WO2011142228A1 - β型サイアロンの製造方法、β型サイアロン及びその利用製品 - Google Patents
β型サイアロンの製造方法、β型サイアロン及びその利用製品 Download PDFInfo
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- WO2011142228A1 WO2011142228A1 PCT/JP2011/059858 JP2011059858W WO2011142228A1 WO 2011142228 A1 WO2011142228 A1 WO 2011142228A1 JP 2011059858 W JP2011059858 W JP 2011059858W WO 2011142228 A1 WO2011142228 A1 WO 2011142228A1
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- sialon
- raw material
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 26
- 239000010439 graphite Substances 0.000 claims abstract description 26
- 229910052582 BN Inorganic materials 0.000 claims abstract description 20
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 45
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 33
- 238000010304 firing Methods 0.000 claims description 31
- 229910001940 europium oxide Inorganic materials 0.000 claims description 4
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract 3
- 239000007858 starting material Substances 0.000 abstract 3
- 239000000843 powder Substances 0.000 description 47
- 238000011049 filling Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010306 acid treatment Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
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- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Definitions
- the present invention relates to ⁇ -sialon, a method for producing the same, a phosphor using the ⁇ -sialon, and a light emitting device using the phosphor.
- a ⁇ -type sialon phosphor is a boron nitride container made of a raw material obtained by mixing at least one of aluminum oxide or silicon oxide, silicon nitride, aluminum nitride, and an optically active element compound typified by europium oxide or cerium oxide. It is manufactured through a firing step of filling in and firing at a temperature of 1820 ° C. or higher and 2200 ° C. or lower.
- Patent Document 1 As a technique for improving the emission intensity of the ⁇ -type sialon phosphor, it is known to perform acid treatment on the fired pulverized product after the firing step (Patent Document 1).
- ⁇ -type sialon is mass-produced by simultaneously firing a plurality of boron nitride containers filled with raw materials in a firing furnace.
- ⁇ -type sialon that does not have the required emission intensity is produced in a plurality of boron nitride containers unless the temperature conditions inside the firing furnace are adjusted. In some cases, the emission intensity was uneven.
- the present inventors have found that the carbon concentration contained in ⁇ -sialon affects the emission intensity, and have completed the present invention.
- the present invention provides a method for producing ⁇ -sialon with improved quality, and an object of the present invention is to provide ⁇ -sialon having high emission intensity by reducing carbon contained in ⁇ -sialon. Another object of the present invention is to provide a phosphor of excellent quality using the ⁇ -sialon, and a further object of the present invention is to provide a light-emitting device having high emission intensity using the phosphor.
- the method for producing ⁇ -sialon according to the present invention uses a raw material of ⁇ -sialon in which silicon nitride, aluminum nitride, at least one of aluminum oxide or silicon oxide, and an optically active element compound are mixed at 1820 ° C. or higher and 2200 ° C. or lower.
- Another structure of the method for producing ⁇ -sialon of the present invention is that a raw material of ⁇ -sialon in which silicon nitride, aluminum nitride, at least one of aluminum oxide or silicon oxide, and an optically active element compound are mixed is used at 1820 ° C. There is a firing step of firing at a temperature of 2200 ° C. or less, and this firing step is performed in a graphite box so that the ⁇ -sialon raw material filled in a plurality of boron nitride containers can be easily contacted with nitrogen gas. It is a step of disposing and firing the upper part of the graphite box in a nitrogen atmosphere.
- the optically active element compound is preferably europium oxide.
- the ⁇ -type sialon of the present invention is represented by a general formula: Si 6-z Al z O z N 8-z , contains Eu, and has a carbon concentration of 200 ppm or less. More preferably, the carbon concentration is 150 ppm or less.
- Another invention is a phosphor using the ⁇ -sialon.
- Still another invention is a light-emitting device having a phosphor using ⁇ -sialon and a light-emitting light source.
- ⁇ -sialon having high emission intensity can be produced with high quality and high productivity.
- the ⁇ -sialon of the present invention is excellent as a green light-emitting phosphor that is excited in a wide wavelength range from ultraviolet to visible light and has a high efficiency and a dominant wavelength in the range of 520 nm to 550 nm. Therefore, it can be suitably used for light emitting devices using various light emitting elements, particularly ultraviolet LEDs or blue LEDs as a light source, alone or in combination with other phosphors.
- ⁇ -sialon has a high light emission intensity, so that a decrease in luminance is small even when it is used at a high temperature, and it has a long life.
- FIG. 4 is a graph showing the relationship between the carbon concentration and the emission intensity of the powdered phosphor obtained in Example 2.
- the method for producing ⁇ -sialon according to the present invention comprises a raw material of ⁇ -sialon in which at least one of aluminum oxide or silicon oxide, silicon nitride, aluminum nitride, and an optically active element compound is mixed.
- the firing step is arranged in a graphite box so that the raw material of ⁇ -sialon filled in a plurality of boron nitride containers can be easily brought into contact with nitrogen gas, It is characterized in that the upper part of the graphite box is opened and the process is performed in a nitrogen atmosphere.
- the shape of the container made of boron nitride used in the firing process may be any of a cube, a rectangular parallelepiped, or a cylinder, but a cylinder or a sphere is preferable for uniform heat propagation, and the stability is also taken into consideration. Then, a cylindrical shape is preferable.
- the size of the container is preferably in a range in which heat propagation is uniform, and in the case of a cylindrical shape, a diameter of 5 cm to 8 cm at the inner diameter and a height of 5 cm to 8 cm at the inner diameter are preferable. .
- the graphite box is a box formed of a graphite plate, has a size capable of accommodating a plurality of boron nitride containers, and has an opening at the top.
- the size of the graphite box is, for example, an internal size of 51 cm long ⁇ 31 cm wide ⁇ 20 cm high. Since the upper part of the graphite box is open, the raw material of ⁇ -sialon filled in a plurality of boron nitride containers is placed in an easy-to-contact state with nitrogen gas and fired in a nitrogen atmosphere. . The carbon concentration contained in the produced ⁇ -sialon is reduced, and ⁇ -sialon having high emission intensity can be obtained.
- “arranging the raw material of ⁇ -sialon in the graphite box so as to be easily in contact with nitrogen gas” means means for arranging a container made of boron nitride along the wall of the graphite box, At least one of three means: a means for arranging the containers in a single stage without stacking up and down, and a means for reducing the raw material powder filling ratio, which is a ratio of the total volume of the raw material powder to the internal volume of the graphite box, to 2% or less.
- the total volume of the raw material powder can be calculated from the total weight of the raw material powder and the density of ⁇ -sialon (3.2 g / cm 3 ).
- the nitrogen gas during the firing step preferably increases the nitrogen partial pressure in the manufacturing atmosphere. By increasing the nitrogen partial pressure, the arrangement of the raw materials during the firing process can be stabilized.
- the carbon content of ⁇ -sialon produced under the above conditions is 200 ppm or less, and the emission intensity is equal to or greater than that of commercially available YAG: Ce (YAG: Ce (grade name: P46Y3) manufactured by Kasei Opto).
- the ⁇ -sialon after the firing step is preferably heat-treated again at 1450 ° C. to 1600 ° C. in an atmospheric pressure argon atmosphere.
- the ⁇ -sialon after the firing step or after the reheating treatment is preferably acid-treated.
- the acid treatment is to disperse ⁇ -sialon in an aqueous solution of acid, to react with stirring for several minutes to several hours, and then wash the ⁇ -sialon with water.
- the acid treatment the light emission inhibiting factor changed upon heating is dissolved and removed, and the fluorescence characteristics can be improved.
- the acid used in the acid treatment include one or more acids of hydrofluoric acid, sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid.
- the ⁇ -type sialon of the present invention has one or more selected from Eu, Mn, Sm, and Ce as a luminescent center in a ⁇ -type sialon host crystal represented by the general formula: Si 6-z Al z O z N 8-z These elements are contained. In particular, those containing Eu are preferable because they are excited in a wide wavelength range from ultraviolet to visible light.
- the ⁇ -sialon of the present invention has a carbon concentration of 200 ppm or less as measured by the infrared absorption method.
- the carbon constituting the ⁇ -sialon is large, the emission intensity is lowered and the light absorption to Eu 2+ which is the emission center is inhibited. That is, ⁇ -sialon having a carbon concentration of 200 ppm or less has high emission intensity. More preferably, the carbon concentration is 150 ppm or less.
- the lattice constant of the ⁇ -sialon of the present invention is mainly governed by the number of substitutions of Si—N bonds to Al—O bonds, that is, the z value. That is, it is preferable that the lattice constant a is in the range of 0.7605 nm to 0.7620 nm and the lattice constant c is in the range of 0.2908 nm to 0.2920 nm.
- the larger the crystal lattice size of ⁇ -type sialon the easier it is to contain Eu.
- the lattice constants a and c are within the above ranges, the amount of Eu necessary to obtain sufficient luminance may be contained. It is preferable because it becomes easy.
- the Eu content may be in a range that can sufficiently obtain the light emission luminance, and is preferably in the range of 0.1% by mass to 3% by mass, for example.
- the light emitting device of the present invention includes a phosphor formed of the above-described ⁇ -sialon and a light source. Using this light emitting device, ⁇ -sialon is irradiated with ultraviolet light or visible light containing a wavelength of 350 nm or more and 500 nm or less as an excitation source. By irradiation, ⁇ -sialon emits light having high emission intensity having a peak in a wavelength range of 520 nm or more and 550 nm or less, whereby the light emitting device of the present invention has high emission intensity.
- an excitation source of the light emitting device there are an ultraviolet LED, a blue LED, a phosphor lamp alone, or a combination thereof. Further, by combining a ⁇ -type sialon phosphor with a red light-emitting phosphor or a blue light-emitting phosphor, the emission color can be changed to white or other wavelength.
- the ⁇ -sialon of the present invention has a small decrease in luminance at high temperatures
- a light-emitting device using the ⁇ -sialon has a small decrease in luminance and chromaticity deviation and does not deteriorate even at high temperatures. Furthermore, since it is excellent in long-term stability in an oxidizing atmosphere and a moisture environment, the state of high brightness becomes long.
- the raw material mixture was mixed by dry using a V-type mixer for 30 minutes and then passed through a nylon sieve having an opening of 150 ⁇ m to obtain a raw material powder for phosphor synthesis.
- Material filling rate the total volume 2,880Cm 3 raw material powder is a value obtained by dividing the internal volume 31,620Cm 3 of the upper lid with graphite box (51cm ⁇ 31cm ⁇ 20cm), the total volume of the raw material powder, the raw material powder
- the total weight is 900 g (9 containers ⁇ 100 g of raw material powder weight per container) divided by the density of ⁇ -sialon (3.2 g / cm 3 ).
- the raw material filling rate is calculated based on the following equation.
- Raw material filling rate 0.9% ((9 ⁇ 100) /3.2) / (51 ⁇ 31 ⁇ 20)
- Example 3 The upper lid of the graphite box was opened, and processing was performed with the same number of containers, firing steps and conditions as in Experimental Example 2 to obtain phosphor powder.
- the emission intensity of the phosphor was calculated by the following operation.
- the phosphor powder was put into a 10 mm ⁇ 10 mm ⁇ 45 mm two-sided transparent quartz cell, tapped 50 times, then the cell direction was changed by 180 degrees, and further tapped 50 times.
- the cell containing the phosphor powder was attached to a cell folder in the sample chamber of the apparatus.
- Monochromatic light dispersed at a predetermined wavelength from a light emitting light source (Xe lamp) was introduced into this cell.
- the phosphor sample was irradiated with this monochromatic light as an excitation source, and the emission intensity of the sample was measured using a spectrophotometer.
- the monochromatic light in this example was blue light having a wavelength of 455 nm.
- the emission intensity was expressed as a relative peak intensity (%) with the emission intensity of YAG: Ce (P46Y3 manufactured by Kasei Optonics Co., Ltd.) as 100%.
- the carbon concentration of the raw material mixed powder and the fluorescent powders of Experimental Examples 1 to 4 and Comparative Example 1 was measured with a carbon analyzer (LE-412 manufactured by LECO Japan Co., Ltd.).
- the carbon concentration of the phosphor was evaluated as follows. 0.1 g of powdered phosphor and 1.0 g of copper powder were placed in an alumina crucible and attached to a sample stage. A high frequency was applied to the cell to melt the phosphor. In an oxidizing atmosphere, the gas discharged from the phosphor was measured by the infrared absorption method. The measurement results are shown in Table 2.
- the carbon concentration in the raw material mixed powder decreases when heat treatment is performed at 2000 ° C. for 10 hours in a pressurized nitrogen atmosphere of 0.9 MPa in an electric furnace of a carbon heater.
- the reduction in the carbon concentration varied depending on the number of containers and the raw material powder filling rate. The lower the raw material filling rate, the lower the carbon concentration. In particular, when the raw material filling rate is 2% or less, the carbon concentration is preferably 200 ppm or less.
- paragraphs it is preferable to arrange
- the relationship between the emission intensity and the carbon concentration is shown in FIG. From Table 1, Table 2, and FIG. 1, the emission intensity was improved by reducing the carbon concentration contained in the synthetic powder. When the carbon concentration was 200 ppm or less, the emission intensity was higher than that of YAG: Ce.
- FIG. 2 shows a scanning electron microscope image (SEM image) of the obtained pulverized powder.
- the particle size of the pulverized powder was controlled by the sample supply speed to the pulverization chamber of the pulverizer and the pulverization air pressure.
- Heat treatment process 15 g of the pulverized powder is filled into a cylindrical boron nitride container (N-1 grade, manufactured by Denki Kagaku Kogyo Co., Ltd.) with a lid having a diameter of 40 mm and a height of 45 mm, and in an atmospheric pressure argon atmosphere in an electric furnace of a carbon heater. And heat treatment at 1450 ° C. for 8 hours.
- the obtained powder did not shrink with firing, had almost the same properties as before heating, and passed through a sieve having an opening of 45 ⁇ m.
- Acid treatment process The powder after the heat treatment was treated in a 1: 1 mixed acid of 50% hydrofluoric acid and 70% nitric acid. During the treatment, the suspension changed from dark green to bright green. Thereafter, it was washed with water and dried to obtain ⁇ -sialon powder.
- Comparative Example 2 The synthetic powder described in Comparative Example 1 was processed under the same processing steps and conditions as in Experimental Example 5 to obtain ⁇ -sialon powder.
- a ⁇ -sialon powder was produced by a production method including a pulverization step, a heat treatment step, an acid treatment step and a classification step (Comparative Example 2).
- Table 3 shows the measurement results of the emission intensity of ⁇ -sialons of Experimental Examples 5 and 6 and Comparative Example 2. The measurement was performed in the same manner as in Example 1.
- FIG. 3 shows the relationship between emission intensity and carbon concentration in Experimental Examples 5 and 6 and Comparative Example 2.
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Abstract
Description
本発明のβ型サイアロンの製造方法は、酸化アルミニウム又は酸化ケイ素の少なくとも一つと、窒化ケイ素と、窒化アルミニウムと、光学活性元素化合物とを混合したβ型サイアロンの原料を、1820℃以上2200℃以下の温度で焼成する焼成工程を有するものであって、焼成工程を、複数の窒化ホウ素製の容器に充填されたβ型サイアロンの原料を窒素ガスと触れやすくなるように黒鉛ボックス内に配置し、黒鉛ボックスの上部を解放して窒素雰囲気下で行うことを特徴とする。
本発明のβ型サイアロンは、一般式:Si6-zAlzOzN8-zで示されるβ型サイアロンのホスト結晶に、発光中心としてEu,Mn,Sm,Ceから選択される1以上の元素が含有されたものである。とくに、Euを含有するものが、紫外線から可視光の幅広い波長域で励起されるため、好ましい。
本発明の発光装置は、上述のβ型サイアロンで形成される蛍光体と、発光光源とを備えて構成されている。この発光装置を用いて、350nm以上500nm以下の波長を含有している紫外光や可視光を励起源として、β型サイアロンに照射する。照射によって、β型サイアロンが520nm以上550nm以下の範囲の波長にピークを持つ高い発光強度を有する光を発し、これにより本発明の発光装置は高い発光強度を有する。発光装置の励起源としては、紫外LED、青色LED、蛍光体ランプの単体又はこれらの組み合わせがある。また、β型サイアロン蛍光体と、赤色発光蛍光体や青色発光蛍光体とを組み合わせることによって、発光色を白色や他の波長の色とすることができる。
α型窒化ケイ素粉末(電気化学工業社製NP-400グレード、酸素含有量0.96質量%)95.4質量%、窒化アルミニウム粉末(トクヤマ社製Fグレード、酸素含有量0.9質量%)3.1質量%、酸化アルミニウム粉末(大明化学社製TM-DARグレード)0.7質量%、及び酸化ユーロピウム粉末(信越化学工業社製RUグレード)0.8質量%を配合し、原料混合物1kgを得た。
<焼成工程>
上記のようにして得た原料粉末を、内寸で直径8cm×高さ8cmの蓋付きの円筒型窒化ホウ素製容器(電気化学工業社製N-1グレード)9個に各容器当たり100g充填し、内寸で51cm×31cm×高さ20cmの上蓋付き黒鉛ボックス内部に壁に沿って容器を配置した(原料充填率=0.9%)。カーボンヒーターの電気炉で0.9MPaの加圧窒素雰囲気中、2000℃で10時間の加熱処理を行った後、得られた粉末を室温まで徐冷した。得られた焼成物は、緩く凝集した塊状であり、清浄なゴム手袋を着用した人の手で軽度の解砕を行った。軽度の解砕をした原料を、目開き150μmの篩を通し、45gの合成粉末を得た。
原料充填率0.9%=((9×100)/3.2)/(51×31×20)
原料を充填した円筒型窒化ホウ素製の容器14個を、黒鉛ボックス内部に5個を3列に配置した。ただし、1列のみ4個とした(原料充填率=1.4%)。他は、実験例1の焼成工程と同じ条件で処理を行い、蛍光体粉末を得た。
黒鉛ボックスの上蓋を開け、実験例2と同じ個数の容器、焼成工程及び条件で処理を行い、蛍光体粉末を得た。
原料を充填した円筒型窒化ホウ素製の容器を19個とし、黒鉛ボックス内部に3列×5列に配置し(原料充填率=1.9%)、更に4個の容器を黒鉛ボックスの壁に沿って上段に配置するよう変更し、実験例1の焼成工程と同じ条件で処理を行い、蛍光体粉末を得た。
原料を充填した円筒型窒化ホウ素製の容器30個を、黒鉛ボックス内部に5個を3列、上下2段に配置する(原料充填率=3.0%)よう変更し、実験例1の焼成工程と同じ処理工程及び条件で処理を行い、蛍光体粉末を得た。
蛍光体粉末を10mm×10mm×45mmの2面透明石英セルに入れ、50回タッピングした後、セルの方向を180度変え、更に50回タッピングした。その蛍光体粉末の入ったセルを上記装置の試料室内にあるセルフォルダーに取り付けた。このセルに、発光光源(Xeランプ)から所定の波長に分光した単色光を導入した。この単色光を励起源として、蛍光体試料に照射し、分光光度計を用いて試料の発光強度を測定した。
本実施例での単色光は、波長455nmの青色光を用いた。
発光強度は、YAG:Ce(化成オプトニクス社製P46Y3)の発光強度を100%とした相対ピーク強度(%)で表した
原料充填率が低くなるほど炭素濃度が低くなっていた。特に原料充填率が2%以下であると、炭素濃度が200ppm以下であり好ましい。
また、上下2段に容器を配置する場合は、黒鉛ボックスの壁に沿って容器を配置することが好ましい。
さらに、Eu含有β型サイアロン用原料粉末を入れた窒化ホウ素製の容器を投入する黒鉛ボックスの蓋を開いた状態で焼成すると炭素含量が低減していた。
表1、表2及び図1より、合成粉末に含まれる炭素濃度を低減することで発光強度が向上していた。炭素濃度が200ppm以下であれば、YAG:Ceより高い発光強度となっていた。
実験例1で得られた合成粉末を超音速ジェット粉砕機(日本ニューマチック工業社製PJM-80SP)により解砕して粉末を得た。図2に、得られた粉砕粉末の走査型電子顕微鏡像(SEM像)を示す。粉砕粉末の粒径の制御は、粉砕機の粉砕室への試料供給速度と粉砕エアー圧力により行った。
粉砕後の粉末15gを、直径40mm×高さ45mmの蓋付きの円筒型窒化ホウ素製の容器(電気化学工業社製N-1グレード)に充填し、カーボンヒーターの電気炉で大気圧アルゴン雰囲気中、1450℃で8時間の加熱処理を行った。得られた粉末には焼成を伴う収縮はなく、加熱前とほとんど同じ性状であり、目開き45μmの篩を全て通過した。
加熱処理後の粉末を50%フッ化水素酸と70%硝酸の1:1混酸中で処理した。処理中に懸濁液は深緑色から鮮やかな緑色に変化した。その後、水洗及び乾燥してβ型サイアロンの粉末を得た。
得られたβ型サイアロンの粉末に対し、湿式沈降法により、微粉除去処理を行った。まず、蛍光体粉末を分散剤としてヘキサメタ燐酸ナトリウムを添加した水溶液中に分散した後、容器に移し、静置した後、上澄み液を除去する操作を、上澄み液が透明になるまで繰り返した。その後、沈殿物をろ過し、分散剤を除去するために十分に水洗し、乾燥を行い微粉除去したβ型サイアロンの粉末を得た(実験例5)。
比較例1に記載の合成粉末を、実験例5と同じ処理工程及び条件で処理を行い、β型サイアロンの粉末を得た。粉砕工程、加熱処理工程、酸処理工程及び分級工程を含む製造方法により、β型サイアロンの粉末を製造した(比較例2)。
Claims (7)
- 酸化アルミニウム又は酸化ケイ素の少なくとも一つと、窒化ケイ素と、窒化アルミニウムと、光学活性元素化合物とを混合したβ型サイアロンの原料を、1820℃以上2200℃以下の温度で焼成する焼成工程を有するβ型サイアロンの製造方法であって、焼成工程が、複数の窒化ホウ素製の容器に充填されたβ型サイアロンの原料を窒素ガスと触れやすくなるように黒鉛ボックス内に配置し窒素雰囲気下で焼成する工程である、β型サイアロンの製造方法。
- 酸化アルミニウム又は酸化ケイ素の少なくとも一つと、窒化ケイ素と、窒化アルミニウムと、光学活性元素化合物とを混合したβ型サイアロンの原料を、1820℃以上2200℃以下の温度で焼成する焼成工程を有するβ型サイアロンの製造方法であって、焼成工程が、複数の窒化ホウ素製の容器に充填されたβ型サイアロンの原料を窒素ガスと触れやすくなるように黒鉛ボックス内に配置し、黒鉛ボックスの上部を解放して窒素雰囲気下で焼成する工程である、β型サイアロンの製造方法。
- 複数の窒化ホウ素製の容器に充填されたβ型サイアロンの原料の総容積が黒鉛ボックスの内容積に対して2%である、請求項1又は2記載のβ型サイアロンの製造方法。
- 前記光学活性元素化合物が、酸化ユーロピウムである、請求項1又は2記載のβ型サイアロンの製造方法。
- 一般式:Si6-zAlzOzN8-zで示され、Euを含有するβ型サイアロンであって、炭素濃度が200ppm以下である、β型サイアロン。
- 請求項5に記載のβ型サイアロンを用いた蛍光体。
- 請求項6記載の蛍光体と、発光光源とを有する発光装置。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020127030865A KR101450991B1 (ko) | 2010-05-13 | 2011-04-21 | β 형 사이알론의 제조 방법, β 형 사이알론 및 그 이용 제품 |
EP11780485.6A EP2570400B1 (en) | 2010-05-13 | 2011-04-21 | Method for producing beta-sialon |
US13/697,556 US8926864B2 (en) | 2010-05-13 | 2011-04-21 | Method of producing β-SiAION, β-SiAION, and products using the same |
JP2012514750A JP5852564B2 (ja) | 2010-05-13 | 2011-04-21 | β型サイアロンの製造方法 |
CN201180023906XA CN102939273A (zh) | 2010-05-13 | 2011-04-21 | β型赛隆的制造方法、β型赛隆及利用该β型赛隆的产品 |
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Cited By (7)
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JP2013163739A (ja) * | 2012-02-09 | 2013-08-22 | Denki Kagaku Kogyo Kk | 蛍光体及び発光装置 |
JP2013163733A (ja) * | 2012-02-09 | 2013-08-22 | Denki Kagaku Kogyo Kk | 蛍光体及び発光装置 |
JP2013163735A (ja) * | 2012-02-09 | 2013-08-22 | Denki Kagaku Kogyo Kk | 蛍光体及び発光装置 |
JP2013163736A (ja) * | 2012-02-09 | 2013-08-22 | Denki Kagaku Kogyo Kk | 蛍光体及び発光装置 |
US9391245B2 (en) * | 2010-09-20 | 2016-07-12 | Samsung Electronics Co., Ltd. | Sialon phosphor, method for producing same, and light-emitting device package using same |
JPWO2017188191A1 (ja) * | 2016-04-25 | 2018-05-10 | 日本特殊陶業株式会社 | 波長変換部材、その製造方法および発光装置 |
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CN105331361B (zh) * | 2015-12-03 | 2017-09-19 | 河北利福光电技术有限公司 | 一种β‑SiAlON∶Eu2+绿色荧光粉及其合成方法 |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006028295A (ja) * | 2004-07-14 | 2006-02-02 | Dowa Mining Co Ltd | 窒化物蛍光体、窒化物蛍光体の製造方法、並びに上記窒化物蛍光体を用いた光源及びled |
WO2006106948A1 (ja) * | 2005-04-01 | 2006-10-12 | Mitsubishi Chemical Corporation | 無機機能材原料用合金粉末及び蛍光体 |
WO2006121083A1 (ja) * | 2005-05-12 | 2006-11-16 | National Institute For Materials Science | β型サイアロン蛍光体 |
JP2007308605A (ja) * | 2006-05-18 | 2007-11-29 | Dowa Holdings Co Ltd | 電子線励起用の蛍光体およびカラ−表示装置 |
JP2008088266A (ja) * | 2006-09-29 | 2008-04-17 | Dowa Holdings Co Ltd | 窒化物蛍光体または酸窒化物蛍光体の製造方法 |
JP2008189811A (ja) * | 2007-02-05 | 2008-08-21 | Osaka Univ | 窒化物又は酸窒化物を母体とする蛍光体、及びその製造方法、並びにそれを使用した蛍光体含有組成物、発光装置、照明装置、及び画像表示装置 |
JP2009019213A (ja) * | 2008-10-29 | 2009-01-29 | Sharp Corp | 蛍光体の製造方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4210761B2 (ja) | 2004-03-12 | 2009-01-21 | 独立行政法人物質・材料研究機構 | 蛍光体とその製造方法 |
JP3921545B2 (ja) * | 2004-03-12 | 2007-05-30 | 独立行政法人物質・材料研究機構 | 蛍光体とその製造方法 |
CN1260179C (zh) * | 2004-07-01 | 2006-06-21 | 北京科技大学 | 一种煤系高岭土合成高纯赛隆材料的方法 |
CN101146890B (zh) * | 2005-03-22 | 2011-06-01 | 独立行政法人物质·材料研究机构 | 荧光体及其制造方法以及发光器具 |
JP2007091960A (ja) * | 2005-09-30 | 2007-04-12 | Nitto Denko Corp | 光半導体素子封止用樹脂組成物およびそれを用いて得られる光半導体装置 |
EP2141215A4 (en) * | 2007-03-30 | 2011-11-30 | Mitsubishi Chem Corp | PHOSPHOR AND METHOD FOR PRODUCING THE SAME, PHOSPHORUS-CONTAINING COMPOSITION, LIGHT-EMITTING DEVICE, IMAGE DISPLAY DEVICE, AND LIGHTING DEVICE |
-
2011
- 2011-04-21 KR KR1020127030865A patent/KR101450991B1/ko active IP Right Grant
- 2011-04-21 WO PCT/JP2011/059858 patent/WO2011142228A1/ja active Application Filing
- 2011-04-21 EP EP11780485.6A patent/EP2570400B1/en active Active
- 2011-04-21 CN CN201180023906XA patent/CN102939273A/zh active Pending
- 2011-04-21 US US13/697,556 patent/US8926864B2/en active Active
- 2011-04-21 JP JP2012514750A patent/JP5852564B2/ja active Active
- 2011-05-12 TW TW100116605A patent/TWI438261B/zh active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006028295A (ja) * | 2004-07-14 | 2006-02-02 | Dowa Mining Co Ltd | 窒化物蛍光体、窒化物蛍光体の製造方法、並びに上記窒化物蛍光体を用いた光源及びled |
WO2006106948A1 (ja) * | 2005-04-01 | 2006-10-12 | Mitsubishi Chemical Corporation | 無機機能材原料用合金粉末及び蛍光体 |
WO2006121083A1 (ja) * | 2005-05-12 | 2006-11-16 | National Institute For Materials Science | β型サイアロン蛍光体 |
JP2007308605A (ja) * | 2006-05-18 | 2007-11-29 | Dowa Holdings Co Ltd | 電子線励起用の蛍光体およびカラ−表示装置 |
JP2008088266A (ja) * | 2006-09-29 | 2008-04-17 | Dowa Holdings Co Ltd | 窒化物蛍光体または酸窒化物蛍光体の製造方法 |
JP2008189811A (ja) * | 2007-02-05 | 2008-08-21 | Osaka Univ | 窒化物又は酸窒化物を母体とする蛍光体、及びその製造方法、並びにそれを使用した蛍光体含有組成物、発光装置、照明装置、及び画像表示装置 |
JP2009019213A (ja) * | 2008-10-29 | 2009-01-29 | Sharp Corp | 蛍光体の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2570400A4 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9391245B2 (en) * | 2010-09-20 | 2016-07-12 | Samsung Electronics Co., Ltd. | Sialon phosphor, method for producing same, and light-emitting device package using same |
JP2013163739A (ja) * | 2012-02-09 | 2013-08-22 | Denki Kagaku Kogyo Kk | 蛍光体及び発光装置 |
JP2013163733A (ja) * | 2012-02-09 | 2013-08-22 | Denki Kagaku Kogyo Kk | 蛍光体及び発光装置 |
JP2013163735A (ja) * | 2012-02-09 | 2013-08-22 | Denki Kagaku Kogyo Kk | 蛍光体及び発光装置 |
JP2013163736A (ja) * | 2012-02-09 | 2013-08-22 | Denki Kagaku Kogyo Kk | 蛍光体及び発光装置 |
JPWO2017188191A1 (ja) * | 2016-04-25 | 2018-05-10 | 日本特殊陶業株式会社 | 波長変換部材、その製造方法および発光装置 |
US10590341B2 (en) | 2016-04-25 | 2020-03-17 | Ngk Spark Plug Co., Ltd. | Wavelength conversion member, production method therefor, and light emitting device |
WO2022209178A1 (ja) * | 2021-03-31 | 2022-10-06 | デンカ株式会社 | ユウロピウム賦活β型サイアロン蛍光体、及び発光装置 |
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EP2570400A1 (en) | 2013-03-20 |
CN102939273A (zh) | 2013-02-20 |
EP2570400A4 (en) | 2014-01-08 |
TW201144409A (en) | 2011-12-16 |
US20130106277A1 (en) | 2013-05-02 |
EP2570400B1 (en) | 2015-10-07 |
KR20130026446A (ko) | 2013-03-13 |
JP5852564B2 (ja) | 2016-02-03 |
TWI438261B (zh) | 2014-05-21 |
US8926864B2 (en) | 2015-01-06 |
JPWO2011142228A1 (ja) | 2013-07-22 |
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