphor-containing inorganic binder material.

Furthermore, such a light-emitting device can be designed: the above-mentioned light-emitting element 60 is fixed on the bottom surface of the concave part of the casing with Ag paste as an adhesive, and then the lead electrodes exposed part of the bottom surface of the concave part and the base are arranged on the base with conductive wires. The conductive patterns on the substrate are connected. For example, the light-emitting device that can be used in this embodiment has a lens for controlling the light distribution of the light-emitting device, and a metal base formed on a part of the bottom surface of the concave portion for improving the heat dissipation of the light-emitting element and supporting the light-emitting element. In addition, it is preferable to place a mold member such as silicone resin in the gap between the lower surface of the lens and the inner wall surface of the recessed portion of the case. With such a configuration, it is possible to obtain a light-emitting device with improved light extraction efficiency from the light-emitting element and high reliability.

Next, a method of manufacturing the light-emitting device of Example 32 will be described. Embodiment 32 employs substantially the same configuration as Embodiments 30 and 31, and description thereof is omitted.

First, the light emitting element 60 is mounted downward on the base substrate 92 . The base substrate 92 and the light emitting element 60 are electrically connected through the flange 96 . A groove is provided on the base substrate 92 so as to serve as a different-type electrode, and an insulating portion flows into the groove to prevent a short circuit between the different-type electrodes.

Next, screen printing is performed on the light emitting element 60 and the base substrate 92 mounted downward using a sieve plate 97 . The layer of the inorganic binder 30 used for screen printing uses the inorganic binder material 99 containing a phosphor. However, it is also possible to use an inorganic binder 99 that does not contain a phosphor. A uniform layer of the inorganic binder 30 was formed on the upper surface and side surfaces of the light emitting element 60 by screen printing. The phosphor-containing inorganic binder 99 was obtained by adding 20 g of YAG phosphor to 10 g of alumina sol, followed by stirring and mixing well. After the inorganic binder 30 is formed on the top and side surfaces of the light-emitting element 60, the inorganic binder 30 is heated in a nitrogen atmosphere at about 80°C for 30 minutes, at 150°C for 30 minutes, and at 240°C for 30 minutes. solidify. This is for removing organic components and the like contained in the inorganic binder 30 . However, the present invention is not particularly limited to such heating conditions, and may be heated at 240° C. for 1 hour after heating at about 100° C. for 30 minutes.

Next, the light emitting element 60 ( 210 ) mounted downward on the base substrate 92 is placed on the lead frame (substrate) 820 . The lead frame 820 is formed with a recess 820a including a wide opening, and the light emitting element 60 (210) is placed on the bottom surface of the recess 820a. Soldering is performed so that the substrate side of the light emitting element 60 (210) is in contact with the bottom surface of the concave portion 820a. The light emitting element 60 ( 210 ) is soldered using an adhesive such as eutectic solder such as Au—Sn. After the process of mounting the light emitting element 60 (210) is completed, the conductive member 91 of the base substrate 92 and the lead electrode are electrically connected by the lead wire 821.

Next, the resin 40 (240) is poured on the surface of the inorganic binder 30 (230) layer using a pouring tool. The pouring of the resin 40 ( 240 ) is performed by dropping directly above the light emitting element 60 ( 210 ) and approximately in the center of the layer of the inorganic binder 30 ( 230 ). The resin 40 (240) permeates rapidly from the central part of the layer surface of the inorganic binder 30 (230) and expands toward the outer peripheral direction, so that the voids inside the inorganic binder 30 (230) can be filled and covered. The entire surface up to the layer of the inorganic binder 30 (230) emits the light of the resin 40 (240). As a result, a uniform film-like resin 40 (240) is formed on the surface of the inorganic binder 30 (230) layer. After soldering, cover the light-emitting element 60 (210) with a layer of inorganic adhesive 30 (230) and a layer of resin 40 (240), and place the lead frame 820 carrying the light-emitting element 60 (210) at a temperature of about 150° C. Resin 840 was cured by heating for about 3 hours. Here, as the silicone resin, a silicone resin for impregnation (trade name: KJF816, manufactured by Shin-Etsu Silicone Co., Ltd.) was used.

Finally, the lead frame 820 is sealed with a cover 826 in a nitrogen atmosphere. The inside of the cover 826 is filled with nitrogen gas. Under the window portion 825 of the cover 826, the recessed portion 820a of the lead frame 820 is disposed. In this way, the light-emitting device of Example 32 was produced.

Embodiment 10

Next, a light-emitting device according to Embodiment 10 of the present invention will be described based on FIG. 44 . FIG. 44 shows a schematic configuration diagram of a light-emitting device 1000 having a light-emitting film according to the tenth embodiment. The light-emitting device 1000 includes: excitation light source 44: used to emit excitation light 42; luminescent material 54: it absorbs the excitation light 42 emitted by the excitation light source 44, and emits illumination light 43 in a predetermined wavelength region after wavelength conversion; optical fiber 46 : one end of it is connected to the excitation light source 44, the other end is connected to the luminescent material 54, and the refractive index of the center portion (core) of the section is improved relative to the peripheral portion (cladding layer), so that the excitation light 42 emitted by the excitation light source 44 is guided to the luminescent material 54.

The excitation light source 44 has a light emitting element 47 , and guides the light emitted from the light emitting element 47 to the optical fiber 46 from the emitting portion 48 . In order to efficiently guide the light emitted from the light emitting element 47 to the emitting portion 48 , a lens 49 is provided between the light emitting element 47 and the emitting portion 48 .

One end of the optical fiber 46 is connected to the output unit 48, and the other end has an output unit 52 for guiding light to the outside. The output 52 has a luminescent material 54 . As the luminescent material 54, an inorganic phosphor 55 is used in this example. The luminescent material 54 absorbs the excitation light 42 emitted from the excitation light source 44 , converts the wavelength thereof, and emits the illumination light 43 in a predetermined wavelength range. Phosphor 55 is mixed in filler member 56 and binder member 57 in advance, and filler member 56 and binder member 57 are placed in output unit 52 . The amount of the phosphor 55 can be adjusted according to the amounts of the filler member 56 and the adhesive member 57 . The filler member 56 is an inorganic filler, and the binder member 57 is an inorganic compound containing at least a hydrated oxide of a metal element. As the hydrated oxide of the metal element contained in the binder member 57, a hydrated oxide of Al, Y, or the like having a boehmite structure or a pseudo-boehmite structure can be used.

When using a light-emitting element 47 having an emission peak wavelength near 400 nm in the short-wave range of visible light, and a phosphor 55 that is a mixture of a phosphor that emits blue light and a phosphor that emits yellow light, the white light emitted by the phosphor 55 It is mainly the illumination light 43 . The light near 400 nm is difficult to be recognized, so it is blue light, yellow light, and white light that are easy to recognize.

When the light-emitting element 47 having a light-emitting peak wavelength near 460 nm in the short-wave range of visible light, a phosphor emitting yellow light, and a phosphor emitting red light are used, the excitation light 42 emitted by the light-emitting element 47 and the light emitted by the phosphor 55 The mixed color light is guided to the outside as illumination light 43 . This illumination light 43 becomes reddish white light.

When using a light-emitting element 47 having an emission peak wavelength in the vicinity of 365nm in the ultraviolet region, and a phosphor 55 that is a mixture of a phosphor that emits blue light and a phosphor that emits yellow light, the white light emitted by the phosphor 55 becomes an illumination. light43. Since the ultraviolet rays cannot be seen by human eyes, only the light emitted by the phosphor 55 is used to convert the ultraviolet rays into visible light as the illumination light 43 . Therefore, the white light emitted by the phosphor 55 becomes the illumination light 43 .

However, considering various combinations of phosphors 55, there are cases where a wide range of hues can be obtained by using the three primary colors (blue, green, red) of light, and blue and yellow, blue-green and red, which are complementary colors, can be used. A case where various hues are obtained from two colors of green and red, blue-violet and yellow-green. One of these colors may be replaced by the light emitted from the light emitting element. The term "complementary colors" here refers to two colors of light in the white region that can be obtained when light of one emission peak wavelength is mixed with light of the other emission peak wavelength. Here, refer to JIS Z8110 for the relationship between the color name and the wavelength range. In addition, various combinations of phosphors 55 may be used in order to obtain high color rendering properties.

The so-called color rendering is the property of the light source that affects the visibility of the color of an object illuminated by a certain light source. Color temperature expresses the color of the light source itself in terms of psychophysics, and is expressed by the absolute temperature (K) of a complete radiator with a chromaticity equal to that of a certain light source. Generally speaking, the visual degree of the color of the object seen under a certain light source is expressed by the difference between it and the visual degree of the color of the object seen under the reference light with the same color temperature. The average color rendering evaluation index (Ra) is calculated based on the average value of the color difference when 8 kinds of color charts are respectively irradiated by the sample light source and the reference light source. The special color rendering evaluation index is calculated based on the color difference of the other 7 color charts other than the above 8 color charts, not the average value of the 7 types. Where R9 represents red.

This light-emitting device 1000 can be used in medical fields such as endoscopes for irradiating and imaging subjects, illumination devices and displays for obtaining various colors by using a plurality of excitation light sources 44 . The light emitted from the light emitting device 1000 is not only visually recognized directly by humans, but also sometimes captured by a CCD camera or the like. The excitation light source 44 and the phosphor 55 can be appropriately selected in accordance with the sensitivity of a display such as a CCD camera.

The function of the light emitting device 1000 will be described below. The excitation light 42 emitted from the light emitting element 47 included in the excitation light source 44 passes through the lens 49 and is guided to the emission portion 48 . The lens 49 focuses the excitation light 42 emitted from the light emitting element 47 in the emitting portion 48 . The excitation light 42 emitted from the emission unit 48 is guided to the optical fiber 46 . The excitation light 42 is repeatedly totally reflected in the optical fiber 46 and guided to the output unit 52 at the other end. The extracted excitation light 42 is irradiated onto the phosphor 55 which is a fluorescent material 54 provided on the output unit 52 , and at least a part of the excitation light 42 is absorbed by the phosphor 55 to convert the wavelength to emit light in a predetermined wavelength range. This light is guided to the outside as illumination light, or is guided to the outside as illumination light obtained by mixing the light emitted by the phosphor 55 and the excitation light 42 . Absorption and scattering of light by the phosphor 55 occur in the output part 52, thereby increasing the optical density. Therefore, a member excellent in heat resistance and light resistance is required to use the inorganic filler 32 and the adhesive member 57 . Thus, white light can be obtained with at least one light emitting element 47 . In addition, since white light can be obtained with only one light emitting element 47, it is possible to provide a light emitting device with less variation in color tone and high color reproducibility. In addition, since the light-emitting element 47 and the phosphor 55 are used, it is possible to provide a light-emitting device that is easy to mix colors and has high color rendering. In addition, it is also possible to provide a light-emitting device with high luminous intensity. Since the phosphor 55 is not coated on the light emitting element 47 , the phosphor 55 does not degrade due to heat generated accompanying the excitation of the light emitting element 47 . Furthermore, when a laser diode element is used as the excitation light source 44 , the resin mixed with the phosphor 55 cannot be used for the output portion 52 because the optical density is extremely high. In contrast, when an adhesive member 57 such as alumina sol or yttrium sol mixed with a phosphor 55 is used for the output part 52, since the light resistance and heat resistance are extremely excellent, it is possible to provide an even comparative A light-emitting device that does not deteriorate even with high optical density and has excellent weather resistance.

(excitation light source)

The excitation light source 44 can emit light for exciting the phosphor 55 , and can use a semiconductor light emitting element, a lamp, an electron beam, plasma, EL, or the like as an energy source. The present invention is not particularly limited, but it is preferable to use the light-emitting element 47 because it is compact and has high luminous intensity. As the light emitting element 47, a light emitting diode element (LED) or a laser diode element (LD) can be used.

(Luminescent material)

The luminescent material 54 is not particularly limited as long as it absorbs the excitation light emitted from the excitation light source 44 and converts the wavelength to emit illumination light in a predetermined wavelength region. Phosphor 55 and pigments can be used. The emission spectrum of the excitation light source 44 is different from the emission spectrum of the luminescent material 54 . Since the light emitted from the excitation light source 44 is used as the excitation light, the luminescent material 54 has an emission peak wavelength on the larger wavelength side of the emission peak wavelength of the excitation light source 44 . In particular, even when a laser diode element is used as the light-emitting element 47, it is easy to see because the illumination light has an emission spectrum with a very wide half-width. The phosphor 55, filler member 56, and adhesive member 57 described above may be used. As a method of coating on the output part 55, in addition to mixing the phosphor 55, the filler member 56, and the adhesive member 57, and disposing it in a predetermined container, and then covering it with glass or a translucent resin, etc. In addition to sealing, the phosphor 55, the filler member 56, and the adhesive member 57 may be mixed and arranged in a predetermined container, and then impregnated with a resin, but these are not particularly limited. Moreover, in order to improve heat release performance, you may arrange|position the inorganic filler which is excellent in thermal conductivity and which has translucency.

(optical fiber)

The optical fiber 46 may have the function of guiding the light emitted by the excitation light source 44 to the luminescent material 54 . From the viewpoint of energy efficiency, it is particularly preferable to guide the light emitted from the excitation light source 44 to the light emitting material 54 without being attenuated. For example, a combination of a material having a high refractive index and a material having a low refractive index and a material using a member with a high reflectance can be used. Specifically, an optical fiber 46 may be used.

The optical fiber 46 is an extremely fine glass fiber used as a transmission path of light when transmitting light. Using quartz glass and plastic as materials, the refractive index of the central part (core) of the cross section is higher than that of the peripheral part (cladding), so that optical signals can be transmitted without attenuation.

Since the optical fiber 46 is movable, it can irradiate the illumination light 43 to a predetermined position. In addition, the optical fiber 46 may be bent into a curved shape. The optical fiber 46 can be designed as a single-filament fiber. The diameter of the core of the monofilament fiber is preferably 400 μm or less.

(interruption member)

As the blocking member, a material capable of blocking 90% or more of light from the excitation light source may be used. For example, when using the light-emitting element 47 that emits ultraviolet rays harmful to the human body, an ultraviolet absorber can be used as a blocking member in order to block the ultraviolet rays. In addition, a predetermined filler may be provided in the output portion 52 to block a predetermined wavelength.

As mentioned above, the light-emitting film, light-emitting device, method of manufacturing the light-emitting film and method of manufacturing the light-emitting device of the present invention can be used in light sources for lighting, LED displays, backlight sources, signals, illuminated switches, various sensors, and various indicators etc.

Claims (34)

1. luminescent film, it is the luminescent film that is used to cover semiconductor light-emitting elements, described luminescent film is characterised in that: be made of filler member that contains luminescent material and binding agent member at least, described binding agent member contains the hydrous oxide of metallic element at least.

2. luminescent film according to claim 1 is characterized in that: described luminescent material is an inorganic phosphor, and described filler member is mineral filler, and described binding agent member is the mineral binder bond based on the hydrous oxide of the metallic element of constant valence mumber.

3. luminescent film according to claim 1, it is characterized in that: described luminescent material is an inorganic phosphor, described filler member is mineral filler, described binding agent member is that the hydrous oxide of described metallic element is the hydrous oxide of IIIA family or IIIB family element based on the mineral binder bond of the hydrous oxide of metallic element.

4. luminescent film according to claim 3 is characterized in that: described IIIA family or IIIB family element contain at least a kind among Sc, Y, Gd, Lu or B, Al, Ga, the In.

5. according to each described luminescent film of claim 1～4, it is characterized in that: the hydrous oxide of the metallic element that contains in the described binding agent member is the hydrous oxide with Al of boehmite structure or pseudo-boehmite structure.

6. luminescent film according to claim 5, it is characterized in that, described binding agent member contains: the hydrous oxide of aluminium, and with the hydrous oxide that with respect to binding agent member content is 0.5 weight %～IIIA family's elements 50 weight %, different with described aluminium or IIIB family element.

7. according to each described luminescent film of claim 1～4, it is characterized in that: the hydrous oxide of the metallic element that contains in the described binding agent member is the hydrous oxide of yttrium.

8. luminescent film according to claim 7, it is characterized in that, described binding agent member contains: the hydrous oxide of yttrium, and with the hydrous oxide that with respect to binding agent member content is 0.5 weight %～IIIA family's elements 50 weight %, different with described yttrium or IIIB family element.

9. luminescent film according to claim 5 is characterized in that: it is boron oxide or the boric acid of 0.5 weight %～50 weight % that described binding agent member contains with respect to binding agent member content.

10. according to each described luminescent film of claim 1～4, it is characterized in that: described binding agent member is the porous insert that is formed crosslinking structure, reticulated structure or polymer architecture by the aggregate of the particle that contains described hydrous oxide.

11. each the described luminescent film according to claim 1～4 is characterized in that: described binding agent member is gel, is wherein filling the inorganic particulate that contains described hydrous oxide.

12. luminescent film according to claim 11 is characterized in that: polycrystal or non-crystal transmitance that the light transmission rate of described luminescent film carries out under this situation of sintering after than sol gel reaction are higher.

13. each the described luminescent film according to claim 1～4 is characterized in that: described binding agent member contains 10 weight % or following hydroxyl or crystal water with respect to the binding agent member.

14. each the described luminescent film according to claim 1～4 is characterized in that: constitute the filler member of described luminescent film and the weight ratio of binding agent member and count 0.05～30 with filler/binding agent.

15. a light-emitting device, it has luminous element and absorbs at least a portion of the light that described luminous element sends and luminous luminescent layer, and described light-emitting device is characterised in that: described luminescent layer is each described luminescent film of claim 1～14.

16. light-emitting device according to claim 15 is characterized in that: described luminescent layer directly covers described luminous element.

17. luminescent film according to claim 2 is characterized in that: described mineral binder bond is flooded by resin with the state that is capped.

18. the manufacture method of a luminescent film, it is the manufacture method of the luminescent film that is used for covering luminous element that is made of filler member that comprises luminescent material and binding agent member at least, described manufacture method is characterised in that, may further comprise the steps: will mix and the step of allotment slip as the metal oxygen alkane colloidal sol that contains metallic element and the filler member of binding agent member, described slip is formed membranaceous step, and by the described slip that forms film is carried out thermofixation at 50 ℃～500 ℃, the particle accumulation that makes the hydrous oxide that contains described metallic element together, thereby use the step of the mineral binder bond member appendix filler member that the structure by this set particle constitutes.

19. the manufacture method of luminescent film according to claim 18 is characterized in that: described metal oxygen alkane colloidal sol is aikyiaiurnirsoxan beta colloidal sol or yttrium oxygen alkane colloidal sol.

20. the manufacture method of luminescent film according to claim 18 is characterized in that: described mineral binder bond is flooded by resin with the state that is capped.

21. the manufacture method of a light-emitting device, it is to have luminous element and the manufacture method of the light-emitting device of the luminescent film that obtains according at least a portion of claim 18 or 19 described manufacture method covering luminous elements, described manufacture method is characterised in that: form in the membranaceous step described, under heat-treat condition, adopt described slip to cover described luminous element and/or separate the zone of luminous element, thereby form membranaceous.

22. light-emitting device, it has the matrix of luminous element and the described luminous element of carrying, described light-emitting device is characterised in that: described luminous element is covered by mineral binder bond, described mineral binder bond contains the hydrous oxide of metallic element at least, and covered by resin, described mineral binder bond floods with described resin, and described mineral binder bond forms the inorganic bond layer of at least a portion that covers described luminous element and described matrix.

23. light-emitting device according to claim 22 is characterized in that: the space landfill that described mineral binder bond is had described mineral binder bond layer by described resin.

24. light-emitting device according to claim 22 is characterized in that: 95% or above space landfill that described mineral binder bond is had described mineral binder bond layer by described resin.

25. light-emitting device according to claim 22 is characterized in that: the step that adopts described resin to cover described mineral binder bond is used pouring means or spraying spraying means, makes described mineral binder bond flood described resin.

26. according to each described light-emitting device of claim 22～25, it is characterized in that: described mineral binder bond contains fluor.

27. light-emitting device according to claim 22 is characterized in that: described resin formation covers the resin layer of at least a portion of described mineral binder bond.

28. light-emitting device according to claim 27 is characterized in that: the surface of described resin layer is level and smooth surface.

29. light-emitting device according to claim 22 is characterized in that: described resin contains at least a among oil plant, gel and the rubber.

30. light-emitting device according to claim 22 is characterized in that: under described resin any situation before moulding and after the moulding, be silicone resin with dialkylsiloxane skeleton.

31. light-emitting device according to claim 22 is characterized in that: on main chain, have dimethyl siloxane before the described resin forming.

32. light-emitting device according to claim 22 is characterized in that: described resin in the key absorption intensity of infrared spectra, the C-Si-O key during resin is formed and the strength ratio of Si-O-Si key be 1.2/1 or more than.

33. the manufacture method of a light-emitting device, it has: luminous element is carried on first operation on the matrix; With second operation of described luminous element with the mineral binder bond covering; With the 3rd operation that described mineral binder bond covers with resin, described manufacture method is characterised in that: described the 3rd operation uses pouring means or spraying spraying means to make described resin cover the described mineral binder bond of the hydrous oxide that contains metallic element at least.

34. the manufacture method of light-emitting device according to claim 33 is characterized in that: described the 3rd operation is to flood in a vacuum.

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