KR20180105563A - Method of producing aluminate fluorescent material, aluminate fluorescent material, and light emitting device - Google Patents

Abstract

[PROBLEMS] To provide a method for producing an aluminate phosphor having high light emission intensity, an aluminate phosphor and a light emitting device.
[MEANS FOR SOLVING PROBLEMS] A method for producing a compound containing at least one metal element selected from the group consisting of Ba, Sr and Ca, a compound containing Mn and a compound containing Eu and a compound containing Al And a compound containing Mg as occasion demands are subjected to a first heat treatment to obtain a first fired product having an average particle diameter D1 of 6 占 퐉 or more as measured by the FSSS method;
At least one compound of at least one metal element selected from the group consisting of Ba, Sr and Ca, a compound containing Mn and a compound containing Eu, a compound containing Al, Is subjected to a second heat treatment to obtain a second fired product by mixing the first fired product having a content of 10% by mass or more and 90% by mass or less with a compound containing Mg as necessary Wherein the phosphor is at least one selected from the group consisting of Al2O3 and Al2O3.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for manufacturing an aluminate fluorescent substance, an aluminate fluorescent substance,

The present invention relates to a process for producing an aluminate phosphor, an aluminate phosphor and a light emitting device.

BACKGROUND ART [0002] Various light emitting devices that emit white light, bulb colors, or orange light by combining a light emitting diode (LED) and a phosphor have been developed. In these light emitting devices, a desired luminescent color can be obtained by the principle of mixing light. As a light emitting device, it is also known to emit white light by combining a light emitting element that emits blue light as an excitation light source, a phosphor that emits green light and a phosphor that emits red light by being excited by light from a light source.

These light-emitting devices are required to be used in a wide variety of fields such as general lighting, vehicle-mounted lighting, displays, and liquid crystal backlights.

As a phosphor that emits green for use in a light emitting device, for example, Patent Document 1 discloses a composition of _{(Ba, Sr) MgAl 10 O} 17: There is manganese activated aluminate phosphors represented by Mn ^{2 +} is disclosed.

Japanese Patent Application Laid-Open No. 2004-155907

However, the manganese-activated aluminate phosphor disclosed in Patent Document 1 is excited by vacuum ultraviolet rays having a wavelength of about 10 nm to 190 nm, specifically, by vacuum ultraviolet rays of 146 nm, and has a high light emission intensity. When the light emitting element is combined with a light emitting element having a luminescence peak wavelength in a range of 485 nm or less (hereinafter also referred to as " near-ultraviolet region "), its luminescence intensity is not sufficient.

Accordingly, an embodiment of the present invention is to provide a method for producing an aluminate fluorescent substance having high light emission intensity by optical excitation in the blue region from near-ultraviolet region, an aluminate fluorescent substance, and a light emitting device.

Means for solving the above-mentioned problems include the following aspects.

In a first aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing a compound containing at least one metal element selected from the group consisting of Ba, Sr, and Ca; a compound containing Mn; Is subjected to a first heat treatment and then subjected to FSSS (Fisher Sub-Sieve Sizer, hereinafter also referred to as " FSSS method " To obtain a first sintered body having an average particle diameter D1 of 6 m or more,

At least one compound of at least one metal element selected from the group consisting of Ba, Sr and Ca, a compound containing Mn and a compound containing Eu, a compound containing Al, Is subjected to a second heat treatment to obtain a second fired product by mixing the first fired product having a content of 10% by mass or more and 90% by mass or less with a compound containing Mg as necessary Wherein the phosphor is at least one selected from the group consisting of Al2O3 and Al2O3.

A second aspect of the present invention is a method for producing a metal oxide fine particle having a volume average particle diameter Dm2 of 20 mu m or more as measured by a laser diffraction scattering type particle size distribution measurement method and having an average particle diameter D2 measured by the FSSS method of 13 mu m or more, I) of the present invention.

X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I)

(In the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s and t satisfy 0.5? P? 1.0, 0.5? P + t? 1.2, 0.1? R + t? 0.7, and 0.2? Q + r? 1.0.

A third aspect of the present invention is an aluminate phosphor having an average circle-equivalent diameter Dc of 13 mu m or more and a composition represented by the following formula (I).

X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I)

(In the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s and t satisfy 0.5? P? 1.0, 0.5? P + t? 1.2, 0.1? R + t? 0.7, and 0.2? Q + r? 1.0.

A fourth aspect of the present invention is a light emitting device comprising the aluminate fluorescent substance and an excitation light source having an emission peak wavelength in a range of 380 nm or more and 485 nm or less.

According to one aspect of the present invention, it is possible to provide a method for producing an aluminate phosphor having high light emission intensity by light excitation in the blue region from the near-ultraviolet region, an aluminate phosphor, and a light emitting device.

1 is a schematic cross-sectional view showing an example of a light emitting device.
2 is an emission spectrum of the relative light emission intensity (%) relative to the wavelength of the aluminate fluorescent substance according to Example 2 and the aluminate fluorescent substance according to Comparative Example 1. FIG.
3 is an SEM photograph of the aluminate phosphor according to Example 2. Fig.
[Fig. 4] Fig. 4 is an SEM photograph of the aluminate phosphor according to Comparative Example 1. Fig.
5 is an image diagram showing a state in which 20 or more aluminate phosphor particles are binarized in an SEM photograph of an aluminate phosphor according to Example 2. Fig.
6 is an image diagram showing a state in which 20 or more aluminate phosphor particles are binarized in an SEM photograph of an aluminate phosphor according to Comparative Example 1. Fig.

Hereinafter, the method for producing the aluminate phosphor and the aluminate phosphor and the light emitting device according to the embodiment of the present invention will be described. However, the embodiment shown below is an example for embodying the technical idea of the present invention, and the present invention is not limited to the following production method of aluminate phosphor, aluminate phosphor and light emitting device using it. The relationship between color names and chromaticity coordinates, the relationship between the wavelength range of light and the color names of monochromatic light is in accordance with JIS Z8110.

Method for producing an aluminate phosphor

A process for producing an aluminate phosphor according to the first embodiment of the present invention is a process for producing an aluminate phosphor which comprises mixing a compound containing at least one metal element selected from the group consisting of Ba, Sr and Ca, And a compound containing Al as the case requires, the first mixture is subjected to a first heat treatment to obtain an average particle size (Fisher sub -sieve sizer's number) to obtain a first sintered body having a diameter D1 of 6 m or more,

At least one compound of at least one metal element selected from the group consisting of Ba, Sr and Ca, a compound containing Mn and a compound containing Eu, a compound containing Al, Is subjected to a second heat treatment to obtain a second fired product by mixing the first fired product having a content of 10 mass% or more and 90 mass% or less with a compound containing Mg as necessary .

According to this embodiment, crystal growth is promoted, and a second fired product having an average particle size can be obtained. The second fired product can be used as an aluminate phosphor having a large average particle diameter and a high emission intensity.

First heat treatment

The first mixture contains at least one compound selected from the group consisting of Ba, Sr and Ca, a compound containing Mn and a compound containing Eu, Compounds and, if necessary, Mg-containing compounds. The first mixture preferably contains a flux in the first mixture and is subjected to a first heat treatment together with the flux to obtain a first fired product having an average particle diameter D1 of 6 m or more as measured by the FSSS method. The first mixture preferably contains a compound containing Mn. The FSSS method is a type of air permeation method in which the specific surface area is measured using the flow resistance of air to obtain the particle diameter.

The first mixture is obtained by weighing the compound containing each element at a desired blending ratio and then pulverizing and mixing the mixture using a ball mill, a vibration mill, a hammer mill, a mortar and a pestle It is also good. The mixing of the first mixture may be carried out using a mixer such as a ribbon blender, a Henschel mixer or a V-type blender, or may be pulverized and mixed by using both a dry mill and a mixer. The mixing may be carried out by dry mixing or by adding a solvent or the like and wet mixing. It is preferable to dry mix the mixture. Drying rather than wetting can shorten the process time, leading to improved productivity.

The first mixture can be heat treated by putting it in a crucible made of carbon material such as graphite, boron nitride (BN), aluminum oxide (alumina), tungsten (W), molybdenum (Mo)

The first heat treatment temperature is preferably 1000 占 폚 to 1800 占 폚, more preferably 1100 占 폚 to 1750 占 폚, still more preferably 1200 占 폚 to 1700 占 폚, still more preferably 1300 占 폚 to 1650 占 폚 Particularly preferably 1400 DEG C or higher and 1600 DEG C or lower. As the heat treatment, for example, electric furnace, gas furnace or the like can be used.

The atmosphere of the first heat treatment can be performed in an inert atmosphere containing argon, nitrogen, a reducing atmosphere containing hydrogen, or an oxidizing atmosphere containing oxygen such as air. The atmosphere of the first heat treatment is preferably a reducing atmosphere, and more specifically, it is more preferably a reducing atmosphere containing hydrogen and nitrogen. In an atmosphere having a high reducing power such as a reducing atmosphere containing hydrogen and nitrogen, the reactivity of the first mixture is improved and the heat treatment can be performed at atmospheric pressure. In the reducing atmosphere, the hydrogen gas is preferably at least 0.5% by volume, more preferably at least 1% by volume, and still more preferably at least 3% by volume.

The first heat treatment time varies depending on the temperature raising rate, the heat treatment atmosphere, etc., and is preferably 1 hour or more, more preferably 2 hours or more after reaching the first heat treatment temperature in the range of 1000 占 폚 to 1800 占 폚 More preferably not less than 3 hours, preferably not more than 20 hours, more preferably not more than 18 hours, even more preferably not more than 15 hours.

The first fired product may be subjected to a dispersion treatment by a dispersion treatment step described later before the second heat treatment as the first heat treatment. The dispersion treatment process performed on the first fired product is a process in which the first fired product is subjected to a classification process such as wet dispersion, wet process, dehydration, drying, dry process or the like to obtain an average particle diameter D1 measured by the FSSS method A first fired body having a thickness of 6 탆 or more may be obtained. As a solvent used for wet dispersion, deionized water can be used, for example. The time for carrying out the wet dispersion varies depending on the solid dispersion medium and the solvent to be used, but is preferably 30 minutes or more, more preferably 60 minutes or more, still more preferably 90 minutes or more, still more preferably 120 minutes or more, Preferably 420 minutes or less. The first baked material is preferably subjected to wet dispersion in a range of from 30 minutes to 420 minutes, so that when the obtained aluminate phosphor is used in a light emitting device, the dispersibility into the resin constituting the fluorescent member of the light emitting device is favorably improved can do.

The first baked material has an average particle diameter D1 measured by the FSSS method of 6 占 퐉 or more, preferably 6.5 占 퐉 or more, more preferably 7 占 퐉 or more, and even more preferably 7.5 占 퐉 or more. The first fired product preferably has a larger average particle diameter D1 measured by the FSSS method, but the average particle diameter D1 of the first fired product is usually less than 13 占 퐉. When the average particle diameter D1 measured by the FSSS method is not less than 6 占 퐉, the first fired material becomes a seed crystal (seed crystal) in the second heat treatment and the crystal growth is promoted. By the FSSS method A second fired product having an average particle diameter of 13 mu m or more can be obtained.

Second heat treatment

The second mixture contains at least one compound selected from the group consisting of Ba, Sr and Ca, a compound containing Mn and a compound containing Eu, And a first fired product having a content of 10 mass% or more and 90 mass% or less with respect to the total amount of the second mixture, and a compound containing Mg if necessary. The second mixture is subjected to a second heat treatment to obtain a second fired product. The second mixture preferably contains a compound containing Mn.

The content of the first calcined product contained in the second mixture is preferably 15% by mass or more and 85% by mass or less, more preferably 20% by mass or more and 80% by mass or less, still more preferably 15% Is not less than 25 mass% and not more than 80 mass%, and more preferably not less than 30 mass% and not more than 80 mass%.

When the first baked material having an average particle diameter D1 of 6 m or more is contained in the second mixture in a range of 10% by mass or more and 90% by mass or less with respect to the total amount of the second mixture, Water becomes seed crystals, crystal growth is promoted, and a large second fired product having an average particle diameter of 13 mu m or more as measured by the FSSS method can be obtained, and this second fired product can be used as the aluminate phosphor. If the content of the first sintered material is less than 10% by mass with respect to the total amount of the second mixture, the content of the first sintered material to be a seed crystal is too small, crystal growth is not promoted in the second heat treatment, 2 It is difficult to obtain a fired product. If the content of the first sintered material exceeds 90% by mass with respect to the total amount of the second mixture, the amount of the compound to be a raw material contained in the second mixture is relatively small and crystal growth is not promoted, 2 No fired product can be obtained.

When mixing the second mixture, the mixing method, mixer, and the like exemplified in the case of obtaining the first mixture can be used. Further, the second mixture can be heat-treated by putting it in a crucible, a boat or the like made of the same material as the first mixture.

The second mixture preferably contains a flux, and the second fired product can be obtained by performing the second heat treatment together with the flux contained in the second mixture.

As the second heat treatment temperature, a temperature in the same range as the first heat treatment temperature described above can be applied. The second heat treatment temperature may be the same as or different from the first heat treatment temperature. For the heat treatment, for example, electric furnace, gas furnace or the like can be used.

As the atmosphere of the second heat treatment, an atmosphere similar to that of the first heat treatment atmosphere described above can be applied. The second heat treatment atmosphere may be the same as the above-mentioned first heat treatment atmosphere, or may be another atmosphere.

The second heat treatment time can be the same as the first heat treatment time described above. The second heat treatment time may be the same as or different from the first heat treatment time described above.

After treatment

The first baked product or the second baked product obtained by the first heat treatment or the second heat treatment is preferably subjected to post treatment to obtain the aluminate phosphors. As the post-treatment, it is preferable to carry out, for example, treatment of at least one of wet dispersion, wet type, dehydration, drying, and dry type.

As a post-treatment, when the fired product is wet-dispersed or wet-sieved, specifically, the obtained fired product is dispersed in a solvent, the dispersed second fired product is placed on the sieve, various vibrations are applied through the sieve The solvent is shed, and the sintered product is passed through a mesh to form a wet sieve. After passing through a wet sieve, sediment classification may be performed to remove microparticles. The fine particles to be removed from the calcined product by sediment classification differs depending on the intended grain size and the like. In the case of removing fine particles from the fired product obtained after the second heat treatment by the post-treatment, it is preferable that the amount of the fired product is 15 mass% or more and 20 mass% or less in the total amount of the fired product obtained after the second heat treatment. The sediment classification may be repeated a plurality of times. After sediment classification, dehydration, drying, and a phosphor may be obtained through a dry body. By dispersing the baked product after the heat treatment in a solvent, it is possible to remove impurities such as calcined residue of the flux and unreacted components of the raw material. For the wet dispersion, a solid dispersion medium such as alumina balls or zirconia balls may be used. As a solvent used for wet dispersion, deionized water can be used, for example. The time for performing the wet dispersion varies depending on the solid dispersion medium and the solvent to be used, but is preferably 10 minutes or more, more preferably 20 minutes or more, still more preferably 30 minutes or more, and preferably 240 minutes or less. The dispersibility of the obtained aluminate phosphor can be improved by subjecting the second baked product to wet dispersion in the range of preferably 10 minutes to 240 minutes.

As the post-treatment, when the baked material is dried and dry-processed, specifically, the baked material is dried at a temperature of about 80 ° C to about 150 ° C. The dried fired product can remove particles having a large particle size not passing through the sieve through the dry sieve. The drying time is preferably 1 hour to 20 hours, more preferably 2 hours to 18 hours.

In the post-treatment, the sieving of the sieving body used in the case of performing the wet sieving or dry sieving is not particularly limited, and a sieved body corresponding to the particle size of the first sintered body or the second sintered body may be used.

The first fired product and / or the second fired product

The first fired product and / or the second fired product preferably have a composition represented by the following formula (I).

X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I)

(In the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s and t satisfy 0.5? P? 1.0, 0.5? P + t? 1.2, 0.1? R + t? 0.7, and 0.2? Q + r? 1.0.

The first fired product and / or the second fired product obtained by the step of obtaining the first fired product and / or the step of obtaining the second fired product can be used as the aluminate phosphor.

Flux

Wherein at least one of the first mixture and the second mixture contains a flux and the flux contains at least one kind of metal element selected from the group consisting of K, Na, Ba, Sr, Ca, Mg, And the like. Wherein the flux comprises at least one metal element selected from the group consisting of Ba, Sr and Ca contained in the first mixture and / or the second mixture, a compound containing Mn, a Mg , And a compound different from the compound containing Al.

It is more preferable that both the first mixture and the second mixture include a flux. When the flux is included in both the first mixture and the second mixture, the flux included in the first mixture and the flux contained in the second mixture may be the same or different.

When the first mixture comprises a flux, the flux promotes the reaction of the materials in the first mixture in the first heat treatment and promotes the growth of the crystals by more uniformly advancing the solid phase reaction . By the presence of the flux, the growth of the original crystals in the first mixture is promoted, so that the first fired product having a relatively large particle diameter can be obtained. The first heat treatment temperature is a temperature at which the compound used as the flux forms a liquid phase or a temperature higher than this temperature. It is considered that the reaction of the raw materials in the first mixture is promoted and the solid phase reaction proceeds more uniformly and the crystal growth is promoted because the flux forms a liquid phase.

When the second mixture contains the flux, the flux accelerates the reaction between the first fired material, which is the seed crystal in the second mixture, and the other materials in the second heat treatment, and makes the solid phase reaction more uniform It is considered that the crystal growth is further promoted from the seed crystal.

The flux is preferably a halide containing at least one kind of metal element selected from the group consisting of K, Na, Ba, Sr, Ca, Mg, Al and Mn, And fluorides including at least one kind of metal element selected from the group consisting of Sr, Ca, Mg, Al and Mn, and chlorides. More preferably, the flux is a fluoride including the above metal element. As the flux, and specifically there may be mentioned a _{KF, NaF, BaF 2, SrF} 2, CaF 2, MgF 2, AlF 3, MnF 2.

The metal element contained in the flux may be included in the composition of the first fired product or the second fired product to be obtained.

The flux is preferably such that the number of moles of Al contained in the first mixture containing no flux and / or the second mixture containing no flux is 10, and the number of moles of the metal element contained in the flux is 0.03 or more and 0.60 or less, Is preferably contained in the first mixture or the second mixture such that the ratio is in the range of 0.04 to 0.55, more preferably 0.05 to 0.50, and even more preferably 0.06 to 0.40. By making the above range, the reaction of the raw materials in the first mixture or the reaction of the raw materials with the first sintered material in the second mixture in the first heat treatment or the second heat treatment can be promoted and the solid phase reaction can be more uniformly advanced , A first fired body or a second fired body having a large particle diameter can be obtained.

When the metal element contained in the flux constitutes a part of the composition of the obtained first sintered body or the second sintered body, the first mixture containing no flux or the molar amount of Al contained in the second mixture containing no flux Is 10, and the flux is added to the first mixture or the second mixture so that the number of moles of the metal element contained in the flux is within the above range.

The flux preferably includes two kinds of fluxes, i.e., a first flux and a second flux. In the case where two fluxes are included as the flux, the first flux is a compound containing at least one metal element selected from the group consisting of Ba, Sr, Ca, Mg, Al and Mn, and the second flux is K And at least one metal element selected from Na. At least one of the first mixture and the second mixture may include two kinds of fluxes, and both of the first mixture and the second mixture may contain two kinds of fluxes And may include two kinds of flux.

As the first flux, by using a compound containing a metal element constituting the matrix of the first fired product or the second fired product, it is possible to suppress the incorporation of impurities into the crystal structure and to prevent the first fired product or the second fired product The composition ratio (molar ratio) of the constituent components can be adjusted to a desired molar ratio.

Further, by using a compound containing at least one kind of metallic element selected from K and Na as the second flux, crystals can be easily grown in the c-axis direction and / or in-plane direction in the hexagonal system crystal structure Thus, an aluminate fluorescent substance having a high light emission intensity can be obtained.

Furthermore, by including the first flux and the second flux of the second flux different in melting point from the first flux, crystal growth at a higher heat treatment temperature can be promoted and the grain size can be increased.

When the first flux and the second flux include two kinds of fluxes, the number of moles of Al contained in the first mixture containing no flux and / or the second mixture containing no flux is 10, The molar number of the metal element contained in the flux is preferably in the range of 0.006 to 0.55, more preferably 0.01 to 0.50, even more preferably 0.02 to 0.45, and still more preferably 0.03 to 0.40.

In the above-mentioned range, in the first heat treatment or the second heat treatment, the reaction of the raw materials in the first mixture or the reaction of the raw materials with the first calcined material in the second mixture is promoted, the solid phase reaction proceeds more uniformly, The crystal structure of the host crystal is stabilized to obtain the first fired body or the second fired body having a large particle size.

In the case where the metal element contained in the first flux constitutes a part of the composition of the obtained first fired product or the second fired product, the first mixture containing no flux or the second mixture containing no flux The flux is added to the first mixture or the second mixture such that the number of moles of the metal element contained in the flux is in the range of 0.006 or more and 0.55 or less.

When the metal element contained in the first flux is Mg or Al and the metal element contained in the second flux is K or Na, the molar ratio (the number of moles of the metal element contained in the first flux: the metal contained in the second flux Is preferably in the range of 20: 1 to 1: 5, more preferably in the range of 15: 1 to 1: 3, and still more preferably in the range of 10: 1 to 1: 2. If the molar ratio of the metal element contained in the first flux to the metal element contained in the second flux is in the range of 20: 1 to 1: 5, the reaction of the materials in the first mixture or the reaction between the first fired material in the second mixture The reaction of the raw material is promoted to progress the solid phase reaction more uniformly and the crystal structure of the host crystal is stabilized to obtain the first sintered body or the second sintered body having a large grain size. If the content of the second flux is too large, the amount of alkali metal Na or K contained in the crystal structure increases, and conversely, the emission intensity may be lowered.

The compound contained in the first mixture or the second mixture

The first mixture or the second mixture is a mixture of at least one compound selected from the group consisting of Ba, Sr and Ca (alkaline earth metal element), a compound containing Mn and a compound containing at least Eu One compound, and a compound containing Al. The first mixture or the second mixture may further contain a compound containing Mg if necessary. Further, it is preferable that the first mixture and the second mixture include a compound containing Mn.

A compound containing an alkaline earth metal element

Examples of the compound containing at least one alkaline earth metal element selected from the group consisting of Ba, Sr and Ca include oxides and hydroxides containing at least one alkaline earth metal element selected from the group consisting of Ba, Sr and Ca , Carbonates, nitrates, sulfates, carboxylates, halides, nitrides and the like. Such a compound may be in the form of a hydrate. Specifically, BaO, Ba (OH) ₂ .8H ₂ O, BaCO ₃ , Ba (NO ₃ ) ₂ , BaSO ₄ , Ba (HCOO) ₂ , Ba (OCOCH ₃ ) ₂ , BaCl ₂ .6H ₂ O, Ba _{3 N 2, SrO, Sr (} OH) 2 · 8H 2 O, SrCO 3, Sr (NO 3) 2 · 4H 2 O, SrSO 4, Sr (HCOO) 2 · 2H 2 O, Sr (OCOCH 3) 2 · 0.5H there may be mentioned _{2 O, SrCl 2 · 6H 2} O, Sr 3 N 2, CaO, Ca (OH) 2, CaCO 3, Ca (NO 3) 2, CaSO 4, CaCl 2, Ca 3 N 2 , etc. . These compounds may be used singly or in combination of two or more kinds. Of these, carbonates and oxides are preferred because they are easy to handle. Since it is easy to decompose by heating and the elements other than the target composition are hard to remain and deterioration of the light emission intensity due to the residual impurity element can be suppressed easily, And a carbonate containing at least one alkaline earth metal element selected from the group consisting of alkaline earth metal elements.

The compound containing Mn

Examples of the compound containing Mn include oxides, hydroxides, carbonates, nitrates, lactates, carboxylates, halides and nitrides containing Mn. The compound containing these manganese may be in the form of a hydrate. _{Specifically, MnO 2, Mn 2 O 2} , Mn 3 O 4, MnO, Mn (OH) 2, MnCO 3, Mn (NO 3) 2, Mn (OCOCH 3) 2 · 2H 2 O, Mn (OCOCH 3 ) ₃ .2H ₂ O, MnCl ₂ .4H ₂ O, and the like. The Mn-containing compound may be used singly or in combination of two or more. Of these, carbonates and oxides are preferred because they are easy to handle. (MnCO ₃ < - > (MnCO _{3) 3)} containing Mn is preferable because it has good stability in air and is easily decomposed by heating and an element other than the objective composition is difficult to remain and deterioration of the emission intensity due to the residual impurity element can be suppressed easily. ) Is more preferable.

Compounds containing Eu

As the compound containing Eu, oxides, hydroxides, carbonates, nitrates, sulfates, halides, nitrides and the like containing Eu can be given. The compound containing these Eu may be in the form of a hydrate. Specifically, EuO, Eu ₂ O ₃ , Eu (OH) ₃ , Eu ₂ (CO ₃ ) ₃ , Eu (NO ₃ ) ₃ , Eu ₂ (SO ₄ ) ₃ , EuCl ₂ and EuF ₃ . The Eu-containing compound may be used singly or in combination of two or more. Of these, carbonates and oxides are preferred because they are easy to handle. It is easy to decompose by heating and the elements other than the target composition are difficult to remain and the decrease of the emission intensity by the residual impurity element can be suppressed easily. Therefore, the oxide containing Eu (Eu ₂ O ₃ ) is more preferable.

Compounds containing Al

As the compound containing Al, oxides, hydroxides, nitrides, oxynitrides, fluorides, chlorides and the like containing Al can be given. These compounds may be hydrates. As the compound containing Al, a single aluminum metal or an aluminum alloy may be used, and a metal single or an alloy may be used instead of at least a part of the compound.

Specific examples of the compound containing Al include Al ₂ O ₃ , Al (OH) ₃ , AlN, AlF ₃ and AlCl ₃ . The compound containing Al may be used singly or in combination of two or more. The compound containing Al is preferably an oxide (Al ₂ O ₃ ). This is because the oxides do not contain any element other than the target composition of the aluminate phosphor as compared with other materials, and it is easy to obtain the phosphor of the desired composition. When a compound containing an element other than the target composition is used, the residual impurity element may be present in the resulting phosphor, and this residual impurity element may become a killer element in light emission, There is a concern.

The compound containing Mg

Examples of the compound containing Mg include oxides, hydroxides, carbonates, nitrates, lactates, carboxylates, halides and nitrides containing Mg. The magnesium-containing compound may be in the form of a hydrate. _{Specifically, MgO, Mg (OH) 2} , 3MgCO 3 · Mg (OH) 2 · 3H 2 O, MgCO 3 · Mg (OH) 2, Mg (NO 3) 2 · 6H 2 O, MgSO 4, Mg ( HCOO) ₂ .2H ₂ O, Mg (OCOCH ₃ ) ₂ .4H ₂ O, MgCl ₂ , and Mg ₃ N ₂ . The Mg-containing compound may be used singly or in combination of two or more. Of these, carbonates and oxides are preferred because they are easy to handle. (MgO) containing Mg is preferable since stability in the air is good, it is easily decomposed by heating, elements other than the target composition are difficult to remain, and deterioration of the light emission intensity due to the residual impurity element can be suppressed easily. Is more preferable.

Aluminate phosphors

The aluminate phosphor according to the second embodiment of the present invention has an average particle diameter D2 (Fisher sub-sieve sizer number) measured by FSSS (Fisher sub-sieve sizer) of 13 mu m or more and / The volume average particle diameter Dm2 measured by the diffraction scattering type particle size distribution measurement method is 20 占 퐉 or more and has a composition represented by the following formula (I). The volume average particle diameter Dm2 is a 50% volume particle diameter in the particle size distribution measured by a laser diffraction scattering particle size distribution measurement method.

X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I)

(In the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s and t satisfy 0.5? P? 1.0, 0.5? P + t? 1.2, 0.1? R + t? 0.7, and 0.2? Q + r? 1.0.

The aluminate phosphor (hereinafter also referred to as "aluminate phosphor (I)") having a composition represented by the formula (I) has an average particle diameter D2 of 13 μm or more as measured by the FSSS method, The volume average particle diameter Dm2 measured by the particle size distribution measurement method is 20 占 퐉 or more, the particle diameter is large, and the luminescence intensity is high. The aluminate phosphor (I) is preferably produced by the above-described method for producing an aluminate phosphor.

The aluminate phosphor (I) preferably has an average particle diameter D2 of 14 mu m or more, more preferably 15 mu m or more, as measured by the FSSS method. The average particle diameter D2 is, for example, 50 占 퐉 or less. A large average particle diameter D2 of the aluminate phosphor (I) has a high emission intensity.

The aluminate phosphor (I) preferably has a volume average particle diameter (Dm2) of 20.5 占 퐉 or more, more preferably 21 占 퐉 or more, as measured by a laser diffraction scattering particle size distribution measurement method, more preferably 22 Mu m or more. The volume average particle diameter Dm2 is 100 mu m or less, for example, less than 80 mu m. A large volume average particle diameter Dm2 of the aluminate phosphor (I) has a high emission intensity. The laser diffraction scattering type particle size distribution measurement method is a method of measuring the particle size without distinguishing the primary particles and the secondary particles by using the scattered light of the laser light irradiated to the particles.

The aluminate phosphor (I) preferably has a degree of dispersion Dm2 / D2 of 1.0 or more and less than 1.6, which is defined as a ratio of the volume average particle diameter Dm2 to the average particle diameter D2. The dispersion degree Dm2 / D2 represents the particle size measured without discriminating the primary particles and the secondary particles with respect to the primary particles, and the larger the value of the dispersion degree Dm2 / D2 is, the more the secondary The amount of particles contained is increased. The closer the dispersion degree Dm2 / D2 is to a value of 1, the smaller the amount containing the secondary particles.

When the aluminate phosphor (I) is used in a light-emitting device, the dispersion degree Dm2 / D2 is preferably in the range of, for example, And the like. The higher the value of the dispersion degree Dm2 / D2, the higher the apparent density of the powder of the aluminate phosphor (I). When the aluminate phosphor (I) is used in a light emitting device, The filling density in the case of the present invention tends to increase. When the dispersion degree Dm2 / D2 of the aluminate phosphor (I) is less than 2.0, the emission intensity tends to decrease slightly as the dispersion degree Dm2 / D2 becomes smaller. When the dispersion degree Dm2 / D2 of the aluminate phosphor (I) is 1.0 or more and 1.6 or less, the light emitting device using the aluminate phosphor (I) having the dispersion degree Dm2 / D2 within this range will have a higher luminous flux. This is presumed to be because the aluminate phosphor (I) having the dispersion degree Dm2 / D2 within the above range is improved in dispersibility in the fluorescent member of the light emitting device, and thus the efficiency of extracting light from the light emitting device is improved . The dispersion degree Dm2 / D2 of the aluminate phosphor (I) is more preferably 1.0 or more and 1.5 or less.

The aluminate phosphor (I) whose dispersion degree Dm2 / D2 is in the range of 1.0 or more and 1.6 or less can be obtained, for example, in a dispersion treatment step performed on the first fired product and / or a post treatment step performed on the second fired product Thus, the aluminate phosphor (I) having a dispersion degree Dm2 / D2 of 1.0 or more and less than 1.6 can be obtained by adjusting the time for wet dispersion. The time for wet dispersion to obtain an aluminate phosphor (I) having a suitable dispersion degree Dm2 / D2 depends on the solvent used for wet dispersion or the solid dispersion medium. For example, when deionized water is used as a solvent and alumina balls are used as a solid dispersion medium, the time for wet dispersion to obtain the aluminate phosphor (I) having a dispersion degree Dm2 / D2 of 1.0 or more and less than 1.6, More preferably not less than 30 minutes, more preferably not less than 60 minutes, even more preferably not less than 90 minutes, even more preferably not less than 120 minutes. The time for wet dispersion is preferably 420 minutes or less in consideration of the production efficiency.

The aluminate phosphor (I) has an inlet ratio D90 / D10 of 90% volume particle diameter D90 to 10% volume particle diameter D10 accumulated from the small diameter side in the particle size distribution by the laser diffraction scattering particle size distribution measurement method Preferably 3.0 or less. The mouth ratio D90 / D10 of the 90% volume particle diameter D90 to the 10% volume particle diameter D10 is also one of indexes indicating the degree of dispersion in the particle size-based particle size distribution. When the particle size ratio D90 / D10 of the aluminate phosphor (I) is 3.0 or less, there is little variation in the size of individual aluminate phosphor (I) particles and the size is relatively uniform. When the mouth ratio D90 / D10 is 3.0 or less, the size of the individual particles of the aluminate phosphor (I) is small and the size is relatively uniform, so that the aluminate phosphor (I) And the light flux extracted from the light emitting device can be increased.

The aluminate phosphor according to the third embodiment of the present invention has an average circle-equivalent diameter Dc of 13 占 퐉 or more and a composition represented by the above formula (I).

The aluminate phosphor (I) has an average circle-equivalent diameter Dc of 13 mu m or more, and thus has a large particle diameter and a high emission intensity. The aluminate phosphor (I) is preferably produced by the above-described method for producing an aluminate phosphor. The average circle-equivalent diameter Dc of the aluminate phosphor (I) is preferably 13.5 占 퐉 or more, and more preferably 14 占 퐉 or more. The average circle equivalent diameter Dc of the aluminate phosphor (I) may be 30 mu m or less.

In the present specification, circle equivalent diameter refers to a value measured as follows. SEM images of aluminate phosphors obtained using a scanning electron microscope (SEM) were subjected to image analysis using image analysis software (for example, WinROOF2013, manufactured by Mitani Co., Ltd.) The binarization treatment is performed on 20 or more aluminate phosphor particles which can confirm the outline of each phosphor particle on the SEM image. The particle diameter in the range that can be confirmed on the SEM image means the longest diameter of the particle. With respect to 20 or more samples subjected to binarization, assuming that the particle shape obtained by binarization is a circle, the diameter of a positive circle equivalent to the area of the circle is defined as a circle-equivalent diameter. The mean value Av and the standard deviation sigma of the particle diameter distribution of the circle equivalent diameters of the 20 or more samples measured are found and the circle equivalent value of the numerical values which do not satisfy the values (Av + standard deviation) The arithmetic average of the circle-equivalent diameters of the remaining samples, excluding the diameters, was defined as the average circle-equivalent diameter Dc.

In the formula (I), X ¹ preferably includes Ba. In the composition of the aluminate phosphor (I), when X ¹ in the formula (I) contains Ba, the emission intensity can be increased.

The variable p in the formula (I) is the total molar ratio of at least one kind of element selected from the group consisting of Ba, Sr and Ca. When the variable p does not satisfy the expression 0. 5? P? 1.0 in the formula (I), the crystal structure of the aluminate phosphor (I) may become unstable, have. The variable p is preferably 0.60 or more, and more preferably 0.80 or more. The variable p may be 0.99 or less.

The variable q in the formula (I) is the molar ratio of Mg. When the variable q exceeds 1.0, the molar ratio of Mg becomes high, and the amount of Mn or Eu which becomes relatively active element becomes small, . Mg may not be contained in the aluminate phosphor (I). The variable q in the formula (I) is preferably a number satisfying 0 < q < = 0.7, more preferably 0 < q = 0.6. The lower limit of the variable q in the formula (I) is more preferably 0.05, and even more preferably 0.1. If the variable q in the formula (I) in the composition of the aluminate phosphor (I) is a number satisfying 0? Q? 1.0, the luminescence spectrum due to photoexcitation in the blue region from outside the near- Nm or less, the reflectance is relatively low, and the luminescence intensity tends to be high.

The variable r in the formula (I) is the molar ratio of Mn. Mn is an active element of the aluminate phosphor (I). Further, the aluminate phosphor (I) preferably contains at least one of Mn and Eu as active elements, and more preferably contains Mn. The aluminate phosphor (I) may further contain rare earth elements such as Eu and Ce in addition to Mn. Particularly, since the aluminate phosphor (I) contains Mn and Eu as active elements, Eu absorbs light to excite electrons, and the excitation energy thereof is transferred from Eu to Mn, and further contributes to the emission of Mn It is expected. Therefore, the light emission intensity of the aluminate phosphor (I) can be increased by photoexcitation in the blue region from the near-ultraviolet region. The variable r in the formula (I) is a molar ratio of Mn. When the variable r exceeds 0.7, the active amount of Mn becomes excessively large, so that the aluminate phosphor (I) The strength tends to be lowered. In the formula (I), the variable r preferably satisfies 0.2? R? 0.7, more preferably 0.4? R? 0.6. In the formula (I), the variable r is more preferably 0.45 or more, and more preferably 0.55 or less.

The variable t in the formula (I) is the molar ratio of Eu. Eu is an active element of the aluminate phosphor (I). When the variable t exceeds 0.5, the light emission intensity of the aluminate phosphor (I) tends to decrease. In the formula (I), the variable t is preferably a number satisfying 0.1? T? 0.5, more preferably 0.2? T? 0.4.

When the variable p + t is less than 0.5 or exceeds 1.2, the sum of the values of p and t in the formula (I) (hereinafter also referred to as " variable p + t ") is the molar ratio of the alkaline earth metal element and Eu. The phosphate salt (I) tends to have an unstable crystal structure, and there is a fear that the emission intensity is lowered. The variable p + t is preferably 0.55 or more, and more preferably 0.60 or more. The variable p + t is preferably 1.10 or less, and more preferably 1.05 or less.

The sum of the variable r and the variable t in the formula (I) (hereinafter also referred to as " variable r + t ") is the total molar ratio of Mn and Eu as the active elements, and when the variable r + t exceeds 0.7, (I) is excited by light in the blue region from outside the near-ultraviolet region, for example, the reflectance tends to be high and the light emission intensity tends to be low. In the formula (I), when the variable r + t is less than 0.1, the activated amount is small, and when the aluminate phosphor (I) is excited with light in the blue region from near extinction, absorption of light is small and it is difficult to increase the light emission intensity It may be canceled.

The sum of the variable q and the variable r in the formula (I) (hereinafter also referred to as " variable q + r ") is a number satisfying 0.2? Q + r? 1.0. If the variable q + r is less than 0.2 or more than 1, a sufficient relative light emission intensity may not be obtained. The variable q + r is preferably a number of 0.3 or more, more preferably 0.4 or more, and is preferably a number of 0.99 or less, more preferably 0.98 or less.

The variable s in the formula (I) is a molar ratio of Al. When the variable s is less than 8.5 or more than 13, the crystal structure becomes unstable, and the aluminate phosphor (I) And when it is excited, the emission intensity tends to decrease. In the formula (I), the variable s is preferably a number satisfying 9.0? S? 13.0. In the formula (I), the variable s is more preferably 12.0 or less, and still more preferably 11.0 or less.

It is preferable that the aluminate phosphor (I) having an average particle diameter D2 of 13 占 퐉 or more or a volume average particle diameter Dm2 of 20 占 퐉 or more is produced according to the production method according to the first embodiment related to the present disclosure. When the aluminate phosphor (I) is a compound containing at least one kind of metal element selected from K and Na as the second flux in the production method according to the first embodiment, the aluminate phosphor I) at least one kind of metal element selected from a small amount of K and Na is sometimes detected. Even in this case, the composition of the aluminate phosphor (I) satisfies the formula (I).

The aluminate phosphor (I) is activated by manganese (Mn), and emits green light by photoexcitation in the blue region from the near-ultraviolet region. Concretely, the aluminate phosphor (I) has an emission peak wavelength in a luminescence spectrum absorbing light in a wavelength range of 380 nm or more and 485 nm or less, preferably 485 nm or more and 570 nm or less, And is in the range of 505 nm or more and 550 nm or less, still more preferably 515 nm or more and 523 nm or less.

Light emitting device

An example of a light emitting device using an aluminate phosphor (I) according to an embodiment of the present invention will be described with reference to the drawings. 1 is a schematic cross-sectional view showing a light emitting device 100 according to a third embodiment of the present invention.

The light emitting device 100 includes a molded body 40, a light emitting element 10, and a fluorescent member 50. The molded body 40 is formed by integrally molding the first lead 20 and the second lead 30 and the resin portion 42 including a thermoplastic resin or a thermosetting resin. The molded body 40 forms a recess having a bottom surface and a side surface, and the light emitting element 10 is placed on the bottom surface of the recessed portion. The light emitting element 10 has a pair of positive and negative electrodes and the electrodes of the pair of the electrodes are electrically connected to the first lead 20 and the second lead 30 through the wires 60, Respectively. The light emitting element 10 is covered with a fluorescent member 50. The fluorescent member 50 includes, for example, a phosphor 70 for wavelength-converting light from the light emitting element 10 and a resin. Further, the phosphor 70 includes a first phosphor 71 and a second phosphor 72. The first lead 20 and the second lead 30 connected to the pair of electrodes of the light emitting element 10 are connected to the first lead 20 toward the outside of the package constituting the light emitting device 100, And a part of the second lead 30 are exposed. The light emitting device 100 can emit light by being supplied with power from the outside through the first lead 20 and the second lead 30. [

The light emitting element 10 is preferably used as an excitation light source and has an emission peak in a wavelength range of 380 nm or more and 485 nm or less. The range of the luminescence peak wavelength of the light emitting element 10 is more preferably from 390 nm to 480 nm, and still more preferably from 420 nm to 470 nm. The aluminate phosphors are efficiently excited by light from an excitation light source having an emission peak wavelength in the range of 380 nm to 485 nm and are excited by the aluminate phosphors having a high emission intensity, It is possible to configure the light emitting device 100 that emits the mixed light of the light from the phosphor 70 and the fluorescent light from the phosphor 70.

The half width of the light emission spectrum of the light emitting element 10 can be, for example, 30 nm or less. The light emitting element 10 is preferably a semiconductor light emitting element using, for example, a nitride semiconductor (In _X Al _Y Ga _{1 -X- Y} N, 0? X, 0? Y, X + _{Y? 1} ) By using the semiconductor light emitting element as the light source, a stable light emitting device having high efficiency, high linearity of output to the input and strong against mechanical impact can be obtained.

The light emitting device 100 comprises at least the aluminate phosphor (I) according to the second embodiment of the present disclosure and an excitation light source having an emission peak wavelength in the range of 380 nm to 485 nm.

The first phosphor 71 mainly contains the aluminate phosphor I according to the second embodiment of the present disclosure and is included in the fluorescent member 50 covering the light emitting element 10, for example. In the light emitting device 100 in which the light emitting element 10 is covered with the fluorescent member 50 containing the first fluorescent material 71, part of the light emitted from the light emitting element 10 is absorbed by the aluminate fluorescent substance, As shown in Fig. By using the light emitting element 10 that emits light having an emission peak wavelength in a range of 380 nm to 485 nm, a light emitting device having high light emitting efficiency can be provided.

The content of the first phosphor 71 may be 10 parts by mass or more and 200 parts by mass or less, preferably 2 parts by mass or more and 40 parts by mass or less, for example, with respect to 100 parts by mass of resin.

The fluorescent member 50 preferably includes a second fluorescent material 72 having a different emission peak wavelength from the first fluorescent material 71. For example, the light emitting device 100 includes a light emitting element 10 that emits light having an emission peak wavelength in a range of 380 nm to 485 nm, a first phosphor 71 that is excited by the light, 2 phosphors 72 are suitably provided, a wide color reproduction range and high color rendering property can be obtained.

The second phosphor 72 may be a phosphor that absorbs light from the light emitting element 10 and performs wavelength conversion with light of a wavelength different from that of the first phosphor 71. For example, (Ca, Sr, Ba) 2 SiO 4: Eu, (Ca, Sr, Ba) 8 MgSi 4 O 16 (F, Cl, Br) 2: Eu, Si 6 - z Al z O z N 8 _{-z: Eu (0 <z≤4.2)} , (Sr, Ba, Ca) Ga 2 S 4: Eu, (Lu, Y, Gd, Lu) 3 (Ga, Al) 5 O 12: Ce, (La, _{Y, Gd) 3 Si 6 N} 11: Ce, Ca 3 Sc 2 Si 3 O 12: Ce, CaSc 4 O 4: Ce, K 2 (Si, Ge, Ti) F 6: Mn, (Ca, Sr, Ba ) ₂ Si ₅ N ₈ : Eu, CaAlSiN ₃ : Eu, (Ca, Sr) AlSiN ₃ : Eu, (Sr, Ca) LiAl ₃ N ₄ : Eu, (Ca, Sr) ₂ Mg ₂ Li ₂ Si ₂ N ₆ : Eu, 3.5MgO · 0.5MgF ₂ · GeO ₂ : Mn, and the like.

When the phosphor member 50 further includes the second phosphor 72, the second phosphor 72 is preferably a red phosphor that emits red light, and it is preferable that light in a wavelength range of 380 nm to 485 nm It is preferable to emit light in a wavelength range of 610 nm to 780 nm. Since the light emitting device includes a red phosphor, it can be more suitably applied to an illumination device, a liquid crystal display device, and the like.

As the red phosphor, Mn activated phosphor of composition formula K ₂ SiF ₆ : Mn, 3.5 MgO · 0.5 MgF ₂ · GeO ₂ : Mn, CaSiAlN ₃ : Eu, (Ca, Sr) AlSiN ₃ : Eu, SrLiAl ₃ N ₄ : Eu , And the like. Among them, the red phosphor is preferably a Mn active fluorophosphor with a half-width of the emission spectrum of 20 nm or less from the viewpoint of increasing the color purity and broadening the color reproduction range.

The first phosphor 71 and the second phosphor 72 (collectively referred to simply as "phosphor 70" hereinafter) constitute a fluorescent member 50 that covers the light emitting element together with the encapsulation material. As the sealing material constituting the fluorescent member 50, a thermosetting resin such as a silicone resin or an epoxy resin can be mentioned.

[Example]

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

Production Example 1

The molecular ratio is Ba _{1 . 0} Mg _{0 . 45} Mn _{0 . 5} Al ₁₀ O _{16 .95} . BaCO ₃ , Al ₂ O ₃ , MgO, and MnCO ₃ were used as raw materials and the respective raw materials were mixed so as to have the molar ratios shown in Table 1 to obtain a first mixture. MgF ₂ was added as the first flux to the first mixture, and NaF was added as the second flux. The first flux MgF ₂ and the second flux NaF are mixed so that the molar ratio of Mg contained in the first flux to the molar amount of Mg contained in the second flux And added to the first mixture so that the number of moles was the number of moles as shown in Table 1. [ First charging a first mixture comprising a flux and a second flux on alumina sense, and by the lid, H ₂ 3% by volume, N ₂ is 1500 ℃ from 97 reducing atmosphere in% by volume, a first heat treatment to 5 hours To thereby obtain a first fired product (1).

Production Examples 2 to 21

Each raw material was mixed so as to have the molar ratio shown in Table 1 to obtain each first mixture. Eu ₂ O ₃ was used as a compound containing Eu. At least one selected from MgF ₂ or AlF ₃ is used as the first flux and at least one species selected from NaF and KF is used as the second flux. The first fired product (2 to 21) was obtained in the same manner as in Example 1 except that each first mixture was used.

Measurement of average particle diameter (D1)

A sample of 1 cm 3 was weighed and taken in an environment of a temperature of 25 ° C and a humidity of 70% RH using a Fisher Sub-Sieve Sizer Model 95 (manufactured by Fisher Scientific Co., Ltd.) for the first fired product (1 to 21) Packed in a dedicated tubular container, dried air at a constant pressure was flowed, and the specific surface area was read from the differential pressure to calculate the average particle diameter D1 according to the FSSS method. The results are shown in Table 1.

As shown in Table 1, the first calcined products (1 to 19) of Production Examples 1 to 19 had an average particle diameter D1 of 6 占 퐉 or more as measured by the FSSS method. On the other hand, the first calcined products (20, 21) of Production Examples 20 and 21 had an average particle diameter D1 of less than 6 占 퐉.

Examples 1 to 7

The molecular ratio, shown in Table 2 Ba _{1. 0} Mg _{0 . 45} Mn _{0 .} So that a composition represented by the ₅ Al ₁₀ O _{16 .95,} the first fired product _{(1), BaCO 3, MgO} , MnCO 3, and using the Al ₂ O _3, and the first fired product (1) for each amount Each raw material was mixed to obtain each second mixture. The content of the first calcined product in each of the examples shown in Table 2 was expressed as% by mass with respect to 100% by mass of the second mixture. Further, by using MgF 2 as the first flux and NaF as the second flux, the number of moles of Mg contained in the first flux and the number of moles of Mg contained in the second flux, which are contained in the second mixture containing no flux, And added to the second mixture so that the number of moles of Na contained was the number of moles shown in Table 2. [ First charging a second mixture comprising a flux and a second flux on alumina sense, and by the lid, H ₂ 3% by volume, N ₂ is 1500 ℃ from 97 reducing atmosphere in% by volume, the second heat treatment to 5 hours To obtain a fired product. The fired product was dispersed in deionized water in a polyethylene container for 30 minutes by using alumina balls as a solid dispersion medium, and then coarse particles were removed by a wet sieve using a sieve mesh of 48 mu m , 15% by mass to 20% by mass of the particles on the side of the fine particles in the fired product obtained by sediment classification were removed, and dehydration and drying were performed to obtain the second fired product &Lt; / RTI &gt;

Comparative Example 1

In Comparative Example 1, the first baked product (1) was made into an aluminate phosphor without preparing the second mixture and without conducting the second heat treatment.

Comparative Example 2

Comparative Example 2 was the same as Example 1 except that the second fired product (1) was subjected to the second heat treatment without preparing the second mixture, and the second fired product (2) of the aluminate phosphor according to Comparative Example 2 &Lt; / RTI &gt; The atomic ratio of the second calcined product of Comparative Example 2 shown in Table 2 is the same as the atomic ratio of the first calcined product (1) of Production Example 1 in Table 1.

Comparative Example 3

In Comparative Example 3, the first baked product (2) was made an aluminate phosphor without preparing the second mixture and without performing the second heat treatment.

Example 8

Example 8, the first firing by using water (2), and also using the _{BaCO 3, MgO, MnCO 3,} Al 2 O 3, shown in Table 2 Ba _{1. 0} Mg _{0 . 45} Mn _{0 . 5} Al ₁₀ O _{16 .95} , the first fired product (2) and each raw material were mixed to obtain a second mixture. The content of the first calcined product in each of the examples shown in Table 2 was expressed as% by mass with respect to 100% by mass of the second mixture. A second fired product, which was the aluminate phosphor according to Example 8, was obtained in the same manner as in Example 2 except that this second mixture was used.

Comparative Example 4

In Comparative Example 4, the first baked material (20) was used, and BaCO ₃ , MgO, MnCO ₃ , and Al ₂ O ₃ were used, and a molecule represented by Ba1.0Mg0.45Mn0.5Al10O16.95 shown in Table 2 The first fired product 20 and each raw material were mixed to obtain a second mixture. A second fired body of the aluminate phosphor according to Comparative Example 4 was obtained in the same manner as in Example 2 except that each of these second mixtures was used.

Comparative Example 5

Comparative Example 5, using the first fired product (21), and further _{BaCO 3, MgO, MnCO 3,} Ba 1 shown in Table 2 using Al ₂ O _{3. 0} Mg _{0 . 45} Mn _{0 . 5} Al ₁₀ O _{16 .95} , the first fired product (21) and each of the raw materials were mixed to obtain a second mixture. The content of the first calcined product in each of the examples shown in Table 2 was expressed as% by mass with respect to 100% by mass of the second mixture. A second fired body, which was the aluminate phosphor according to Comparative Example 5, was obtained in the same manner as in Example 2 except that each of these second mixtures was used.

Comparative Example 6

In Comparative Example 6, the first fired product (3) was an aluminate phosphor without preparing the second mixture and without performing the second heat treatment.

Example 9

Example 9, the first firing with water (3) and also using a _{BaCO 3, MgO, MnCO 3,} Al 2 O 3, shown in Table 2 Ba _{1. 0} Mg _{0 . 45} Mn _{0 . 5} Al ₁₀ O _{16 .95} , the first fired product (3) and each raw material were mixed to obtain a second mixture. The content of the first calcined product in each of the examples shown in Table 2 was expressed as% by mass with respect to 100% by mass of the second mixture. A second fired body of the aluminate phosphor according to Example 9 was obtained in the same manner as in Example 2 except that this second mixture was used.

Comparative Example 7

In Comparative Example 7, the first baked product (4) was an aluminate phosphor without preparing the second mixture and without performing the second heat treatment.

Examples 10, 11, 12

Examples 10, 11 and 12, using the first fired product (4), and further BaCO _3, MnCO _3, Ba ₁ shown in Table 2 using Al ₂ O _{3. 0} Mn _{0 . 5} Al ₁₀ O _{16 .5} , and the respective raw materials were mixed to obtain each second mixture. The content of the first calcined product in each of the examples shown in Table 2 was expressed as% by mass with respect to 100% by mass of the second mixture. Further, by using AlF _{3 as} the first flux and NaF as the second flux to the second mixture, the molar ratio of Al contained in the second mixture which does not include the first flux of AlF ₃ and the second flux of NaF , And the number of moles of Al contained in the first flux and the number of moles of Na contained in the second flux were adjusted so as to be the numbers of moles shown in Table 2. The results are shown in Table 1, Thereby obtaining a second calcined product which is a phosphate salt.

Comparative Example 8

Comparative Example 8 was the same as Example 2 except that the second fired product (4) was subjected to the second heat treatment without preparing the second mixture, and the second aluminate phosphor of Comparative Example 8 A fired product was obtained. The atomic ratio of the second calcined product of Comparative Example 8 shown in Table 2 is the same as the atomic ratio of the first calcined product of Production Example 4. [

Comparative Example 9

In Comparative Example 9, the first fired product (5) was an aluminate phosphor without preparing the second mixture and without performing the second heat treatment.

Example 13

Example 13, using the first fired product (5), and further _{BaCO 3, Eu 2 O 3,} MgO, MnCO 3, by using the Al ₂ O _3, Ba ₀ shown in Table _{2. 9} Eu _{0 . 1} Mg _{0 . 5} Mn _{0 . 5} Al ₁₀ O ₁₇ , and the respective raw materials were mixed to obtain a second mixture. The content of the first calcined product in each of the examples shown in Table 2 was expressed as% by mass with respect to 100% by mass of the second mixture. A second fired body of the aluminate phosphor according to Example 13 was obtained in the same manner as in Example 2 except that this second mixture was used.

Example 2A

In Example 2A, a second fired product, which is the aluminate phosphor according to Example 2A, was obtained in the same manner as in Example 2.

Example 14

In Example 14, the first fired product (1) obtained in Production Example 1 was dispersed in deionized water in a container made of polyethylene, dispersed for 240 minutes using alumina balls as a solid dispersion medium, , Drying, and drying were performed in this order. A fired product was obtained in the same manner as in Example 2 by using the first fired product (1) after the dispersion treatment and then subjected to post-treatment in the same manner as in Example 2 to obtain a second fired product of the aluminate phosphor according to Example 14. In Example 14, the atomic ratio of the first fired product (1), the molar ratio of the flux, and the atomic ratio of the second fired product are the same as those of the second embodiment.

Measurement of particle size and dispersion

The aluminate phosphors according to Examples 1 to 13, 2A, and 14 and Comparative Examples 1 to 9 were measured for the average particle diameter D2 in accordance with the FSSS method in the same manner as in the first calcination of each production example, The volume average particle diameter Dm2 (50% volume particle diameter) was measured by a particle size distribution measuring method. From these values, the degree of dispersion Dm2 / D2 of each example and comparative example was calculated. The results are shown in Table 2 or Table 4. Further, 10% volume particle diameter D10 and 90% volume particle diameter D90 accumulated from the small diameter side in the particle size distribution by the laser diffraction scattering type particle size distribution measurement method were measured for the aluminate phosphors according to Examples 2A and 14 And the mouth opening ratio D90 / D10 was calculated. The results are shown in Table 4.

Measurement of luminescence spectrum

The luminescent characteristics of the aluminate phosphors related to Examples 1 to 13, 2A, and 14 and Comparative Examples 1 to 9 were measured. Light having an excitation wavelength of 450 nm was irradiated to each phosphor using a quantum efficiency measuring device (Otsuka Electronics Co., Ltd., QE-2000), and the luminescence spectrum at room temperature (25 캜 5 캜) was measured. Fig. 2 shows the emission spectra of the relative emission intensity (%) relative to the wavelength for the aluminate phosphors of Example 2 and Comparative Example 1. Fig.

Luminescence peak wavelength (nm)

For the aluminate phosphors related to Examples 1 to 13 and Comparative Examples 1 to 9, the wavelength at which the luminescence spectrum became the maximum was measured as the luminescence peak wavelength (nm). The results are shown in Table 2.

Relative light emission intensity (%)

The emission spectra of the aluminate phosphors of Examples 1 to 8, 2A, and 14 and Comparative Examples 1 to 5 were compared with those of Comparative Examples 1 and 2, and the emission intensity at the emission peak wavelength of Comparative Example 1 was taken as 100% Respectively. The results are shown in Table 2 or Table 4.

Relative light emission intensities of the aluminate phosphors relating to Example 9 and Comparative Example 6 were calculated from the measured luminescence spectrum at the luminescence intensity at the luminescence peak wavelength of Comparative Example 6 as 100%. The results are shown in Table 2.

Relative light emission intensities of the aluminate phosphors of Examples 10 to 12 and Comparative Examples 7 and 8 were calculated from the measured luminescence spectrum at the luminescence intensity at the luminescence peak wavelength of Comparative Example 7 as 100%. The results are shown in Table 2.

Relative luminescence intensities of the aluminate phosphors of Example 13 and Comparative Example 9 were calculated from the measured luminescence spectrum with the luminescence intensity at the luminescence peak wavelength of Comparative Example 9 taken as 100%. The results are shown in Table 2.

SEM picture

SEM photographs of the aluminate fluorescent substance of Example 2 and the aluminate fluorescent substance of Comparative Example 1 were obtained using a scanning electron microscope (SEM). Fig. 3 is an SEM photograph of the aluminate fluorescent substance according to Example 2, and Fig. 4 is an SEM photograph of the aluminate fluorescent substance according to Comparative Example 1. Fig.

Average circle equivalent diameter Dc

SEM images of the aluminate phosphor of Example 2 and the aluminate phosphor of Comparative Example 1 were obtained at a magnification of 1000 times using a scanning electron microscope (SEM), and the SEM images were analyzed by image analysis software (WinROOF2013, Image analysis was carried out using a particle size analyzer (manufactured by Mitani Co., Ltd.), and binarization processing was performed on 20 or more phosphor particles in which the outline of each phosphor particle can be confirmed on the SEM image, except for the phosphor particles having a particle size of 1 m or less. On the SEM image, the particle diameter of the phosphor particles was set to the longest diameter of the particles. For 20 or more samples subjected to binarization, assuming that the particle shape obtained by binarization is a circle, a diameter of a positive circle equal to the area of the circle is defined as a circle-equivalent diameter. The average value Av and the standard deviation sigma of the particle diameter distribution of the circle equivalent diameters of 20 or more samples measured are compared with each other (average Av + standard deviation sigma) or more (mean value Av + standard deviation sigma) , The arithmetic average value of the circle equivalent diameters of the remaining samples (15 samples in Example 2 and 16 samples in Comparative Example 1) was defined as the average circle equivalent diameter Dc. The results are shown in Table 3. The average value Av of the circle-equivalent diameter of the aluminate phosphor according to Example 2 was 13.8 占 퐉, and the standard deviation? Was 3.95. In addition, the average value Av of the circle-equivalent diameter of the aluminate phosphor according to Comparative Example 1 was 12.2 占 퐉, and the standard deviation was 4.00.

Light emitting device

Each of the aluminate phosphors according to Examples 2A and 14 was used as a first phosphor, the second phosphor and a silicone resin were mixed and dispersed and defoamed to obtain a composition for a fluorescent member. In the composition for a fluorescent member, the compounding ratio was adjusted such that x and y were 0.22 (x = 0.26, y = 0.22) in the xy chromaticity coordinates defined by CIE 1931 of the mixed color light emitted by the light emitting device to be produced. A composition for a fluorescent member was filled on a blue light emitting LED (light emitting element) having an emission peak wavelength of 450 nm and cured to prepare a light emitting device 100 as shown in Fig.

Relative speed

The luminous fluxes of the respective light emitting devices using the respective aluminate phosphors according to Examples 2A and 14 were measured using a total luminous flux measuring device using an integrating sphere. The luminous flux of the light emitting device using the aluminate phosphor according to Example 14 was calculated as a relative luminous flux by setting the luminous flux of the light emitting device using the aluminate fluorescent substance according to Example 2A to 100%. The results are shown in Table 4.

As shown in Table 2, the aluminate phosphors according to Examples 1 to 13 were subjected to the second heat treatment on the second mixture using the first fired product having an average particle diameter D1 of 6 占 퐉 or more, whereby the first fired product Seed crystals are grown to promote the growth, whereby an aluminate phosphor having an average particle diameter D2 of 13 mu m or more by the FSSS method and having a volume average particle diameter Dm2 of 20 mu m or more by laser diffraction scattering particle size distribution measurement is obtained there was. The relative luminous intensities of the aluminate phosphors of Examples 1 to 13 were higher than those of Comparative Examples 1, 6, 7 and 9.

As shown in Examples 2 to 6, when the second mixture containing 30% by mass or more and 80% by mass or less of the first baked material having an average particle diameter D1 of 6 占 퐉 or more was used, the relative light emission intensity exceeded 110%.

On the other hand, in the aluminate phosphors according to Comparative Examples 2 and 8, since the second heat treatment was performed without preparing the second mixture and without using the flux, the crystal growth was not sufficient, The average particle diameter D2 was less than 13 占 퐉, and the volume average particle diameter Dm2 measured by the laser diffraction scattering particle size distribution measurement method was less than 20 占 퐉. The relative luminous intensity of the aluminate phosphors of Comparative Example 2 was lower than that of the aluminate phosphors of Examples 1 to 7. The relative luminous intensity of the aluminate fluorescent substance of Comparative Example 8 was lower than that of the aluminate fluorescent substance of Examples 10, 11, and 12.

The aluminate phosphors according to Example 8 used the first fired product (2) having a particle diameter smaller than that of the first fired product (1) used in Comparative Example 1, but the second fired product The crystal was grown by the heat treatment of the mixture, and both of the average particle diameter D2 and the volume average particle diameter Dm2 of the second baked product were larger than those of Comparative Example 1, and the relative light emission intensity was also increased. On the other hand, the relative luminous intensity of the aluminate phosphor of Comparative Example 3 was lower than that of Example 8 or Comparative Example 1. This is considered to be because the average particle diameter D1 of the first fired product is smaller than the average particle diameter D1 of the first fired product used as the aluminate phosphor according to Comparative Example 1. [

The aluminate phosphors of Comparative Examples 4 and 5 had lower relative emission intensity than the aluminate phosphor of Example 8 and lower relative emission intensity than the aluminate phosphor of Comparative Example 1. [ This is presumably because crystal growth was not sufficient even when the second heat treatment was performed using the second mixture containing the first fired product having an average particle diameter D1 of less than 6 占 퐉 according to the FSSS method.

As shown in Table 3, the aluminate phosphor according to Example 2 had an average circle-equivalent diameter Dc as large as 14.3 mu m. On the other hand, the aluminate phosphor according to Comparative Example 1 has an average circle-equivalent diameter Dc of less than 13 mu m. The relative luminous intensity of the aluminate fluorescent substance of Example 2 was higher than that of the aluminate fluorescent substance of Comparative Example 1.

As shown in Table 4, the dispersion degree Dm2 / D2 of the aluminum phosphate phosphor of Example 14 is 1.3. On the other hand, the aluminate phosphor according to Example 2A has a dispersion degree Dm2 / D2 of more than 1.6. The relative luminous intensity of the aluminate fluorescent substance of Example 14 was lower than that of the aluminate fluorescent substance of Example 2A, but the relative luminous flux was increased. From this result, it was found that the aluminate phosphor according to Example 14 had a dispersion degree Dm2 / D2 of 1.3, so that the dispersibility in the fluorescent member of the light emitting device 100 became good and the filling rate with the fluorescent member became high, It is presumed that the light flux extracted from the light emitting device becomes large.

As shown in Table 4, the aluminate phosphors related to Example 14 had an inlet ratio D90 / D10 of 2.5, a good degree of dispersion in the particle size distribution on the volume basis, There are fewer disparities in size, and a relatively even size. Therefore, it is presumed that the dispersibility in the fluorescent member of the light emitting device 100 is further improved, and the light flux extracted from the light emitting device becomes larger.

2, the luminescence spectrum of the aluminate phosphor according to Example 2 was similar to that of the aluminate phosphor according to Comparative Example 1 in that the luminescence peak wavelength did not change and the relative luminescence intensity It can be confirmed that it is getting higher.

As shown in the SEM photograph of Fig. 3, the aluminate fluorescent substance according to Example 2 was a plate-like crystal having at least one hexagonal hexagonal crystal structure. As shown in the SEM photograph of Fig. 4, the aluminate phosphor according to Comparative Example 1 was also a plate-like crystal having a hexagonal crystal structure and at least one side being hexagonal. The average particle diameter of the aluminate phosphor of Example 2 shown in Fig. 3 was larger than the average particle diameter of the aluminate phosphor of Comparative Example 1 shown in Fig. 4, but it was confirmed that there was no significant difference in particle shape.

Fig. 5 is an image obtained by binarizing arbitrary 20 or more phosphor particles in an SEM photograph of the aluminate phosphor according to Example 2, and Fig. 6 is a graph showing the results of binarization of an arbitrary 20 or more phosphor particles in the SEM photograph of the aluminate phosphor according to Comparative Example 1 Is an image obtained by binarizing 20 or more arbitrary phosphor particles in a photograph. In the SEM photograph of the aluminate phosphor of Example 2 of Fig. 5, the image obtained by binarizing 20 or more phosphor particles and the SEM photograph of the aluminate phosphor of Comparative Example 1 of Fig. In the image obtained by binarizing the phosphor particles, the aluminate phosphor of Example 2 shown in Fig. 5 appears to have many phosphor particles having a large particle diameter. The aluminate phosphor of Example 2 had an average circle-equivalent diameter Dc as large as 14.3 占 퐉, and the aluminate phosphor of Comparative Example 1 had an average circle-equivalent diameter Dc of less than 13 占 퐉.

The aluminate phosphors obtained according to the production method of one embodiment of the present invention have a high light emission intensity and the light emitting device using the aluminate phosphors can be used for general lighting, vehicle lighting, display, liquid crystal backlight, And the like.

10: Light emitting element
40: molded article
50: fluorescent member
71: First phosphor
72: second phosphor
100: Light emitting device.

Claims (17)

As a method for producing an aluminate phosphor,
At least one compound of at least one metal element selected from the group consisting of Ba, Sr and Ca, a compound containing Mn and a compound containing Eu, a compound containing Al, And a compound containing Mg is mixed with the first mixture to obtain a first fired product having an average particle diameter D1 of 6 占 퐉 or more as measured by the FSSS method;
At least one compound of at least one metal element selected from the group consisting of Ba, Sr and Ca, a compound containing Mn and a compound containing Eu, a compound containing Al, Is subjected to a second heat treatment to obtain a second fired product by mixing the first fired product having a content of 10% by mass or more and 90% by mass or less with a compound containing Mg as necessary &Lt; / RTI &gt; The method according to claim 1,
Wherein at least one of the first mixture and the second mixture further comprises a flux and the flux is at least one kind of metal element selected from the group consisting of K, Na, Ba, Sr, Ca, Mg, Wherein the aluminate phosphor is a compound containing an aluminate phosphor. 3. The method of claim 2,
Wherein the flux is a fluoride. The method according to claim 2 or 3,
Wherein the number of moles of the metal element contained in the flux is in the range of 0.03 or more and 0.6 or less, and the number of moles of Al contained in the first mixture containing no flux and / or the second mixture containing no flux is 10, A method for producing an aluminate phosphor. The method according to claim 2 or 3,
Wherein the flux includes two kinds of fluxes of a first flux and a second flux, and the first flux contains at least one metal element selected from the group consisting of Ba, Sr, Ca, Mg, Al and Mn And the second flux is a compound containing at least one kind of metallic element selected from K and Na. 6. The method of claim 5,
Wherein the number of moles of Al contained in the first mixture containing no flux and / or the second mixture containing no flux is 10, and the number of moles of the metal element contained in the first flux is in a range of 0.006 to 0.55. A method for producing an aluminate phosphor. 6. The method of claim 5,
Wherein when the metal element contained in the first flux is Mg or Al and the metal element contained in the second flux is K or Na, the metal element contained in the first flux and the metal element contained in the second flux Wherein the molar ratio of the aluminate phosphor is in the range of 20: 1 to 1: 5. 4. The method according to any one of claims 1 to 3,
Wherein the first baked product and / or the second baked product has a composition represented by the following formula (I).
X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I)
(In the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s and t satisfy 0.5? P? 1.0, 0.5? P + t? 1.2, 0.1? R + t? 0.7, and 0.2? Q + r? 1.0. 4. The method according to any one of claims 1 to 3,
Wherein the content of the first calcined product in the second mixture is 25 mass% or more and 80 mass% or less in the step of obtaining the second calcined product. As the aluminate fluorescent substance,
(I) having a composition represented by the following formula (I), wherein the average particle diameter D2 measured by the FSSS method is 13 占 퐉 or more and / or the volume average particle diameter Dm2 measured by the laser diffraction scattering type particle size distribution measurement method is 20 占 퐉 or more Characterized by an aluminate phosphor.
X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I)
(In the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s and t satisfy 0.5? P? 1.0, 0.5? P + t? 1.2, 0.1? R + t? 0.7, and 0.2? Q + r? 1.0. 11. The method of claim 10,
Wherein a dispersion degree Dm2 / D2 defined as a ratio of the volume average particle diameter Dm2 to the average particle diameter D2 is 1.0 or more and less than 1.6. 12. The method of claim 11,
Wherein the dispersion degree Dm2 / D2 is 1.0 or more and 1.5 or less. 13. The method according to any one of claims 10 to 12,
Wherein an inlet ratio D90 / D10 of a 90% volume particle diameter D90 to a 10% volume particle diameter D10 accumulated from a small diameter side in a particle size distribution by a laser diffraction scattering particle size distribution measurement method is 3.0 or less. An average circle equivalent diameter Dc of 13 mu m or more and a composition represented by the following formula (I).
X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I)
(In the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s and t satisfy 0.5? P? 1.0, 0.5? P + t? 1.2, 0.1? R + t? 0.7, and 0.2? Q + r? 1.0. 15. A method according to any one of claims 10 to 12,
In the formula (I), X ¹ represents Ba. 15. A method according to any one of claims 10 to 12,
Wherein q, r and s in the formula (I) satisfy 0 &lt; q? 0.7, 0.2? R? 0.7 and 9.0? S? 13.0. As a light emitting device,
17. A light emitting device comprising the aluminate fluorescent substance according to any one of claims 10 to 16 and an excitation light source having an emission peak wavelength in a range of 380 nm to 485 nm.

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