JPH02133386A - Production of fine particle of yttrium-aluminum-garnet and fine particle of yttrium-aluminum-garnet phosphor - Google Patents
Production of fine particle of yttrium-aluminum-garnet and fine particle of yttrium-aluminum-garnet phosphorInfo
- Publication number
- JPH02133386A JPH02133386A JP1020462A JP2046289A JPH02133386A JP H02133386 A JPH02133386 A JP H02133386A JP 1020462 A JP1020462 A JP 1020462A JP 2046289 A JP2046289 A JP 2046289A JP H02133386 A JPH02133386 A JP H02133386A
- Authority
- JP
- Japan
- Prior art keywords
- yttrium
- reaction
- aluminum
- yag
- fine particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010419 fine particle Substances 0.000 title claims abstract description 45
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003746 yttrium Chemical class 0.000 claims abstract description 5
- 150000001217 Terbium Chemical class 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- -1 yttrium compound Chemical class 0.000 claims description 10
- 150000003502 terbium compounds Chemical class 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 11
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052771 Terbium Inorganic materials 0.000 abstract description 9
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 6
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 64
- 239000000243 solution Substances 0.000 description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000007787 solid Substances 0.000 description 33
- 239000002245 particle Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 238000002441 X-ray diffraction Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 238000010908 decantation Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 101100323029 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) alc-1 gene Proteins 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-O 1H-indol-1-ium Chemical compound C1=CC=C2[NH2+]C=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-O 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- 229910009454 Y(OH)3 Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910003451 terbium oxide Inorganic materials 0.000 description 1
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〕
本発明は、イットリウム・アルミニウム・ガーネット（
以下、ＹＡＧと称する。）、およびこれをテルビウムで
賦活したＹＡＧ系蛍光体微粒子の製造方法に関する。[Detailed Description of the Invention] (Industrial Application Field) The present invention provides yttrium aluminum garnet (
Hereinafter, it will be referred to as YAG. ), and a method for producing YAG-based phosphor fine particles activated with terbium.
ＹＡＧは組成式Ｙ ｓ Ａ ｌ ｓ Ｏ＋□で表される
酸化物であり、レーザー発振素子の原料や人造宝石等と
しての用途がある。このＹＡＧの固溶系においてＹの一
部をテルビウムで置換したものは組成式ＴｂっＹｓ−Ａ
ｌｓｏ。 （ただし、Ｘは置換量を表す３未満の数であ
る。）で表される蛍光体材料となり、特にｘ−０，１５
付近において効率良く蛍光を発することが知られている
。この材料は発光飽和レベルが高く、投影型テレビジシ
ン、ビームインデックス管、航空機の計器表示等の高輝
度蛍光面に適している。YAG is an oxide represented by the composition formula Y s Al s O+□, and is used as a raw material for laser oscillation elements, artificial jewelry, and the like. In this YAG solid solution system, a part of Y is replaced with terbium, and the composition formula is TbYs-A.
lso. (However, X is a number less than 3 representing the amount of substitution.), especially x-0,15
It is known that it efficiently emits fluorescence in the vicinity. This material has a high luminous saturation level and is suitable for high-brightness fluorescent screens such as projection televisions, beam index tubes, and aircraft instrument displays.
ＹＡＧ系蛍光体の特性を左右する要因としては、粒度、
均一性９分散性、純度等がある。これらを最適化するこ
とにより近年の高精細度ビジョン等のように微細化され
た蛍光体パターンを有する陰掻線管の高解像度化、高画
質化等も可能となるため、有望な材料として研究が進め
られている。Factors that affect the characteristics of YAG-based phosphors include particle size,
Uniformity 9 Dispersibility, purity, etc. By optimizing these, it will be possible to increase the resolution and image quality of occultation tubes with miniaturized phosphor patterns, such as those used in recent high-definition vision systems, so this is a promising material for research. is in progress.
ＹＡＧおよびＹＡＧ系蛍光体は同様の手順により合成す
ることができる。YAG and YAG-based phosphors can be synthesized by similar procedures.
まずＹＡＧの代表的な合成方法としては、酸化イツトリ
ウムと酸化アルミニウムとを焼結助剤等と共にボールミ
ル等で粉砕混合し、１５００℃の高温にて一定時間固相
反応させた後、再びボールミル等で微粒子化して篩で分
級する方法、あるいは上述の固相反応時にフラックスを
添加し、ＹＡＧ微粒子に加わる物理的な歪みを低減させ
る改良法等がある。First, a typical method for synthesizing YAG is to pulverize and mix yttrium oxide and aluminum oxide together with a sintering aid in a ball mill, etc., perform a solid phase reaction at a high temperature of 1500°C for a certain period of time, and then use a ball mill again. There is a method in which the particles are made into fine particles and classified using a sieve, or an improved method in which a flux is added during the above-mentioned solid phase reaction to reduce the physical strain applied to the YAG fine particles.
ＹＡＧ系蛍光体を合成する際には、上述の酸化イツトリ
ウムと酸化アルミニウムに加えて酸化テルビウムを使用
し、同様の操作を行っている。When synthesizing a YAG-based phosphor, terbium oxide is used in addition to the above-mentioned yttrium oxide and aluminum oxide, and similar operations are performed.
しかしながら、これらの従来の方法では固相反応により
得られた生成物をボールミルで粉砕することにより微粒
子化を行っているので、得られるＹＡＧ微粒子もしくは
ＹＡＧ系蛍光体微粒子の粒度分布が２〜３０．ｇｍと広
く、粗大粒子の混入は避けられない。また、粉砕作業に
長時間を要するため金属酸化物等の不純物が混入しやす
い。フラックスを使用した場合にも微粒子化に限度があ
り、通常粒径１０μｍ以下の粒子を得ることは困難であ
る。However, in these conventional methods, the product obtained by solid-phase reaction is made into fine particles by pulverizing it with a ball mill, so that the particle size distribution of the obtained YAG fine particles or YAG-based phosphor fine particles is 2 to 30. gm, and the contamination of coarse particles is unavoidable. In addition, since the grinding process takes a long time, impurities such as metal oxides are likely to be mixed in. Even when a flux is used, there is a limit to the particle size reduction, and it is usually difficult to obtain particles with a particle size of 10 μm or less.
このような問題点は、特にＹＡＧ系蛍光体微粒子を高精
細度ビジョン等に通用する場合にエネルギー変換効率の
劣化、不要な着色、解像度の低下等の不都合を招く。Such problems cause inconveniences such as deterioration of energy conversion efficiency, unnecessary coloring, and deterioration of resolution, especially when YAG-based phosphor fine particles are used for high-definition vision and the like.
そこで本発明は、上述の課題を解決し、微細で粒径分布
が狭く、かつ高純度のＹＡ（、微粒子およびＹＡＧ系蛍
光体微粒子の製造を可能とする方法を提供することを目
的とする。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method that solves the above-mentioned problems and makes it possible to produce YA particles and YAG-based phosphor particles that are fine, have a narrow particle size distribution, and have high purity.
本発明者らは上述の目的を達成するために鋭意検討を行
った結果、アルカリ水溶液に可溶となされたイツトリウ
ムとアルミニウムとを所定の温度以上に加熱反応させる
ことにより、微細で粒径分布の均一なＹＡＧｉ１粒子が
単相で得られることを見出した。In order to achieve the above object, the present inventors conducted intensive studies and found that by heating and reacting yttrium and aluminum, which are soluble in an alkaline aqueous solution, to a predetermined temperature or higher, fine particle size distribution can be achieved. It has been found that uniform YAGi1 particles can be obtained in a single phase.
さらに本発明者らは、上記イツトリウムとアルミニウム
に加えてアルカリ水溶液に可溶となされたテルビウムを
賦活元素として添加することにより、同様の操作により
微細で粒径分布の均一なＹＡＧ系蛍光体微粒子が単相で
得られることを見出した。Furthermore, the present inventors added terbium, which is soluble in an alkaline aqueous solution, as an activating element in addition to the above-mentioned yttrium and aluminum, and by the same operation, fine YAG-based phosphor fine particles with a uniform particle size distribution were obtained. It was found that it can be obtained in a single phase.
本発明はかかる知見にもとづいて完成されたものである
。すなわち、本発明の第１の発明にかかるＹＡＧｖＩＩ
粒子の製造方法は、イツトリウム化合物の加水分解生成
物またはイツトリウム塩と、アルミニウム化合物の加水
分解生成物またはアルミニウム塩とをｐＨ１０，０以上
のアルカリ水溶液中、反応温度２７０℃以上にて反応さ
せることを特徴とするものである。The present invention was completed based on this knowledge. That is, YAGvII according to the first invention of the present invention
The method for producing particles involves reacting a hydrolysis product of a yttrium compound or a yttrium salt with a hydrolysis product of an aluminum compound or an aluminum salt in an alkaline aqueous solution with a pH of 10.0 or higher at a reaction temperature of 270°C or higher. This is a characteristic feature.
本発明の第２の発明にかかるＹＡＧ系蛍光体微粒子の製
造方法は、イツトリウム化合物の加水分解生成物または
イツトリウム塩と、アルミニウム化合物の加水分解生成
物またはアルミニウム塩と、テルビウム化合物の加水分
解生成物またはテルビウム塩とをｐＨ１ｏ、０以上のア
ルカリ水溶液中、反応温度２７０℃以上にて反応させる
ことを特徴とするものである。The method for producing YAG-based phosphor fine particles according to the second aspect of the present invention includes a method for producing YAG-based phosphor fine particles, which includes a hydrolysis product of a yttrium compound or a yttrium salt, a hydrolysis product of an aluminum compound or an aluminum salt, and a hydrolysis product of a terbium compound. Alternatively, it is characterized by reacting with a terbium salt in an alkaline aqueous solution with a pH of 1o or more at a reaction temperature of 270° C. or more.
本発明によれば、ＹＡＧ微粒子およびＹＡＧ系蛍光体微
粒子は水溶液系における液相反応により製造されるので
、原料となるインドリウム、アルミニウム、およびテル
ビウムも可溶化されていることが必要である。そのため
には、これらの元素を含む化合物の加水分解生成物、あ
るいはこれらの元素の塩が使用される。According to the present invention, since the YAG fine particles and the YAG-based phosphor fine particles are produced by a liquid phase reaction in an aqueous solution system, the raw materials indolium, aluminum, and terbium must also be solubilized. For this purpose, hydrolysis products of compounds containing these elements or salts of these elements are used.
まず上述の加水分解生成物を得るためには、イツトリウ
ム、アルミニウム、テルビウムのハロゲン化物や後述の
各種の塩を水に溶解させるか、もしくはその水溶液をＬ
ｉＯＨ，ＮａＯＨ，ＫＯＨ。First, in order to obtain the above-mentioned hydrolyzed product, yttrium, aluminum, terbium halides and various salts described below are dissolved in water, or the aqueous solution is
iOH, NaOH, KOH.
ＮＨ，ＯＨ等のアルカリ水溶液で加水分解させれば良い
。Hydrolysis may be carried out using an alkaline aqueous solution such as NH or OH.
また上記塩としては、硝酸塩、硫酸塩等の酸素酸塩、酢
酸塩等の有機酸塩等が挙げられる。Examples of the above-mentioned salts include oxyacid salts such as nitrates and sulfates, and organic acid salts such as acetates.
上述の原料を溶解させるアルカリ溶液としては、Ｌｉ、
Ｎａ、に等のアルカリ金属の水酸化物を水溶液としたも
のを使用する。The alkaline solution for dissolving the above-mentioned raw materials includes Li,
An aqueous solution of an alkali metal hydroxide such as Na or Ni is used.
本発明の反応においては、ｐＨと反応温度を適切に選ぶ
必要がある。In the reaction of the present invention, it is necessary to appropriately select the pH and reaction temperature.
まずｐＨは、１０．０以上に選ばれる。ＰＨ１０，０未
満では十分に単相が達成されず、純度が不十分となる。First, the pH is selected to be 10.0 or higher. If the pH is less than 10.0, a single phase cannot be achieved sufficiently, resulting in insufficient purity.
この純度は、Ｘ線回折により確認することができる。Ｙ
ＡＧ微粒子の場合、好ましいＰ）ｌの範囲は１０．０〜
１３．３であり、さらにｐＨ１１，０〜１２．６におい
て単相の生成物が高収率で得られる。またＹＡＧ系蛍光
体微粒子の場合は、好ましいｐＨの範囲は１０．２〜１
４．１であり、さらにＰＨ１１，０〜１３．５において
単相の生成物が高収率で得られる。ｐＨは得られるＹＡ
Ｇ微粒子およびＹＡＧ系蛍光体微粒子の粒径に影響する
ので、所望の特性に応じて適宜設定する必要がある。This purity can be confirmed by X-ray diffraction. Y
In the case of AG fine particles, the preferred range of P)l is 10.0 to
13.3, and a single-phase product can be obtained in high yield at pH 11.0 to 12.6. In addition, in the case of YAG-based phosphor fine particles, the preferred pH range is 10.2 to 1.
4.1, and a single-phase product can be obtained in high yield at pH 11.0 to 13.5. The pH is the obtained YA
Since it affects the particle size of the G fine particles and the YAG-based phosphor fine particles, it is necessary to set it appropriately according to the desired characteristics.
また、温度は２７０’Ｃ以上とする。２７０℃未満では
目的の生成物以外の生成物に由来するＸ線回折強度が強
くなり、純度が劣化する。反応時間を短縮して効率良い
合成を行う観点からは、３００℃以上とすることが一層
望ましい。反応温度の上限は特に限定されるものではな
いが、反応系の臨界蒸気圧を考慮しておおよそ３９０℃
とされる。Further, the temperature is set to 270'C or higher. If it is lower than 270°C, the X-ray diffraction intensity derived from products other than the target product becomes strong, and the purity deteriorates. From the viewpoint of shortening the reaction time and performing efficient synthesis, it is more desirable to set the temperature to 300°C or higher. The upper limit of the reaction temperature is not particularly limited, but is approximately 390°C in consideration of the critical vapor pressure of the reaction system.
It is said that
なお、反応時間は５分以上、より好ましくは１０分以上
とする。Note that the reaction time is 5 minutes or more, more preferably 10 minutes or more.
反応終了後は、ＹＡＧ微粒子あるいはＹＡＧ系蛍光体微
粒子が沈澱として得られるので、冷水または温水を用い
てデカンテーション、遠心分離。After the reaction is completed, YAG fine particles or YAG-based phosphor fine particles are obtained as a precipitate, so decantation and centrifugation are performed using cold or hot water.
あるいは濾過を行うことにより洗浄する。このようにし
て沈澱に吸着されているアルカリ溶液中のＬｉ、Ｎａ、
に等の金属イオンを除去した後、乾燥させる。Alternatively, it is washed by filtering. In this way, Li, Na, in the alkaline solution adsorbed on the precipitate,
After removing metal ions such as , it is dried.
なお、本発明のＹＡＧ系蛍光体微粒子には、輝度の向上
を目的としてさらにＧａが添加されていでも良い。Note that Ga may be further added to the YAG-based phosphor fine particles of the present invention for the purpose of improving brightness.
本発明においては、従来のような固相合成と物理的粉砕
の組合せとは異なり、液相合成により微細で粒径分布の
狭いＹＡＧ粒子あるいはＹＡＧ系蛍光体微粒子を高収率
に得ることができる。また、固相合成よりは温かに低い
温度にて迅速な反応が可能である。また、ボールミル等
による長時間の物理的粉砕を行う必要がないので、金属
酸化物の混入等も防止することができ、純度の高いＹＡ
Ｇ微粒子およびＹＡＧ系蛍光体微粒子が得られる。In the present invention, unlike the conventional combination of solid phase synthesis and physical pulverization, fine YAG particles or YAG-based phosphor fine particles with a narrow particle size distribution can be obtained in high yield by liquid phase synthesis. . In addition, rapid reactions are possible at warmer or lower temperatures than solid phase synthesis. In addition, since there is no need for long-term physical pulverization using a ball mill, etc., it is possible to prevent the contamination of metal oxides and produce highly pure YA.
G fine particles and YAG-based phosphor fine particles are obtained.
以下、本発明の好適な実施例について図面を参照しなが
ら説明する。Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.
第１の実施例
本実施例は、硝酸イツトリウムＹ（ＮＯ２）ｓ・３．５
Ｈ，Ｏと、塩化アルミニウムＡｌＣｊｌ！、・６ ｔ−
ｔｔ。First Example This example uses yttrium nitrate Y(NO2)s・3.5
H, O and aluminum chloride AlCjl! ,・6t-
tt.
とからＹＡＧ微粒子を製造した例である。This is an example in which YAG fine particles were manufactured from.
まず、硝酸イツトリウムＹ（Ｎｏり！・３．５Ｈ，０６
，３４ｇと塩化アルミニウムＡ Ｉ Ｃｌ ３・６Ｈ２
０１１，３ｇを純水４０ｍｊ！に溶解し、溶液Ａを調製
した。First, yttrium nitrate Y (No!・3.5H, 06
, 34g and aluminum chloride A I Cl 3.6H2
011.3g to 40mj of pure water! to prepare solution A.
次に、所定量の水酸化ナトリウムを純水４０ｍ！！、に
溶解して調製した溶液Ｂの中に、上記溶液Ａをゲル化が
生じないように攪拌しながらゆっくりと滴下し、さらに
純水を加えて１００ｍ１の反応溶液Ｃとした。ここで、
上記反応溶液ＣのｐＨ値は水酸化ナトリウムの添加量を
調節することにより変化させた。Next, add a predetermined amount of sodium hydroxide to 40m of pure water! ! The above solution A was slowly dropped into solution B prepared by dissolving it in , while stirring to prevent gelation, and pure water was added to make 100 ml of reaction solution C. here,
The pH value of the reaction solution C was changed by adjusting the amount of sodium hydroxide added.
上記反応溶液Ｃを白金からなる内容器を備えたオートク
レーブに入れ、攪拌しながら３６０℃にて１時間反応さ
せた０反応終了後、純水を使用してデカンテーションを
繰り返すことにより、上記反応で生成した白色沈澱物か
らアルカリ金属イオン等を除去し、さらに濾過水洗を行
い、乾燥話中で１００”Ｃにて一晩乾燥させて、白色固
体を得た。The above reaction solution C was placed in an autoclave equipped with an inner container made of platinum, and reacted at 360°C for 1 hour while stirring. After the reaction was completed, the above reaction was carried out by repeating decantation using pure water. Alkali metal ions and the like were removed from the generated white precipitate, which was further filtered and washed with water, and dried overnight at 100''C in a drying oven to obtain a white solid.
ここで、反応溶液ＣのｐＨ値を１２．３とした場合に得
られた白色固体について、ＣｕＫα線によるＸ線回折を
行った。この結果を第１図に示す。図中、縦軸は回折強
度（任意単位）を表し、横軸は回折角２θ（’ ）を表
す。このＸ線回折パターンはＪＣＰＤＳ （ジゴイント
・コミンティー・オン・パウダー・ディフラクシジン・
スタンダーズ：ＪｏｉｎｔＣｏｎｕ＋＋１ｔｔｅｅ ｏ
ｎ Ｐｏｗｄｅｒ Ｄｉｆｆｒａｃｔｉｏｎ ５ｔａｎ
ｄａｒｄｓ）カード３３−４０と一致することから、立
方晶のＹＡＧ（Ｙ ｚ Ａ ｌ ｓ Ｏ＋ ｔ ）であ
ることが確認された。Here, the white solid obtained when the pH value of reaction solution C was set to 12.3 was subjected to X-ray diffraction using CuKα rays. The results are shown in FIG. In the figure, the vertical axis represents the diffraction intensity (arbitrary unit), and the horizontal axis represents the diffraction angle 2θ('). This X-ray diffraction pattern is based on the JCPDS
Standards:JointConu++1ttee o
n Powder Diffraction 5tan
dards) card 33-40, it was confirmed that it was cubic YAG (Y z Al s O+ t ).
さらに、この白色固体を走査電子顕微鏡により観察した
際の写真を第２図に示す。この図によれば、粒径２〜３
μｍでしかも粒度が極めて良く揃ったＹＡ（［粒子が得
られていることがわかる。Further, FIG. 2 shows a photograph of this white solid observed using a scanning electron microscope. According to this figure, the particle size is 2-3
It can be seen that YA ([particles] with very uniform particle size in μm were obtained.
次に、ＹＡＧ＠粒子の製造条件を最適化するため、反応
溶液ＣのｐＨｌ１．反応温度および反応時間について検
討した。Next, in order to optimize the manufacturing conditions for YAG@particles, the pH of reaction solution C was 1. The reaction temperature and reaction time were studied.
まずｐＨ依存性は以下のようにして検討した。First, pH dependence was examined as follows.
すなわち、使用する水酸化ナトリウムの量を変えること
により反応？８液ＣのｐＨ値を種々に変化させ、それぞ
れの場合について同様に反応を行った。That is, by changing the amount of sodium hydroxide used? The pH value of 8 liquid C was varied variously, and the reaction was carried out in the same manner in each case.
続いて得られた各白色固体のＸ線回折を行ってＹＡＧの
相対生成量を（４２０）面からの回折に対応するピーク
の面積として求め、ＰＨに対してプロットした。この結
果を第３図に示す。図中、縦軸はＹＡＧの相対生成量（
％）を表し、横軸は反応溶液ＣのｐＨ値を表す。この図
より、ｐＨ１０，０〜１３．３の範囲でＹＡＧが生成し
ており、特にＰＨ１１，０〜１２．６の範囲において高
収率で生成していることが明らかとなった。Subsequently, each of the obtained white solids was subjected to X-ray diffraction, and the relative amount of YAG produced was determined as the area of the peak corresponding to the diffraction from the (420) plane, and was plotted against the PH. The results are shown in FIG. In the figure, the vertical axis is the relative production amount of YAG (
%), and the horizontal axis represents the pH value of the reaction solution C. This figure reveals that YAG is produced in the pH range of 10.0 to 13.3, and particularly in a high yield in the pH range of 11.0 to 12.6.
また温度依存性は以下のようにして検討した。In addition, temperature dependence was investigated as follows.
すなわち、反応溶液ＣのｐＨ（ａを１２．３とし、反応
温度を種々に変化させて１時間反応を行った。続いて得
られた各白色固体のＸ線回折を行って同様にＹＡＧの相
対生成量を求め、反応温度に対してプロットした。この
結果を第４図に示す。図中、縦軸はＹＡＧの相対生成量
（％）を表し、横軸は反応温度（℃）を示す。この図よ
り、２７０℃以上の温度でＹＡＧが生成し、約３６０℃
で最も効率良く反応が進行することがわかった。That is, the pH (a) of reaction solution C was set to 12.3, and the reaction was carried out for 1 hour while varying the reaction temperature. Subsequently, each of the obtained white solids was subjected to X-ray diffraction, and the relative proportion of YAG was similarly determined. The amount produced was determined and plotted against the reaction temperature. The results are shown in Figure 4. In the figure, the vertical axis represents the relative amount of YAG produced (%), and the horizontal axis represents the reaction temperature (° C.). From this figure, YAG is generated at a temperature of 270℃ or higher, and about 360℃
It was found that the reaction proceeded most efficiently.
最後に反応時間は以下のようにして検討した。Finally, the reaction time was examined as follows.
すなわち、反応溶液ＣのｐＨ値を１２，３、反応温度を
３６０℃として、反応時間を種々に変化させて反応を行
った。続いて得られた各白色固体のＸ線回折を行って同
（ヱにＹＡＧの相対生成量を求め、反応時間に対してプ
ロットした。この結果を第５図に示す。図中、継軸はＹ
ＡＧの相対生成量（％）を表し、横軸は反応時間（分）
を示す。この図より、ＹＡＧの生成は反応開始後数分で
始まり、約１０分後に生成量が飽和に達することが明ら
かとなった。That is, the reaction was carried out by setting the pH value of reaction solution C to 12.3, the reaction temperature to 360° C., and varying the reaction time. Subsequently, each white solid obtained was subjected to X-ray diffraction to determine the relative amount of YAG produced and plotted against the reaction time. The results are shown in Figure 5. In the figure, the axis is Y
Represents the relative production amount (%) of AG, and the horizontal axis is the reaction time (minutes).
shows. From this figure, it is clear that the production of YAG begins several minutes after the start of the reaction, and the production amount reaches saturation after about 10 minutes.
第２の実施例
本実施例は、塩化インドリウムＹＣ１，と塩化アルミニ
ウムＡ Ｉ Ｃｌ ｓとからＹＡＧ＠粒子を製造した例
である。Second Example This example is an example in which YAG@ particles were produced from indium chloride YC1 and aluminum chloride A I Cl s.
まず、塩化イツトリウムＹＣＩ、３６．６ｇと塩化アル
ミニウムＡＮＣｆｆｉｔ６２．５ｇとを純水４００ｍ１
゜にｌ容解し、７容液Ａを調製した。次に、水酸化ナト
リウム水溶液４００ｍｊ２の中に、上記／８液Ａをゲル
化が生じないように贋！↑しながらゆっくりと滴下し、
さらに純水を加えて１０１００Ｏ！の反応溶液Ｃとした
。この反応？ＷＷＣはｐＨ１２，６であった。First, 36.6 g of yttrium chloride YCI and 62.5 g of aluminum chloride ANCffit were added to 400 ml of pure water.
7 volumes of solution A was prepared. Next, add the above /8 solution A to 400 mj2 of aqueous sodium hydroxide solution to prevent gelation. While ↑, slowly drip the
Add pure water to 10100O! A reaction solution C was prepared. This reaction? WWC was pH 12.6.
上記反応／８液Ｃを白金からなる内容器を備えたオート
クレーブに入れ、攪拌しながら３６０℃にて６時間反応
させた。反応終了後、デカンテーションおよびｉｌｌ過
水洗により、上記反応で生成した白色沈澱物を洗浄し、
乾燥話中で１００℃にて１２時間乾燥させて、白色固体
を得た。The above reaction/8 liquid C was placed in an autoclave equipped with an inner container made of platinum, and reacted at 360° C. for 6 hours with stirring. After the reaction is completed, the white precipitate generated in the above reaction is washed by decantation and ill water washing,
Drying at 100° C. for 12 hours in a drying oven yielded a white solid.
この白色固体は、Ｘ線回折および電子顕微鏡観察の結果
、高純度、微細かつ粒径の均一なＹＡＧ微粒子であるこ
とが確認された。As a result of X-ray diffraction and electron microscopic observation, this white solid was confirmed to be YAG fine particles of high purity, fine, and uniform in particle size.
第３の実施例
本実施例は、硝酸イツトリウムＹ（ＮＯ３）、・３．５
８ｔＯと塩化アルミニウムＡｌＣ１，・６ＨｚＯとから
ＹＡＧ微粒子を製造するにあたり、反応溶液中のアルミ
ニウムの添加量について検討した例である。Third Example In this example, yttrium nitrate Y (NO3), 3.5
This is an example in which the amount of aluminum added to the reaction solution was studied when producing YAG fine particles from 8tO and aluminum chloride AlC1,.6HzO.
まず、硝酸イツトリウムＹ（ＮＯ３）３・３．５Ｈ，０
６３，４ｇと塩化アルミニウムＡｌＣｌ３・６ Ｈ，Ｏ
７５，４ｇとを純水４００ｍｆに溶解し、溶液Ａを調製
した。First, yttrium nitrate Y(NO3)3.3.5H,0
63.4g and aluminum chloride AlCl3.6H,O
A solution A was prepared by dissolving 75.4 g of the solution in 400 mf of pure water.
次に、水酸化ナトリウム水溶液４００ｍｊ！の中に上記
溶液Ａをゲル化が生じないように攪拌しながらゆっくり
と滴下した。この溶液を１０等分し、各溶液に対して塩
化アルミニウムｌ’１．ｃ１．を０ｇ＋７．５４ｇ、
１５．１ｇ、・・・、 ６７．９ｇのように段階的に
最初の量の１０％ずつを順次追加する形で添加し、さら
に純水を加えて各々１００ｍ１の反応溶液Ｃ０〜Ｃ１と
した。つまり、反応溶液Ｃ０はＹＡＧを合成するために
化学量論的に必要な量のアルミニウムを含み、Ｃ７〜Ｃ
９はその量の１０％増しないし９０％増しとなっている
わけである。これらの各溶液のＰＨ値は水酸化ナトリウ
ム水溶液を用いて１２．６に調整した。Next, 400 mj of sodium hydroxide aqueous solution! The above solution A was slowly added dropwise into the solution while stirring to prevent gelation. This solution was divided into 10 equal parts, and aluminum chloride l'1 for each solution. c1. 0g + 7.54g,
15.1 g, . . . , 67.9 g were added stepwise in 10% increments of the initial amount, and pure water was further added to give 100 ml of each reaction solution C0 to C1. In other words, the reaction solution C0 contains the stoichiometrically necessary amount of aluminum to synthesize YAG, and contains C7-C
9 is an increase of 10% or 90% of that amount. The pH value of each of these solutions was adjusted to 12.6 using an aqueous sodium hydroxide solution.
上記反応溶液００〜Ｃ１を白金からなる内容器を備えた
オートクレーブにそれぞれ入れ、攪拌しながら３６０℃
にて１時間反応させた。反応終了後、デカンテーション
および濾過水洗により、上記反応で生成した白色沈澱物
を洗浄し、乾燥品中で１００℃にて一晩乾燥させ白色固
体を得た。The above reaction solutions 00 to C1 were placed in an autoclave equipped with an inner container made of platinum, and heated to 360°C while stirring.
The mixture was reacted for 1 hour. After the reaction was completed, the white precipitate produced in the above reaction was washed by decantation, filtration and washing with water, and dried overnight at 100°C in a dry product to obtain a white solid.
この白色固体をＸ線回折により分析したところ、反応溶
液Ｃ１〜Ｃ１から得られた白色固体は第１図のＸ線回折
パターンとほぼ同じパターンを示し、高純度のＹＡＧで
あることが確認された。しかし、００〜Ｃ２から合成さ
れた白色固体のＸ線回折パターンには、水酸化イツトリ
ウムＹ（ＯＨ）３の混在を示すピークがみられた。これ
より、反応に際してはイツトリウムに対してアルミニウ
ムが化学量論的に必要とされる量よりおよそ３０％は過
剰に必要であることがわかる。When this white solid was analyzed by X-ray diffraction, the white solid obtained from reaction solutions C1 to C1 showed almost the same X-ray diffraction pattern as shown in Fig. 1, and it was confirmed that it was high-purity YAG. . However, in the X-ray diffraction pattern of the white solid synthesized from 00-C2, a peak indicating the presence of yttrium hydroxide Y(OH)3 was observed. From this, it can be seen that approximately 30% of aluminum is required in excess of the stoichiometric amount of aluminum relative to yttrium in the reaction.
第４の実施例
本実施例は、硝酸イツトリウムＹ（ＮＯｓ）３・３．５
Ｈ６０と塩化アルミニウムＡｌ−Ｃｌ３・６Ｈ２０とか
らＹＡＧ微粒子を製造するにあたり、反応溶液ＣのｐＨ
によるＹＡＧ微粒子の粒径の変化について検討した例で
ある。Fourth Example This example uses yttrium nitrate Y (NOs) 3.3.5
When producing YAG fine particles from H60 and aluminum chloride Al-Cl3.6H20, the pH of the reaction solution C
This is an example in which changes in the particle size of YAG fine particles were investigated.
まず、硝酸イツ） ’Ｊ ’７ ムＹ （Ｎ ０ｓ）ｓ
Ｊ、５Ｈｔ。First, nitric acid) 'J '7 MuY (N 0s)s
J, 5Ht.
２５．３ ｇと塩化アルミニウムＡＩ！、Ｃ１，・６Ｈ
２０４５，２ｇを純水１６０ｍｆに溶解し、溶液Ａを調
製した０次に、水酸化ナトリウム水溶？＆１００ｍ１中
に上記溶液Ａをゲル化が生じないように攪拌しながらゆ
っくりと滴下し、純水を加えて３２０ｍｆｆ１の溶液を
調製した。この溶液を４等分し、各溶液に水酸化ナトリ
ウム溶液と純水を加えて１００ｍＩＶ、とじ、それぞれ
ｐ Ｈｌｌ、６． ｐ ＨＩ３゜３． ｐ ＨＩ３
．６． ｐ ＨＩ３．０の溶液０１〜ＣＩＶを調製し
た。25.3 g and aluminum chloride AI! ,C1,・6H
2045.2g was dissolved in 160mf of pure water to prepare solution A.Next, sodium hydroxide aqueous solution? The above solution A was slowly dropped into 100ml of the solution while stirring to prevent gelation, and pure water was added to prepare a solution of 320mff1. Divide this solution into 4 equal parts, add sodium hydroxide solution and pure water to each solution, add 100 mIV, close, pH Hll, 6. p HI3゜3. pHI3
．． 6. Solutions 01-CIV were prepared at pH HI 3.0.
上記反応溶液Ｃ３〜ＣＩＶを白金からなる内容器を備え
たオートクレーブにそれぞれ入れ、攪拌しながら３６０
℃にて１時間反応させた０反応終了後、デカンテーショ
ンおよび濾過水洗により、上記反応で生成した白色沈澱
物を洗浄し、乾燥品中で１００℃にて一晩乾燥させ白色
固体を得た。The above reaction solutions C3 to CIV were each placed in an autoclave equipped with an inner container made of platinum, and heated for 360 min while stirring.
After the reaction was completed at 1 hour at 0.degree. C., the white precipitate produced in the above reaction was washed by decantation, filtration and washing with water, and dried overnight at 100.degree. C. to obtain a white solid.
この白色固体をＸ線回折により分析したところ、反応溶
液ＣＩ”−Ｃ＋ ｖから得られた各白色固体は回折強度
がやや異なるものの、高純度なＹＡＧであることがわか
った。When this white solid was analyzed by X-ray diffraction, it was found that each white solid obtained from the reaction solution CI''-C+v was highly pure YAG, although the diffraction intensities were slightly different.
さらにこれらの白色固体の電子顕微鏡観察を行ったとこ
ろ、ｐＨ１１，６の反応溶液Ｃ１から得られた白色固体
の粒径は約０．１μｍ、ｐＨ１３，０の反応溶液ＣＩＶ
から得られた白色固体の粒径は約１０μｍであり、ｐＨ
値の調節により粒径の制御がおおよそ０．１−１０μｍ
の範囲で制御可能であることがわかった。Furthermore, when these white solids were observed using an electron microscope, the particle size of the white solid obtained from the reaction solution C1 with pH 11.6 was approximately 0.1 μm, and the particle size of the white solid obtained from the reaction solution CIV with pH 13.0 was found to be approximately 0.1 μm.
The particle size of the white solid obtained from
Particle size can be controlled approximately 0.1-10μm by adjusting the value
It was found that control was possible within the range of .
第５の実施例
本実施例は、硝酸イツトリウムＹ（ＮＯ３）２・３．５
Ｈ，Ｏと、塩化アルミニウムＡｌＣｌ、・６Ｈ２０と、
塩化テルビウムＴｂＣ，１，とからＹＡＧ系蛍光体微粒
子を製造した例である。Fifth Example This example uses yttrium nitrate Y(NO3)2.3.5
H, O, aluminum chloride AlCl, 6H20,
This is an example in which YAG-based phosphor fine particles were manufactured from terbium chloride TbC,1.
まず、水酸化ナトリウム１９．７ｇを純水に溶解して６
０ｍｆｆ１としたアルカリ水溶液中に、硝酸イツトリウ
ムＹ（ＮＯｓ）ｓ・３．５ＨｚＯ１２，０４ｇ、 塩
化アルミニウムＡ１．Ｃ１，・６ Ｈ，０２２，６１ｇ
、および塩化テルビウムＴ ｂ Ｃｌｓ Ｏ，４９７
ｇを攪拌しながら徐々に添加し、さらに純水を加えて１
００ｍ１の反応溶液りとした。First, dissolve 19.7 g of sodium hydroxide in pure water and
In an alkaline aqueous solution adjusted to 0 mff1, 12.04 g of yttrium nitrate Y(NOs)s.3.5HzO, aluminum chloride A1. C1, 6 H, 022, 61g
, and terbium chloride T b Cls O, 497
Gradually add g while stirring, then add pure water and make 1
00ml of reaction solution was prepared.
上記反応溶液りを白金からなる内容器を備えたオートク
レーブ゛に入れ、攪１牢しながら３７０℃にて１時間反
応させた０反応終了後、純水を使用してデカンテーショ
ンを繰り返すことにより、上記反応で生成した白色沈澱
物からアルカリ金属イオン等を除去し、さらに濾過水洗
を行い、乾燥話中で１００ ’Ｃにて一晩乾燥させて、
白色固体を得た。The above reaction solution was placed in an autoclave equipped with an inner container made of platinum, and reacted at 370°C for 1 hour with stirring. After the reaction was completed, decantation was repeated using pure water. Alkali metal ions etc. were removed from the white precipitate generated in the above reaction, further filtered and washed with water, and dried overnight at 100'C in a drying oven.
A white solid was obtained.
上記白色固体について、ＣｕＫα線によるＸ線回折を行
った。この結果を第６図に示す。図中、縦軸は回折強度
（任意単位）を表し、横軸は回折角２θじ）を表す。こ
のＸ線回折パターンは、前述のＪＣＰＤＳカード３３−
４０に示される立方晶ＹＡＧ （ＹｓＡ ｌ ｓｏ ＋
ｚ）のパターンとほぼ一致していた。The white solid was subjected to X-ray diffraction using CuKα rays. The results are shown in FIG. In the figure, the vertical axis represents the diffraction intensity (arbitrary unit), and the horizontal axis represents the diffraction angle (2θ). This X-ray diffraction pattern is based on the JCPDS card 33-
Cubic YAG (YsA l so +
It almost matched the pattern of z).
この白色固体に波長２５４〜３６６ｎｍの紫外線を照射
したところ、緑色の蛍光を発した。また、既知の組成を
有するｒｂうＹ、□Ａｐ、ｓｏ＋ｚの標準試料を使用し
て蛍光Ｘ線分析を行ったところ、ｘ−〇、１５の標準試
料が示すパターンと一致し、上記白色固体の組成はＴ
ｂ ｏ、 ＋ｓＹｔ、 ａｓＡ Ｉ Ｓｏ Ｉ！である
ことが確認された。このときのＸ線回折ピークにもとづ
いて算出された格子定数は１２．０２５人であった。When this white solid was irradiated with ultraviolet light with a wavelength of 254 to 366 nm, it emitted green fluorescence. In addition, when fluorescent X-ray analysis was performed using standard samples of rbY, □Ap, and so+z with known compositions, the pattern matched with the pattern shown by the standard sample of x-〇, 15, and the above white solid The composition is T
b o, +sYt, asA I So I! It was confirmed that The lattice constant calculated based on the X-ray diffraction peak at this time was 12.025.
さらに、この白色固体を走査電子顕微鏡により観察した
際の写真を第７図に示す０粒度が極めて良く揃ったＹＡ
Ｇ系蛍光体微粒子が得られていることがわかる。Furthermore, when this white solid was observed using a scanning electron microscope, the photograph of the Y
It can be seen that G-based phosphor fine particles were obtained.
次に、ＹＡＧ系蛍光体微粒子の製造条件を最適化するた
め、反応溶＞ｔＩＤのＰ）（値１反応部度および反応時
間について第１の実施例の場合と同様に検討した。Next, in order to optimize the manufacturing conditions for YAG-based phosphor fine particles, the reaction solution>tID (P) (value 1) The reaction site degree and reaction time were investigated in the same manner as in the first example.
まず、ｐＨ依存性について検討した結果を第８図に示す
０図中、縦軸はＹＡＧ系蛍光体の相対生成量（％）を表
し、横軸は反応溶液りのｐＨ値を表す０反応条件は３７
４℃，１時間である。この図より、ｐＨ１０，２〜１４
．１の範囲でＹＡＧ系蛍光体が生成しており、特にｐＨ
１１，０〜１３．５の範囲において高収率で生成してい
ることが明らかとなった。First, the results of examining the pH dependence are shown in Figure 8. In the diagram, the vertical axis represents the relative production amount (%) of YAG-based phosphor, and the horizontal axis represents the pH value of the reaction solution under the reaction conditions. is 37
4°C for 1 hour. From this figure, pH10.2-14
．． YAG-based phosphors are generated in the range of pH 1, especially at pH
It became clear that the product was produced in high yield in the range of 11.0 to 13.5.
次に、温度依存性の検討結果を第９図に示す。Next, FIG. 9 shows the results of examining temperature dependence.
図中、縦軸はＹＡＧ系蛍光体の相対生成量（％）を表し
、横軸は反応温度（℃）を示す。反応溶液ＤＯＰ Ｈ値
は１２．５．反応時間は１時間である。この図より、２
７５ ”Ｃ以上の温度でＹＡＧ系蛍光体が生成し、約３
６０ ”Ｃで最も効率良く反応が進行することがわかっ
た。また２５０℃以下の温度では別の相に由来する回折
ピークが大きくなり、合成には適さないこともわかった
。In the figure, the vertical axis represents the relative production amount (%) of the YAG-based phosphor, and the horizontal axis represents the reaction temperature (° C.). The reaction solution DOP H value was 12.5. Reaction time is 1 hour. From this figure, 2
YAG-based phosphor is generated at a temperature of 75"C or higher, and
It was found that the reaction proceeded most efficiently at 60''C. It was also found that at temperatures below 250°C, the diffraction peaks derived from other phases become large, making it unsuitable for synthesis.
最後に反応時間について検討した結果を第１０図に示す
。図中、縦軸はＹＡＧ系蛍光体の相対生成量（％）を表
し、横軸は反応時間（時間）を示す。反応ｔ？ＪｔｉＤ
（７） ｐ Ｈ値は１２．５．反応温度は３７４°ｃ
である。この図より、ＹＡＧ系蛍光体の生成は反応開始
後数分で始まり、約１０分後に生成量が飽和に達するこ
とが明らかとなった。Finally, the results of the study on reaction time are shown in FIG. In the figure, the vertical axis represents the relative production amount (%) of the YAG-based phosphor, and the horizontal axis represents the reaction time (hours). Reaction t? JtiD
(7) pH value is 12.5. Reaction temperature is 374°C
It is. From this figure, it is clear that the production of YAG-based phosphor begins several minutes after the start of the reaction, and the production amount reaches saturation after about 10 minutes.
第６の実施例
本実施例は、第５の実施例の反応？８液りにおいて塩化
アルミニウムＡｆＣ１！、・６Ｈ！０と塩化テルビウム
ＴｂＣＬの添加Ｍを変えた場合のＹＡＧ系蛍光体の組成
および格子定数の変化を検討した例である。Sixth Example Is this example the reaction of the fifth example? Aluminum chloride AfC1 in 8 liquids! ,・6H! This is an example of examining changes in the composition and lattice constant of a YAG-based phosphor when the addition M of 0 and terbium chloride TbCL is changed.
まず、適当量の水酸化ナトリウムを含有する純水中に硝
酸イツトリウムＹ（ＮＯ，）３・３．５Ｈ，０１２，０
４ｇ、および後述の第１表に示す量の塩化アルミニウム
ＡｌＣ１，・６Ｈ２０と塩化テルビウムＴｂＣＮ、を攪
拌しながら徐々に添加し、純水を加えて１００ｄとした
反応溶ｆｉＤを７種類調製した。First, yttrium nitrate Y(NO,)3.3.5H,012,0 was added to pure water containing an appropriate amount of sodium hydroxide.
4g of aluminum chloride AlC1,.6H20 and terbium chloride TbCN in amounts shown in Table 1 below were gradually added with stirring, and purified water was added to make 100d to prepare seven types of reaction solutions fiD.
これら各反応溶９＆Ｄを、オートクレーブ中で攪拌しな
から３７４℃で２時間反応させた。生成した白色沈澱物
から、同様の操作により白色固体を得た。これらの白色
固体のＸ線蛍光分析を行い、各白色固体の組成を決定し
た。この結果を、第１表に示す。Each of these reaction solutions 9 & D was allowed to react in an autoclave at 374° C. for 2 hours without stirring. A white solid was obtained from the produced white precipitate by the same operation. These white solids were subjected to X-ray fluorescence analysis to determine the composition of each white solid. The results are shown in Table 1.
第１表
これらのＹＡＧ系蛍光体微粒子（Ｔｂ工Ｙ ３−Ａ ｌ
５０１ｔ） についてそれぞれＸ線回折を行ったとこ
ろ、各回折パターンは第６図に示すものと同相を呈して
いたが、回折ピーク角度がそれぞれ若干シフトしていた
。これらの回折ピーク角度にもとづいて格子定数を算出
し、テルビウムの置換ＩＪｘに対してプロットした結果
を第１１図に示す。この図より、テルビウムの置換ｉ１
ｘと格子定数の間には直線関係が成立していることがわ
かる。Table 1 These YAG-based phosphor fine particles (Tb engineering Y 3-A l
When X-ray diffraction was performed on each of the 501t), each diffraction pattern exhibited the same phase as that shown in FIG. 6, but the diffraction peak angles were slightly shifted. The lattice constants were calculated based on these diffraction peak angles and plotted against the substitution IJx of terbium, and the results are shown in FIG. From this figure, the substitution i1 of terbium
It can be seen that a linear relationship is established between x and the lattice constant.
第７の実施例
本実施例は、上記反応溶液りにおけるアルミニウムの添
加量によるＹＡＧ系蛍光体微粒子の組成変化について調
べた例である。Seventh Example In this example, changes in the composition of YAG-based phosphor fine particles depending on the amount of aluminum added to the reaction solution were investigated.
まず、塩化テルビウムＴ ｂ Ｃｌｘ ２．４８５ ｇ
、硝酸イツトリウムＹ（Ｎｏｔ）ｚ、３．５ＨｔＯ６０
，２ｇ。First, terbium chloride T b Clx 2.485 g
, yttrium nitrate Y(Not)z, 3.5HtO60
,2g.
塩化アルミニウムＡｌＣ１，・６ Ｈｚｏ ７５．３
ｇを２００ｍｊ！の純水中に溶解し、水酸化ナトリウム
を加えて中和した。Aluminum chloride AlC1, 6 Hzo 75.3
G to 200mj! It was dissolved in pure water and neutralized by adding sodium hydroxide.
次にこの溶液を５等分し、塩化アルミニウムを７．５３
ｇ、 １５．１ｇ、・・・、 ３７．７ｇのように段階
的に最初の量の１０％ずつを１ｌｌｉ次追加する形で添
加し、さらに純水を加えて各々ｌｏｏｍｊ！の反応溶液
Ｄ〜Ｄ、を調製した。これらの反応溶液Ｄ１〜Ｄ。Next, this solution was divided into 5 equal parts, and aluminum chloride was divided into 7.53 parts.
g, 15.1g,..., 37.7g, add 10% of the initial amount step by step, add pure water, and loomj each! Reaction solutions D to D were prepared. These reaction solutions D1-D.
のｐＨは、水酸化ナトリウムを添加することにより１３
．３に調整した。The pH of is reduced to 13 by adding sodium hydroxide.
．． Adjusted to 3.
上記各反応溶液り、−Ｄ、を、オートクレーブ中で攪拌
しなから３６０℃で１時間反応させた。生成した白色沈
澱物から、同様の操作により白色固体を得た。これらの
白色固体のＸ線回折を行ったところ、反応溶液り、〜Ｄ
、から得られた白色固体の回折パターンは第６図に示す
ものとほぼ同様であったが、反応溶液り、および反応溶
ＨＤ ｚから得られた白色固体には若干の水酸化イツト
リウムＹ（ＯＨ）３の混在が認められた。この事実より
、アルカリ水溶液中の反応において水酸化イツトリウム
ｙ（ＯＨ）ｚの生成を抑制するためには、少なくともイ
ツトリウムの２．３倍程度のモル数のアルミニウムが必
要であることがわかる。Each of the above reaction solutions -D was allowed to react in an autoclave at 360° C. for 1 hour without stirring. A white solid was obtained from the produced white precipitate by the same operation. When these white solids were subjected to X-ray diffraction, the reaction solution was ~D
The diffraction pattern of the white solid obtained from the reaction solution was almost the same as that shown in FIG. ) 3 were observed. This fact shows that in order to suppress the formation of yttrium hydroxide y(OH)z in a reaction in an alkaline aqueous solution, at least about 2.3 times as many moles of aluminum as yttrium are required.
第８の実施例
本実施例は、反応溶液りのｐＨによるＹＡＧ系蛍光体の
粒径の変化について検討した例である。Eighth Example This example is an example in which changes in the particle size of a YAG-based phosphor depending on the pH of the reaction solution were studied.
まず、３５０ｒｒ＋１の純水中に塩化テルビウムＴｂＣ
１ｘ３．４８ｇ、硝酸インドリウムＹ （Ｎ Ｏｘ）
ｉ、３．５ＨｚＯ８４，３ｇ、塩化アルミニウム、１１
（１３，６Ｈ，Ｏ１５８，３ｇを溶解し、水酸化ナトリ
ウムを加えて中和した。First, terbium chloride TbC was added to 350rr+1 pure water.
1x3.48g, indium nitrate Y (N Ox)
i, 3.5HzO84.3g, aluminum chloride, 11
(158.3 g of 13,6H,O was dissolved and neutralized by adding sodium hydroxide.
次にこの溶液を７等分し、各溶液に所定量の水酸化ナト
リウムと純水を加えてｌｏＯｍｊ！とじ、後述の第２表
に示すｐＨ値の反応溶液り、〜Ｄ１．を調整した。Next, divide this solution into seven equal parts, add a predetermined amount of sodium hydroxide and pure water to each solution, and create loOmj! Seal the reaction solution with a pH value shown in Table 2 below, ~D1. adjusted.
上記各反応溶液り、〜［）＋ｚを、オートクレーブ中で
攪拌しながら３７４℃で１時間反応させた。生成した白
色沈澱物から、同様の操作により白色固体を得た。これ
らの白色固体のＸ線回折を行ったところ、各々ピーク強
度は異なったが同一の相のＹＡＣ，系蛍光体であること
が確認された。Each of the above reaction solutions ~[)+z was reacted at 374°C for 1 hour while stirring in an autoclave. A white solid was obtained from the produced white precipitate by the same operation. When these white solids were subjected to X-ray diffraction, it was confirmed that they were YAC-based phosphors of the same phase, although their peak intensities were different.
さらにこれらの白色固体を走査電子顕微鏡により観察し
たところ、ｐＨの変化によって０．２〜５ＩＩｍの粒径
のＹＡＧ系蛍光体が得られていることがわかった。この
結果を第２表に示す。Furthermore, when these white solids were observed using a scanning electron microscope, it was found that YAG-based phosphors having a particle size of 0.2 to 5 IIm were obtained depending on the pH change. The results are shown in Table 2.
第２表
このように、反応溶液りのＰＨにより生成するＹＡＣ系
蛍光体微粒子の粒径を制御できることがわがった。Table 2 As shown, it was found that the particle size of the YAC-based phosphor fine particles produced could be controlled by adjusting the pH of the reaction solution.
以上の説明からも明らかなように、本発明において得ら
れるＹＡＧ微粒子およびＹＡＧ系蛍光体微粒子は、粒径
が極めて小さい０粒度分布が均一である１粒径が反応溶
液のｐＨによって制御可能である。製造過程において金
属酸化物等の混入の虞れがないといった優れた特性を有
する。特にこのような長所を有するＹＡＧ系蛍光体微粒
子は、高解像度の要求される極線管用の蛍光体として極
めて有効なものである。As is clear from the above description, the YAG fine particles and YAG-based phosphor fine particles obtained in the present invention have an extremely small particle size, a uniform particle size distribution, and a particle size that can be controlled by the pH of the reaction solution. . It has an excellent property that there is no risk of contamination with metal oxides etc. during the manufacturing process. In particular, YAG-based phosphor fine particles having such advantages are extremely effective as phosphors for cathode ray tubes that require high resolution.
光体微粒子の相対生成量のＰＨ依存性を示す特性図、第
９図はＹＡＧ系蛍光体微粒子の相対生成量の温度依存性
を示す特性図、第１０図はＹＡＧ系蛍光体微粒子の相対
生成量の反応時間依存性を示す特性図、第１１図はＹＡ
Ｇ系蛍光体微粒子の格子定数のテルビウム置換量依存性
を示す特性図である。A characteristic diagram showing the PH dependence of the relative production amount of photonic particles, Fig. 9 is a characteristic diagram showing the temperature dependence of the relative production quantity of YAG-based phosphor particles, and Fig. 10 shows the relative production of YAG-based phosphor particles. A characteristic diagram showing the reaction time dependence of the amount, Figure 11 is YA
FIG. 2 is a characteristic diagram showing the dependence of the lattice constant of G-based phosphor fine particles on the amount of terbium substitution.
Claims (2)
トリウム塩と、アルミニウム化合物の加水分解生成物ま
たはアルミニウム塩とをｐＨ１０．０以上のアルカリ水
溶液中、反応温度２７０℃以上にて反応させることを特
徴とするイットリウム・アルミニウム・ガーネット微粒
子の製造方法。(1) It is characterized by reacting a hydrolysis product of a yttrium compound or a yttrium salt with a hydrolysis product of an aluminum compound or an aluminum salt in an alkaline aqueous solution with a pH of 10.0 or higher at a reaction temperature of 270°C or higher. Method for producing yttrium aluminum garnet fine particles.
トリウム塩と、アルミニウム化合物の加水分解生成物ま
たはアルミニウム塩と、テルビウム化合物の加水分解生
成物またはテルビウム塩とをｐＨ１０．０以上のアルカ
リ水溶液中、反応温度２７０℃以上にて反応させること
を特徴とするイットリウム・アルミニウム・ガーネット
系蛍光体微粒子の製造方法。(2) A hydrolysis product of a yttrium compound or a yttrium salt, a hydrolysis product of an aluminum compound or an aluminum salt, and a hydrolysis product of a terbium compound or a terbium salt in an alkaline aqueous solution with a pH of 10.0 or more at a reaction temperature. A method for producing yttrium-aluminum-garnet-based phosphor fine particles, which comprises reacting at 270°C or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2046289A JP2705183B2 (en) | 1988-07-30 | 1989-01-30 | Method for producing yttrium aluminum garnet fine particles and yttrium aluminum garnet-based phosphor fine particles |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-191472 | 1988-07-30 | ||
| JP19147288 | 1988-07-30 | ||
| JP2046289A JP2705183B2 (en) | 1988-07-30 | 1989-01-30 | Method for producing yttrium aluminum garnet fine particles and yttrium aluminum garnet-based phosphor fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02133386A true JPH02133386A (en) | 1990-05-22 |
| JP2705183B2 JP2705183B2 (en) | 1998-01-26 |
Family
ID=26357427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2046289A Expired - Fee Related JP2705183B2 (en) | 1988-07-30 | 1989-01-30 | Method for producing yttrium aluminum garnet fine particles and yttrium aluminum garnet-based phosphor fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2705183B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0465053A (en) * | 1990-07-04 | 1992-03-02 | Natl Inst For Res In Inorg Mater | Image display apparatus |
| JPH11500584A (en) * | 1996-09-20 | 1999-01-12 | シーメンス アクチエンゲゼルシヤフト | Casting material for wavelength conversion, method of using the same, and method of manufacturing the same |
| JP2002523610A (en) * | 1998-08-27 | 2002-07-30 | スーペリア マイクロパウダーズ リミテッド ライアビリティ カンパニー | Phosphorescent powder, method for producing phosphorescent powder, and apparatus using the same |
| WO2006106745A1 (en) * | 2005-03-31 | 2006-10-12 | Fujifilm Corporation | Light-transparent material and process for producing the same |
| WO2013111811A1 (en) | 2012-01-25 | 2013-08-01 | エム・テクニック株式会社 | Manufacturing processes for garnet precursor microparticles and microparticles of garnet structure |
| US9196800B2 (en) | 1996-06-26 | 2015-11-24 | Osram Gmbh | Light-radiating semiconductor component with a luminescence conversion element |
-
1989
- 1989-01-30 JP JP2046289A patent/JP2705183B2/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0465053A (en) * | 1990-07-04 | 1992-03-02 | Natl Inst For Res In Inorg Mater | Image display apparatus |
| US9196800B2 (en) | 1996-06-26 | 2015-11-24 | Osram Gmbh | Light-radiating semiconductor component with a luminescence conversion element |
| JP2012238909A (en) * | 1996-09-20 | 2012-12-06 | Osram Ag | Casting material, method of manufacturing the same, and light emitting element |
| JPH11500584A (en) * | 1996-09-20 | 1999-01-12 | シーメンス アクチエンゲゼルシヤフト | Casting material for wavelength conversion, method of using the same, and method of manufacturing the same |
| JP2008103756A (en) * | 1996-09-20 | 2008-05-01 | Siemens Ag | Casting composition and method for producing same, and luminescence device |
| JP2009071336A (en) * | 1996-09-20 | 2009-04-02 | Siemens Ag | Led chip |
| JP2002523610A (en) * | 1998-08-27 | 2002-07-30 | スーペリア マイクロパウダーズ リミテッド ライアビリティ カンパニー | Phosphorescent powder, method for producing phosphorescent powder, and apparatus using the same |
| WO2006106745A1 (en) * | 2005-03-31 | 2006-10-12 | Fujifilm Corporation | Light-transparent material and process for producing the same |
| US7691765B2 (en) | 2005-03-31 | 2010-04-06 | Fujifilm Corporation | Translucent material and manufacturing method of the same |
| JP2006282447A (en) * | 2005-03-31 | 2006-10-19 | Fuji Photo Film Co Ltd | Translucent material and method for manufacturing the same |
| WO2013111811A1 (en) | 2012-01-25 | 2013-08-01 | エム・テクニック株式会社 | Manufacturing processes for garnet precursor microparticles and microparticles of garnet structure |
| KR20140125763A (en) | 2012-01-25 | 2014-10-29 | 엠. 테크닉 가부시키가이샤 | Manufacturing processes for garnet precursor microparticles and microparticles of garnet structure |
| EP2808301A4 (en) * | 2012-01-25 | 2015-11-04 | M Tech Co Ltd | Manufacturing processes for garnet precursor microparticles and microparticles of garnet structure |
| US9260315B2 (en) | 2012-01-25 | 2016-02-16 | M. Technique Co., Ltd. | Methods for producing garnet precursor microparticles and microparticles having garnet structure |
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|---|---|
| JP2705183B2 (en) | 1998-01-26 |
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