JP2006070109A - Phosphor and light source - Google Patents

Phosphor and light source Download PDF

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JP2006070109A
JP2006070109A JP2004253312A JP2004253312A JP2006070109A JP 2006070109 A JP2006070109 A JP 2006070109A JP 2004253312 A JP2004253312 A JP 2004253312A JP 2004253312 A JP2004253312 A JP 2004253312A JP 2006070109 A JP2006070109 A JP 2006070109A
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phosphor
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light
element
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JP4543251B2 (en
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Masahiro Goto
Akira Nagatomi
Katayuki Sakane
Shuji Yamashita
堅之 坂根
修次 山下
昌大 後藤
晶 永富
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Dowa Mining Co Ltd
同和鉱業株式会社
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphor for a white LED which hardly undergoes changes in luminous intensity and can maintain high luminance even when the temperature of the phosphor is raised by heat generation in a luminous part, or the like, and to provide a light source and an LED using the phosphor. <P>SOLUTION: Ca<SB>3</SB>N<SB>2</SB>(2N), AlN(3N), Si<SB>3</SB>N<SB>4</SB>(3N) and Eu<SB>2</SB>O<SB>3</SB>(3N) are prepared as raw materials, weighed so that the molar ratio of each element satisfies the relationship (Ca+Eu):Al:Si=1:1:1, and mixed. The resultant mixture is kept and baked in an inert atmosphere at 1,500°C for 3 hr and subsequently pulverized to give the phosphor of a compositional formula: Ca<SB>0.985</SB>SiAlN<SB>3</SB>:Eu<SB>0.015</SB>. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to phosphors used in display devices such as CRT, PDP, FED, EL, etc., and lighting devices such as fluorescent display tubes and fluorescent lamps, and in particular, excited by light such as ultraviolet and blue. The present invention relates to a phosphor that emits visible light or white light, and a light source such as an LED, an illumination device, or a display device using the phosphor.

  At present, discharge fluorescent lamps and incandescent lamps used as lighting devices have various problems such as containing harmful substances such as mercury and short life. However, in recent years, LEDs emitting blue and ultraviolet light have been developed one after another, and by combining ultraviolet to blue light generated from the LED and a phosphor having an excitation band in the ultraviolet to blue wavelength range, Research and development has been actively conducted on whether the body emits white light and whether the white light can be used as next-generation lighting. This white LED illumination is composed of a semiconductor element and a phosphor with little heat generation, so it does not break like a conventional incandescent bulb, has a long life, and contains harmful substances such as mercury. There is an advantage that it is unnecessary, and it is an ideal lighting device.

  Here, in order to obtain white light by combining the LED and the phosphor described above, two methods are generally considered. One is a combination of an LED that emits blue light and a phosphor that receives the blue light emission and is excited to emit yellow light, and obtains white light emission by combining the blue light emission and the yellow light emission.

The other is an LED that emits near ultraviolet / ultraviolet light, a phosphor that emits red (R) light when excited by the near ultraviolet / ultraviolet light emission, a phosphor that emits green (G) light, and a fluorescent light that emits blue (B) light. The body and the other are combined to obtain white light emission by the other light of RGB. This method of obtaining white light emission by RGB other light can obtain any light emission color other than white light depending on the combination and mixing ratio of RGB other phosphors, and has an application range as a lighting device. wide. Then, as the phosphor used in such applications, if the red phosphor, for example, Y 2 O 2 S: Eu , La 2 O 2 S: Eu, 3.5MgO · 0.5MgF 2 · GeO 2: If there is Mn, (La, Mn, Sm) 2 O 2 S · Ga 2 O 3 : Eu and a green phosphor, for example, ZnS: Cu, Al, SrAl 2 O 4 : Eu, BAM: Eu, Mn In the case of a yellow phosphor, for example, YAG: Ce is present, and in the case of a blue phosphor, for example, BAM: Eu, Sr 5 (PO 4 ) 3 Cl: Eu, ZnS: Ag, (Sr, Ca , Ba, Mg) 10 (PO 4 ) 6 Cl 2 : Eu. Then, by combining these RGB and other phosphors with a light emitting part such as an LED that emits near ultraviolet light or ultraviolet light, it is attempted to obtain a light source or an illuminating device such as a white or desired LED. ing.

However, white LED illumination using a combination of a blue LED and a yellow phosphor (YAG: Ce) results in insufficient light emission on the long wavelength side in the visible light region, resulting in light emission with a slight bluish white. Can not get a slightly reddish white light like a light bulb.
Also, in white LED illumination using a combination of near-ultraviolet / ultraviolet LEDs and RGB and other phosphors, the red phosphor of the three color phosphors has lower excitation efficiency on the longer wavelength side than the other phosphors, and the luminous efficiency Therefore, it is necessary to increase the mixing ratio of only the red phosphor, and the phosphor for improving the luminance is insufficient, so that a high luminance white color cannot be obtained. Furthermore, since the emission spectrum of the phosphor is sharp, there is a problem that the color rendering property of the obtained light is poor.
Therefore, recently, an oxynitride glass phosphor that has good excitation on the long wavelength side and a broad emission half-width emission peak (see, for example, Patent Document 1), and a phosphor based on sialon (for example, a patent) References 2 and 3) and phosphors containing nitrogen such as silicon nitride (for example, see Patent References 4 and 5) have been reported. The phosphor containing nitrogen has a characteristic of having a good excitation band even in light having a wavelength of 400 nm or more because the ratio of the covalent bond is larger than that of the oxide phosphor and the like. Has attracted attention as a body.

JP 2001-214162 A JP 2003-336059 A JP 2003-124527 A Special table 2003-515655 gazette JP 2003-277746 A

  In addition to the above-described method of using a blue or near ultraviolet / ultraviolet LED as the light emitting unit and combining the light emitting unit and the phosphor to produce a light source, an ultraviolet discharge lamp or the like is used as the light emitting unit, There is also a method for producing a light source by combining an electric lamp or the like with a phosphor.

  The present inventors made various light sources described above and studied their light emission characteristics. Then, it has been found that there are some light sources in which the light emission intensity decreases or the color of light emission changes with the light emission time. Any of these reductions in emission intensity and changes in the color of light emission are obstacles to using the light source for general purposes. Here, since almost no change is observed in the LED and the ultraviolet discharge lamp after a predetermined emission time has elapsed, the cause of the decrease in the emission intensity and the change in the color of the emission is due to the deterioration of the phosphor. it was thought. Therefore, the present invention aims to provide a phosphor in which the emission intensity does not decrease or the color of the emitted light does not change with the emission time, and further provides a light source using the phosphor. For the purpose.

In order to solve the above-mentioned problems, the present inventors have investigated the cause of deterioration of the phosphor. As a result, when the above-described light source emits light, the light emitting portion generates heat due to the current injected to cause the LED or ultraviolet discharge lamp incorporated in the light source to emit light, and this heat generation also raises the temperature of the phosphor. Then, it turned out that the luminous intensity of the phosphor is reduced due to the temperature rise of the phosphor, and that the brightness of the white LED is lowered and the color tone is changed due to the collapse of the emission intensity ratio of each phosphor. .
The present inventors have developed and tested a phosphor having a small change in emission intensity over a wide temperature range based on the elucidated results. As a result, it has been found that if the light emission intensity change is within a predetermined range, a phenomenon in which the light emission intensity decreases or the color of light emission changes with the light emission time can be suppressed. Further, it has also been found that if the rate of decrease in emission intensity due to temperature rise of each phosphor used is approximately the same, the change in color of emitted light can be further suppressed.
The present invention is based on the above elucidated results.

That is, the first configuration for solving the above-described problem is:
A phosphor that emits visible light when excited by excitation light in the ultraviolet to green range,
The value of the relative intensity of the maximum peak in the emission spectrum at 25 ° C. of the phosphor irradiated with the predetermined excitation light is defined as the emission intensity P 25 .
When the value of the relative intensity of the maximum peak at 200 ° C. of the phosphor irradiated with the predetermined excitation light is defined as emission intensity P 200 ,
(P 25 −P 200 ) / P 25 ≦ 0.25.

The second configuration is
A phosphor that emits visible light when excited by excitation light in the ultraviolet to green range,
The value of the relative intensity of the maximum peak in the emission spectrum at 25 ° C. of the phosphor irradiated with the predetermined excitation light is defined as the emission intensity P 25 .
When the value of the relative intensity of the maximum peak at 100 ° C. of the phosphor irradiated with the predetermined excitation light is defined as emission intensity P 100 ,
(P 25 −P 100 ) / P 25 ≦ 0.10.

The third configuration is
Composition formula MmAaBbOoNn: Z (where M element is one or more elements having a valence of II, A element is one or more elements having a valence of III, and B element is an IV valence) One or more elements having a valence, O is oxygen, N is nitrogen, Z element is an activator, m> 0, a> 0, b> 0, o ≧ 0, n = 2 / 3m + a + 4 / 3b-2 / 3o). The phosphor according to the first or second configuration, characterized in that

The fourth configuration is
The M element is one or more elements selected from Mg, Ca, Sr, Ba, and Zn, and the A element is one or more elements selected from B (boron), Al, and Ga, The phosphor according to the third configuration, wherein the B element is Si and / or Ge, and the Z element is one or more elements selected from rare earths and transition metals.

The fifth configuration is
The phosphor according to the third or fourth configuration, wherein the A element is Al and the B element is Si.

The sixth configuration is
The phosphor according to any one of the third to fifth configurations, wherein the M element is Ca and the Z element is Eu.

The seventh configuration is
The phosphor according to any one of the third to sixth configurations, wherein the values of m, a, and b are m = a = b = 1.

The eighth configuration is
The phosphor according to any one of the first to seventh configurations, which is represented by a composition formula CaAlSiN 3 : Eu.

The ninth configuration is
The phosphor according to any one of the third to sixth configurations, wherein the values of m, a, and b are m = 1, a = 2, 4.0 ≦ b <6.0. .

The tenth configuration is
The phosphor according to any one of the first to sixth configurations or the ninth configuration, which is represented by a composition formula CaAl 2 Si 4 N 8 : Eu.

The eleventh configuration is
The phosphor according to any one of the first to tenth configurations, wherein the phosphor is in a powder form.

The twelfth configuration is
The phosphor according to the eleventh configuration, wherein the phosphor has an average particle size of 20 μm or less and 1 μm or more.

The thirteenth configuration is
The phosphor according to any one of the first to twelfth configurations, and a light emitting unit that emits light of a predetermined wavelength, wherein a part of the light of the predetermined wavelength is used as an excitation source, and the phosphor is the predetermined wavelength The light source is characterized by emitting light at a different wavelength.

The fourteenth configuration is
The predetermined wavelength is a light source according to the thirteenth configuration, which is any wavelength of 250 nm to 550 nm.

The fifteenth configuration is
The light source according to the thirteenth or fourteenth configuration, wherein the light emitting unit is an LED.

The phosphor according to the first configuration has (P 25 -P 200 ) / P 25 when the emission intensity when the phosphor is 25 ° C. is P 25 and the emission intensity when 200 ° C. is P 200. Since ≦ 0.25, even if the temperature of the phosphor is increased to 200 ° C., the decrease in emission intensity remains within 25%. For example, even when an ultraviolet discharge lamp or the like is used as the light emitting portion, it is remarkable. There is no significant decrease in light intensity, and it is suitable as a phosphor used in a light source installed in a warehouse, hallway, or the like.

The phosphor according to the second configuration has (P 25 −P 100 ) / P 25 where the emission intensity when the phosphor is 25 ° C. is P 25 and the emission intensity when the phosphor is 100 ° C. is P 100. Since ≦ 0.10, even if the temperature of the phosphor is increased to 100 ° C., the decrease in emission intensity remains within 10%. There is no change in taste, and it is suitable as a phosphor used for a light source installed in an office, a living room or the like.

  The phosphor described in any one of the third to twelfth structures represented by the composition formula MmAaBbOoNn: Z has high heat resistance and is incorporated in the light source together with the light emitting part, and is heated by the light emitting part. However, it is a phosphor suitable for producing various light sources in combination with an ultraviolet discharge lamp, an LED, or the like with little decrease in emission intensity.

  The light source described in any one of the thirteenth to fifteenth configurations generates little heat, has a long life, and does not have a significant decrease in light intensity even when used for a long time, or has a remarkable light color. It is an excellent light source that does not feel any change.

(The phosphor of the first example)
As a phosphor of the first example that satisfies the characteristics of (P 25 −P 200 ) / P 25 ≦ 0.25 and (P 25 −P 100 ) / P 25 ≦ 0.10, the composition formula MmAaBbOoNn: Z The phosphor described will be described.
In the phosphor represented by the composition formula MmAaBbOoNn: Z, the M element is one or more elements having a valence of II, the A element is one or more elements having a valence of III, and B The element is one or more elements having a valence of IV. O is oxygen and N is nitrogen. The Z element is an element that acts as an activator, and is at least one element selected from rare earth elements or transition metal elements. The phosphor according to the present invention having the composition can stably obtain high emission intensity over a wide temperature range.

  In addition, when the phosphor has a chemically stable structure, an impurity phase that does not contribute to light emission is less likely to be generated in the structure. Here, in order for the phosphor to have a chemically stable structure, when the phosphor is represented by the above-described composition formula MmAaBbOoNn: Z, m> 0, a> 0, b> 0, o ≧ A structure represented by 0, n = 2 / 3m + a + 4 / 3b-2 / 3o is preferable.

  Here, the M element is one or more elements selected from Mg, Ca, Sr, Ba, and Zn, and the A element is one or more elements selected from B (boron), Al, and Ga. It is preferable that the B element is Si and / or Ge, and the Z element is one or more elements selected from rare earths or transition metals.

  Further, when the A element is Al, the B element is Si, and m = a = b = 1, the phosphor has the general formula MAlSiOoNn: Z (where o ≧ 0, n = 3-2). / 3o), the phosphor of the first example shows particularly high-efficiency and high-luminance emission.

In addition, in the above-described composition formula MAlSiOoNn: Z, when the M element is Ca, the Z element is Eu, and o = 0, the phosphor is represented by CaAlSiN 3 : Eu, The phosphor of the first example exhibits particularly high-efficiency and high-luminance red light emission, and becomes an excellent red phosphor.

(Phosphor of the second example)
Next, as a phosphor of the second example satisfying the characteristics of (P 25 −P 200 ) / P 25 ≦ 0.25 and (P 25 −P 100 ) / P 25 ≦ 0.10, the same as in the first example The phosphor represented by the composition formula MmAaBbOoNn: Z will be described.
Also in the phosphor of the second example, as in the first example, the M element is one or more elements having a valence of II, and the A element is one or more elements having a valence of III. The element B is one or more elements having an IV valence. O is oxygen, N is nitrogen, and the Z element is at least one element selected from rare earth elements or transition metal elements. As in the first example, a structure represented by m> 0, a> 0, b> 0, o ≧ 0, n = 2 / 3m + a + 4 / 3b−2 / 3o is preferable. Unlike the example, it is preferable that m = 1, a = 2, 4.0 ≦ b <6.0.

Here, when m = 1, a = 2, 4.0 ≦ b <6.0, the phosphor has the general formula MAl 2 SibOoNn: Z (where o ≧ 0, 4.0 ≦ b <6). 0.0, n = 8/3 + 4 / 3b-2 / 3o), and in this case, the phosphor exhibits particularly high-efficiency and high-luminance emission. Since the phosphor can shift the emission wavelength by changing the type of M element and the O content, it is required to change the emission wavelength of the phosphor when manufacturing a lighting device such as a white LED. In this case, the optimum emission color can be obtained by changing the kind of M element and the amount of O.

In the above-described composition formula MAl 2 SibOoNn: Z, when the M element is Ca, the Z element is Eu, and b = 4 and o = 0, the phosphor of the second example is CaAl 2 It becomes a phosphor represented by Si 4 N 8 : Eu. The phosphor represented by the general formula CaAl 2 Si 4 N 8 : Eu exhibits orange light emission with particularly high efficiency and high luminance, and becomes an excellent orange phosphor.

(Method for producing phosphor of first example)
As an example of the manufacturing method in the case where the composition formula MmAaBbOoNn: Z does not contain oxygen (that is, o = 0), the M element in the composition formula MmAaBbOoNn: Z is Ca, the A element is Al, and the B element is Si. An explanation will be given by taking, as an example, CaAlSiN 3 : Eu (where Eu / (Ca + Eu) molar ratio = 0.015), which is the phosphor of the first example shown by m = a = b = 1 and o = 0.

First, Ca 3 N 2 (2N), AlN (3N), and Si 3 N 4 (3N) are prepared as raw materials of Ca, Al, and Si, respectively. Eu 2 O 3 (3N) is prepared as the Eu raw material.

  These raw materials are weighed and mixed so that the molar ratio of each element is m = a = b = 1. In order to replace a part of the Ca site with Eu, it is actually weighed and mixed so that (Ca + Eu): Al: Si = 1: 1: 1. The mixing may be a normal mixing method using a mortar or the like, but it is convenient to operate in a glove box under an inert atmosphere such as nitrogen.

  The reason why it is convenient to operate the mixing in a glove box under an inert atmosphere is that when the operation is performed in the atmosphere, the ratio of the oxygen concentration contained in the matrix constituent element due to oxidation or decomposition of the raw material is increased. This is because there is a possibility that the light emission characteristics may deteriorate and the composition of the manufactured phosphor may deviate from the target composition. Furthermore, since the nitride of each raw material element is easily affected by moisture, it is preferable to use an inert gas from which moisture has been sufficiently removed. When a nitride raw material is used as each raw material element, the dry mixing is preferable as a mixing method in order to avoid decomposition of the raw material. Specifically, a normal dry mixing method using a ball mill, a mortar, or the like may be used.

  The mixed raw material is filled in a boron nitride crucible as a firing container and fired in an inert atmosphere such as nitrogen. Here, the firing temperature may be 1000 ° C. or higher, preferably 1400 ° C. or higher. The holding time can be shortened because the firing proceeds more rapidly as the firing temperature is higher. Even if the firing temperature is low, the desired light emission characteristics can be obtained by holding for a long time. This is because as the firing time is longer, the particle growth proceeds and the particle size becomes larger. Therefore, an arbitrary firing time may be set depending on the target particle size. For example, when firing at 1500 ° C., it is preferable to raise the temperature up to 1500 ° C. at a rate of 15 ° C./min and then hold and fire at 1500 ° C. for 3 hours.

After completion of the firing, cooling from 1500 ° C. to 200 ° C. in one hour, further cooling to room temperature, and then using a pulverizing means such as a mortar and a ball mill, a predetermined (preferably 1 μm to 20 μm) average particle size Thus, the phosphor having the composition formula CaSiAlN 3 : Eu (Eu / (Ca + Eu) molar ratio = 0.015) can be produced.
Incidentally, it is considered that a small amount of oxygen is present in the composition of the product due to oxygen from Eu 2 O 3, but can be ignored in a normal case.

  When it is desired to change the Eu / (Ca + Eu) molar ratio setting value, the blending amount at the time of charging each raw material is adjusted to a predetermined composition formula. A phosphor can be manufactured.

  In addition to the above-described method of manufacturing using nitride as a raw material, an imide method of manufacturing using a compound such as an imide that substantially becomes a nitride by being decomposed during firing, and direct nitriding of a raw metal Direct nitridation method for synthesis, reduction nitridation method for synthesis by nitriding oxide by adding raw material oxide and carbon, and other methods for producing organic metal compounds containing nitrogen as raw materials, etc. Can also be produced. These production methods can also be applied as a method for producing a phosphor containing nitrogen, which will be described later.

Next, as an example of a manufacturing method when oxygen is included in the composition formula MmAaBbOoNn: Z (that is, o ≠ 0), the M element is Ca, the A element is Al, and the B element is Si, and m = a = b = 1 A method for producing CaAlSiO 0.5 N 2.67 : Eu (where Eu / (Ca + Eu) molar ratio = 0.015) in which o = 0.5 will be described.

First, Ca 3 N 2 (2N), AlN (3N), and Si 3 N 4 (3N) are prepared as the raw materials of Ca, Al, and Si, respectively, and CaO (2N) is prepared as the O raw material. Here, Al 2 O 3 or SiO 2 may be used as the O raw material. Eu 2 O 3 (3N) is prepared as the Eu raw material.

These raw materials are weighed and mixed so that m = a = b = 1 and o = 0.5. In order to replace a part of the Ca site with Eu, it is actually weighed and mixed so that (Ca + Eu): Al: Si = 1: 1: 1. Further, the amount of O that gives o = 0.5 is adjusted by controlling the ratio of addition of Ca 3 N 2 and CaO, for example, when CaO is used as a raw material for supplying O. That is, in order to make the target composition CaAlSiO 0.5 N 2.67 : Eu (Eu / (Ca + Eu) molar ratio = 0.015), each raw material is Ca 3 N 2 : Eu 2 O. 3 : CaO: AlN: Si 3 N 4 = (0.985−0.50) /3:0.015/2:0.50:1:1/3 may be weighed and mixed. When Al 2 O 3 is used as a raw material for supplying O, depending on the addition ratio of Al 2 O 3 and AlN, and when SiO 2 is used as a raw material for supplying O, SiO 2 and Si 3 N The amount of O may be adjusted by the addition ratio of 4 . The mixing may be a normal mixing method using a mortar or the like, but it is convenient to operate in a glove box under an inert atmosphere such as nitrogen.

  The weighing / mixing is conveniently performed in a glove box under an inert atmosphere. Since the nitride of each raw material element is easily affected by moisture, it is preferable to use an inert gas from which moisture has been sufficiently removed. When a nitride raw material is used as each raw material element, the mixing method is preferably dry mixing in order to avoid decomposition of the raw material, and a normal dry mixing method using a ball mill or a mortar may be used.

  The mixed raw material is placed in a crucible and fired in an inert atmosphere such as nitrogen at 1000 ° C. or higher, preferably 1400 ° C. or higher, more preferably 1500 ° C. for 3 hours. The holding time can be shortened because the sintering proceeds more rapidly as the sintering temperature is higher. On the other hand, even when the sintering temperature is low, the desired light emission characteristics can be obtained by maintaining the temperature for a long time. However, the longer the sintering time is, the more the particle growth proceeds and the larger the particle size. Therefore, the sintering time may be set according to the target particle size.

The material used for the crucible is preferably a material that can be used in an inert atmosphere such as BN (boron nitride), alumina, carbon, silicon nitride, aluminum nitride, sialon, SiC, and the purity of the crucible is high. preferable. Among them, it is preferable to use a high-purity BN (boron nitride) crucible because it can avoid mixing of impurities from the crucible. After firing is completed, the fired product is taken out from the crucible, and ground to a predetermined average particle size using a grinding means such as a mortar and a ball mill, and the composition formula CaAlSiO 0.5 N 2.67 : Eu Can be manufactured. However, since Eu 2 O 3 is added to replace the Ca site with Eu, a part of nitrogen that should have been taken into the phosphor from Ca 3 N 2 is derived from Eu 2 O 3 . Oxygen is replaced and the product composition becomes CaAlSiO 0.523 N 2.66 : Eu. Therefore, it is considered that there is a slight shift in the composition of oxygen and nitrogen, but in the normal case, it is ignored. be able to.

(Method for producing phosphor of second example)
Next, a phosphor having a composition formula CaAl 2 Si 4 N 8 : Eu (provided that Eu / (Ca + Eu) molar ratio = 0.03) does not contain oxygen (o = 0) as an example. A method for manufacturing the phosphor of the second example will be described.

First, Ca 3 N 2 (2N), AlN (3N), and Si 3 N 4 (3N) are prepared as raw materials of Ca, Al, and Si, respectively. Eu 2 O 3 (3N) is prepared as the Eu raw material.
These raw materials are weighed and mixed so that the molar ratio of each element is m: a: b = 1: 2: 4. In order to replace a part of the Ca site with Eu, it is actually weighed and mixed so that (Ca + Eu): Al: Si = 1: 2: 4. The subsequent steps may be carried out in the same manner as in the first example phosphor (containing no oxygen), but the firing temperature is preferably 1800 ° C.

Further, a phosphor represented by the composition formula CaAl 2 Si 4 O 0.5 N 7.67 : Eu (where Eu / (Ca + Eu) molar ratio = 0.03) containing oxygen (o ≠ 0) ) As an example, a method for manufacturing the phosphor of the second example will be described.

First, Ca 3 N 2 (2N), AlN (3N), and Si 3 N 4 (3N) are prepared as the raw materials of Ca, Al, and Si, respectively, and CaO (2N) is prepared as the O raw material. Here, Al 2 O 3 or SiO 2 may be used as the O raw material. Eu 2 O 3 (3N) is prepared as the Eu raw material.

These raw materials are weighed and mixed so that the molar ratio of each element is m: a: b = 1: 2: 4. In order to replace a part of the Ca site with Eu, it is actually weighed and mixed so that (Ca + Eu): Al: Si = 1: 2: 4. Further, the amount of O that gives o = 0.5 is adjusted by controlling the ratio of addition of Ca 3 N 2 and CaO, for example, when CaO is used as a raw material for supplying O. That is, in order to make the target composition CaAl 2 Si 4 O 0.5 N 7.67 : Eu (Eu / (Ca + Eu) molar ratio = 0.03), each raw material is made of Ca 3 N 2. : Eu 2 O 3 : CaO: AlN: Si 3 N 4 = (0.97−0.50) /3:0.03/2:0.50:2:4/3 Weigh and mix. That's fine. When Al 2 O 3 is used as a raw material for supplying O, depending on the addition ratio of Al 2 O 3 and AlN, and when SiO 2 is used as a raw material for supplying O, SiO 2 and Si 3 N The amount of O may be adjusted by the addition ratio of 4 . The mixing may be a normal mixing method using a mortar or the like, but it is convenient to operate in a glove box under an inert atmosphere such as nitrogen. The subsequent steps may be performed in the same manner as in the first example phosphor (containing oxygen) manufacturing method described above, but the firing temperature is preferably 1800 ° C.

(Particle size of the phosphor according to the present invention)
The phosphors of the first and second examples described above are powdered in consideration of ease of application or filling, but the average particle size of the phosphor powder should be 20 μm or less. preferable. This is because, in the phosphor powder, light emission is considered to occur mainly on the particle surface, so if the average particle size is 20 μm or less, a surface area per unit weight of the powder can be secured and a decrease in luminance can be avoided. It is. Further, if the average particle size is 20 μm or less, the phosphor powder can be paste-like, and the coating density of the phosphor powder can be increased even when the phosphor powder is applied to a light emitting device or the like. Also from this viewpoint, it is possible to avoid a decrease in luminance. On the other hand, according to the study by the present inventors, although the detailed reason is unknown, it has also been found that the average particle diameter of the phosphor powder is preferably larger than 1 μm from the viewpoint of the luminous efficiency of the phosphor powder. did. From the above, the average particle diameter of the phosphor powder according to the present invention is preferably 1 μm or more and 20 μm or less.

(Measurement of emission intensity change of phosphor according to the present invention)
Described measurement of the change in the emission intensity P T and the light emission intensity of at temperature T ° C. of the phosphor according to the present invention.
The emission intensity PT is a spectrum of light emitted from the phosphor when the phosphor is placed in an environment at 25 ° C. and irradiated with excitation light having a predetermined wavelength described later. It determines the peak with the greatest intensity in the measured spectrum and the maximum peak, the value of the relative intensity of the peak and P 25. Next, the phosphor is placed in an environment of T ° C., and the same excitation light as that irradiated at 25 ° C. is irradiated, and the spectrum of light emitted from the phosphor is measured. In the measurement spectrum, the relative intensity of the peak corresponding to the peak determined as the maximum peak at the time of 25 ° C. measurement is obtained, and the value is defined as PT . (P 25 −P T ) / P 25 is calculated from P 25 thus obtained and PT .

The excitation light to be irradiated may be placed in a wavelength range of 250 nm to 550 nm, and a predetermined wavelength may be determined as necessary. As a point for determining the wavelength range of the excitation light, it is preferable to match the phosphor with the emission wavelength range of an ultraviolet discharge lamp, an LED or the like combined with the phosphor as an excitation light source.
The number of measurement wavelengths in the excitation light in the wavelength range is preferably 2 or more.

When the measurement was performed, both the phosphors of the first example and the second example described above satisfy (P 25 −P 200 ) / P 25 ≦ 0.25 and (P 25 −P 100 ) / P 25. It was found that ≦ 0.10.

(Production of light source using phosphor according to the present invention)
The phosphor according to the present invention manufactured by the above-described manufacturing method was combined with the light emitting part by a known method to produce a light source. A near ultraviolet / ultraviolet LED and an ultraviolet discharge lamp were used as the light emitting part. This is because the emission wavelength range is suitable as excitation light for a phosphor used as a light source.
After the light source was produced, a lighting test was performed to observe whether a decrease in emission intensity of the light source or a change in light emission color could be confirmed.
As a result, in the case of a light source using an ultraviolet discharge lamp as the light emitting part, a phenomenon in which the light emission intensity decreases with the light emission time was not observed. In the case of a light source using a near-ultraviolet / ultraviolet LED as the light emitting part, a phenomenon in which the color of light emission changes with the light emission time was hardly observed. In particular, it has also been found that when the phosphors of the first and second examples described above are used in combination, the change in the color of light emission can be further suppressed. Of course, also in the phosphors of other colors used by mixing with the phosphors of the first example and / or the second example, (P 25 -P 200 ) / P 25 , or (P 25 -P 100 ) / P 25 It is preferable to use a value close to that of the phosphors of the first and second examples.

Hereinafter, based on an Example, this invention is demonstrated more concretely.
Example 1
Commercially available Ca 3 N 2 (2N), AlN (3N), Si 3 N 4 (3N), and Eu 2 O 3 (3N) were prepared, and the molar ratio of each element was Ca: Al: Si: Eu = 0. Each raw material was weighed so as to be 985: 1: 1: 0.015, and mixed using a mortar in a glove box under a nitrogen atmosphere. The mixed raw material is filled in a crucible made of boron nitride, and 15 ° C./min. After heating at 1500 ° C. for 3 hours and firing, the mixture was cooled from 1500 ° C. to 200 ° C. for 1 hour, further cooled to room temperature, and the composition formula Ca 0.985 SiAlN 3 : Eu 0. 015 phosphor was obtained. The average particle diameter of the powder produced by pulverizing the obtained phosphor using a mortar was 4.65 μm.

With respect to the obtained phosphor, emission spectra were measured at temperatures of 25, 50, 100, 150, and 200 ° C. using near ultraviolet light having a wavelength of 380 nm and blue light having a wavelength of 460 nm as an excitation light source. The phosphor emission spectrum at each temperature is obtained by enclosing the phosphor powder in a metal sample holder having a glass surface, and heating the sample holder with a heater from the rear to adjust the sample temperature to the target measurement temperature. It was measured with a spectrophotometer in the atmosphere. The maximum peak was obtained from the measurement result of the spectrum, and the relative intensity of the peak value is shown in Tables 1 and 2. Table 1 shows the case of excitation at a wavelength of 380 nm, and Table 2 shows the case of excitation at a wavelength of 460 nm.
Also shown in Table 1 and Table 2 also rate of change of the emission intensity P T at T ° C. from the emission intensity P 25 at 25 ℃ (100 × (P 25 -P T) / P 25).
Furthermore, among the emission spectra, the measurement results at 25, 100, and 200 ° C., the emission spectrum when the excitation light is set to a wavelength of 380 nm, and the emission spectrum when the excitation light is set to a wavelength of 460 nm are shown in FIG. As shown in FIG. 3 and 4 are graphs in which the horizontal axis represents the wavelength of light (nm) and the vertical axis represents the relative emission intensity. The relative emission intensity of the vertical axis of the graph according to Figure 3 is obtained by normalizing the P 25 as 1.00. Similarly, the relative emission intensity of the vertical axis of the graph according to Figure 4 also, is obtained by normalizing the P 25 as 1.00. 3 and 4, the emission spectrum at 25 ° C. is indicated by a solid line, the emission spectrum at 100 ° C. is indicated by a one-dot chain line, and the emission spectrum at 200 ° C. is indicated by a broken line.

(Example 2)
Commercially available Ca 3 N 2 (2N), AlN (3N), Si 3 N 4 (3N), and Eu 2 O 3 (3N) were prepared, and the molar ratio of each element was Ca: Al: Si: Eu = 0. Each raw material was weighed so as to be 97: 2: 4: 0.03 and mixed using a mortar in a glove box under a nitrogen atmosphere. The mixed raw material is filled in a crucible made of boron nitride, and 15 ° C./min. And heated at 1800 ° C. for 3 hours, fired, cooled from 1800 ° C. to 200 ° C. in 1 hour, further cooled to room temperature, and the composition formula CaSi 2 Al 4 N 8 : Eu 0. 03 phosphor was obtained. The average particle size of the powder produced by pulverizing the obtained phosphor using a mortar was 5.23 μm.

  For the obtained phosphor, in the same manner as in Example 1, near-ultraviolet light having a wavelength of 380 nm and blue light having a wavelength of 460 nm were used as an excitation light source, and an emission spectrum at each temperature of 25, 50, 100, 150, and 200 ° C. Was measured. The measurement results are shown in Tables 1 and 2 and FIGS. 5 and 6, the emission spectrum at 25 ° C. is indicated by a solid line, the emission spectrum at 100 ° C. is indicated by a one-dot chain line, and the emission spectrum at 200 ° C. is indicated by a broken line.

(Comparative Example 1)
In Comparative Example 1, a Ca 2 Si 5 N 8 : Eu phosphor described in Patent Documents 4 and 5 was produced as a sample according to the comparative example.
Commercially available Ca 3 N 2 (2N), AlN (3N), Si 3 N 4 (3N) and Eu 2 O 3 (3N) were prepared, and Ca 3 N 2 , Si 3 N 4 and Eu 2 O 3 were prepared. Were weighed so that the molar ratio of Ca: Si: Eu = 1.97: 5: 0.03. The weighed raw materials were mixed in a mortar in a glove box under a nitrogen atmosphere. At this time, sufficient care was taken so that the raw materials were not subjected to excessive oxidation. The mixed raw material was filled in a boron nitride crucible, and baked at 1500 ° C. for 3 hours in nitrogen while taking care not to oxidize the raw material and to completely remove oxygen in the raw material. 1 and cooled to obtain a phosphor of the composition formula Ca 1.97 Si 5 N 8 : Eu 0.03 . The average particle size of the powder produced by pulverizing the obtained phosphor using a mortar was 4.77 μm.

  For the obtained phosphor, in the same manner as in Example 1, near-ultraviolet light having a wavelength of 380 nm and blue light having a wavelength of 460 nm were used as an excitation light source, and an emission spectrum at each temperature of 25, 50, 100, 150, and 200 ° C. Was measured. The measurement results are shown in Tables 1 and 2 and FIGS. 7 and 8, the emission spectrum at 25 ° C. is indicated by a solid line, the emission spectrum at 100 ° C. is indicated by a one-dot chain line, and the emission spectrum at 200 ° C. is indicated by a broken line.

(Contrast of Examples 1 and 2 and Comparative Example 1)
In order to compare Examples 1 and 2 and Comparative Example 1, a graph with the horizontal axis representing the temperature of the phosphor and the vertical axis representing the relative emission intensity of the phosphor was prepared from the data in Table 1. Data is shown by a solid line, data of Example 2 is shown by a one-dot chain line, and data of Comparative Example 1 is shown by a two-dot chain line as shown in FIG. Similarly, a graph with the horizontal axis representing the phosphor temperature and the vertical axis representing the relative emission intensity of the phosphor is created from the data in Table 2, with the solid line representing the data of Example 1 and one point of the data of Example 2. The data of Comparative Example 1 is shown by a two-dot chain line in FIG.

As apparent from Table 1 and FIG. 1, when the phosphor according to Example 1 was excited by near-ultraviolet light having a wavelength of 380 nm, the rate of decrease in emission intensity when the temperature was increased from 25 ° C. to 100 ° C. Was 7.4%, and the rate of decrease in emission intensity when the temperature was raised from 25 ° C. to 200 ° C. was 22.2%.
On the other hand, in the case of the phosphor according to Example 2, when the temperature is increased from 25 ° C. to 100 ° C., the decrease rate of the emission intensity is 9.9%, and when the temperature is increased from 25 ° C. to 200 ° C. The decrease rate of the emission intensity was 24.3%.
On the other hand, in the case of the phosphor according to Comparative Example 1, when the temperature was increased from 25 ° C. to 100 ° C., the decrease rate of the emission intensity was 23.7%, and the temperature was increased from 25 ° C. to 200 ° C. In this case, the decrease rate of the emission intensity was 70.9%, which resulted in a significant decrease in emission intensity.

The same applies when the excitation wavelength is changed to blue light of 460 nm. The rate of decrease in emission intensity when the temperature of the phosphor according to Example 1 is increased from 25 ° C. to 100 ° C. is 8.3%, from 25 ° C. When the temperature was raised to 200 ° C., the rate of decrease in emission intensity was 23.3%.
On the other hand, in the case of the phosphor according to Example 2, the decrease rate of the emission intensity when the temperature is increased from 25 ° C. to 100 ° C. is 9.8%, and the temperature is increased when the temperature is increased from 25 ° C. to 200 ° C. The decrease rate of the emission intensity was 23.6%.
On the other hand, when the temperature of the phosphor according to Comparative Example 1 was increased from 25 ° C. to 100 ° C., the decrease rate of the emission intensity was 23.8%, and the emission when the temperature was increased from 25 ° C. to 200 ° C. The rate of decrease in intensity was 71.0%, which resulted in a significant decrease in emission intensity.

From the above results, it has been found that the phosphor according to the present invention exhibits stable emission intensity over a wide temperature range as compared with the conventional phosphor. Furthermore, in the vicinity of 100 ° C., which is considered to be close to the temperature at the time of actual LED use, the phosphor according to the present invention exhibits a particularly high emission intensity maintenance rate and may exhibit a higher emission intensity than conventional phosphors. found.
As described above, the phosphors according to Examples 1 and 2 are manufactured using the phosphor because the luminance of the phosphor hardly decreases even when the temperature of the phosphor rises due to heat generation of the light emitting part. Even when a large current is injected into the white LED, it is possible to obtain light emission with high luminance and little change in color tone, and thus it is considered suitable for lighting devices such as white LEDs. In addition, the phosphors according to Examples 1 and 2 are used in combination because the rate of decrease in emission intensity due to the temperature rise of each phosphor is the same, and mixed with the phosphors of the first and second examples. Even in the phosphors of other colors used in this case, the values of (P 25 -P 200 ) / P 25 and (P 25 -P 100 ) / P 25 are close to those of the phosphors of the first and second examples. By using a thing, the change of the color of light emission by the temperature rise can be suppressed further low.

It is a figure which shows the emitted light intensity of the fluorescent substance in each measurement temperature. It is a figure which shows the emitted light intensity of the fluorescent substance in each measurement temperature. It is a figure which shows the emission spectrum when the fluorescent substance which concerns on Example 1 is irradiated with the excitation light of wavelength 380nm. It is a figure which shows the emission spectrum when the fluorescent substance which concerns on Example 1 is irradiated with excitation light with a wavelength of 460 nm. It is a figure which shows the emission spectrum when irradiating the phosphor which concerns on Example 2 with the excitation light of wavelength 380nm. It is a figure which shows the emission spectrum when the fluorescent substance which concerns on Example 2 is irradiated with the excitation light of wavelength 460nm. It is a figure which shows the emission spectrum when the fluorescent substance which concerns on the comparative example 1 is irradiated with the excitation light of wavelength 380nm. It is a figure which shows the emission spectrum when the fluorescent substance which concerns on the comparative example 1 is irradiated with the excitation light of wavelength 460nm.

Claims (15)

  1. A phosphor that emits visible light when excited by excitation light in the ultraviolet to green range,
    The value of the relative intensity of the maximum peak in the emission spectrum at 25 ° C. of the phosphor irradiated with the predetermined excitation light is defined as the emission intensity P 25 .
    When the value of the relative intensity of the maximum peak at 200 ° C. of the phosphor irradiated with the predetermined excitation light is defined as emission intensity P 200 ,
    (P 25 −P 200 ) / P 25 ≦ 0.25.
  2. A phosphor that emits visible light when excited by excitation light in the ultraviolet to green range,
    The value of the relative intensity of the maximum peak in the emission spectrum at 25 ° C. of the phosphor irradiated with the predetermined excitation light is defined as the emission intensity P 25 .
    When the value of the relative intensity of the maximum peak at 100 ° C. of the phosphor irradiated with the predetermined excitation light is defined as emission intensity P 100 ,
    A phosphor characterized by (P 25 −P 100 ) / P 25 ≦ 0.10.
  3.   Composition formula MmAaBbOoNn: Z (where M element is one or more elements having a valence of II, A element is one or more elements having a valence of III, and B element is an IV valence) One or more elements having a valence, O is oxygen, N is nitrogen, Z element is an activator, m> 0, a> 0, b> 0, o ≧ 0, n = 2 / 3m + a + 4 / 3b-2 / 3o). The phosphor according to claim 1 or 2, wherein
  4.   The M element is one or more elements selected from Mg, Ca, Sr, Ba, and Zn, and the A element is one or more elements selected from B (boron), Al, and Ga, 4. The phosphor according to claim 3, wherein the B element is Si and / or Ge, and the Z element is one or more elements selected from rare earths and transition metals.
  5.   The phosphor according to claim 3 or 4, wherein the A element is Al and the B element is Si.
  6.   The phosphor according to any one of claims 3 to 5, wherein the M element is Ca and the Z element is Eu.
  7.   The phosphor according to any one of claims 3 to 6, wherein the values of m, a, and b are m = a = b = 1.
  8. The phosphor according to any one of claims 1 to 7, wherein the phosphor is represented by a composition formula CaAlSiN 3 : Eu.
  9.   The phosphor according to any one of claims 3 to 6, wherein the values of m, a, and b are m = 1, a = 2, 4.0 ≦ b <6.0.
  10. The phosphor according to any one of claims 1 to 6, or 9, wherein the phosphor is represented by a composition formula CaAl 2 Si 4 N 8 : Eu.
  11.   The phosphor according to any one of claims 1 to 10, wherein the phosphor is in a powder form.
  12.   The phosphor according to claim 11, wherein an average particle size of the phosphor is 20 μm or less and 1 μm or more.
  13.   13. The phosphor according to claim 1, and a light emitting unit that emits light having a predetermined wavelength, wherein a part of the light having the predetermined wavelength is used as an excitation source, and the phosphor is different from the predetermined wavelength. A light source that emits light at a wavelength.
  14.   The light source according to claim 13, wherein the predetermined wavelength is any wavelength of 250 nm to 550 nm.
  15.   The light source according to claim 13 or 14, wherein the light emitting unit is an LED.
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