JP2005042125A - Light emitter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light emitter which has a high light-emitting efficiency and emits a slightly reddish warm-colored white light and to provide a phosphor which is used together with a blue light emitting device or the like and has a light-emitting spectrum in the range from yellow to red. <P>SOLUTION: This light emitter has a Mn-added Sr-Ca-Si-N:Eu silicon nitride phosphor 11 which absorbs a part of light from the blue light emitting device 10 having a first light-emitting spectrum, performs a wavelength conversion and emits light having a second light-emitting spectrum in the range from yellow to red. <P>COPYRIGHT: (C)2005,JPO&amp;NCIPI

Description

  The present invention relates to a light-emitting device used for illumination such as a display, a liquid crystal backlight, a fluorescent lamp, and more particularly to a phosphor used in a light-emitting device.

  The light-emitting device is small, has high power efficiency, and emits bright colors. In addition, since the light-emitting element used for the light-emitting element lamp is a semiconductor element, there is no fear of a broken ball. Further, it has excellent initial driving characteristics and is strong against vibration and repeated on / off lighting. Due to such excellent characteristics, the light emitting device is used as various light sources.

A part of the light of the light emitting element is wavelength-converted by a phosphor, and the wavelength-converted light and the light of the light emitting element that is not wavelength-converted are mixed and emitted to emit a light emission color different from that of the light of the light emitting element. Light emitting devices have been developed.
For example, in the case of a white light emitting device, the phosphor is thinly coded on the surface of the light emitting element of the light emitting source. The light emitting element is a blue light emitting element using an InGaN-based material. For the coding layer, a YAG phosphor represented by a composition formula of (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ is used.
The emission color of the white light emitting device is obtained by the principle of light color mixing. The blue light emitted from the light emitting element enters the phosphor layer, and after being repeatedly absorbed and scattered several times in the layer, is emitted to the outside. On the other hand, blue light absorbed by the phosphor serves as an excitation source and emits yellow fluorescence. This yellow light and blue light are mixed and appear as white to the human eye.

  However, a known light emitting device that emits white light has a slightly pale white light emitting device because light emission on the long wavelength side in the visible light region is difficult to obtain. In particular, there is a strong demand for warm red light emitting devices that are slightly reddish for lighting for store displays and for medical sites. In addition, since light emitting elements generally have a longer life than human light bulbs and are easy on human eyes, a white light emitting device close to the color of a light bulb is strongly demanded.

  Usually, when redness increases, the light emission characteristics of the light emitting device deteriorate. The color perceived by the human eye gives a sense of brightness to electromagnetic waves in the region of 380 nm to 780 nm. One index that represents this is the visibility characteristic. The visibility characteristic has a mountain shape, and has a peak at 550 nm. This is because when the same electromagnetic wave is incident on the wavelength range of the reddish component in the vicinity of 580 nm to 680 nm and in the vicinity of 550 nm, the wavelength range of the reddish component is felt darker. Therefore, in order to feel the same level of brightness as the green and blue regions, the red region requires high-density electromagnetic wave incidence.

  Further, conventional red light emitting phosphors are not sufficiently efficient and durable due to excitation of blue light from near ultraviolet rays, and have not yet been put into practical use.

  Accordingly, an object of the present invention is to provide a slightly reddish warm-colored white light-emitting device with good luminous efficiency. Another object of the present invention is to provide a phosphor having an emission spectrum in the yellow to red region used in combination with a blue light emitting element or the like. It is another object of the present invention to provide a phosphor with improved efficiency and durability.

  In order to solve the above problems, the present invention absorbs at least part of light having at least nitrogen and having a first emission spectrum, and has light having a second emission spectrum different from the first emission spectrum. A phosphor that emits light, wherein the phosphor includes at least one selected from the group consisting of II, Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, and C, Si, Ge, Sn, A silicon nitride having crystallinity having at least one selected from the group consisting of Ti, Zr, and Hf, and at least one activator selected from the group consisting of N and a rare earth element, and Mn. It relates to a certain phosphor.

The present invention is a phosphor that contains at least nitrogen, absorbs at least part of light having a first emission spectrum, and emits light having a second emission spectrum different from the first emission spectrum. The phosphor is L _X M _Y N _{(2 / 3X + 4 / 3Y)} : R or L _X M _Y O _Z N _{(2 / 3X + 4 / 3Y-2 / 3Z)} : R (L is Be, Mg, Ca , Sr, Ba, Zn, Cd, Hg, at least one selected from the group consisting of II, M is at least one selected from the group consisting of C, Si, Ge, Sn, Ti, Zr, Hf, IV Species, R is at least one activator selected from the group consisting of rare earth elements, X is 1 ≦ X ≦ 2, Y is 5 ≦ Y ≦ 7), and Mn is added to the composition Fluorescence, a crystalline silicon nitride On.

The present invention relates to a semiconductor light emitting device that emits light having a first emission spectrum, and light having a second emission spectrum that absorbs at least a part of the light of the first emission spectrum and is different from the first emission spectrum. A phosphor that emits, wherein the phosphor includes a first phosphor that is the silicon nitride, and Y ₃ Al ₅ O ₁₂ : Ce (a part of Y and Al, Ce, or And a second phosphor that is entirely replaceable with another element).

  The present invention relates to a semiconductor light emitting device that emits light having a first emission spectrum, and light having a second emission spectrum that absorbs at least a part of the light of the first emission spectrum and is different from the first emission spectrum. A phosphor that emits light, wherein the phosphor is a first phosphor that is the silicon nitride, and a second phosphor that emits light on a shorter wavelength side than the first phosphor. And a light emitting device containing the phosphor.

  The present invention relates to a semiconductor light emitting device that emits light having a first emission spectrum, and light having a second emission spectrum that absorbs at least a part of the light of the first emission spectrum and is different from the first emission spectrum. A phosphor that emits light, wherein the phosphor is a first phosphor that is the silicon nitride, and a second phosphor that emits blue, green, or yellow light. And a light emitting device containing the same.

  The light emitting device has a special color rendering index R9 of 60 or more.

  The light-emitting device has a semiconductor light-emitting element having a light emission peak wavelength at 360 nm to 550 nm, and emits light in a light bulb color.

  The present invention is a phosphor that contains at least nitrogen, absorbs at least part of light having a first emission spectrum, and emits light having a second emission spectrum different from the first emission spectrum. The phosphor is at least one selected from the group consisting of valences of Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, and IV of C, Si, Ge, Sn, Ti, Zr, and Hf. The present invention relates to a phosphor that is a crystalline silicon nitride having at least one selected from the group consisting of valence, at least one activator selected from the group consisting of N and a rare earth element, and Mn. Thereby, a phosphor having the second emission spectrum on the long wavelength side can be provided. In this principle, when the phosphor is irradiated with light having a first emission spectrum near 460 nm, the wavelength of the first emission spectrum is converted, and the second emission spectrum is provided on the long wavelength side near 580 nm to 700 nm. Because.

  When using a silicon nitride phosphor to which Mn or a Mn compound is added in the manufacturing process, luminous efficiency such as emission luminance, quantum efficiency, energy efficiency, etc. is improved compared to a silicon nitride phosphor to which Mn is not added. Was planned. This is probably because Mn or a Mn compound promotes the diffusion of the activator, increases the particle size, and improves the crystallinity. Further, it is considered that Mn worked as a sensitizer and increased the light emission intensity of the activator. Fluorescence sensitization refers to co-activation of a sensitizer that serves as an energy donor for the purpose of increasing the emission intensity using an energy transfer function.

  The first emission spectrum is light from a light emitting element, a light emitting element lamp or the like having a peak wavelength on the short wavelength side of 360 nm to 495 nm. A blue light emitting element having a peak wavelength mainly in the vicinity of 440 nm to 480 nm is preferable. On the other hand, the second emission spectrum has a second emission spectrum different from the first emission spectrum by absorbing at least a part of the light of the first emission spectrum and performing wavelength conversion. At least a part of the second emission spectrum preferably has a peak wavelength in the vicinity of 560 nm to 700 nm. The phosphor according to the present invention has a peak wavelength in the vicinity of 600 nm to 680 nm.

  In the above-mentioned and later-described silicon nitride phosphor, Mn or a Mn compound is added in the production process, but Mn is scattered in the firing step, and the composition of the silicon nitride phosphor that is the final product is In some cases, Mn contains a trace amount of Mn from the initial addition amount. Therefore, in the composition of the phosphor of silicon nitride, which is the final product, only a smaller amount than the initial blending amount is included in the composition.

The present invention is a phosphor that contains at least nitrogen, absorbs at least part of light having a first emission spectrum, and emits light having a second emission spectrum different from the first emission spectrum. The phosphor is L _X M _Y N _{(2 / 3X + 4 / 3Y)} : R or L _X M _Y O _Z N _{(2 / 3X + 4 / 3Y-2 / 3Z)} : R (L is Be, Mg, Ca , Sr, Ba, Zn, Cd, Hg, at least one selected from the group consisting of II, M is at least one selected from the group consisting of C, Si, Ge, Sn, Ti, Zr, Hf, IV Species, R is at least one activator selected from the group consisting of rare earth elements, X is 1 ≦ X ≦ 2, Y is 5 ≦ Y ≦ 7), and Mn is added to the composition Fluorescence, a crystalline silicon nitride On. Thereby, a phosphor having the second emission spectrum on the long wavelength side can be provided. In this principle, when the phosphor is irradiated with light having a first emission spectrum near 460 nm, the wavelength of the first emission spectrum is converted, and the second emission spectrum is provided on the long wavelength side near 580 nm to 700 nm. Because.

The present invention relates to a semiconductor light emitting device that emits light having a first emission spectrum, and light having a second emission spectrum that absorbs at least a part of the light of the first emission spectrum and is different from the first emission spectrum. A phosphor that emits, wherein the phosphor includes a first phosphor that is the silicon nitride, and Y ₃ Al ₅ O ₁₂ : Ce (a part of Y and Al, Ce, or And a second phosphor that is entirely replaceable with another element). As a result, a light emitting device having excellent color rendering can be provided.

  The present invention relates to a semiconductor light emitting device that emits light having a first emission spectrum, and light having a second emission spectrum that absorbs at least a part of the light of the first emission spectrum and is different from the first emission spectrum. A phosphor that emits light, wherein the phosphor is a first phosphor that is the silicon nitride, and a second phosphor that emits light on a shorter wavelength side than the first phosphor. And a light emitting device containing the phosphor. Thereby, a desired luminescent color can be realized.

  The present invention relates to a semiconductor light emitting device that emits light having a first emission spectrum, and light having a second emission spectrum that absorbs at least a part of the light of the first emission spectrum and is different from the first emission spectrum. A phosphor that emits light, wherein the phosphor is a first phosphor that is the silicon nitride, and a second phosphor that emits blue, green, or yellow light. And a light emitting device containing the same. Thereby, a desired emission spectrum can be obtained.

  The light emitting device has a special color rendering index R9 of 60 or more.

  The light-emitting device has a semiconductor light-emitting element having a light emission peak wavelength at 360 nm to 550 nm, and emits light in a light bulb color.

  A phosphor having a wavelength converted at least part of the first emission spectrum and having at least one second emission spectrum in a region different from the first emission spectrum, wherein the phosphor is doped with Mn The present invention relates to a phosphor that is Sr—Ca—Si—N: Eu-based silicon nitride. Thereby, a phosphor having the second emission spectrum on the long wavelength side can be provided. In this principle, when the phosphor is irradiated with light having a first emission spectrum near 460 nm, the wavelength of the first emission spectrum is converted, and the second emission spectrum is provided on the long wavelength side near 580 nm to 700 nm. Because.

When a phosphor of Sr—Ca—Si—N: Eu-based silicon nitride to which Mn or a Mn compound is added is used in the manufacturing process, Sr—Ca—Si—N: Eu-based silicon nitride to which Mn is not added Luminous efficiency such as luminous brightness, quantum efficiency, energy efficiency, and the like was improved as compared with the above phosphors. This is considered to be because Mn or a Mn compound promotes diffusion of Eu ²⁺ as an activator, increases the particle size, and improves the crystallinity. In addition, in the phosphor using Eu ²⁺ as an activator, it is considered that Mn worked as a sensitizer and intended to increase the emission intensity of the activator Eu ²⁺ . Fluorescence sensitization refers to co-activation of a sensitizer that serves as an energy donor for the purpose of increasing the emission intensity using an energy transfer function.

  The first emission spectrum is light from a light emitting element, a light emitting element lamp, or the like having an emission spectrum on the short wavelength side of 360 nm to 495 nm. A blue light emitting element mainly having an emission spectrum in the vicinity of 440 nm to 480 nm is preferable. On the other hand, the second emission spectrum wavelength-converts at least part of the first emission spectrum and has one or more emission spectra in a region different from the first emission spectrum. At least a part of the second emission spectrum preferably has a peak wavelength in the vicinity of 560 nm to 700 nm. The phosphor according to the present invention has a peak wavelength in the vicinity of 600 nm to 680 nm.

  In the above-mentioned and later-described silicon nitride phosphor, Mn or a Mn compound is added in the production process, but Mn is scattered in the firing step, and the composition of the silicon nitride phosphor that is the final product is In some cases, Mn contains a trace amount of Mn from the initial addition amount. Therefore, in the composition of the phosphor of silicon nitride, which is the final product, only a smaller amount than the initial blending amount is included in the composition.

A phosphor having a wavelength converted at least part of the first emission spectrum and having at least one second emission spectrum in a region different from the first emission spectrum, wherein the phosphor is doped with Mn The present invention relates to a phosphor that is Sr—Si—N: Eu-based silicon nitride. By adding Mn to the Sr—Si—N: Eu-based silicon nitride in the manufacturing process, the luminous efficiency can be improved as compared with the case where Mn is not added. The effect of Mn on Sr—Si—N: Eu-based silicon nitride is the same as described above, and Mn promotes diffusion of Eu ²⁺ as an activator, increases the particle size, and improves crystallinity. This is probably because In the phosphor using Eu ²⁺ as an activator, it is considered that Mn worked as a sensitizer and increased the emission intensity of the activator Eu ²⁺ . The phosphor of Sr—Si—N: Eu-based silicon nitride according to the present invention has a composition and emission spectrum different from those of the phosphor of Sr—Ca—Si—N: Eu-based silicon nitride described above, It has a peak wavelength in the vicinity of 630 nm.

  A phosphor having a wavelength converted at least part of the first emission spectrum and having at least one second emission spectrum in a region different from the first emission spectrum, wherein the phosphor is doped with Mn It is related with the fluorescent substance characterized by being Ca-Si-N: Eu type | system | group silicon nitride. The effect when Mn is added is the same as described above. However, Ca—Si—N: Eu-based silicon nitride to which Mn is added has a peak wavelength in the vicinity of 600 nm to 620 nm.

Mn added to the above-mentioned silicon nitride phosphor is usually added as an oxide such as MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , MnOOH, or oxide hydroxide, but is not limited thereto. Instead, it may be Mn metal, Mn nitride, imide, amide, or other inorganic salts, or may be contained in other raw materials in advance. The silicon nitride contains O in its composition. It is considered that O is introduced from various Mn oxides as raw materials or promotes the effects of Eu diffusion, grain growth, and crystallinity improvement by Mn of the present invention. In other words, the same effect can be obtained by adding Mn even if the Mn compound is changed to metal, nitride, or oxide, but the effect when using an oxide is rather great. As a result, a silicon nitride composition containing a trace amount of O is produced. Accordingly, the basic constituent elements are Sr—Ca—Si—O—N: Eu, Sr—Si—O—N: Eu, and Ca—Si—O—N: Eu. As a result, even when an Mn compound that does not contain oxygen is used, O is introduced by other raw materials such as Eu ₂ O ₃ , the atmosphere, etc., and the above problem can be solved without using a compound containing O. can be solved.

  The content of O is preferably 3% by weight or less with respect to the total composition amount. This is because the luminous efficiency can be improved.

The silicon nitride preferably contains at least one selected from the group consisting of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni. By containing at least component constituent elements such as Mn, Mg, and B in the silicon nitride, it is possible to improve luminous efficiency such as luminous luminance and quantum efficiency. The reason for this is not clear, but it is considered that the inclusion of a component constituent element such as Mn or B in the basic constituent element makes the particle size of the powder uniform and large, and the crystallinity is remarkably improved. By improving the crystallinity, the wavelength of the first emission spectrum can be converted with high efficiency, and the phosphor having the second emission spectrum with good emission efficiency can be obtained. Further, the afterglow characteristics of the phosphor can be arbitrarily adjusted. In a display device such as a display or a PDP in which display is performed continuously and repeatedly, afterglow characteristics become a problem. Therefore, afterglow can be suppressed by adding a small amount of B, Mg, Cr, Ni, Al, or the like to the basic constituent elements of the phosphor. Thereby, the phosphor according to the present invention can be used in a display device such as a display. In addition, additives such as Mn and B do not deteriorate the light emission characteristics even when an oxide such as MnO ₂ , Mn ₂ O ₃ , Mn ₃ O _4, or H ₃ BO ₃ is added. As such, O may also play an important role in the diffusion process. Thus, the inclusion of component constituent elements such as Mn, Mg, and B in the silicon nitride changes the particle size, crystallinity, and energy transfer path of the phosphor, thereby changing absorption, reflection, and scattering, and light emission. This is because it greatly affects the light emission characteristics of the light emitting device such as light extraction and afterglow.

  In the Sr—Ca—Si—N: Eu-based silicon nitride, the molar ratio of Sr and Ca is preferably Sr: Ca = 1 to 9: 9 to 1. In particular, in the Sr—Ca—Si—N: Eu-based silicon nitride, the molar ratio of Sr and Ca is preferably Sr: Ca = 1: 1. By changing the molar ratio of Sr and Ca, the second emission spectrum can be shifted to the longer wavelength side. In Table 1 described later, the phosphors having the composition of Sr: Ca = 9: 1 and Sr: Ca = 1: 9 have peak wavelengths of 624 nm and 609 nm, whereas Sr: Ca = 7: 3 and Sr. : Ca = 6: 4 and Sr: Ca = 3: 7, Sr: Ca = 4: 6, and when the molar ratio of Sr and Ca is gradually changed, the peak wavelengths are 639 nm, 643 nm, 636 nm, and 642 nm as long wavelengths The peak wavelength can be shifted to the side. Thus, a phosphor having a peak wavelength on the longer wavelength side can be produced. Furthermore, when the molar ratio of Sr and Ca is changed, when Sr: Ca = 1: 1, a phosphor having a peak wavelength of 644 nm and the peak wavelength on the longest wavelength side can be manufactured. In addition, the luminance of light emission can be improved by changing the molar ratio of Sr and Ca. In Table 1, the light emission characteristic when Sr: Ca = 9: 1 is 100%. When the molar amount of Ca is increased with respect to Sr, the emission luminance is improved by 170.3% and 70.3% when Sr: Ca = 1: 9. Also, the quantum efficiency can be improved by changing the molar ratio of Sr and Ca. In Table 1, the quantum efficiency, which was 100% when Sr: Ca = 9: 1, is 167.7% when Sr: Ca = 5: 5, and the quantum efficiency is improved. Thus, the luminous efficiency can be improved by changing the molar ratio of Sr and Ca.

  It is preferable that the compounding quantity of Eu of the said phosphor is 0.003-0.5 mol with respect to corresponding Sr-Ca, Sr, and Ca. In particular, the Eu content of the phosphor is preferably 0.005 to 0.1 mol with respect to the corresponding Sr—Ca, Sr, and Ca. By changing the amount of Eu, the peak wavelength can be shifted to the long wavelength side. In addition, light emission efficiency such as light emission luminance and quantum efficiency can be improved. Tables 2 to 4 to be described later show test results obtained by changing the amount of Eu contained in silicon nitride of Sr—Ca—Si—N: Eu. In Table 2, for example, in Sr: Ca = 7: 3, when Eu is 0.005 mol with respect to Sr—Ca, the peak wavelength is 624 nm, the emission luminance is 100%, and the quantum efficiency is 100%. When Eu is 0.03 mol, the peak wavelength is 637 nm, the emission luminance is 139.5%, the quantum efficiency is 199.2%, and the emission efficiency is very good.

  The amount of Mn added to the phosphor is preferably 0.001 to 0.3 mol with respect to the corresponding Sr—Ca, Sr, and Ca. In particular, the amount of Mn added to the phosphor is preferably 0.0025 to 0.03 mol with respect to the corresponding Sr—Ca, Sr, and Ca. By adding Mn to the phosphor of silicon nitride during the raw material or the manufacturing process, it is possible to improve the light emission efficiency such as light emission luminance, energy efficiency, and quantum efficiency. Tables 5 to 9, which will be described later, show test results obtained by changing the amount of Mn added in the Ca—Si—N: Eu silicon nitride. In Tables 5 to 9, for example, silicon nitride added with 0.015 mol of Mn with respect to Ca, assuming that the emission luminance is 100% and the quantum efficiency is 100% with reference to a phosphor of silicon nitride without addition of Mn. The Ride phosphor has an emission luminance of 115.3% and a quantum efficiency of 117.4%. In this way, it is possible to improve light emission efficiency such as light emission luminance and quantum efficiency.

  As the phosphor, it is preferable to use a phosphor comprising a combination of any one of claims 1 and 2, claims 1 and 3, and claims 1 to 3. For example, the phosphors according to claims 1 and 2 are phosphors in which a phosphor of Sr—Ca—Si—N: Eu-based silicon nitride and a phosphor of Sr—Si—N: Eu-based silicon nitride are mixed. Say. For example, a phosphor of Sr—Ca—Si—N: Eu silicon nitride has an emission spectrum near 650 nm, whereas a phosphor of Sr—Si—N: Eu silicon nitride emits light near 620 nm. Has a spectrum. This is because a phosphor having a peak wavelength at a desired position in the wavelength range of 620 nm to 650 nm can be produced by mixing a desired amount of this. Here, the present invention is not limited to the above combinations, but a phosphor obtained by mixing a phosphor of Sr—Ca—Si—N: Eu-based silicon nitride and a phosphor of Ca—Si—N: Eu-based silicon nitride, Sr—Ca— A phosphor in which a phosphor of Si-N: Eu-based silicon nitride, a phosphor of Sr-Si-N: Eu-based silicon nitride and a phosphor of Ca-Si-N: Eu-based silicon nitride are mixed is also manufactured. can do. Even with these combinations, a phosphor having a peak wavelength at a desired position in the wavelength range of 600 nm to 680 nm can be produced.

  The phosphor is preferably a phosphor having an average particle diameter of 3 μm or more. The phosphors of Sr—Ca—Si—N: Eu, Sr—Si—N: Eu, and Ca—Si—N: Eu silicon nitride to which Mn is not added have an average particle size of about 1 to 2 μm. However, the silicon nitride to which Mn is added has an average particle size of 3 μm or more. Due to the difference in particle size, there is an advantage that if the particle size is large, the light emission luminance is improved and the light extraction efficiency is increased.

  The phosphor preferably has a residual amount of Mn of 5000 ppm or less. This is because the above effect can be obtained by adding Mn to the phosphor. However, since Mn is scattered during firing, the amount of Mn added to the raw material is different from the amount of Mn in the composition after production.

  A light emitting device having a first emission spectrum, and a fluorescence having at least a part of the first emission spectrum converted in wavelength and having at least one second emission spectrum in a region different from the first emission spectrum. A light emitting device having at least a phosphor, wherein the phosphor uses the phosphor according to the present invention. By using a blue light emitting device having a first emission spectrum in the vicinity of 440 nm to 480 nm, converting the wavelength of the first emission spectrum, and using the phosphor according to the present invention having a second emission spectrum of 600 nm to 660 nm. Thus, it is possible to provide a light-emitting device that mixes blue light emitted from a blue light-emitting element and yellow-red light wavelength-converted by a phosphor to emit warm red light that is slightly reddish.

The phosphors include yttrium / aluminum oxide phosphors activated with cerium, yttrium / gadolinium / aluminum oxide phosphors activated with cerium, and yttrium / gallium / aluminum oxide phosphors activated with cerium. It is preferable that the body is contained. An example of the yttrium-aluminum oxide phosphor activated with cerium is Y ₃ Al ₅ O ₁₂ : Ce. An example of the yttrium-gadolinium-aluminum oxide phosphor activated with cerium is (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce. An example of the yttrium gallium aluminum oxide phosphor activated with cerium is Y ₃ (Al _0.8 Ga _0.2 ) ₅ O ₁₂ : Ce. By combining the phosphor according to the present invention and the yttrium-aluminum oxide phosphor activated with cerium with the blue light-emitting element, a light-emitting device emitting desired white light can be provided. The light emitting device composed of the combination of the blue light emitting element and the yttrium aluminum oxide phosphor activated with cerium has a slightly pale white color and lacks a warm color. By containing the body, it is possible to supplement warm colors and to provide white light emitting devices of various colors by appropriately changing the blending amount of the phosphor.

  As described above, the light-emitting device according to the present invention has the technical significance that it can provide a slightly reddish warm-colored white light-emitting device with good luminous efficiency. Further, it has a technical significance that a phosphor having an emission spectrum in a yellow to red region used in combination with a blue light emitting element or the like can be provided. Furthermore, it has a very important technical significance that a phosphor with improved efficiency and durability can be provided.

  Hereinafter, the phosphor and the method for producing the same according to the present invention will be described using embodiments and examples. However, the present invention is not limited to this embodiment and example.

  A light emitting device according to the present invention converts a light emitting element having a first emission spectrum and at least a part of the first emission spectrum, and at least a second emission spectrum in a region different from the first emission spectrum. And a phosphor having at least one phosphor. An example of a specific light-emitting device will be described with reference to FIG. FIG. 1 is a diagram showing a light emitting device according to the present invention.

  The light emitting device includes a semiconductor layer 2 stacked on the sapphire substrate 1, a lead frame 13 conductively connected by conductive wires 14 extending from positive and negative electrodes 3 formed on the semiconductor layer 2, and the sapphire substrate 1. And the phosphor 11 and the coating member 12 provided in the cup of the lead frame 13a so as to cover the outer periphery of the light emitting element 10 composed of the semiconductor layer 2 and the outer peripheral surfaces of the phosphor 11 and the lead frame 13 And a mold member 15 for covering.

A semiconductor layer 2 is formed on the sapphire substrate 1, and positive and negative electrodes 3 are formed on the same plane side of the semiconductor layer 2. The semiconductor layer 2 is provided with a light emitting layer (not shown), and an emission peak output from the light emitting layer has an emission spectrum near 460 nm in the blue region.
The light-emitting element 10 is set on a die bonder, face-up to a lead frame 13a provided with a cup, and die-bonded (adhered). After die bonding, the lead frame 13 is transferred to a wire bonder, the negative electrode 3 of the light emitting element is wire bonded to the lead frame 13a provided with a cup with a gold wire, and the positive electrode 3 is wire bonded to the other lead frame 13b. .
Next, it transfers to a molding apparatus and inject | pours the fluorescent substance 11 and the coating member 12 in the cup of the lead frame 13 with the dispenser of a molding apparatus. The phosphor 11 and the coating member 12 are uniformly mixed in a desired ratio in advance.
After the phosphor 11 is injected, the lead frame 13 is immersed in a mold mold in which a mold member 15 is previously injected, and then the mold is removed to cure the resin, and a bullet-type light emitting device as shown in FIG. To do.

  Hereinafter, constituent members of the light emitting device according to the present invention will be described in detail.

(Phosphor)
The phosphor according to the present invention includes Sr—Ca—Si—N: Eu, Ca—Si—N: Eu, Sr—Si—N: Eu, Sr—Ca—Si—O—N: Eu to which Mn is added. Ca—Si—O—N: Eu, Sr—Si—O—N: Eu-based silicon nitride. The basic constituent elements of this phosphor are represented by the general formula L _X Si _Y N _{(2 / 3X + 4 / 3Y)} : Eu or L _X Si _Y O _Z N _{(2 / 3X + 4 / 3Y-2 / 3Z)} : Eu (L is Sr, Ca, or any one of Sr and Ca.) In the general formula, X and Y are preferably X = 2, Y = 5, or X = 1, Y = 7, but any can be used. Specifically, the basic constituent elements, Mn is added _{(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-X Si 7 N} 10: Eu, SrSi 7 N 10: Eu, CaSi 7 N 10: it is preferable to use a phosphor represented by Eu, during the composition of the phosphor, Mg, At least one selected from the group consisting of Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni may be contained. However, the present invention is not limited to this embodiment and examples.

  L is any one of Sr, Ca, Sr and Ca. The mixing ratio of Sr and Ca can be changed as desired.

  By using Si for the composition of the phosphor, it is possible to provide an inexpensive phosphor with good crystallinity.

Europium Eu, which is a rare earth element, is used for the emission center. Europium mainly has bivalent and trivalent energy levels. The phosphor of the present invention uses Eu ²⁺ as an activator with respect to the base alkaline earth metal silicon nitride. Eu ²⁺ is easily oxidized and is commercially available with a trivalent Eu ₂ O ₃ composition. However, in commercially available Eu ₂ O ₃ , O is greatly involved and it is difficult to obtain a good phosphor. Therefore, it is preferable to use a material obtained by removing O from Eu ₂ O ₃ out of the system. For example, it is preferable to use europium alone or europium nitride. However, this is not the case when Mn is added.

Mn as an additive promotes diffusion of Eu ²⁺ and improves luminous efficiency such as luminous luminance, energy efficiency, and quantum efficiency. Mn is contained in the raw material, or Mn alone or a Mn compound is contained in the manufacturing process and fired together with the raw material. However, Mn is not contained in the basic constituent elements after firing, or even if contained, only a small amount remains compared to the initial content. This is probably because Mn was scattered in the firing step.

  The phosphor has at least one selected from the group consisting of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr, O and Ni in the basic constituent element or together with the basic constituent element. Contains the above. These elements have actions such as increasing the particle diameter and increasing the luminance of light emission. Further, B, Al, Mg, Cr, and Ni have an effect that afterglow can be suppressed. Usually, a phosphor to which no additive such as B, Mg, Cr or the like is added has a time required for 1/10 of the afterglow compared to a phosphor to which an additive is added. It can be shortened to the extent.

  The phosphor 11 according to the present invention absorbs part of the blue light emitted by the light emitting element 10 and emits light in the yellow to red region. By using the phosphor 11 in the light emitting device having the above-described configuration, a light emitting device that emits warm white light by mixing the blue light emitted from the light emitting element 10 and the red light of the phosphor is provided.

  In particular, the phosphor 11 preferably contains an yttrium-aluminum oxide phosphor activated with cerium in addition to the phosphor according to the present invention. This is because it can be adjusted to a desired chromaticity by containing the yttrium aluminum oxide phosphor. The yttrium / aluminum oxide phosphor activated with cerium absorbs part of the blue light emitted by the light emitting element 10 and emits light in the yellow region. Here, the blue light emitted by the light emitting element 10 and the yellow light of the yttrium / aluminum oxide fluorescent material emit light blue-white by mixing colors. Therefore, by combining the phosphor 11 in which the yttrium aluminum oxide phosphor and the phosphor are mixed together with a translucent coating member and the blue light emitted from the light emitting element 10, a warm color system is obtained. A white light-emitting device can be provided. This warm white light emitting device has an average color rendering index Ra of 75 to 95 and a color temperature of 2000K to 8000K. Particularly preferred is a white light emitting device in which the average color rendering index Ra and the color temperature are located on the locus of black body radiation in the chromaticity diagram. However, in order to provide a light emitting device having a desired color temperature and average color rendering index, the blending amounts of the yttrium / aluminum oxide phosphor and the phosphor can be appropriately changed. This warm white light-emitting device aims to improve the special color rendering index R9. A conventional light emitting device that emits white light in a combination of a blue light emitting element and an yttrium aluminum oxide fluorescent material activated with cerium has a special color rendering index R9 of almost 0 and lacks a red component. Therefore, increasing the special color rendering index R9 has been a problem to be solved. However, by including the phosphor according to the present invention in the yttrium aluminum oxide phosphor, the special color rendering index R9 is increased to 60 to 70. be able to.

(Phosphor production method)
Next, with reference to FIG. 2, the phosphor according to the present invention: is described a method of manufacturing the _{((Sr X Ca 1-X} ) 2 Si 5 N 8 Eu), but is not limited to this manufacturing method. The phosphor contains Mn and O.

Raw materials Sr and Ca are pulverized (P1). The raw materials Sr and Ca are preferably used alone, but compounds such as imide compounds and amide compounds can also be used. The raw materials Sr and Ca may contain B, Al, Cu, Mg, Mn, Al ₂ O ₃ or the like. The raw materials Sr and Ca are pulverized in a glove box in an argon atmosphere. Sr and Ca obtained by pulverization preferably have an average particle diameter of about 0.1 μm to 15 μm, but are not limited to this range. The purity of Sr and Ca is preferably 2N or higher, but is not limited thereto. In order to improve the mixed state, at least one of the metal Ca, the metal Sr, and the metal Eu can be alloyed, nitrided, pulverized, and used as a raw material.

The raw material Si is pulverized (P2). The raw material Si is preferably a simple substance, but a nitride compound, an imide compound, an amide compound, or the like can also be used. For example, Si ₃ N ₄ , Si (NH ₂ ) ₂ , Mg ₂ Si, or the like. The purity of the raw material Si is preferably 3N or more, but Al ₂ O ₃ , Mg, metal borides (Co ₃ B, Ni ₃ B, CrB), manganese oxide, H ₃ BO ₃ , B ₂ O ₃ , Compounds such as Cu ₂ O and CuO may be contained. Si is also pulverized in a glove box in an argon atmosphere or a nitrogen atmosphere in the same manner as the raw materials Sr and Ca. The average particle size of the Si compound is preferably about 0.1 μm to 15 μm.

  Next, the raw materials Sr and Ca are nitrided in a nitrogen atmosphere (P3). This reaction formula is shown in Chemical Formula 1.

Ｓｒ、Ｃａを、窒素雰囲気中、６００℃〜９００℃、約５時間、窒化する。Ｓｒ、Ｃａは、混合して窒化しても良いし、それぞれ個々に窒化しても良い。これにより、Ｓｒ、Ｃａの窒化物を得ることができる。Ｓｒ、Ｃａの窒化物は、高純度のものが好ましいが、市販のものも使用することができる。

Sr and Ca are nitrided in a nitrogen atmosphere at 600 to 900 ° C. for about 5 hours. Sr and Ca may be mixed and nitrided, or may be individually nitrided. Thereby, a nitride of Sr and Ca can be obtained. Sr and Ca nitrides are preferably of high purity, but commercially available ones can also be used.

  The raw material Si is nitrided in a nitrogen atmosphere (P4). This reaction formula is shown in Chemical Formula 2.

ケイ素Ｓｉも、窒素雰囲気中、８００℃〜１２００℃、約５時間、窒化する。これにより、窒化ケイ素を得る。本発明で使用する窒化ケイ素は、高純度のものが好ましいが、市販のものも使用することができる。

Silicon Si is also nitrided in a nitrogen atmosphere at 800 ° C. to 1200 ° C. for about 5 hours. Thereby, silicon nitride is obtained. The silicon nitride used in the present invention is preferably highly pure, but commercially available ones can also be used.

  Sr, Ca or nitride of Sr-Ca is pulverized (P5). Sr, Ca, and Sr—Ca nitrides are pulverized in a glove box in an argon atmosphere or a nitrogen atmosphere.

  Similarly, Si nitride is pulverized (P6).

Similarly, Eu compound Eu ₂ O ₃ is pulverized (P7). Europium oxide is used as the Eu compound, but metal europium, europium nitride, and the like can also be used. In addition, as the raw material Z, an imide compound or an amide compound can be used. Europium oxide is preferably highly purified, but commercially available products can also be used. The average particle size of the alkaline earth metal nitride, silicon nitride and europium oxide after pulverization is preferably about 0.1 μm to 15 μm.

The raw material may contain at least one selected from the group consisting of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr, O, and Ni. Further, the above elements such as Mg, Zn, and B can be mixed by adjusting the blending amount in the following mixing step (P8). These compounds can be added alone to the raw material, but are usually added in the form of compounds. Such compounds include H ₃ BO ₃ , Cu ₂ O ₃ , MgCl ₂ , MgO · CaO, Al ₂ O ₃ , metal borides (CrB, Mg ₃ B ₂ , AlB ₂ , MnB), B ₂ O ₃ , Cu ₂ O, CuO, and the like.

After the pulverization, Sr, Ca, Sr—Ca nitride, Si nitride, and Eu compound Eu ₂ O ₃ are mixed, and Mn is added (P8). Since these mixtures are easily oxidized, they are mixed in a glove box in an Ar atmosphere or a nitrogen atmosphere.

Finally, a mixture of Sr, Ca, Sr—Ca nitride, Si nitride, and Eu compound Eu ₂ O ₃ is fired in an ammonia atmosphere (P9). The phosphor represented by (Sr _X Ca _1-X ) ₂ Si ₅ N ₈ : Eu to which Mn is added can be obtained by firing (P10). The reaction formula of basic constituent elements by this firing is shown in Chemical Formula 3.

ただし、各原料の配合比率を変更することにより、目的とする蛍光体の組成を変更することができる。

However, the composition of the target phosphor can be changed by changing the blending ratio of each raw material.

For firing, a tubular furnace, a small furnace, a high-frequency furnace, a metal furnace, or the like can be used. The firing temperature can be in the range of 1200 ° C to 1700 ° C, but a firing temperature of 1400 ° C to 1700 ° C is preferred. For firing, it is preferable to use one-stage firing in which the temperature is gradually raised and firing is performed at 1200 to 1500 ° C. for several hours. However, the first-stage firing is performed at 800 to 1000 ° C. and heated gradually. Two-stage baking (multi-stage baking) in which the second baking is performed at 1200 to 1500 ° C. can also be used. The raw material of the phosphor 11 is preferably fired using a crucible or boat made of boron nitride (BN). Besides the crucible made of boron nitride, a crucible made of alumina (Al ₂ O ₃ ) can also be used.

  By using the above manufacturing method, it is possible to obtain a target phosphor.

(Light emitting element)
The light emitting element 10 is preferably a group III nitride compound light emitting element. The light emitting element 10 includes, for example, an n-type GaN layer in which Si is undoped, an n-type contact layer made of n-type GaN doped with Si, an undoped GaN layer, and a multiple quantum well structure on a sapphire substrate 1 via a GaN buffer layer. Luminescent layer (GaN barrier layer / InGaN well layer quantum well structure), Mg-doped p-type GaN p-type GaN cladding layer, Mg-doped p-type GaN p-type contact layer Are sequentially stacked, and electrodes are formed as follows. However, a light emitting element 10 different from this configuration can also be used.

  The p ohmic electrode is formed on almost the entire surface of the p-type contact layer, and the p pad electrode 3 is formed on a part of the p ohmic electrode.

  The n-electrode is formed in the exposed portion by removing the undoped GaN layer from the p-type contact layer by etching to expose a part of the n-type contact layer.

  In the present embodiment, the light emitting layer having a multiple quantum well structure is used. However, the present invention is not limited to this, and for example, a single quantum well structure using InGaN may be used. GaN doped with Zn may be used.

  The light emitting layer of the light emitting element 10 can change the main light emission peak in the range of 420 nm to 490 nm by changing the In content. The emission wavelength is not limited to the above range, and those having an emission wavelength of 360 nm to 550 nm can be used.

(Coating material)
The coating member 12 (light transmissive material) is provided in the cup of the lead frame 13 and is used by mixing with the phosphor 11 that converts the light emission of the light emitting element 10. Specific materials for the coating member 12 include transparent resins, silica sol, glass, inorganic binders, and the like that are excellent in temperature characteristics and weather resistance, such as epoxy resins, urea resins, and silicone resins. In addition to the phosphor 11, a diffusing agent, barium titanate, titanium oxide, aluminum oxide, or the like may be included. Moreover, you may contain a light stabilizer and a coloring agent.

(Lead frame)
The lead frame 13 includes a mount lead 13a and an inner lead 13b.

  The mount lead 13a is for placing the light emitting element 10 thereon. The upper portion of the mount lead 13a has a cup shape, and the light emitting element 10 is die-bonded in the cup, and the outer peripheral surface of the light emitting element 10 is covered with the phosphor 11 and the coating member 12 inside the cup. . A plurality of light emitting elements 10 can be arranged in the cup, and the mount lead 13 a can be used as a common electrode of the light emitting elements 10. In this case, sufficient electrical conductivity and connectivity with the conductive wire 14 are required. Die bonding (adhesion) between the light emitting element 10 and the cup of the mount lead 13a can be performed with a thermosetting resin or the like. Examples of the thermosetting resin include an epoxy resin, an acrylic resin, and an imide resin. In addition, Ag paste, carbon paste, metal bump, or the like can be used for die-bonding and electrical connection with the mount lead 13a by the face-down light emitting element 10 or the like. An inorganic binder can also be used.

  The inner lead 13b is intended to be electrically connected to the conductive wire 14 extending from the electrode 3 of the light emitting element 10 disposed on the mount lead 13a. The inner lead 13b is preferably disposed at a position away from the mount lead 13a in order to avoid a short circuit due to electrical contact with the mount lead 13a. In the case where the plurality of light emitting elements 10 are provided on the mount lead 13a, it is necessary that the conductive wires be arranged so as not to contact each other. The inner lead 13b is preferably made of the same material as the mount lead 13a, and iron, copper, iron-containing copper, gold, platinum, silver, or the like can be used.

(Conductive wire)
The conductive wire 14 is for electrically connecting the electrode 3 of the light emitting element 10 and the lead frame 13. The conductive wire 14 preferably has good ohmic properties, mechanical connectivity, electrical conductivity, and thermal conductivity with the electrode 3. Specific materials for the conductive wire 14 are preferably metals such as gold, copper, platinum, and aluminum, and alloys thereof.

(Mold member)
The mold member 15 is provided to protect the light emitting element 10, the phosphor 11, the coating member 12, the lead frame 13, the conductive wire 14, and the like from the outside. In addition to the purpose of protection from the outside, the mold member 15 also has the purposes of widening the viewing angle, relaxing the directivity from the light emitting element 10, and converging and diffusing the emitted light. In order to achieve these objects, the mold member can have a desired shape. Further, the mold member 15 may have a structure in which a plurality of layers are stacked in addition to the convex lens shape and the concave lens shape. As a specific material of the mold member 15, a material excellent in translucency, weather resistance, and temperature characteristics such as epoxy resin, urea resin, silicone resin, silica sol, and glass can be used. The mold member 15 may contain a diffusing agent, a colorant, an ultraviolet absorber, or a fluorescent material. As the diffusing agent, barium titanate, titanium oxide, aluminum oxide or the like is preferable. In order to reduce the resilience of the material with the coating member 12, it is preferable to use the same material in consideration of the refractive index.

  Hereinafter, the phosphor and the light emitting device according to the present invention will be described with reference to examples, but the present invention is not limited to these examples.

  The temperature characteristics are shown as relative luminance with the emission luminance at 25 ° C. being 100%. The particle size is F.R. S. S. S. No. (Fisher Sub Sieve Sizer's No.) Value by air permeation method.

<Examples 1 to 7>
Table 1 shows the chemical characteristics and physical characteristics of Examples 1 to 7 of the phosphor according to the present invention.

  3 to 5 show the light emission characteristics of the phosphor of Example 4. FIG. FIG. 3 is a diagram showing an emission spectrum when the phosphor of Example 4 is excited at Ex = 460 nm. FIG. 4 is a diagram showing an excitation spectrum of the phosphor of Example 4. FIG. 5 is a diagram showing the reflection spectrum of the phosphor of Example 4. As shown in FIG. FIG. 6 is a graph showing an emission spectrum when the phosphors of Examples 1 to 7 are excited at Ex = 460 nm.

実施例１乃至７は、本発明に係るＭｎを添加したＳｒ−Ｃａ−Ｓｉ−Ｎ：Ｅｕで表される蛍光体の化学的特性や物理的特性を調べた結果である。表１における原料混合比は、原料をモル比で表したものである。この蛍光体は、Ｍｎが添加された一般式Ｓｒ_ＸＣａ_{（１．９４−Ｘ）}Ｅｕ_０．０６Ｓｉ_５Ｎ_８（０≦Ｘ≦１．９４）で表される、若しくは微量の酸素を含有するものを使用する。実施例１乃至７において、Ｅｕ濃度は０．０３である。Ｅｕ濃度は、Ｓｒ−Ｃａのモル濃度に対してのモル比である。また、Ｓｉの５に対してＭｎの添加量は０．０１５である。実施例１乃至７は、Ｓｒ濃度とＣａ濃度との比を適宜変更した結果である。

Examples 1 to 7 are the results of examining the chemical characteristics and physical characteristics of phosphors represented by Sr—Ca—Si—N: Eu to which Mn is added according to the present invention. The raw material mixing ratio in Table 1 represents the raw materials in molar ratio. This phosphor is represented by the general formula Sr _X Ca _(1.94-X) Eu _0.06 Si ₅ N ₈ (0 ≦ X ≦ 1.94) to which Mn is added, or contains a small amount of oxygen. Use what you want. In Examples 1 to 7, the Eu concentration is 0.03. Eu concentration is a molar ratio with respect to the molar concentration of Sr—Ca. The amount of Mn added is 0.015 with respect to 5 of Si. Examples 1 to 7 are results obtained by appropriately changing the ratio between the Sr concentration and the Ca concentration.

First, strontium nitride, calcium nitride, silicon nitride, and europium oxide are mixed in a glove box in a nitrogen atmosphere. In Example 1, the mixing ratio (molar ratio) of the raw materials was as follows: strontium nitride Sr ₃ N ₂ : calcium nitride Ca ₃ N ₂ : silicon nitride Si ₃ N ₄ : europium oxide Eu ₂ O ₃ = X: (1.94− X): 5: 0.06. Mn was added in a molar ratio of 0.015. The raw material may contain several ppm to several hundred ppm of at least one of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni.

The above compounds are mixed and fired. The firing conditions were put in a boron nitride crucible in an ammonia atmosphere, gradually heated from room temperature over about 5 hours, fired at about 1350 ° C. for 5 hours, and slowly cooled to room temperature over 5 hours. . In the Sr _X Ca _(1.94-X) Eu _0.06 Si ₅ N ₈ (0 ≦ X ≦ 1.94) after firing, about several ppm to several tens of ppm of Mn remains.

  In Example 1, the molar ratio of Sr: Ca is 9: 1. The light emission luminance of the silicon nitride phosphor of Example 1 is set to 100% and the quantum efficiency is set to 100%, and the light emission efficiencies of Examples 2 to 7 are defined based on this blending ratio. When the proportion of Ca to Sr is increased, when the molar ratio of Sr: Ca is 7: 3, the quantum efficiency of the silicon nitride phosphor is 126.9% and the peak wavelength is 639 nm. For this reason, quantum efficiency is improved, and in particular, the peak wavelength is shifted to the longer wavelength side. Furthermore, when the compounding ratio of Ca with respect to Sr is increased and the molar ratio of Sr: Ca is 5: 5, that is, 1: 1, the emission luminance of the silicon nitride phosphor is 111.2%, and the quantum efficiency is 167. 7%, the peak wavelength is 644 nm. From this result, the light emission efficiency such as the light emission luminance and the quantum efficiency is improved more than when Sr: Ca = 9: 1. In particular, since the peak wavelength is shifted to the longer wavelength side, a reddish phosphor can be manufactured. Also, the temperature characteristics are very good. Further, when the blending ratio of Ca with respect to Sr is increased, the peak wavelength shifts to the short wavelength side. Even in this case, light emission luminance and quantum efficiency are not lowered, and good light emission characteristics can be obtained. In particular, since Sr is more expensive than Ca, the manufacturing cost can be reduced by increasing the proportion of Ca.

  The phosphors of Examples 1 to 7 and Sr—Si—N: Eu added with Mn described later, Ca—Si—N: Eu added with Mn, or Sr—Ca—Si—O added with Mn. Producing a phosphor having a desired peak wavelength by appropriately combining Sr—Si—O—N: Eu, Mn added, and Ca—Si—O—N: Eu added with —N: Eu, Mn Can do. Since these have almost the same composition and do not buffer each other, they have good light emission characteristics.

  The phosphor according to the example uses a boron nitride crucible and is fired in an ammonia atmosphere. Under this firing condition, the furnace and the crucible are not eroded, so that no impurities are mixed into the fired product. Although a boron nitride crucible can be used, it is less preferred to use a molybdenum crucible. When a molybdenum crucible is used, it is considered that the crucible is eroded and molybdenum is contained in the phosphor, causing a decrease in light emission characteristics.

  As described above, the improvement of the light emission characteristics can provide a light emitting material that emits brighter white light. In addition, the improvement of the light emission characteristics can increase the energy efficiency, so that power saving can be achieved.

  In addition, the temperature characteristic indicates whether the phosphor composition is not changed when the phosphor is provided on the surface of the light emitting element, and shows a high light emission characteristic. The higher the temperature characteristic, the more stable the phosphor. It shows that there is.

<Examples 8 to 11>
Table 2 shows the chemical characteristics and physical characteristics of Examples 8 to 11 of the phosphor according to the present invention. FIG. 7 is a diagram showing emission spectra when the phosphors of Examples 8, 9, 11, 12, 13, 15, 21, 22, and 24 are excited at Ex = 460 nm.

実施例８乃至１１は、本発明に係るＭｎを添加したＳｒ−Ｃａ−Ｓｉ−Ｎ：Ｅｕで表される蛍光体のＥｕ濃度を変化させたときの化学的特性や物理的特性を調べた結果である。この蛍光体は、Ｍｎが添加された一般式Ｓｒ_ＸＣａ_{（２−Ｔ−Ｘ）}Ｅｕ_ＴＳｉ_５Ｎ_８（０≦Ｘ＜２）で表される、若しくは、微量の酸素を含有するものを使用する。ＳｒとＣａとの原料の配合割合は、Ｓｒ：Ｃａ＝Ｘ：２−Ｔ−Ｘ＝７：３である。Ｅｕの配合割合は、Ｔ＝０．０１、０．０３、０．０６及び０．１２のものを使用する。この場合のＥｕ濃度は、０．００５、０．０１５、０．０３、０．０６である。Ｅｕ濃度は、Ｓｒ−Ｃａのモル濃度に対してのモル比である。また、Ｓｉの５に対してＭｎの添加量は０．０１５である。

In Examples 8 to 11, the chemical characteristics and physical characteristics when the Eu concentration of the phosphor represented by Sr—Ca—Si—N: Eu to which Mn was added according to the present invention were changed were examined. It is. This phosphor is represented by the general formula Sr _X Ca _(2- TX ₎ Eu _T Si ₅ N ₈ (0 ≦ X <2) to which Mn is added or contains a trace amount of oxygen. use. The blending ratio of the raw materials of Sr and Ca is Sr: Ca = X: 2-TX = 7: 3. Eu compounding ratios are T = 0.01, 0.03, 0.06 and 0.12. The Eu concentration in this case is 0.005, 0.015, 0.03, and 0.06. Eu concentration is a molar ratio with respect to the molar concentration of Sr—Ca. The amount of Mn added is 0.015 with respect to 5 of Si.

  In Examples 8 to 11, the same manufacturing steps as in Examples 1 to 7 are performed. The raw material may contain several ppm to several hundred ppm of at least one of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni.

The luminous efficiency is shown based on the phosphor of Example 8. In Example 10 where the Eu concentration was 0.03, the emission luminance was most improved. If the Eu concentration is low, light is not emitted sufficiently. If the Eu concentration is too high, concentration quenching, or reaction with Sr ₂ N ₃ or Ca ₂ N ₃ is performed, and a composition having a composition different from the target basic constituent element is produced. Therefore, the light emission efficiency is reduced. In Example 11, the quantum efficiency is the best. On the other hand, the peak wavelength is shifted to the long wavelength side as the Eu concentration is increased. Although this principle is not clear, as the Eu concentration increases, Mn promotes the diffusion of Sr ₂ N ₃ and Ca ₂ N ₃ , thereby further promoting the mixed crystal of Sr and Ca and increasing the peak wavelength. It is thought that it was shifted to the wavelength side. In all of Examples 8 to 11, the temperature characteristics are extremely good.

<Examples 12 to 20>
Table 3 shows the chemical characteristics and physical characteristics of Examples 12 to 20 of the phosphor according to the present invention.

実施例１２乃至２０は、本発明に係るＭｎを添加したＳｒ−Ｃａ−Ｓｉ−Ｎ：Ｅｕで表される蛍光体のＥｕ濃度を変化させたときの化学的特性や物理的特性を調べた結果である。この蛍光体は、Ｍｎが添加された一般式Ｓｒ_ＸＣａ_{（２−Ｔ−Ｘ）}Ｅｕ_ＴＳｉ_５Ｎ_８（０≦Ｘ＜２）で表される、若しくは、微量の酸素を含有するものを使用する。ＳｒとＣａとの原料の配合割合は、Ｓｒ：Ｃａ＝Ｘ：２−Ｔ−Ｘ＝５：５である。実施例１２乃至１５におけるＥｕの配合割合は、Ｔ＝０．０１、０．０３、０．０６、０．１２のものを使用する。この場合のＥｕ濃度は、０．００５、０．０１５、０．０３、０．０６である。Ｅｕ濃度は、Ｓｒ−Ｃａのモル濃度に対してのモル比である。実施例１６乃至２０は、実施例１２乃至１５と異なり市販の原料を使用した。実施例１６乃至２０におけるＥｕの配合割合は、Ｔ＝０．１２、０．２、０．３、０．４、０．６のものを使用する。この場合のＥｕ濃度は、０．０６、０．１、０．１５、０．２、０．３である。実施例１２乃至２０におけるＭｎの添加量は、Ｓｉの５に対してＭｎの添加量は０．０１５である。

In Examples 12 to 20, the chemical characteristics and physical characteristics when the Eu concentration of the phosphor represented by Sr—Ca—Si—N: Eu to which Mn was added according to the present invention were changed were examined. It is. This phosphor is represented by the general formula Sr _X Ca _(2- TX ₎ Eu _T Si ₅ N ₈ (0 ≦ X <2) to which Mn is added or contains a trace amount of oxygen. use. The blending ratio of the raw materials of Sr and Ca is Sr: Ca = X: 2-TX = 5: 5. The mixing ratio of Eu in Examples 12 to 15 is T = 0.01, 0.03, 0.06, 0.12. The Eu concentration in this case is 0.005, 0.015, 0.03, and 0.06. Eu concentration is a molar ratio with respect to the molar concentration of Sr—Ca. In Examples 16 to 20, unlike Examples 12 to 15, commercially available raw materials were used. The mixing ratios of Eu in Examples 16 to 20 are T = 0.12, 0.2, 0.3, 0.4, and 0.6. The Eu concentration in this case is 0.06, 0.1, 0.15, 0.2, 0.3. The amount of Mn added in Examples 12 to 20 is 0.015 with respect to 5 for Si.

  In Examples 12 to 20, the same manufacturing steps as in Examples 1 to 7 are performed. The raw material may contain several ppm to several hundred ppm of at least one of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni.

The luminous efficiency is shown based on the phosphor of Example 12. In Example 14 where the Eu concentration was 0.03, the emission luminance was most improved. If the Eu concentration is low, light is not emitted sufficiently. If the Eu concentration is too high, concentration quenching, or reaction with Sr ₂ N ₃ or Ca ₂ N ₃ is performed, and a composition having a composition different from the target basic constituent element is produced. Therefore, the light emission efficiency is reduced. In Example 15, the quantum efficiency is the best. In Examples 16 to 20, the emission luminance was lowered, but this was considered to be due to the fact that impurities were contained in the raw material because the raw material was used, and the emission characteristics were lowered. In Examples 12 to 16, in Examples 16 to 20, the peak wavelength is shifted to the longer wavelength side as the Eu concentration is increased. Although this principle is not clear, as the Eu concentration increases, Mn promotes the diffusion of Sr ₂ N ₃ and Ca ₂ N ₃ , thereby further promoting the mixed crystal of Sr and Ca and increasing the peak wavelength. It is thought that it was shifted to the wavelength side. The temperature characteristics of Examples 12 to 20 are extremely good.

<Examples 21 to 24>
Table 4 shows the chemical characteristics and physical characteristics of Examples 21 to 24 of the phosphor according to the present invention.

実施例２１乃至２４は、本発明に係るＭｎを添加したＳｒ−Ｃａ−Ｓｉ−Ｎ：Ｅｕで表される蛍光体のＥｕ濃度を変化させたときの化学的特性や物理的特性を調べた結果である。この蛍光体は、Ｍｎが添加された一般式Ｓｒ_ＸＣａ_{（２−Ｔ−Ｘ）}Ｅｕ_ＴＳｉ_５Ｎ_８（０≦Ｘ＜２）で表される、若しくは、微量の酸素を含有するものを使用する。ＳｒとＣａとの原料の配合割合は、Ｓｒ：Ｃａ＝Ｘ：２−Ｔ−Ｘ＝３：７である。実施例１２乃至１５におけるＥｕの配合割合は、Ｔ＝０．０１、０．０３、０．０６、０．１２のものを使用する。この場合のＥｕ濃度は、０．００５、０．０１５、０．０３、０．０６である。Ｅｕ濃度は、Ｓｒ−Ｃａのモル濃度に対してのモル比である。実施例２１乃至２４におけるＭｎの添加量は、Ｓｉの５に対してＭｎの添加量は０．０１５である。

In Examples 21 to 24, the chemical characteristics and physical characteristics were examined when the Eu concentration of the phosphor represented by Sr—Ca—Si—N: Eu to which Mn was added according to the present invention was changed. It is. This phosphor is represented by the general formula Sr _X Ca _(2- TX ₎ Eu _T Si ₅ N ₈ (0 ≦ X <2) to which Mn is added or contains a trace amount of oxygen. use. The blending ratio of the raw materials of Sr and Ca is Sr: Ca = X: 2-TX = 3: 7. The mixing ratio of Eu in Examples 12 to 15 is T = 0.01, 0.03, 0.06, 0.12. The Eu concentration in this case is 0.005, 0.015, 0.03, and 0.06. Eu concentration is a molar ratio with respect to the molar concentration of Sr—Ca. In Examples 21 to 24, the added amount of Mn is 0.015 with respect to 5 of Si.

  In Examples 21 to 24, the same manufacturing steps as in Examples 1 to 7 are performed. The raw material may contain several ppm to several hundred ppm of at least one of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni.

  The light emission efficiency is shown based on the phosphor of Example 21. As in the examples in Tables 1 to 3, the emission luminance was most improved when the Eu concentration was 0.03 and in Examples 21 to 24 at 23. From the viewpoint of light emission luminance, it seems that an optimum phosphor can be manufactured when the Eu concentration is 0.03. Further, Example 23 has the best quantum efficiency as well as the light emission luminance. In Examples 21 to 24, the peak wavelength is shifted to the longer wavelength side as the Eu concentration is increased. The temperature characteristics of Examples 21 to 24 are extremely good.

<Examples 25 to 32>
Table 5 shows the chemical and physical properties of Examples 25 to 32 of the phosphor according to the present invention.

実施例２５乃至３２は、本発明に係るＣａ−Ｓｉ−Ｎ：Ｅｕで表される蛍光体のＭｎの添加量を変化させたときの化学的特性や物理的特性を調べた結果である。表５における原料混合比は、原料をモル比で表したものである。このようにして造られた蛍光体は、Ｍｎが添加された一般式Ｃａ_{（２−Ｔ）}Ｅｕ_ＴＳｉ_５Ｎ_８若しくは、微量の酸素を含有する形で表される。Ｍｎを添加していないものを実施例２５に示す。実施例２６乃至３２の蛍光体は、Ｍｎの添加量を、０．００５、０．０１、０．０１５、０．０３、０．０６、０．１及び０．２のものを使用する。この場合のＭｎ濃度は、０．００２５、０．００５、０．００７５、０．０１５、０．０３、０．０５及び０．１であり、Ｍｎ濃度は、Ｃａのモル濃度に対してのモル比である。Ｅｕ濃度は、０．００７５と一定である。

Examples 25 to 32 are results of examining chemical characteristics and physical characteristics when the amount of Mn added to the phosphor represented by Ca-Si-N: Eu according to the present invention is changed. The raw material mixing ratio in Table 5 represents the raw materials in molar ratio. The phosphor thus produced is represented by a general formula Ca _(2-T) Eu _T Si ₅ N ₈ to which Mn is added or a form containing a small amount of oxygen. Example 25 to which Mn was not added is shown in Example 25. As the phosphors of Examples 26 to 32, phosphors having Mn addition amounts of 0.005, 0.01, 0.015, 0.03, 0.06, 0.1 and 0.2 are used. In this case, the Mn concentration is 0.0025, 0.005, 0.0075, 0.015, 0.03, 0.05, and 0.1, and the Mn concentration is the mole with respect to the molar concentration of Ca. Is the ratio. The Eu concentration is constant at 0.0075.

  In Examples 25 to 32, the same manufacturing steps as those in Examples 1 to 7 are performed. The raw material may contain several ppm to several hundred ppm of at least one of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni.

  The luminous efficiency is shown with reference to the phosphor of Example 25 not containing Mn. In Example 28 where the Mn concentration was 0.0075 and Example 29 where the Mn concentration was 0.015, the emission luminance was most improved. This is because when the Mn concentration is low, the raw material is not sufficiently diffused and the particles are not grown much. On the other hand, it is considered that when the Mn concentration is too high, Mn hinders the composition formation and crystal growth of Ca—Si—N: Eu. In Examples 26 to 29, the quantum efficiency is very good. The temperature characteristics in Examples 25 to 31 are very good even when the amount of Mn added is changed. The peak wavelength is constant even when the amount of Mn added is changed.

<Examples 33 to 35>
Table 6 shows the chemical characteristics and physical characteristics of Examples 33 to 35 of the phosphor according to the present invention.

実施例３３乃至３５は、本発明に係るＣａ−Ｓｉ−Ｎ：Ｅｕで表される蛍光体のＭｎの添加量を変化させたときの化学的特性や物理的特性を調べた結果である。表６における原料混合比は、原料をモル比で表したものである。Ｅｕ濃度は、０．０１５と一定である。このようにして造られた蛍光体は、Ｍｎが添加された一般式Ｃａ_{（２−Ｔ）}Ｅｕ_ＴＳｉ_５Ｎ_８若しくは、微量の酸素を含有する形で表される。Ｍｎを添加していないものを実施例３３に示す。実施例３３乃至３５の蛍光体におけるＭｎの添加量は、原料の総重量に対して１００ｐｐｍ及び５００ｐｐｍのものを使用する。

Examples 33 to 35 are results of examining chemical characteristics and physical characteristics when the amount of Mn added to the phosphor represented by Ca—Si—N: Eu according to the present invention is changed. The raw material mixing ratio in Table 6 represents the raw materials in molar ratio. The Eu concentration is constant at 0.015. The phosphor thus produced is represented by a general formula Ca _(2-T) Eu _T Si ₅ N ₈ to which Mn is added or a form containing a small amount of oxygen. Example 33 to which Mn was not added is shown in Example 33. The amount of Mn added in the phosphors of Examples 33 to 35 is 100 ppm and 500 ppm based on the total weight of the raw materials.

  In Examples 33 to 35, the same manufacturing steps as those in Examples 1 to 7 are performed. First, calcium nitride, silicon nitride, and europium oxide are mixed in a glove box in a nitrogen atmosphere. The raw material may contain several ppm to several hundred ppm of at least one of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni.

  The luminous efficiency is shown based on the phosphor of Example 33 not containing Mn. In both cases where the addition amount of Mn was 100 ppm and 500 ppm, the emission luminance and the quantum efficiency were improved. Also, the temperature characteristics are improved. Thus, even if the amount of Mn added is small, it is possible to improve light emission characteristics such as light emission luminance, quantum efficiency, and temperature characteristics.

<Examples 36 and 37>
Table 7 shows the chemical and physical characteristics of Examples 36 and 37 of the phosphor according to the present invention. 8A and 8B are photographs obtained by photographing the particle diameter of the phosphor of Example 36, and FIG.

実施例３６及び３７は、本発明に係るＣａ−Ｓｉ−Ｎ：Ｅｕで表される蛍光体のＭｎの添加量を変化させたときの化学的特性や物理的特性を調べた結果である。表７における原料混合比は、原料をモル比で表したものである。このようにして造られた蛍光体は、Ｍｎが添加された一般式Ｃａ_{（２−Ｔ）}Ｅｕ_ＴＳｉ_５Ｎ_８若しくは、微量の酸素を含有する形で表される。Ｍｎを添加していないものを実施例３６に示す。実施例３７の蛍光体は、Ｍｎの添加量を、０．０４モルのものを使用する。この場合のＭｎ濃度は、０．０２であり、Ｍｎ濃度は、Ｃａのモル濃度に対してのモル比である。Ｅｕ濃度は、０．０２と一定である。

Examples 36 and 37 are results of examining chemical characteristics and physical characteristics when the amount of Mn added to the phosphor represented by Ca—Si—N: Eu according to the present invention is changed. The raw material mixing ratio in Table 7 represents the raw materials in molar ratio. The phosphor thus produced is represented by a general formula Ca _(2-T) Eu _T Si ₅ N ₈ to which Mn is added or a form containing a small amount of oxygen. Example 36 to which Mn was not added is shown in Example 36. As the phosphor of Example 37, 0.04 mol of Mn is used. The Mn concentration in this case is 0.02, and the Mn concentration is a molar ratio with respect to the molar concentration of Ca. The Eu concentration is constant at 0.02.

  In Examples 36 and 37, the same manufacturing steps as those in Examples 1 to 7 are performed. The raw material may contain several ppm to several hundred ppm of at least one of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni.

  The luminous efficiency is shown with reference to the phosphor of Example 36 not containing Mn. In Example 37 where the Mn concentration was 0.02, improvements in light emission luminance and quantum efficiency were observed. The reason for this is considered to be the same as described above.

  When measuring the average particle size of Examples 36 and 37, the average particle size of Example 36 is 2.9 μm, whereas the average particle size of Example 37 is 6.4 μm. The difference in the average particle diameter seems to cause a difference in the emission luminance.

  In FIG. 8, the photograph which image | photographed the particle size of the fluorescent substance which did not add Mn and the fluorescent substance which added Mn is shown. The average particle size of the phosphor of Example 36 to which Mn is not added is 2.8 μm, whereas the average particle size of the phosphor of Example 37 to which Mn is added is 6.4 μm. Thus, the phosphor added with Mn has a relatively large particle size compared to the phosphor not added with Mn. This difference in particle size is considered to increase the luminance.

<Examples 38 to 42>
Table 8 shows the chemical and physical properties of Examples 38 to 42 of the phosphor according to the present invention.

実施例３８乃至４２は、本発明に係るＳｒ−Ｓｉ−Ｎ：Ｅｕで表される蛍光体のＭｎの添加量を変化させたときの化学的特性や物理的特性を調べた結果である。表８における原料混合比は、原料をモル比で表したものである。このようにして造られた蛍光体は、Ｍｎが添加された一般式Ｓｒ_{（２−Ｔ）}Ｅｕ_ＴＳｉ_５Ｎ_８若しくは、微量の酸素を含有する形で表される。Ｍｎを添加していないものを実施例３８に示す。実施例３９乃至４２の蛍光体は、Ｍｎの添加量を、０．０１、０．０３、０．１及び０．２のものを使用する。この場合のＭｎ濃度は、０．００５、０．０１５、０．０５及び０．１であり、Ｍｎ濃度は、Ｓｒのモル濃度に対してのモル比である。Ｅｕ濃度は、０．０３と一定である。

Examples 38 to 42 are results of examining chemical characteristics and physical characteristics when the amount of Mn added to the phosphor represented by Sr—Si—N: Eu according to the present invention is changed. The raw material mixing ratio in Table 8 represents the raw materials in molar ratio. The phosphor thus produced is represented by a general formula Sr _(2-T) Eu _T Si ₅ N ₈ to which Mn is added or a form containing a small amount of oxygen. Example 38 to which Mn was not added is shown in Example 38. As the phosphors of Examples 39 to 42, those having an addition amount of Mn of 0.01, 0.03, 0.1, and 0.2 are used. The Mn concentrations in this case are 0.005, 0.015, 0.05, and 0.1, and the Mn concentration is a molar ratio with respect to the molar concentration of Sr. The Eu concentration is constant at 0.03.

  In Examples 38 to 42, the same manufacturing steps as those in Examples 1 to 7 are performed. The raw material may contain several ppm to several hundred ppm of at least one of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni.

  The luminous efficiency is shown with reference to the phosphor of Example 38 not containing Mn. In Examples 39 to 41, the emission luminance was improved. Particularly, in Example 40 where the Mn concentration was 0.015, the emission luminance was most improved. In Examples 39 to 41, the quantum efficiency is extremely good. Furthermore, the temperature characteristics in Examples 39 to 42 are very good even when the amount of Mn added is changed. The peak wavelength shifts to the longer wavelength side as the amount of Mn added is increased. Although this reason is not certain, it is considered that Mn promotes diffusion of raw materials, particularly Eu.

<Examples 43 to 51>
Table 9 shows the chemical characteristics and physical characteristics of Examples 43 to 51 of the phosphor according to the present invention.

実施例４３乃至５１は、本発明に係るＳｒ−Ｃａ−Ｓｉ−Ｎ：Ｅｕで表される蛍光体のＭｎの添加量を変化させたときの化学的特性や物理的特性を調べた結果である。表９における原料混合比は、原料をモル比で表したものである。このようにして造られた実施例４３乃至５１の蛍光体は、一般式Ｓｒ_ＸＣａ_{（２−Ｘ−Ｔ）}Ｅｕ_ＴＳｉ_５Ｎ_８若しくは、微量の酸素を含有する形で表される。

Examples 43 to 51 are results obtained by examining chemical characteristics and physical characteristics when the amount of Mn added to the phosphor represented by Sr—Ca—Si—N: Eu according to the present invention is changed. . The raw material mixing ratio in Table 9 represents the raw materials in molar ratio. The phosphors of Examples 43 to 51 produced in this way are represented by a general formula Sr _X Ca _(2- XT ₎ Eu _T Si ₅ N ₈ or a form containing a trace amount of oxygen.

  In Examples 43 to 51, the same manufacturing steps as those in Examples 1 to 7 are performed. The raw material may contain several ppm to several hundred ppm of at least one of Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni.

  The molar ratio of Sr and Ca in Examples 43 to 47 is Sr: Ca = 5: 5. Example 43 without Mn is shown in Example 43. As the phosphors of Examples 44 to 47, those having an addition amount of Mn of 0.01, 0.03, 0.1 and 0.2 are used. In this case, the Mn concentration is 0.005, 0.015, 0.05, and 0.1, and the Mn concentration is a molar ratio with respect to the molar concentration of Sr—Ca. The Eu concentration is constant at 0.02.

  The luminous efficiency is shown with reference to the phosphor of Example 43 not containing Mn. In Examples 44 to 47 where the Mn concentration was 0.005, 0.015, 0.05 and 0.1, the emission luminance was improved. Also, the quantum efficiency is improved. Furthermore, the temperature characteristics are also very good. Thus, by adding Mn to the phosphor represented by Sr—Ca—Si—N: Eu, the emission characteristics can be improved.

  In Examples 48 and 49, phosphors according to the present invention were produced using commercially available raw materials. The molar ratio of Sr and Ca in Examples 48 and 49 is Sr: Ca = 5: 5. Example 48 without Mn added is shown in Example 48. For the phosphor of Example 49, 0.04 Mn is used. In this case, the Mn concentration is 0.02, and the Mn concentration is a molar ratio with respect to the molar concentration of Sr—Ca. The Eu concentration is 0.02.

  The luminous efficiency is shown based on the phosphor of Example 48 to which Mn is not added. Even when the production is carried out using commercially available raw materials, the emission characteristics can be improved by adding Mn.

  In Examples 50 and 51, phosphors according to the present invention were produced using commercially available raw materials. The molar ratio of Sr and Ca in Examples 50 and 51 is Sr: Ca = 7: 3. Example 50 without Mn added is shown in Example 50. As the phosphor of Example 51, 0.02 Mn is used. The Mn concentration in this case is 0.01, and the Mn concentration is a molar ratio with respect to the molar concentration of Sr—Ca. The Eu concentration is 0.01.

  The luminous efficiency is shown with reference to the phosphor of Example 50 not containing Mn. In Example 51 having a Mn concentration of 0.01, the light emission characteristics can be improved.

<Examples 48 and 49>
Table 10 shows the results of a composition analysis of the phosphors represented by Sr—Ca—Si—N: Eu in Examples 48 and 49 according to the present invention.

上記分析結果から、上記蛍光体におけるＭｎの有無を明確にすることができた。また、上記組成中には、Ｏが１〜２％含有されている。

From the above analysis results, the presence or absence of Mn in the phosphor could be clarified. Moreover, 1-2% of O is contained in the above composition.

<Light-emitting device 1>
The light emitting device 1 relates to a white light emitting device to which a reddish component is added. FIG. 1 is a diagram showing a light emitting device 1 according to the present invention. FIG. 9 is a diagram showing an emission spectrum of the light emitting device 1 according to the present invention. FIG. 10 is a diagram illustrating the color rendering evaluation of the light emitting device according to the present invention.

In the light emitting device 1, a semiconductor layer 2 of n-type and p-type GaN layers is formed on a sapphire substrate 1, and an electrode 3 is provided on the n-type and p-type semiconductor layer 2. The wire 14 is electrically connected to the lead frame 13. The upper part of the light emitting element 10 is covered with the phosphor 11 and the coating member 12, and the outer periphery of the lead frame 13, the phosphor 11, the coating member 12, and the like is covered with the mold member 15. The semiconductor layer 2 is laminated on the sapphire substrate 1 in the order of n ⁺ GaN: Si, n-AlGaN: Si, n-GaN, GaInN QWs, p-GaN: Mg, p-AlGaN: Mg, p-GaN: Mg. ing. Part of the n ⁺ GaN: Si layer is etched to form an n-type electrode. A p-type electrode is formed on the p-GaN: Mg layer. The lead frame 13 uses iron-containing copper. A cup for mounting the light-emitting element 10 is provided on the upper portion of the mount lead 13a, and the light-emitting element 10 is die-bonded to the bottom surface of the substantially central portion of the cup. Gold is used for the conductive wire 14, and Ni plating is applied to the bump 4 for conductively connecting the electrode 3 and the conductive wire 14. The phosphor 11 is mixed with the phosphor of Example 49 and the YAG phosphor. As the coating member 12, a material obtained by mixing an epoxy resin, a diffusing agent, barium titanate, titanium oxide, and the phosphor 11 at a predetermined ratio is used. The mold member 15 uses an epoxy resin. The bullet-type light emitting device 1 is a cylindrical type in which the upper part of the mold member 15 having a radius of 2 to 4 mm and a height of about 7 to 10 mm is a hemisphere.

  When a current is passed through the light emitting device 1, the blue light emitting element 10 having the first emission spectrum excited at about 460 nm emits light, and the phosphor 11 covering the semiconductor layer 2 performs color tone conversion on the first emission spectrum. , Having a second emission spectrum different from the first emission spectrum. In addition, the YAG phosphor contained in the phosphor 11 exhibits a third emission spectrum by the first emission spectrum. It is possible to provide the light emitting device 1 that emits reddish white light in which the first, second, and third emission spectra are mixed with each other.

  Table 11 shows the light emission characteristics of the light emitting device 1 according to the present invention and the light emitting device 2 to be compared. 9, FIG. 10, and Table 11 also show the measurement results of the light emitting device 1 according to the present invention and the light emitting device 2 to be compared.

本発明に係る発光装置１の蛍光体１１は、実施例４９の蛍光体と、コーティング部材１２と、セリウムで付活されたイットリウム・ガドリニウム・アルミニウム酸化物蛍光物質（Ｙ−Ｇｄ−Ａｌ−Ｏ：Ｃｅ）とを混合した蛍光体を用いる。本発明に係る発光装置１及び２は、（Ｙ_０．８Ｇｄ_０．２）_３Ａｌ_５Ｏ_１２：Ｃｅの蛍光体を使用する。

The phosphor 11 of the light-emitting device 1 according to the present invention includes the phosphor of Example 49, the coating member 12, and the yttrium-gadolinium-aluminum oxide phosphor (Y-Gd-Al-O: activated with cerium). A phosphor mixed with Ce) is used. The light emitting devices 1 and 2 according to the present invention use a phosphor of (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce.

  When excited at Ex = 460 nm, the peak wavelength of the phosphor of Y—Gd—Al—O: Ce is 562 nm. Similarly, the peak wavelength of the phosphor of Example 49 is 650 nm.

  The weight ratio of these phosphors 11 is coating member: (Y-Gd-Al-O: Ce) phosphor: phosphor of Example 49 = 10: 3.8: 0.6. On the other hand, the phosphor of the light-emitting device 2 that is a combination of a blue light-emitting element and a phosphor of Y-Gd-Al-O: Ce is a phosphor of a coating member: (Y-Gd-Al-O: Ce) = 10: Mixed at a weight ratio of 3.6.

  The light emitting device 1 according to the present invention is compared with the light emitting device 2 using a blue light emitting element and a phosphor of Y-Gd-Al-O: Ce. Although the color tone is hardly changed as compared with the light emitting device 2, the color rendering is improved. As is clear from FIG. 10, the light emitting device 2 lacks the special color rendering index R9, but the light emitting device 1 has improved R9. Further, the other special color rendering evaluation numbers R8, R10, etc. are improved to values close to 100%. The lamp efficiency is as high as 24.9 lm / W.

<Light-emitting device 3>
The light emitting device 3 relates to a light emitting device having a light bulb color. FIG. 11 is a diagram showing an emission spectrum of the light emitting device 3 according to the present invention. FIG. 12 is a diagram showing a color rendering evaluation of the light emitting device 3 according to the present invention. FIG. 13 is a diagram showing chromaticity coordinates of the light emitting device 3 according to the present invention. Table 12 shows the light emission characteristics of the light emitting device 3 according to the present invention. The light emitting device 3 has the same configuration as the light emitting device 1 of FIG.

本発明に係る発光装置３の蛍光体１１は、実施例４９の蛍光体と、コーティング部材１２と、セリウムで付活されたイットリウム・ガリウム・アルミニウム酸化物蛍光物質（Ｙ−Ｇａ−Ａｌ−Ｏ：Ｃｅ）とを混合した蛍光体を用いる。本発光装置３では、Ｙ_３（Ａｌ_０．８Ｇａ_０．２）_５Ｏ_１２：Ｃｅの組成の蛍光体を使用する。

The phosphor 11 of the light emitting device 3 according to the present invention includes the phosphor of Example 49, the coating member 12, and an yttrium gallium aluminum oxide phosphor (Y-Ga-Al-O: activated with cerium). A phosphor mixed with Ce) is used. In the light emitting device 3, a phosphor having a composition of Y ₃ (Al _0.8 Ga _0.2 ) ₅ O ₁₂ : Ce is used.

  When excited at Ex = 460 nm, the peak wavelength of the phosphor of Y—Ga—Al—O: Ce is 533 nm. Similarly, the peak wavelength of the phosphor of Example 49 is 650 nm.

  The weight ratios of these phosphors 11 were mixed at a weight ratio of coating member: (Y—Ga—Al—O: Ce): phosphor of Example 49 = 10: 4.0: 1.08. Yes.

  The light emitting device 3 using the phosphors mixed in this way emits light in a light bulb color. According to FIG. 13 showing the chromaticity coordinates of the light emitting device 3, the color tone x and the color tone y are located in the warm color white light emission region. The special color rendering index R9 of the light emitting device 3 is 60%, which improves the color rendering. The peak wavelength is also in the red region of 620.7 nm, and a white light emitting device with a light bulb color can be obtained. The color temperature is 2832K. The color rendering property Ra is 90.4, and has a light emission characteristic close to that of a light bulb. The light emitting device 3 has a high light emission characteristic of 19.2 lm / W.

<Light-emitting device 4>
FIG. 14 is a diagram showing a light emitting device 4 according to the present invention.

  As the light emitting layer, the light emitting element 101 having a 460 nm InGaN-based semiconductor layer whose emission peak is in the blue region is used. The light-emitting element 101 includes a p-type semiconductor layer and an n-type semiconductor layer (not shown), and the p-type semiconductor layer and the n-type semiconductor layer have conductive wires connected to the lead electrode 102. 104 is formed. An insulating sealing material 103 is formed so as to cover the outer periphery of the lead electrode 102 to prevent a short circuit. Above the light emitting element 101, a translucent window 107 extending from a lid 106 at the top of the package 105 is provided. A uniform mixture of the phosphor 108 and the coating member 109 according to the present invention is applied to the entire inner surface of the translucent window 107. In the light emitting device 1, the phosphor of Example 1 is used. The package 105 is a square having a side with a corner portion of 8 mm to 12 mm.

The emission spectrum of the blue light emitted from the semiconductor light emitting device 101 includes the indirect emission spectrum reflected by the reflector and the emission spectrum directly emitted from the semiconductor light emitting device 101, which is irradiated onto the nitride phosphor 108 of the present invention. The phosphor emits white light. The nitride phosphor 108 of the present invention includes a green light emitting phosphor SrAl ₂ O ₄ : Eu, Y ₂ SiO ₅ : Ce, Tb, MgAl ₁₁ O ₁₉ : Ce, Tb, Sr ₇ Al ₁₂ O ₂₅ : Eu, ( At least one of Mg, Ca, Sr, and Ba) Ga ₂ S ₄ : Eu, blue light emitting phosphor Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrCaBa) ₅ (PO ₄ ) ₃ Cl: Eu, BaCa) ₅ (PO ₄ ) ₃ Cl: Eu, (at least one of Mg, Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu, Mn, (at least one of Mg, Ca, Sr, Ba) ) (PO ₄ ) ₆ Cl ₂ : Eu, Mn, red light emitting phosphor Y ₂ O ₂ S: Eu, La ₂ O ₂ S: Eu, Y ₂ O ₃ : Eu, Ga ₂ O ₂ S: Eu, etc. By doping, the place It is possible to obtain an emission spectrum of the.

  When a white LED lamp is formed using the light emitting device formed as described above, the yield is 99%. Thus, by using the light-emitting diode of the present invention, a light-emitting device can be produced with high productivity, and a light-emitting device with high reliability and less color unevenness can be provided.

  The light emitting device of the present invention can be used for a light emitting device used for illumination such as a display, a backlight for liquid crystal, and a fluorescent lamp.

It is a figure which shows the light-emitting device 1 which concerns on this invention. It is a figure which shows the manufacturing method of the fluorescent substance which concerns on this invention. It is a figure which shows the emission spectrum when the fluorescent substance of Example 4 is excited by Ex = 460nm. It is a figure which shows the excitation spectrum of the fluorescent substance of Example 4. It is a figure which shows the reflection spectrum of the fluorescent substance of Example 4. It is a figure which shows the emission spectrum when the fluorescent substance of Example 1 thru | or 7 is excited by Ex = 460nm. It is a figure which shows the emission spectrum when the fluorescent substance of Example 8, 9, 11, 12, 13, 15, 21, 22, 24 is excited by Ex = 460 nm. (A) is a photograph of Example 36, and (b) is a photograph of the particle size of the phosphor of Example 37. It is a figure which shows the emission spectrum of the light-emitting device 1 which concerns on this invention. It is a figure which shows the color rendering evaluation of the light-emitting device 1 which concerns on this invention. It is a figure which shows the emission spectrum of the light-emitting device 3 which concerns on this invention. It is a figure which shows the color rendering evaluation of the light-emitting device 3 which concerns on this invention. It is a figure which shows the chromaticity coordinate of the light-emitting device 3 which concerns on this invention. It is a figure which shows the light-emitting device 4 which concerns on this invention.

Explanation of symbols

P1 Raw materials Sr and Ca are pulverized.
P2 Raw material Si is pulverized.
Pr raw materials Sr and Ca are nitrided in a nitrogen atmosphere.
P4 Raw material Si is nitrided in a nitrogen atmosphere.
The nitride of P5 Sr, Ca, Sr—Ca is pulverized.
P6 Si nitride is pulverized.
P7 Eu compound Eu ₂ O ₃ is ground.
P8 Sr, Ca, nitride of Sr—Ca, nitride of Si, Eu compound Eu ₂ O _{3 and the} like are mixed, and Mn is added.
A mixture of Sr, Ca, Sr—Ca nitride, Si nitride, and Eu compound Eu ₂ O ₃ to which P9 Mn is added is fired in an ammonia atmosphere.
A phosphor represented by (Sr _X Ca _1-X ) ₂ Si ₅ N ₈ : Eu to which P10 Mn is added.
DESCRIPTION OF SYMBOLS 1 Substrate 2 Semiconductor layer 3 Electrode 4 Bump 10 Light emitting element 11 Phosphor 12 Coating member 13 Lead frame 13a Mount lead 13b Inner lead 14 Conductive wire 15 Mold member 101 Light emitting element 102 Lead electrode 103 Insulating sealing material 104 Conductive wire 105 Package 106 Lid 107 Window 108 Phosphor 109 Coating member

Claims (7)

A phosphor containing at least nitrogen and absorbing at least part of light having a first emission spectrum and emitting light having a second emission spectrum different from the first emission spectrum;
The phosphor is at least one selected from the group consisting of II, such as Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, and an IV value of C, Si, Ge, Sn, Ti, Zr, and Hf. A phosphor characterized by being a crystalline silicon nitride having at least one selected from the group consisting of: N, at least one activator selected from the group consisting of rare earth elements; and Mn. . A phosphor containing at least nitrogen and absorbing at least part of light having a first emission spectrum and emitting light having a second emission spectrum different from the first emission spectrum;
The phosphor is L _X M _Y N _{(2 / 3X + 4 / 3Y)} : R or L _X M _Y O _Z N _{(2 / 3X + 4 / 3Y-2 / 3Z)} : R (L is Be, Mg, Ca, At least one selected from the group consisting of II values of Sr, Ba, Zn, Cd and Hg, M is at least one selected from the group consisting of IV values of C, Si, Ge, Sn, Ti, Zr and Hf , R is at least one activator selected from the group consisting of rare earth elements, X is 1 ≦ X ≦ 2, Y is 5 ≦ Y ≦ 7), and Mn is added to the composition A phosphor characterized by being a silicon nitride having properties. A semiconductor light emitting device that emits light having a first emission spectrum, and a phosphor that absorbs at least part of the light of the first emission spectrum and emits light of a second emission spectrum different from the first emission spectrum; A light emitting device comprising:
The phosphor is a first phosphor according to claim 1 or 2, and
And a second phosphor which is Y ₃ Al ₅ O ₁₂ : Ce (Y or Al, part or all of Ce can be replaced by another element) and light emission apparatus. A semiconductor light emitting device that emits light having a first emission spectrum, and a phosphor that absorbs at least part of the light of the first emission spectrum and emits light of a second emission spectrum different from the first emission spectrum; A light emitting device comprising:
The phosphor is a first phosphor according to claim 1 or 2, and
And a second phosphor having an emission color on a shorter wavelength side than the first phosphor. A semiconductor light emitting device that emits light having a first emission spectrum, and a phosphor that absorbs at least part of the light of the first emission spectrum and emits light of a second emission spectrum different from the first emission spectrum; A light emitting device comprising:
The phosphor is a first phosphor according to claim 1 or 2, and
And a second phosphor having an emission color of blue, green, or yellow. 6. The light emitting device according to claim 3, wherein the light emitting device has a special color rendering index R9 of 60 or more. The light emitting device according to claim 3, wherein the semiconductor light emitting element has a light emission peak wavelength in a range of 360 nm to 550 nm and emits light of a light bulb color.

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