JP2007189254A - Light emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphor that emits white light with excellent light emission characteristics, and to provide a phosphor exhibiting high luminance light emission characteristics with extremely low yield.
At least a part of a first emission spectrum is converted, and at least one second emission spectrum is provided in a region different from the first emission spectrum, and at least nitrogen is contained as a basic constituent element. A method for producing a nitride phosphor, comprising the step (P9) of firing in an ammonia atmosphere.
[Selection] Figure 1

Description

  The present invention is used for fluorescent display tubes, displays, PDPs, CRTs, FLs, FEDs, projection tubes, and the like, in particular, white light emitting devices that have extremely excellent light emission characteristics using blue light emitting diodes or ultraviolet light emitting diodes as light sources. The present invention relates to a nitride phosphor and a manufacturing method thereof. In addition, the white light-emitting device having the nitride phosphor according to the present invention can be used for fluorescent lamps for storefront display lighting, medical site lighting, etc., as well as backlights for mobile phones and light-emitting diodes. It can also be applied to the field of (LED).

  A known light-emitting device that emits white light has been a light-emitting device that emits a slightly yellowish white light because it is difficult to obtain light on the long wavelength side in the visible light region. However, there is a strong demand for a light emitting device that emits a slightly reddish white light for store display lighting or medical site lighting.

It is already known as a phosphor that emits white light using a blue light emitting diode as a light source (see, for example, Patent Document 1). This phosphor contains at least one alkaline earth metal composed of M _x Si _{YN Z} : Eu (M is a group of Ca, Sr, Ba, Zn. Z is Z = 2 / 3X + 4 / 3Y. It is a phosphor having a composition represented by This phosphor absorbs a short wavelength of 250 nm to 450 nm in the visible light region and reflects strongly at a wavelength of 450 nm to 500 nm or more. Therefore, since this phosphor absorbs short wavelengths of visible light indigo and blue to blue-green, it strongly reflects on the wavelength side such as green, yellow, and red. By utilizing this characteristic, for example, a combination with a blue light emitting diode, it is possible to obtain slightly reddish white light.

International Publication Number 01/40403

  However, although the phosphor of the invention according to Patent Document 1 has useful light emission characteristics, it has a drawback that it is difficult to manufacture. Moreover, there is a drawback that the light emission luminance is low. In accordance with the examples described in the application specification of Patent Document 1, the test was performed several times under almost the same conditions. The test results are shown in Table 1 described in the embodiment of the invention.

Test 1 is the result of blending and firing based on Patent Document 1. The compounding ratio of Ca ₃ N ₂ , Si ₃ N ₄ and Eu ₂ O ₃ is Ca ₃ N ₂ : Si ₃ N ₄ : Eu ₂ O ₃ = 2: 5: 0.2. With this blending ratio, firing was performed at 1200 ° C. to 1400 ° C. (1300 ° C. to 1575 ° C. in Patent Document 1) in a mixed gas atmosphere of hydrogen (3.75%) and nitrogen (400 l / h). Other test operations and firing conditions are the same as in Patent Document 1. The phosphor manufactured from Test 1 was observed only with a part of the eye, and only a part of the phosphor was emitted. Moreover, the brightness of the phosphor manufactured from Test 1 was low and was insufficient to emit light in combination with the light emitting diode.

  In view of the above, the present invention provides a phosphor with high emission luminance that converts a part of the first emission spectrum and has the second emission spectrum in a region different from the first emission spectrum. An object of the present invention is to use a light emitting diode having an emission spectrum in the ultraviolet to blue region as a light source, convert the emission spectrum from the light emitting diode, and provide a phosphor having excellent emission characteristics that emits white light. . It is another object of the present invention to provide a stable product of a phosphor exhibiting extremely high yield and high luminance light emission characteristics, and to provide a manufacturing method with good manufacturing efficiency. It is another object of the present invention to provide a light emitting device that emits white light by combining a blue light emitting diode and the phosphor.

  In order to solve the above problems, the present invention provides a semiconductor light emitting device that emits light having a first emission spectrum, and absorbs at least a part of the light of the first emission spectrum, A phosphor that emits light of a different second emission spectrum, wherein the phosphor includes a first phosphor and a second phosphor, and the first phosphor is A nitride phosphor that emits light of the second emission spectrum in a yellow to red region, and the second phosphor is a phosphor having an emission color on a shorter wavelength side than the first phosphor. The light-emitting device relates to a light-emitting device that exhibits light-emitting characteristics close to a light bulb color.

  The nitride 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, Ti, Zr, and Hf. At least one selected from the group consisting of IV values, and at least selected from the group consisting of N, Eu, Cr, Mn, Pb, Sb, Ce, Tb, Pr, Sm, Tm, Ho, Er, Yb, Nd It is preferable that the phosphor has crystallinity having a kind of activator.

  The second phosphor may have a light emission color of blue, green, or yellow.

  The semiconductor light emitting device has an emission peak wavelength at 360 to 550 nm, and the intensity of the emission peak wavelength of the phosphor is larger than the intensity of the emission peak wavelength of the semiconductor light emitting device.

  This has a very important technical significance that a light emitting device close to the color of a light bulb can be manufactured.

  The present invention converts at least a part of the first emission spectrum, and has at least one second emission spectrum in a region different from the first emission spectrum, and contains at least nitrogen as a basic constituent element. The present invention relates to a method for manufacturing a nitride phosphor, comprising a step of firing in an ammonia atmosphere.

  In a known phosphor production method, raw materials such as a well-purified base material and an activator are mixed and then placed in a molybdenum crucible and baked in a furnace. The present invention can pass through almost the same steps as this known phosphor manufacturing method, but can also pass through different steps.

  In Patent Document 1, the firing step is performed in a mixed gas atmosphere of hydrogen (3.75%) and nitrogen (400 l / h), but the present invention is performed in an ammonia atmosphere. By using the manufacturing method according to the present invention, it is possible to obtain a phosphor exhibiting extremely high yield and high luminance emission characteristics.

  The comparison results between the comparative example and the example of the present invention are shown in Table 2 and Table 3 (detailed in [Embodiments of the Invention]). In Tables 2 and 3, the comparative example and the example of the present invention are fired under the same conditions except for the firing step. The comparative example is fired in a hydrogen and nitrogen atmosphere, and the examples of the present invention are fired in an ammonia atmosphere. As a result, the brightness of the example of the present invention is 18% higher than that of the comparative example. This improvement in luminance of 18% shows a very excellent effect and has technical significance. In addition, energy efficiency is improved by 17.6%. Furthermore, the quantum efficiency is improved by 20.7%. From these results, through the manufacturing process according to the present invention, it is possible to supply a stable product of a phosphor exhibiting an extremely high yield and high-luminance emission characteristics, and nitriding with extremely good manufacturing efficiency. It has been proved that a method for producing a phosphor can be provided. Furthermore, a nitride phosphor having very good temperature characteristics can be provided.

  The firing step according to the present invention is preferably performed under a temperature condition in the range of 1200 ° C to 1600 ° C. More preferably, it is the range of 1200 to 1400 degreeC. The firing step according to the present invention is preferably performed through a one-step firing step of firing for several hours in the range of 1200 ° C. to 1400 ° C., but the first firing is performed at 700 ° C. to 1000 ° C. for several hours. Furthermore, it is possible to pass through a two-stage baking process in which the temperature is raised and the second baking is performed at 1200 to 1400 ° C. for several hours.

  The nitride phosphor preferably has at least one second emission spectrum in the yellow to red region. This is because a phosphor that emits white light can be manufactured in combination with the blue light emitting diode. More preferably, at least one second emission spectrum is present in the yellow-red region showing a wavelength of 580 nm to 630 nm.

  The firing is preferably performed using a crucible made of boron nitride. In Patent Document 1, a molybdenum crucible is used. Molybdenum crucibles may inhibit light emission or the reaction system. On the other hand, when the boron nitride crucible in the present invention is used, light emission is not inhibited or the reaction system is not inhibited, so that a very high purity nitride phosphor can be produced. Further, since the boron nitride crucible is decomposed in hydrogen nitrogen, it cannot be used in the synthesis method of Patent Document 1.

The nitride phosphor is L _X M _Y N _{(2 / 3X + 4 / 3Y)} : Z (L is at least selected from the group consisting of Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg II values) M contains at least one selected from the group consisting of IV values of C, Si, Ge, Sn, Ti, Zr, and Hf, where Z is an activator). It is preferable to contain at least the basic constituent elements represented. Thereby, a nitride phosphor having high brightness, high energy efficiency, and high quantum efficiency can be provided. Nitride phosphor _{is, L X M Y N (2} / 3X + 4 / 3Y): in addition to the basic structure element represented by Z, impurities remain contained in the raw material. For example, Co, Mo, Ni, Cu, Fe, etc. Since these impurities also cause a decrease in light emission luminance and inhibit the activity of the activator, it is preferable to remove them as much as possible from the system.

The nitride _{phosphor, L X M Y N (2} / 3X + 4 / 3Y): Z (L contains Mg, Ca, Sr, at least one selected from the group consisting of II valent Ba .M Is Si. Z is an activator) It is preferable to contain at least a basic constituent element represented by: This nitride phosphor has a peak wavelength in the vicinity of 560 nm to 680 nm when irradiated with the nitride phosphor according to the present invention using a blue light emitting diode having a wavelength of 400 nm to 460 nm in the first emission spectrum, This is because a phosphor that emits white light can be manufactured.

  It is preferable to include a step of mixing L nitride, M nitride and Z compound. This is because it is possible to manufacture a nitride phosphor with a very low yield and a very good manufacturing efficiency. The mixing step is preferably performed before firing, but may be mixed and refired during firing during firing. The compounding ratio of the nitride of L, the nitride of M, and the compound of Z which are raw materials or synthetic intermediates is the nitride of L: the nitride of M: the compound of Z = 1.80-2.20: 4-6 : It is preferable that it is 0.01-0.10. Thereby, a more uniform phosphor can be obtained.

The activator represented by Z is preferably Eu. _{L X M Y N (2 /} 3X + 4 / 3Y): By using the Eu to activator of the basic constituent elements represented by Z, because absorb a first emission spectrum around 250Nm～480nm. This is because the second emission spectrum can be provided in a region different from the first emission spectrum by this absorption. In particular, a phosphor that emits white light can be provided by combining a blue light emitting diode and the nitride phosphor of the present invention.

The L and the Z preferably have a molar ratio of L: Z = 1: 0.001-1. L _X M _Y N _{(2 / 3X + 4 / 3Y)} : By setting the blending ratio of Z in the basic constituent element represented by Z within the above range, a high-luminance nitride phosphor can be obtained. In addition, a nitride phosphor having good temperature characteristics can be provided. More preferably, the relationship is a molar ratio of L: Z = 1: 0.003 to 0.05. This is because a nitride phosphor having high luminance and good temperature characteristics can be provided within this range. Further, since the raw material Eu compound is expensive, it is possible to manufacture a cheaper phosphor by reducing the compounding ratio of the Eu compound.

  The present invention converts at least a part of the first emission spectrum, and has at least one second emission spectrum in a region different from the first emission spectrum, and contains at least nitrogen as a basic constituent element. The present invention relates to a nitride phosphor, wherein the nitride phosphor is a nitride phosphor manufactured by the method for manufacturing a nitride phosphor. Thereby, a nitride phosphor exhibiting light emission characteristics such as high luminance, high energy efficiency, and high quantum efficiency can be provided. In addition, a nitride phosphor having very good temperature characteristics can be provided.

  The present invention relates to a semiconductor light emitting device having a first emission spectrum, at least a part of the first emission spectrum, and having at least one second emission spectrum in a region different from the first emission spectrum. A nitride phosphor containing at least nitrogen as a basic constituent element, wherein the nitride phosphor is manufactured from the method for manufacturing a nitride phosphor The present invention relates to a light emitting device that is a phosphor. Thus, by combining a semiconductor light emitting element and a phosphor having extremely excellent light emission characteristics, a light emitting device capable of emitting various colors in addition to blue, green, and red can be provided. In particular, it is possible to provide a light-emitting device that emits light reddish white, which is highly demanded by the market.

The alkaline earth metal-based silicon nitride phosphor that is an example of the nitride phosphor of the present invention absorbs a short wavelength of 250 nm to 450 nm in the visible light region and reflects at a long wavelength of 580 nm to 650 nm. For example, a slightly reddish white light emitting device can be manufactured by irradiating the alkaline earth metal-based silicon nitride phosphor of the present invention with a blue light emitting diode. When a known Y ₃ Al ₅ O ₁₂ phosphor is used as a blue light emitting diode, visible light in a blue region and visible light in a yellow-orange region are combined to supply visible light in a white region. it can.

  As described above, the present invention provides a nitride phosphor excellent in light emission characteristics such as high luminance, high energy efficiency, and high quantum efficiency, and a method for manufacturing the same, and a stable light emitting device in which light emission is always performed. And has a technical significance that it is possible to provide a method for producing a nitride phosphor with good production efficiency.

  The present invention provides a phosphor having high emission luminance by converting a part of the first emission spectrum and having the second emission spectrum in a region different from the first emission spectrum, specifically, as a light source. By using a light emitting diode having an emission spectrum in the ultraviolet to blue region, the emission spectrum from the light emitting diode is converted, and a phosphor having excellent emission characteristics that emits white light can be provided. In addition, it is possible to provide a stable product of a phosphor having a high yield and high luminance emission characteristics, and a manufacturing method with good manufacturing efficiency. Furthermore, a light emitting device that emits white light by combining a blue light emitting diode and the phosphor can be provided. As described above, the present invention solves a problem that has not been solved conventionally, and has extremely excellent technical significance.

<Embodiment>
Hereinafter, a nitride phosphor, a manufacturing method thereof, and a light-emitting device according to the present invention will be described using embodiments of the invention and examples. However, the present invention is not limited to this embodiment and example. For comparative purposes, cerium-activated yttrium / aluminum / garnet phosphor (hereinafter referred to as YAG) is used.

  First, the nitride phosphor according to the present invention and the method for manufacturing the same will be described with reference to FIG.

  The raw material L is pulverized (P1). The raw material L contains at least one selected from the group consisting of Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg. In particular, the raw material L is preferably an alkaline earth metal composed of a group of Be, Mg, Ca, Sr, and Ba, more preferably a simple alkaline earth metal, but it may contain two or more. As the raw material L, an imide compound, an amide compound or the like can also be used. The raw material L is pulverized in a glove box in an argon atmosphere. The alkaline earth metal obtained by pulverization preferably has an average particle size of about 0.1 μm to 15 μm, but is not limited to this range. The purity of L is preferably 2N or higher, but is not limited thereto. In order to improve the mixed state, at least one of the metal L, the metal M, and the metal activator may be alloyed, nitrided, and used as a raw material after pulverization.

The raw material Si is pulverized (P2). Basic constituent elements _{L X M Y N (2 /} 3X + 4 / 3Y): M for Z, C, Si, Ge, containing at least one selected from the group consisting of IV value of Sn. As the raw material M, an imide compound, an amide compound, or the like can also be used. Of M, since it is inexpensive and easy to handle, the manufacturing method will be described using Si, but is not limited thereto. Si, Si ₃ N ₄ , Si (NH ₂ ) ₂ or the like can also be used. Similarly to the raw material L, Si is pulverized in a glove box in an argon atmosphere or a nitrogen atmosphere. The average particle size of the Si compound is preferably about 0.1 μm to 15 μm. The purity of Si is preferably 3N or higher.

  Next, the raw material L is nitrided in a nitrogen atmosphere (P3). This reaction formula is shown in [Chemical Formula 1].

ＩＩ価のＬを、窒素雰囲気中、６００℃〜９００℃、約５時間、窒化する。これにより、Ｌの窒化物を得ることができる。Ｌの窒化物は、高純度のものが好ましいが、市販のもの（高純度化学製）も使用することができる。

II-valent L is nitrided in a nitrogen atmosphere at 600 ° C. to 900 ° C. for about 5 hours. Thereby, the nitride of L can be obtained. The nitride of L is preferably high-purity, but a commercially available one (made by high-purity chemical) 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（宇部製）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 of high purity, but commercially available products (manufactured by Ube) can also be used.

L nitride L ₃ N ₂ is pulverized (P5). The nitride of L is pulverized in a glove box in an argon atmosphere or a nitrogen atmosphere.

Similarly, silicon nitride Si ₃ N ₄ is also pulverized (P6).

Similarly, Eu compound Eu ₂ O ₃ is also pulverized (P7). Basic constituent elements _{L X M Y N (2 /} 3X + 4 / 3Y): Z a Z is an activator, Eu, Cr, Mn, Pb , Sb, Ce, Tb, Pr, Sm, Tm, Ho, from Er At least one selected from the group consisting of: Of Z, the manufacturing method according to the present invention will be described using Eu that emits light in the red region, but is not limited thereto. Europium oxide is used as the Eu compound, but europium nitride or 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 preferably has a high purity, but commercially available products (manufactured by Shin-Etsu) 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.

After the above pulverization, L ₃ N ₂ , Si ₃ N ₄ and Eu ₂ O ₃ are mixed (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 L ₃ N ₂ , Si ₃ N ₄ and Eu ₂ O ₃ is fired in an ammonia atmosphere (P9). The target phosphor of L _X Si _Y N _Z : Eu could be obtained by firing (P10). The reaction formula by this firing is shown in [Chemical Formula 3].

ただし、目的とする蛍光体の組成を変更することにより、各混合物の配合比率は、適宜変更することができる。［化３］において、酸素が本発明に係る窒化物蛍光体に含有されているが、本発明の目的を達成することができるため、窒化物蛍光体には、基本構成元素Ｌ_ＸＭ_ＹＮ_{（２／３Ｘ＋４／３Ｙ）}：Ｚを含有していれば良い。

However, the mixing ratio of each mixture can be changed as appropriate by changing the composition of the target phosphor. In [Chemical Formula 3], oxygen is contained in the nitride phosphor according to the present invention. Since the object of the present invention can be achieved, the nitride phosphor includes a basic constituent element L _X M _Y N. _{(2 / 3X + 4 / 3Y)} : Z may be contained.

For firing, a tubular furnace, a small furnace, a high-frequency furnace, a metal furnace, or the like can be used. The firing temperature may be in the range of 1200 ° C. to 1600 ° C., but preferably the firing temperature is 1200 ° C. to 1400 ° C. It is preferable to use 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. This is because even when an alumina crucible is used, light emission is not inhibited in an ammonia atmosphere.

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

Hereinafter, in the nitride phosphor according to the present invention, L _X Si _Y N _Z : Eu, in the method for producing a nitride phosphor according to the present invention, L nitride, M nitride, Z, which is a synthetic intermediate thereof, The compound of will be described. The description will be made with reference to an alkaline earth metal nitride as the nitride of L, silicon nitride as the nitride of M, and europium oxide as the compound of Z, but the present invention is not limited thereto.

Z of the nitride phosphor of the present invention has europium Eu, which is a rare earth element, as the emission center. Europium mainly has bivalent and trivalent energy levels. Nitride phosphor of the present invention, an alkali earth metal-based silicon nitride maternal Eu ²⁺ is used as an activator. 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.

The raw material II-valent L is also easily oxidized. For example, commercially available Ca metal contains 0.66% O and 0.01% N. In order to nitride this Ca metal in the manufacturing process, commercially available calcium nitride Ca ₃ N ₂ (purchased from high purity chemical) was purchased and measured for O and N. As a result, O was 1.46% and N was 16.98. After opening, it was sealed again and allowed to stand for 2 weeks. As a result, O changed to 6.80% and N changed to 13.20%. Further, in another commercial calcium nitride _Ca 3 _{N 2,} O is 26.25%, N was 6.54%. Since this O becomes an impurity and causes deterioration of light emission, it is preferable to remove it from the system as much as possible. For this reason, nitriding of calcium was performed in a nitrogen atmosphere at 800 ° C. for 8 hours. As a result, the calcium nitride in which O was reduced to 0.67% was obtained. At this time, N in the calcium nitride was 15.92%.
[Comparative example]

Hereinafter, in order to clarify the characteristics of the present invention, a known alkaline earth metal-based silicon nitride phosphor Ca ₂ Si ₅ N ₈ : Eu was manufactured and measured. The test results are shown in Table 1.

比較例１は、公知の蛍光体Ｃａ_２Ｓｉ_５Ｎ_８：Ｅｕである。原料の配合比率は、窒化カルシウムＣａ_３Ｎ_２：窒化ケイ素Ｓｉ_３Ｎ_４：酸化ユウロピウムＥｕ_２Ｏ_３＝４：５：０．２である。この３化合物原料を、ＢＮるつぼに入れ、１４００℃、水素／窒素雰囲気下、小型炉で５時間、焼成を行った。温度は、室温から５時間かけて１４００℃まで、徐々に加熱し、１４００℃で５時間焼成を行った後、さらに５時間かけて室温まで、徐々に冷却を行った。この結果、体色が橙色、発光も橙色の蛍光体粉末が得られたが、肉眼観察を行ったところ、発光輝度が極めて低かった。

Comparative Example 1 is a known phosphor Ca ₂ Si ₅ N ₈ : Eu. The mixing ratio of the raw materials is calcium nitride Ca ₃ N ₂ : silicon nitride Si ₃ N ₄ : europium oxide Eu ₂ O ₃ = 4: 5: 0.2. The three compound raw materials were placed in a BN crucible and fired at 1400 ° C. in a hydrogen / nitrogen atmosphere in a small furnace for 5 hours. The temperature was gradually heated from room temperature to 1400 ° C. over 5 hours, calcined at 1400 ° C. for 5 hours, and then gradually cooled to room temperature over 5 hours. As a result, a phosphor powder having a body color of orange and light emission of orange was obtained. However, when observed with the naked eye, the emission luminance was extremely low.

  About Comparative Examples 2-5, it baked by changing the conditions of baking of a furnace, baking temperature, atmosphere, and shape. In Comparative Examples 2 to 4, firing is performed in a hydrogen / nitrogen atmosphere. The nitride phosphors obtained under the conditions of Comparative Examples 2 to 4 had extremely low emission luminance as observed with the naked eye. In Comparative Example 5, firing was performed in a hydrogen atmosphere, but no light was emitted by visual observation. Even when these tests were repeated, similar test results were obtained.

<Comparison test>
In order to clarify the effects of the present invention, firing was performed under the same conditions except for the difference in atmosphere. The results are shown in Tables 2 and 3. FIG. 2 is a diagram showing an emission spectrum when Example 2 and Comparative Example 6 are excited at Ex = 460 nm.

実施例１及び比較例６は原料の配合比率は、窒化カルシウムＣａ_３Ｎ_２：窒化ケイ素Ｓｉ_３Ｎ_４：酸化ユウロピウムＥｕ_２Ｏ_３＝１．９７：５：０．０３である。この３化合物原料を、ＢＮるつぼに入れ、室温から徐々に昇温を行い約８００℃で３時間、焼成を行い、さらに徐々に昇温を行い約１３５０℃で５時間、焼成を行い、焼成後、ゆっくりと５時間をかけて室温まで冷却した。比較例６は、水素／窒素雰囲気中で焼成を行った。実施例１のアンモニアの流量を１とした場合に、比較例６の水素／窒素の流量は、水素：窒素＝０．１：３の割合である。一方、実施例１は、アンモニア雰囲気中で焼成を行った。

In Example 1 and Comparative Example 6, the mixing ratio of the raw materials is calcium nitride Ca ₃ N ₂ : silicon nitride Si ₃ N ₄ : europium oxide Eu ₂ O ₃ = 1.97: 5: 0.03. The three compound raw materials are put in a BN crucible, heated gradually from room temperature and fired at about 800 ° C. for 3 hours, further heated gradually and fired at about 1350 ° C. for 5 hours. Cool slowly to room temperature over 5 hours. In Comparative Example 6, firing was performed in a hydrogen / nitrogen atmosphere. When the flow rate of ammonia in Example 1 is 1, the flow rate of hydrogen / nitrogen in Comparative Example 6 is a ratio of hydrogen: nitrogen = 0.1: 3. On the other hand, in Example 1, firing was performed in an ammonia atmosphere.

  As is clear from Tables 2 and 3 and FIG. 2, the emission luminance of Comparative Example 6 is 59.9%, whereas the emission luminance of Example 1 is 77.9%, which is 18%. Increased brightness. This difference in light emission luminance is extremely important from the viewpoint of light emission efficiency. The energy efficiency of Comparative Example 6 was 57.1%, whereas the energy efficiency of Example 1 was improved by 17.6% to 74.7%. Further, the quantum efficiency of Comparative Example 6 was 57.3%, whereas the quantum efficiency of Example 1 was improved by 20.7% to 78.0%. Thus, by changing the atmosphere, extremely remarkable light emission characteristics could be obtained. Such an improvement in 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.

  Furthermore, in Example 2, it baked on the same conditions except the difference in a baking pattern compared with Example 1. FIG. The firing pattern of Example 2 was gradually heated from room temperature, fired at about 1350 ° C. for 5 hours, and slowly cooled to room temperature over 5 hours. At this time, the light emission luminance was 82.0%, which was 22.1% higher than that of Comparative Example 6. The energy efficiency was 78.8%, an improvement of 21.7% compared to Comparative Example 6. Further, the quantum efficiency was 79.1%, which was improved by 21.8% compared with Comparative Example 6. Further, looking at the temperature characteristics by the relative luminance change of the lot to be measured when the room temperature is 100, in Comparative Example 6, it is 62.8 at a temperature of 200 ° C., whereas in Example 2, 67. A high value of 1 was shown. Moreover, at 300 degreeC, 23.5 of Example 2 was shown with the high numerical value with respect to 18.2 of the comparative example 6. FIG. This temperature characteristic indicates whether the composition of the nitride phosphor does not change when the nitride phosphor is provided on the surface of the light emitting element, and exhibits high light emission characteristics. It shows that it is so stable. From the results of Tables 2 and 3, it is clear that the nitride phosphor according to the present invention has better temperature characteristics and higher reliability than Comparative Example 6. As described above, extremely remarkable light emission characteristics were exhibited as compared with Comparative Example 6. Thereby, the improvement of the light emission characteristic which has not been solved conventionally can be achieved very easily.

<Examples 2 to 4>
Tables 4 and 5 show Examples 2 to 4 of the nitride phosphor according to the present invention. 3 to 5 show the light emission characteristics of Examples 2 to 4. FIG. FIG. 3 is a diagram illustrating an emission spectrum when Examples 2 to 4 are excited at Ex = 460 nm. FIG. 4 shows the excitation spectra of Examples 2-4. FIG. 5 shows the reflection spectra of Examples 2-4.

実施例２〜４は、本発明に係る窒化物蛍光体Ｌ_ＸＭ_ＹＮ_{（２／３Ｘ＋４／３Ｙ）}：Ｚの化学的特性や物理的特性を調べた結果である。窒化物蛍光体Ｌ_ＸＭ_ＹＮ_{（２／３Ｘ＋４／３Ｙ）}：Ｚには、（Ｃａ_１−ｔＥｕ_ｔ）_２Ｓｉ_５Ｎ_８である。実施例２〜４は、賦活剤ＺにＥｕを用いており、該Ｅｕの配合割合ｔを変更したものである。実施例２は、０．０１５、実施例３は、０．００５、実施例４は、０．０３、Ｅｕを含有している。焼成条件は、実施例２と同様で、室温から徐々に昇温を行い約１３５０℃で５時間、焼成を行い、ゆっくりと５時間かけて室温まで冷却した。

Examples 2-4, the nitride phosphor according to the present invention _{L X M Y N (2 /} 3X + 4 / 3Y): the results obtained by examining the chemical properties and physical properties of Z. Nitride phosphor _{L X M Y N (2 /} 3X + 4 / 3Y): The _Z, a _{(Ca 1-t Eu t)} 2 Si 5 N 8. In Examples 2 to 4, Eu is used as the activator Z, and the mixing ratio t of the Eu is changed. Example 2 contains 0.015, Example 3 contains 0.005, Example 4 contains 0.03, and Eu. The firing conditions were the same as in Example 2. The temperature was gradually raised from room temperature, fired at about 1350 ° C. for 5 hours, and slowly cooled to room temperature over 5 hours.

  It is clear that Example 2 has high temperature characteristics when compared with Example 3. Since generally used light-emitting elements rise in temperature to a temperature range of 100 ° C. to 150 ° C., when a nitride phosphor is to be formed on the surface of the light-emitting element, it is preferable that the light-emitting element is stable in the temperature range. From this point of view, Example 3 has excellent technical significance because of extremely good temperature characteristics.

  Example 4 has higher emission luminance and higher quantum efficiency than Example 2. Therefore, Example 4 shows extremely good light emission characteristics.

<Examples 5-7>
Table 6 shows Examples 5 to 7 of the nitride phosphor according to the present invention.

表６における実施例５は、Ｃａ_１．８Ｓｉ_５Ｎ_８：Ｅｕ_０．２である。原料の配合比率は、窒化カルシウムＣａ_３Ｎ_２：窒化ケイ素Ｓｉ_３Ｎ_４：酸化ユウロピウムＥｕ_２Ｏ_３＝１．８：５：０．２である。
Ｃａ_３Ｎ_２（高純度化学製） １．２８４ｇ
Ｓｉ_３Ｎ_４（宇部製） ３．３７６ｇ
Ｅｕ_２Ｏ_３（信越製） ０．３３９ｇ
この３化合物原料を、ＢＮるつぼに入れ、１２００℃から１３５０℃、アンモニア雰囲気下、管状炉で５時間、焼成を行った。温度は、室温から５時間かけて１３５０℃まで、徐々に加熱し、５時間焼成を行った後、さらに５時間かけて室温まで、徐々に冷却を行った。アンモニアガスは、２ｌ／ｍｉｎの割合で、終始流し続けた。この結果、体色が橙色、発光も橙色の窒化物蛍光体粉末が得られた。この蛍光体粉末は、肉眼観察において、蛍光体粉末全体が、橙色に発光している。このように、蛍光体全体が均一に発光が行われているため、製造効率の向上、安定した窒化物蛍光体の提供、製造コストの低廉を図ることができる。

Examples in Table 6 _5, Ca _1.8 Si ₅ N _8: a _{Eu 0.2.} The mixing ratio of the raw materials is calcium nitride Ca ₃ N ₂ : silicon nitride Si ₃ N ₄ : europium oxide Eu ₂ O ₃ = 1.8: 5: 0.2.
Ca ₃ N ₂ (manufactured by high purity chemical) 1.284 g
Si ₃ N ₄ (Ube) 3.376 g
Eu ₂ O ₃ (manufactured by Shin-Etsu) 0.339 g
The three compound raw materials were put in a BN crucible and fired in a tubular furnace at 1200 to 1350 ° C. in an ammonia atmosphere for 5 hours. The temperature was gradually heated from room temperature to 1350 ° C. over 5 hours, baked for 5 hours, and then gradually cooled to room temperature over 5 hours. Ammonia gas continued to flow at a rate of 2 l / min throughout. As a result, a nitride phosphor powder having a body color of orange and light emission of orange was obtained. In the phosphor powder, the whole phosphor powder emits orange light when observed with the naked eye. As described above, since the entire phosphor emits light uniformly, the production efficiency can be improved, the stable nitride phosphor can be provided, and the production cost can be reduced.

Example 6 is a phosphor Ca _1.96 Eu _0.04 Si ₅ N ₈ . The compounding ratio of the raw materials is calcium nitride Ca ₃ N ₂ : silicon nitride Si ₃ N ₄ : europium oxide Eu ₂ O ₃ = 1.96: 5: 0.04.
Ca ₃ N ₂ (manufactured by high purity chemical) 2.888 g
Si ₃ N ₄ (manufactured by Ube) 6.971 g
Eu ₂ O ₃ (manufactured by Shin-Etsu) 0.140 g
This three-compound raw material was also fired by the same test method as in Example 5. As a result, as in Example 5, a phosphor powder having an orange body color and an orange light emission was obtained.

Example 7 is the phosphor Ca _1.985 Eu _0.015 Si ₅ N ₈ . The mixing ratio of the raw materials is calcium nitride Ca ₃ N ₂ : silicon nitride Si ₃ N ₄ : europium oxide Eu ₂ O ₃ = 1.98: 5: 0.02.
Ca ₃ N ₂ (manufactured by High Purity Chemical) 2.930G
Si ₃ N ₄ (Ube) 7.00 g
Eu ₂ O ₃ (manufactured by Shin-Etsu) 0.070 g
This three-compound raw material was also fired by the same test method as in Example 5. As a result, as in Example 5, a phosphor powder having an orange body color and an orange light emission was obtained. In addition, the nitride phosphor obtained in Example 7 had higher luminance than the comparative example in the naked eye observation. Further, the phosphor obtained in this Example 7 exhibited a light emission luminance substantially similar to that in Example 6.

<Measurement results of phosphors obtained in Examples 6 and 7>
As a representative example, the nitride phosphors of Examples 6 and 7 were measured. The test results are shown in FIGS. FIG. 6 is a graph showing an emission spectrum when Examples 6 and 7 are excited at Ex = 400 nm. FIG. 7 is a diagram showing an emission spectrum when Examples 6 and 7 are excited at Ex = 460 nm. FIG. 8 is a diagram showing the reflectance of Examples 6 and 7. In FIG. FIG. 9 is a diagram showing excitation spectra of Examples 6 and 7.

  The nitride phosphors of Examples 6 and 7 were irradiated with light in the visible light region having a wavelength of 400 nm. In FIG. 6, the nitride phosphors of Examples 6 and 7 emit the most at 610 nm.

  The nitride phosphors of Examples 6 and 7 were irradiated with light in the visible light region having a wavelength of 460 nm. In FIG. 7, Example 6 emits most at 620 nm, and Example 7 emits most at 610 nm. Thus, since Example 6 is shifted to the long wavelength side with respect to Example 7, it emits more red light. Since 460 nm is the wavelength with the highest emission luminance among the emission wavelengths of known blue light emitting diodes, a slightly reddish white nitride phosphor is produced by combining blue and yellow-red emission spectra. can do. The reflectance of the nitride phosphor of Example 7 is higher than that of the nitride phosphor of Example 6. Both the nitride phosphors of Examples 6 and 7 absorb light on the short wavelength side in the visible light region. The excitation spectrum of the nitride phosphor of Example 6 is higher than that of the nitride phosphor of Example 7.

  6 to 9, light emission in the yellow-red visible light region was confirmed.

<Examples 8 and 9>
Example 8 is a phosphor _{Sr 1.97 Eu 0.03 Si 5 N 8} . The mixing ratio of the raw materials is calcium nitride Sr ₃ N ₂ : silicon nitride Si ₃ N ₄ : europium oxide Eu ₂ O ₃ = 1.97: 5: 0.03. This three-compound raw material is put in a BN crucible, fired at 800 ° C. to 1000 ° C. for 3 hours in a tubular furnace, then fired at 1250 ° C. to 1350 ° C. for 5 hours, and gradually cooled to room temperature over 5 hours. Went. Ammonia gas continued to flow from start to finish at a rate of 1 l / min. As a result, a nitride phosphor emitting pink light with the naked eye was obtained when the body color was pink and irradiation with 365 nm light was performed. The temperature characteristics at 200 ° C. of the nitride phosphor of Example 8 are as extremely high as 87.7%. Tables 7 and 8 show Examples 8 and 9 of the nitride phosphor according to the present invention.

実施例９は、蛍光体Ｓｒ_１．４Ｃａ_０．６Ｓｉ_５Ｎ_８：Ｅｕである。実施例９は、実施例８と同様の焼成条件で焼成を行った。図１０は、実施例９を、Ｅｘ＝４６０ｎｍで励起したときの発光スペクトルを示す図である。図１０から明らかなように、Ｅｘ＝４６０ｎｍの発光スペクトルの光を照射したところ、ＩＩ価のＳｒを単独で用いたときよりも、ＳｒとＣａを組み合わせたときの方が、長波長側にシフトした。発光スペクトルのピークは、６５５ｎｍである。これにより、青色発光素子と実施例９の蛍光体とを組み合わせると赤みを帯びた白色に発光する蛍光体を得ることができる。また、実施例９の蛍光体Ｓｒ_１．４Ｃａ_０．６Ｓｉ_５Ｎ_８：Ｅｕの量子効率は、８６．７％と、良好である。

Example 9, the phosphor _{Sr 1.4 Ca 0.6 Si 5 N 8} : is Eu. In Example 9, firing was performed under the same firing conditions as in Example 8. FIG. 10 is a graph showing an emission spectrum when Example 9 is excited at Ex = 460 nm. As is clear from FIG. 10, when the light having an emission spectrum of Ex = 460 nm is irradiated, the combination of Sr and Ca is shifted to the longer wavelength side than when II-valent Sr is used alone. did. The peak of the emission spectrum is 655 nm. Thereby, when the blue light emitting element and the phosphor of Example 9 are combined, a phosphor emitting reddish white light can be obtained. In addition, the quantum efficiency of the phosphor Sr _1.4 Ca _0.6 Si ₅ N ₈ : Eu of Example 9 is as good as 86.7%.

<Other embodiments>
Various examples of nitride phosphors are shown. Nitride phosphor according to the present _{invention, L X M Y N (2} / 3X + 4 / 3Y): is a nitride phosphor represented by Z. L, which is a basic constituent element of the nitride phosphor, contains at least one selected from the group consisting of II, Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, and M is It contains at least one selected from the group consisting of IV values of C, Si, Ge, and Sn, and Z is an activator. The activator Z is preferably Eu, but Cr, Mn, Pb, Sb, Ce, Tb, Sm, Pr, Tm, Ho, Er, and the like can also be used.

The nitride phosphors are Sr ₂ Si ₅ N ₈ : Eu, Ba ₂ Si ₅ N ₈ : Eu, Mg ₂ Si ₅ N ₈ : Eu, Zn ₂ Si ₅ N ₈ : Eu, SrSi ₇ N ₁₀ : Eu, BaSi ₇ N ₁₀ : Eu, MgSi ₇ N ₁₀ : Eu, ZnSi ₇ N ₁₀ : Eu, Sr ₂ Ge ₅ N ₈ : Eu, Ba ₂ Ge ₅ N ₈ : Eu, Mg ₂ Ge ₅ N ₈ : Eu, Zn ₂ Ge ₅ N ₈ : Eu, SrGe ₇ N ₁₀ : Eu, BaGe ₇ N ₁₀ : Eu, MgGe ₇ N ₁₀ : Eu, ZnGe ₇ N ₁₀ : Eu, Sr _1.8 Ca _0.2 Si ₅ N ₈ : Eu, Ba _1.8 Ca _0.2 Si ₅ N ₈ : Eu, Mg _1.8 Ca _0.2 Si ₅ N ₈ : Eu, Zn _1.8 Ca _0.2 Si ₅ N ₈ : Eu, Sr _0.8 Ca _{0 .2} Si ₇ N _{10: u, Ba 0.8 Ca 0.2 Si 7} N 10: Eu, Mg 0.8 Ca 0.2 Si 7 N 10: Eu, Zn 0.8 Ca 0.2 Si 7 N 10: Eu, Sr 0. ₈ Ca _0.2 Ge ₇ N ₁₀ : Eu, Ba _0.8 Ca _0.2 Ge ₇ N ₁₀ : Eu, Mg _0.8 Ca _0.2 Ge ₇ N ₁₀ : Eu, Zn _0.8 Ca _0.2 Ge ₇ N ₁₀ : Eu, Sr _0.8 Ca _0.2 Si ₆ GeN ₁₀ : Eu, Ba _0.8 Ca _0.2 Si ₆ GeN ₁₀ : Eu, Mg _0.8 Ca _0.2 Si ₆ GeN ₁₀ : _{Eu, Zn 0.8 Ca 0.2 Si 6} GeN 10: Eu, Sr 2 Si 5 N 8: Pr, Ba 2 Si 5 N 8: Pr, Sr 2 Si 5 N 8: Tb, BaGe 7 N 10: Ce Can be manufactured. However, the present invention is not limited to this nitride phosphor.

<Light-emitting device 1>
FIG. 11 is a diagram showing a light emitting device 1 according to the present invention.

  The LED chip uses a semiconductor light emitting device 1 having a 460 nm InGaN-based semiconductor layer having a light emission peak in a blue region as a light emitting layer. The semiconductor light emitting device 1 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 are electrically connected to the lead electrode 2. A wire 4 is formed. An insulating sealing material 3 is formed so as to cover the outer periphery of the lead electrode 2 to prevent a short circuit. Above the semiconductor light emitting element 1, a translucent window portion 7 extending from a lid 6 at the top of the package 5 is provided. The nitride phosphor 8 according to the present invention is applied to the entire inner surface of the translucent window portion 7.

The emission spectrum emitted in blue by the semiconductor light emitting device 1 is that the indirect emission spectrum reflected by the reflector and the emission spectrum directly emitted from the semiconductor light emitting device 1 are applied to the nitride phosphor 8 of the present invention. The phosphor emits white light. The nitride phosphor 8 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 desired It is possible to obtain a light spectrum.

  When a white LED lamp is formed using the light emitting diode formed as described above, the yield is 99%. As described above, 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.

<Light-emitting device 2>
FIG. 12 is a diagram showing a light emitting device 2 according to the present invention. FIG. 13 is a diagram showing an emission spectrum of the light emitting device 2 according to the present invention. FIG. 14 is a diagram showing chromaticity coordinates of the light emitting device 2 according to the present invention.

  The light emitting device 2 includes a semiconductor layer 12 stacked on an upper part of a sapphire substrate 11, a lead frame electrically connected by a wire extending from an electrode formed on the semiconductor layer 12, and the sapphire substrate 11 and the semiconductor layer 12. The nitride phosphor 14 according to the present invention is provided so as to cover the outer periphery of the semiconductor light emitting device, and the epoxy resin 15 covering the outer peripheral surfaces of the nitride phosphor 14 and the lead frame 13. Yes.

  A large number of 350 μm-square semiconductor light-emitting elements are prepared in which a nitride semiconductor layer 12 having a double hetero structure is formed on a sapphire substrate 11 and a positive electrode and a negative electrode are formed on the same plane side of the nitride semiconductor layer 12. . The semiconductor layer 12 is provided with a light emitting layer, and an emission peak output from the light emitting layer has an emission spectrum of 460 nm in the blue region. As the semiconductor light emitting device composed of the sapphire substrate 11 and the semiconductor layer 12, a known semiconductor light emitting device can be used, but a semiconductor light emitting device having a GaN composition is preferably used.

  Next, this semiconductor light-emitting element is set on a die bonder, face-up to a lead frame 13 provided with a cup, and die bonded. After die bonding, the lead frame 13 is transferred to a wire bonder, the negative electrode of the semiconductor light emitting element is wire bonded to the lead frame 13a provided with a cup with a gold wire, and the positive electrode is wire bonded to the other lead frame 13b.

  Next, the nitride phosphor 14 is transferred into the cup of the lead frame 13 using a dispenser of the molding apparatus.

  After the nitride phosphor 14 is injected, the lead frame 13 is immersed in a mold mold in which the epoxy resin 15 is previously injected, and then the mold is removed to cure the resin, and a bullet-type LED as shown in FIG. And

  The nitride phosphor 14 of the light emitting device 2 uses the nitride phosphor 8a according to the present invention. When an electric current is passed through the semiconductor layer 12, a blue LED having an emission spectrum excited at 460 nm emits light, and this emission spectrum is converted by the nitride phosphor 8a covering the semiconductor layer 12, and an emission spectrum different from the emission spectrum. Have Thereby, the light emitting device 2 that emits reddish white light can be obtained.

  Tables 9 and 10 show the light emission characteristics of the light emitting device 2 according to the present invention. FIG. 14, Table 9 and Table 10 also show the measurement results of a light emitting device using a YAG phosphor as a comparison target of the light emitting device 2 according to the present invention.

本発明に係る発光装置２の窒化物蛍光体８ａは、実施例２の窒化物蛍光体と、樹脂と、セリウムで付活されたイットリウム・アルミニウム・ガーネット蛍光物質（以下、ＹＡＧという。）とを混合したものを用いる。これらの重量比は、樹脂：ＹＡＧ：実施例２の窒化物蛍光体＝２５：６：３である。一方、青色半導体発光素子とＹＡＧの蛍光体との組み合わせの発光装置の蛍光体は、樹脂：ＹＡＧ＝２５：６の重量比で混合している。本発明に係る発光装置２は、発光ピークが青色領域にある４６０ｎｍのＩｎＧａＮ系半導体層を有する半導体発光素子１（以下、青色ＬＥＤという。）を用いる。青色ＬＥＤの発光スペクトルを、窒化物蛍光体８ａが変換し、やや赤みを帯びた白色に発光する発光装置２を得ることができる。

The nitride phosphor 8a of the light emitting device 2 according to the present invention includes the nitride phosphor of Example 2, a resin, and an yttrium / aluminum / garnet phosphor (hereinafter referred to as YAG) activated with cerium. Use a mixture. These weight ratios are resin: YAG: nitride phosphor of Example 2 = 25: 6: 3. On the other hand, the phosphor of the light emitting device in which the blue semiconductor light emitting element and the YAG phosphor are combined is mixed in a weight ratio of resin: YAG = 25: 6. The light emitting device 2 according to the present invention uses a semiconductor light emitting element 1 (hereinafter referred to as a blue LED) having a 460 nm InGaN-based semiconductor layer having an emission peak in a blue region. The emission spectrum of the blue LED is converted by the nitride phosphor 8a, and the light-emitting device 2 that emits light reddish white can be obtained.

  The light emitting device 2 according to the present invention is compared with a light emitting device using a blue LED and a YAG phosphor. The YAG phosphor has a peak wavelength of 463.47 nm, whereas the nitride phosphor 8a has an emission spectrum at a position different from 596.00 nm. Also in the chromaticity coordinates, a light emitting device using a YAG phosphor is white which emits light with a relatively pale blue color tone x = 0.348 and color tone y = 0.367. On the other hand, the light emitting device 2 using the nitride phosphor 8a has a reddish white color represented by a color tone x = 0.454 and a color tone y = 0.416. The color temperature is 2827.96K, and has a light emission characteristic close to that of a light bulb. Further, in terms of color rendering, the light emitting device 2 using the nitride phosphor 8a exhibits almost the same color rendering as the light emitting device using the YAG phosphor. Furthermore, the light emitting device 2 according to the present invention has a high luminous efficiency of 24.87 lm / W.

  For this reason, it has a very important technical significance that a light emitting device close to a light bulb color can be manufactured.

  The nitride phosphor of the present invention can be used for fluorescent display tubes, displays, PDPs, CRTs, FLs, FEDs, projection tubes and the like, in particular, light emitting devices using blue light emitting diodes or ultraviolet light emitting diodes as light sources. Moreover, the light-emitting device can be used for fluorescent lamps for storefront display lighting, medical field lighting, etc., and can also be applied to the field of mobile phone backlights and light-emitting diodes (LEDs). it can.

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 Example 2 and Comparative Example 6 are excited by Ex = 460 nm. It is a figure which shows the emission spectrum when Examples 2-4 are excited by Ex = 460nm. The excitation spectrum of Examples 2-4 is shown. The reflection spectrum of Examples 2-4 is shown. It is a figure which shows the emission spectrum when Example 6 and 7 is excited by Ex = 400 nm. It is a figure which shows the emission spectrum when Example 6 and 7 is excited by Ex = 460nm. It is a figure which shows the reflectance of Example 6 and 7. It is a figure which shows the excitation spectrum of Example 6 and 7. It is a figure which shows the emission spectrum when Example 9 is excited by Ex = 460 nm. It is a figure which shows the light-emitting device 1 which concerns on this invention. It is a figure which shows the light-emitting device 2 which concerns on this invention. It is a figure which shows the emission spectrum of the light-emitting device 2 which concerns on this invention. It is a figure which shows the chromaticity coordinate of the light-emitting device 2 which concerns on this invention.

Explanation of symbols

P1 Raw material L is pulverized.
P2 Raw material Si is pulverized.
P3 Raw material L is nitrided in a nitrogen atmosphere.
P4 The raw material Si is nitrided in a nitrogen atmosphere.
The P6 silicon nitride Si ₃ N ₄ that grinds the P5 L nitride L ₃ N ₂ is ground.
The P7 Eu compound Eu ₂ O ₃ is ground.
_{P8 L 3 N 2, Si 3} N 4, mixing _Eu 2 _{O 3.}
A mixture of P9 L ₃ N ₂ , Si ₃ N ₄ and Eu ₂ O ₃ is fired in an ammonia atmosphere.
P10 L _X Si _Y N _Z: it is possible to obtain a phosphor represented by Eu.
DESCRIPTION OF SYMBOLS 1 Semiconductor light-emitting device 2 Lead electrode 3 Insulating sealing material 4 Conductive wire 5 Package 6 Lid 7 Translucent window part 8 Phosphor 11 of the present invention Sapphire substrate 12 Semiconductor layers 13, 13 a, 13 b Lead frame 14 Nitride fluorescence Body 8a
15 Epoxy resin

Claims (4)

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 has a first phosphor and a second phosphor,
The first phosphor is a nitride phosphor that emits light of the second emission spectrum in a yellow to red region,
The second phosphor is a phosphor having an emission color on a shorter wavelength side than the first phosphor,
The light emitting device has a light emission characteristic close to a light bulb color. The nitride 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, Ti, Zr, and Hf. At least one selected from the group consisting of IV values, and at least selected from the group consisting of N, Eu, Cr, Mn, Pb, Sb, Ce, Tb, Pr, Sm, Tm, Ho, Er, Yb, Nd The light-emitting device according to claim 1, wherein the phosphor has crystallinity having a kind of activator. The light emitting device according to claim 1, wherein the second phosphor has a light emission color of blue, green, or yellow. The semiconductor light emitting device has an emission peak wavelength in a range of 360 nm to 550 nm, and the intensity of the emission peak wavelength of the phosphor is larger than the intensity of the emission peak wavelength of the semiconductor light emitting device. Item 4. The light emitting device according to Item 1.

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