JP5849961B2 - Method for producing nitride phosphor using co-precipitation raw material, nitride phosphor, and raw material thereof - Google Patents
Method for producing nitride phosphor using co-precipitation raw material, nitride phosphor, and raw material thereof Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 81
- 150000004767 nitrides Chemical class 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 239000002994 raw material Substances 0.000 title claims description 28
- 238000000975 co-precipitation Methods 0.000 title claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 42
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 40
- 239000012190 activator Substances 0.000 claims description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- -1 amide compound Chemical class 0.000 claims description 19
- 229910052693 Europium Inorganic materials 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 9
- 229910052771 Terbium Inorganic materials 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 9
- 229910052691 Erbium Inorganic materials 0.000 claims description 8
- 229910052689 Holmium Inorganic materials 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 8
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- 229910052775 Thulium Inorganic materials 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical group [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 22
- 239000000843 powder Substances 0.000 description 22
- 238000010304 firing Methods 0.000 description 21
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- 239000012298 atmosphere Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 150000002484 inorganic compounds Chemical class 0.000 description 7
- 229910010272 inorganic material Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical group N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Description
本発明は窒化物蛍光体の製造方法、その方法で得られる窒化物蛍光体、及びそれに使用される原料にも関する。 The present invention also relates to a method for producing a nitride phosphor, a nitride phosphor obtained by the method, and a raw material used therefor.
近年白色ＬＥＤの開発により、ＬＥＤを用いたバックライトや、照明装置が登場し、そのエネルギー消費の少なさから、急速に従来の白熱電球や、蛍光灯との置き換わりが生じている。
この白色ＬＥＤは、ＧａＮ系青色発光ダイオードの発する青色領域の可視光を吸収して黄色光を発光することから、蛍光体に吸収されなかったダイオードの青色光との混色により白色の発光が得られるものが多く用いられている。しかしながら、かかる黄色発光の蛍光体のみを使用する青色ＬＥＤと黄色蛍光体の白色発光素子は、演色性、あるいは色再現範囲の点では、不十分なものであった。In recent years, with the development of white LEDs, backlights and lighting devices using LEDs have appeared, and due to their low energy consumption, they are rapidly replacing conventional incandescent bulbs and fluorescent lamps.
This white LED absorbs the visible light in the blue region emitted by the GaN-based blue light-emitting diode and emits yellow light, so that white light emission can be obtained by mixing with the blue light of the diode that was not absorbed by the phosphor. Many things are used. However, a blue LED and a yellow phosphor white light-emitting element that use only such a yellow light-emitting phosphor are insufficient in terms of color rendering properties or a color reproduction range.
このため、近年この青ＬＥＤと黄色蛍光体の組み合わせに、赤色蛍光体を加えたり、あるいは青ＬＥＤと緑蛍光体と赤色蛍光体を用いる方法、さらには使用するＬＥＤを紫から近紫外線とし、これに青色蛍光体と緑蛍光体と赤色蛍光体を用いる方法などが提案されている。そしてこれらに使用される蛍光体としては、窒化物、あるいは酸窒化物蛍光体（以下両者合わせて窒化物系蛍光体という）が新たに開発され、できるだけ高効率、高輝度の蛍光体であることが求められている。
特に赤色蛍光体に関しては、近紫外線での励起が弱く、他の蛍光体からの、可視範囲にある光を吸収して光るため、効率と輝度を向上させることの重要性は高い。For this reason, in recent years, red phosphors have been added to this combination of blue LEDs and yellow phosphors, or blue LEDs, green phosphors, and red phosphors have been used. In addition, a method using a blue phosphor, a green phosphor and a red phosphor has been proposed. As phosphors used for these, nitride or oxynitride phosphors (hereinafter referred to collectively as nitride-based phosphors) have been newly developed, and are phosphors with the highest possible efficiency and brightness. Is required.
In particular, red phosphors are weakly excited by near-ultraviolet light and absorb light from the other phosphors in the visible range, so that it is highly important to improve efficiency and luminance.
現在LED用の赤色蛍光体として開発されている蛍光体としては、いわゆる２５８蛍光体（特許文献１参照）、ＣＡＳＮ蛍光体（特許文献２参照、製造方法は、特許文献３などに詳しい記載があるので参照）、１１４７蛍光体（特許文献４参照）などが知られている。そしてこれら蛍光体の多くは、アルカリ土類金属元素と、ケイ素と窒素を主要構成元素として含み、ここに賦活剤となる元素がドープされている。これらの元素は、それぞれ窒化物または酸化物の形で混合され、窒素雰囲気下、高温で焼成することにより、蛍光体とされている。窒化物と酸化物とでは、特定の目的、あるいは量的に実質的に影響がほとんど無い限り、酸素の混入を減らすために窒化物が好ましいとして使用されている。また、それぞれの構成元素を窒化物とするのではなく、これらの全てあるいは一部を合金化し、これを窒化する方法も行われている。 As phosphors currently developed as red phosphors for LEDs, so-called 258 phosphors (refer to Patent Document 1), CASN phosphors (refer to Patent Document 2 and the manufacturing method is described in detail in Patent Document 3). 1147 phosphor (see Patent Document 4) and the like are known. Many of these phosphors contain an alkaline earth metal element, silicon and nitrogen as main constituent elements, and are doped with an element serving as an activator. These elements are mixed in the form of nitrides or oxides, respectively, and are fired at a high temperature in a nitrogen atmosphere to form a phosphor. For nitrides and oxides, nitrides are used as preferred to reduce oxygen contamination unless there is a substantial impact for a specific purpose or quantity. Further, instead of using nitrides as the respective constituent elements, there is a method in which all or part of these elements are alloyed and nitrided.
しかしながらかかる高効率、高輝度な蛍光体に関しては、常に更なる改良を要求されており、１％でも効率が高く、高輝度の蛍光体を得るべく、研究開発が進められている。
また、製造方法としては、安価で効率のよい方法が望まれており、新たな、安価で高輝度、高効率な蛍光体の製造方法が待ち望まれている。
すなわち本発明の目的は、安価で特性の優れた窒化物蛍光体の製造方法と、該製造方法により得られる高輝度な窒化物蛍光体を提供することである。
さらに、本発明の別の目的は、このような蛍光体を容易に得ることのできる共沈窒化物の原料を提供することである。However, such high-efficiency and high-brightness phosphors are always required to be further improved, and research and development are underway to obtain a high-brightness phosphor with high efficiency even at 1%.
In addition, as a manufacturing method, an inexpensive and efficient method is desired, and a new, inexpensive, high-luminance and high-efficiency phosphor manufacturing method is desired.
That is, an object of the present invention is to provide a method for producing a nitride phosphor that is inexpensive and excellent in characteristics, and a high-luminance nitride phosphor obtained by the production method.
Furthermore, another object of the present invention is to provide a raw material for coprecipitated nitride from which such a phosphor can be easily obtained.
そこで本発明者らは、鋭意検討の結果、窒化物蛍光体の製造の際に、共沈法により得られた、少なくとも1種のアルカリ土類金属元素と、賦活剤として働く少なくとも1種の元素を含有する窒化物を原料として用いることにより、窒化物蛍光体の輝度を向上させることが出来ることを見いだし、本発明に到達した。 Therefore, as a result of intensive studies, the present inventors have obtained at least one alkaline earth metal element obtained by a coprecipitation method and at least one element acting as an activator when producing a nitride phosphor. It has been found that the brightness of the nitride phosphor can be improved by using a nitride containing as a raw material, and the present invention has been achieved.
すなわち本発明は、以下の要旨を有するものである。
（１）アンモニア液体中で少なくとも１種のアルカリ土類金属元素と、賦活剤として働く少なくとも１種の元素とを共沈させて得られた、少なくとも１種のアルカリ土類金属元素と、賦活剤として働く少なくとも１種の元素とを含有する窒化物を、原料として用いる、少なくとも１種のアルカリ土類金属元素と賦活剤として働く少なくとも１種の元素を有する窒化物蛍光体の製造方法。
（２）前記窒化物が、アミド化合物及び／またはイミド化合物である上記（１）に記載の窒化物蛍光体の製造方法。
（３）窒化物蛍光体が、下記式（１）で表される上記（１）又は（２）に記載の窒化物蛍光体の製造方法。
Ｍ２Ｍ３Ｍ４Ｘ３：Ｚ （１）
（ただし、Ｍ２は、少なくとも１種のアルカリ土類金属元素を含み、Ｚ元素以外の２価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ３は、３価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ４は、４価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｘは、Ｏ、Ｎ、及びＦからなる群から選ばれる１種または２種以上の元素であり、ＺはＭｎ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、及びＹｂからなる群から選ばれる１種または２種以上の元素である。）
That is, the present invention has the following gist.
(1) At least one alkaline earth metal element obtained by coprecipitation of at least one alkaline earth metal element and at least one element working as an activator in an ammonia liquid, and an activator A method for producing a nitride phosphor having at least one alkaline earth metal element and at least one element working as an activator, using a nitride containing at least one element working as a raw material.
(2) The method for producing a nitride phosphor according to (1), wherein the nitride is an amide compound and / or an imide compound.
( 3 ) The method for producing a nitride phosphor according to the above (1) or (2) , wherein the nitride phosphor is represented by the following formula (1) .
M2M3M4X3: Z (1)
(However, M2 is one or more elements selected from the group consisting of divalent metal elements other than Z element, including at least one alkaline earth metal element, and M3 is a trivalent element. One or more elements selected from the group consisting of metal elements, M4 is one or more elements selected from the group consisting of tetravalent metal elements, and X is O, N , And one or more elements selected from the group consisting of F, and Z is a group consisting of Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb. One or more elements selected.)
（４）窒化物蛍光体が、下記式（２）で表される上記（１）又は（２）に記載の窒化物蛍光体の製造方法。
Ｍ２Ｍ３Ｍ４４Ｘ７：Ｚ （２）
（ただし、Ｍ２は、少なくとも１種のアルカリ土類金属元素を含み、Ｚ元素以外の２価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ３は、３価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ４は、４価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｘは、Ｏ、Ｎ、及びＦからなる群から選ばれる１種または２種以上の元素、ＺはＭｎ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、及びＹｂからなる群から選ばれる１種または２種以上の元素である。）
（５）窒化物蛍光体が、下記式（３）で表される上記（１）又は（２）に記載の窒化物蛍光体の製造方法。
Ｍ２２Ｍ４５Ｘ８：Ｚ （３）
（ただし、Ｍ２は、少なくとも１種のアルカリ土類金属元素を含み、Ｚ元素以外の２価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ４は、４価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｘは、Ｏ、Ｎ、及びＦからなる群から選ばれる１種または２種以上の元素であり、ＺはＭｎ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、及びＹｂからなる群から選ばれる１種または２種以上の元素である。）
（６）アンモニア液体中で少なくとも１種のアルカリ土類金属元素と、賦活剤として働く少なくとも１種の元素とを共沈させて得られる、アルカリ土類金属元素と賦活剤元素の共沈アミド化合物を８００〜１３００℃で熱分解することを特徴とする当該アルカリ土類金属と賦活剤元素の共沈窒化物の製造方法。
（７）アルカリ土類金属元素が、カルシウム又はストロンチウムである上記（６）に記載の共沈窒化物の製造方法。
（８）賦活剤元素が、ユーロピウム又はセリウムである上記（６）又は（７）に記載の共沈窒化物の製造方法。
（９）窒素ガス下、熱分解することを特徴とする上記（６）乃至（８）のいずれかに記載の共沈窒化物の製造方法。
(4) nitride compound phosphor, the production method of the nitride phosphor according to (1) or (2) represented by the following formula (2).
M2M3M44X7: Z (2)
(However, M2 is one or more elements selected from the group consisting of divalent metal elements other than Z element, including at least one alkaline earth metal element, and M3 is a trivalent element. One or more elements selected from the group consisting of metal elements, M4 is one or more elements selected from the group consisting of tetravalent metal elements, and X is O, N , And one or more elements selected from the group consisting of F, Z is selected from the group consisting of Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb One or more elements.)
(5) nitride compound phosphor, the production method of the nitride phosphor according to (1) or (2) represented by the following formula (3).
M22M45X8: Z (3)
(However, M2 is one or more elements selected from the group consisting of divalent metal elements other than Z element, including at least one alkaline earth metal element, and M4 is a tetravalent element. One or more elements selected from the group consisting of metal elements, X is one or more elements selected from the group consisting of O, N, and F, and Z is Mn, Ce , Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb, or one or more elements selected from the group consisting of Yb.)
( 6 ) A coprecipitated amide compound of an alkaline earth metal element and an activator element obtained by coprecipitation of at least one alkaline earth metal element and at least one element acting as an activator in an ammonia liquid Is produced by co-precipitation of the alkaline earth metal and the activator element.
( 7 ) The method for producing a coprecipitated nitride as described in ( 6 ) above, wherein the alkaline earth metal element is calcium or strontium.
( 8 ) The method for producing a coprecipitated nitride according to the above ( 6 ) or ( 7 ), wherein the activator element is europium or cerium.
( 9 ) The method for producing a coprecipitated nitride as described in any one of ( 6 ) to ( 8 ) above, wherein pyrolysis is performed under nitrogen gas.
本発明により、従来より高輝度の窒化物系蛍光体を容易にかつ安価に製造することができる。 According to the present invention, it is possible to easily and inexpensively manufacture a nitride-based phosphor having higher brightness than conventional ones.
本発明の最大の特徴は、窒化物蛍光体の製造方法において、共沈法により得られた、少なくとも1種のアルカリ土類金属元素と、賦活剤として働く少なくとも1種の元素（以下、賦活剤元素と略記することがある。）を含有する窒化物を原料として用いることにある。
共沈法とは、一般に２種以上の元素を、何らかの媒体中に溶解させ、それを析出させることにより、極めて均一な混合物を得る方法をいう。
ここで用いられるアルカリ土類金属元素は、特に限定はされないが、一般的にＣａ、Ｓｒ、Ｂａが用いられ、好ましくはＣａ及び／又はＳｒである。The greatest feature of the present invention is that at least one alkaline earth metal element obtained by a coprecipitation method and at least one element acting as an activator (hereinafter referred to as an activator) obtained by the coprecipitation method in the method for producing a nitride phosphor. In some cases, a nitride containing element) is used as a raw material.
The coprecipitation method generally refers to a method of obtaining an extremely uniform mixture by dissolving two or more elements in some medium and precipitating them.
The alkaline earth metal element used here is not particularly limited, but Ca, Sr, and Ba are generally used, and Ca and / or Sr are preferable.
また、用いられる賦活剤として働く元素としては、特に限定はされないが、好ましくはＭｎ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、及びＹｂからなる群から選ばれる１種または２種以上の元素である。このうち特に好ましくはＭｎ、Ｃｅ、Ｅｕ、Ｔｂ、Ｄｙであり、最も好ましくはＣｅまたはＥｕである。
かかる賦活剤として働く少なくとも１種の元素と、少なくとも１種のアルカリ土類金属元素を含有する共沈窒化物は、少なくとも１種のアルカリ土類金属元素と、賦活剤として働く少なくとも１種の元素とをアンモニア液体中で共沈させて得る。下に一例を挙げる。
The element that acts as the activator used is not particularly limited, but is preferably selected from the group consisting of Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb. One or more elements. Among these, Mn, Ce, Eu, Tb, and Dy are particularly preferable, and Ce or Eu is most preferable.
The coprecipitated nitride containing at least one element acting as an activator and at least one alkaline earth metal element is composed of at least one alkaline earth metal element and at least one element acting as an activator. Are co-precipitated in an ammonia liquid. An example is given below.
まず、アンモニア液体中に所望のモル比でアルカリ土類金属元素と賦活剤元素を溶解させる。次にアンモニアを蒸発させ、共沈させたアミド化合物またはイミド化合物を得る。
得られたアミド化合物またはイミド化合物を還元性あるいは不活性ガス雰囲気中で５００〜１２００℃程度で熱処理することにより、少なくともアルカリ土類金属元素と賦活剤元素とを含む窒化物共沈品を製造することが出来る。First, an alkaline earth metal element and an activator element are dissolved in a desired molar ratio in an ammonia liquid. Next, ammonia is evaporated to obtain a co-precipitated amide compound or imide compound.
The obtained amide compound or imide compound is heat-treated at about 500 to 1200 ° C. in a reducing or inert gas atmosphere to produce a nitride coprecipitate product containing at least an alkaline earth metal element and an activator element. I can do it.
以下にこの共沈窒化物の製造方法についてより詳しく説明する。
共沈窒化物を製造する方法は、公知の種々の方法が使用可能であるが、以下にその一例として、アミド化合物を経由する方法について説明する。
アルカリ土類金属元素と賦活剤元素を、目的とする共沈窒化物のモル比に合わせ秤量する。
これらを、アンモニアと反応させアミド化合物を製造する。
通常は圧力容器内に秤量したアルカリ土類金属元素と賦活剤元素を入れ、好ましくは真空引きした後、アンモニアを入れ、反応させる。Hereinafter, the method for producing the coprecipitated nitride will be described in more detail.
Various known methods can be used as a method for producing the coprecipitated nitride, and a method via an amide compound will be described below as an example.
The alkaline earth metal element and the activator element are weighed in accordance with the molar ratio of the desired coprecipitated nitride.
These are reacted with ammonia to produce an amide compound.
Usually, a weighed alkaline earth metal element and an activator element are put in a pressure vessel, preferably after evacuation, and then ammonia is added and reacted.
アンモニアの使用量は、アルカリ土類金属元素１モルに対して、２モル以上が好ましく、アンモニアは溶媒も兼ねているため、多ければ多いほど好ましい。また、アルカリ土類金属元素、賦活剤元素とアンモニアの反応温度は、元素の組合せによって適宜決定すればよいが、−７７〜３００℃が好ましく、２０〜２００℃がより好ましく、５０〜１００℃が更に好ましい。アルカリ土類金属元素、賦活剤元素とアンモニアは液相を形成することから、これらアルカリ土類金属と賦活剤元素は均一に分散され、その後、アルカリ土類金属元素アミドと賦活剤元素アミドを含有する組成物となる。従って、反応時間は液相が形成されるまでの時間であり、通常１分〜７２時間が好ましく、特に１時間〜３時間程度が好ましい。 The amount of ammonia used is preferably 2 mol or more with respect to 1 mol of the alkaline earth metal element. Since ammonia also serves as a solvent, the more it is, the more preferable. Moreover, what is necessary is just to determine suitably the reaction temperature of an alkaline-earth metal element, an activator element, and ammonia by the combination of an element, -77-300 degreeC is preferable, 20-200 degreeC is more preferable, 50-100 degreeC is preferable. Further preferred. Since alkaline earth metal elements, activator elements and ammonia form a liquid phase, these alkaline earth metals and activator elements are uniformly dispersed, and then contain alkaline earth metal element amides and activator element amides. Composition. Accordingly, the reaction time is the time until the liquid phase is formed, and is usually preferably 1 minute to 72 hours, particularly preferably about 1 hour to 3 hours.
尚、液相を形成する際に、目的の蛍光体の必要に応じ、アルミニウム等の３価の金属元素等を加えることもできる。好ましい３価の金属元素としてはアルミニウムである。
このようにして得られた少なくともアルカリ土類金属元素と賦活剤元素とを含むアミド化合物は焼成することにより共沈窒化物とすることができる。In forming the liquid phase, a trivalent metal element such as aluminum can be added as required for the target phosphor. A preferred trivalent metal element is aluminum.
The thus obtained amide compound containing at least an alkaline earth metal element and an activator element can be coprecipitated by firing.
このようなアルカリ土類金属と賦活剤元素を含むアミド化合物を熱分解反応する温度は、５００℃以上が好ましく、更に５１０℃以上が好ましく、８００℃以上がより好ましく、１０００℃以上がさらに好ましい。温度の上限値は、アルカリ土類金属元素窒化物と賦活剤元素窒化物が分解しない温度であるが、熱分解反応炉の耐熱性や加熱を行う際の経済性から、１５００℃以下とすることが好ましい。従って、アルカリ土類金属アミドを熱分解反応する温度は、５１０〜１５００℃が好ましく、さらに好ましくは８００〜１３００℃、特に好ましくは１０００〜１２００℃である。 The temperature at which the amide compound containing such an alkaline earth metal and an activator element undergoes a thermal decomposition reaction is preferably 500 ° C. or higher, more preferably 510 ° C. or higher, more preferably 800 ° C. or higher, and even more preferably 1000 ° C. or higher. The upper limit of the temperature is a temperature at which the alkaline earth metal element nitride and the activator element nitride are not decomposed, but it should be 1500 ° C. or less from the heat resistance of the thermal decomposition reactor and the economic efficiency when heating. Is preferred. Accordingly, the temperature at which the alkaline earth metal amide is thermally decomposed is preferably 510 to 1500 ° C, more preferably 800 to 1300 ° C, and particularly preferably 1000 to 1200 ° C.
出発原料の前記アミド化合物は、空気中で酸化しやすいので、熱分解反応は、真空下又は窒素ガス若しくはアルゴンガス等の不活性ガス雰囲気下で行うことが好ましく、特に窒素ガス又はアルゴンガス等の不活性ガス下で行うことが好ましい。また、不活性ガス雰囲気下で熱分解反応を行う場合、その圧力は特に制限はないが、常圧で行うのが経済的で好ましい。また、熱分解は、バッチ式でも連続式でもよいが、量産する場合は、連続式が好ましい。 Since the amide compound as a starting material is easily oxidized in the air, the thermal decomposition reaction is preferably performed under vacuum or in an inert gas atmosphere such as nitrogen gas or argon gas, particularly nitrogen gas or argon gas or the like. It is preferable to carry out under an inert gas. Moreover, when performing a thermal decomposition reaction in inert gas atmosphere, the pressure does not have a restriction | limiting in particular, However, It is economical and preferable to carry out at a normal pressure. In addition, the thermal decomposition may be a batch type or a continuous type, but in the case of mass production, a continuous type is preferable.
熱分解反応時間は、装置、反応温度、原料使用量などにより適宜決定すればよいが、通常１０分〜４８時間とすることが好ましく、１時間〜２４時間がさらに好ましく、特に３時間〜１２時間が好ましい。
熱分解反応装置は、１５００℃程度の熱に耐えられる装置であればよく、例えば、管状炉、電気炉、バッチ式キルン、ロータリーキルンなどを用いればよい。
熱分解反応終了後は、例えばバッチ式の場合には、熱分解反応装置内には目的とする共沈窒化物のみが粉体状で残存するので、回収は極めて容易である。The thermal decomposition reaction time may be appropriately determined depending on the apparatus, reaction temperature, amount of raw material used, etc., but it is usually preferably 10 minutes to 48 hours, more preferably 1 hour to 24 hours, particularly 3 hours to 12 hours. Is preferred.
The pyrolysis reaction apparatus may be an apparatus that can withstand heat of about 1500 ° C., and for example, a tubular furnace, an electric furnace, a batch kiln, a rotary kiln, or the like may be used.
After the pyrolysis reaction is completed, for example, in the case of a batch type, only the target coprecipitated nitride remains in the form of powder in the pyrolysis reactor, so that the recovery is very easy.
一方、連続式の場合には、例えば、Ｎ2やＡｒで内部が満たされたロータリーキルンを用いれば、容易に共沈窒化物が連続的に回収される。
本方法により得られる共沈窒化物は、熱分解反応により容易に内部まで反応が進行すること、賦活剤元素が極めて均一に分散しているため、高純度、高均一性であり、窒化物蛍光体の製造に適している。
特に本発明に用いられる共沈窒化物は、アルカリ土類金属としてカルシウム及び／又はストロンチウムを含有することが好ましく、賦活剤元素としてはユーロピウム及び／又はセリウムを含有することが好ましい。On the other hand, in the case of the continuous type, for example, if a rotary kiln filled with N 2 or Ar is used, the coprecipitated nitride is easily recovered continuously.
The coprecipitated nitride obtained by this method has a high purity and high uniformity because the reaction easily proceeds to the inside by a thermal decomposition reaction, and the activator elements are very uniformly dispersed. Suitable for body production.
In particular, the coprecipitated nitride used in the present invention preferably contains calcium and / or strontium as the alkaline earth metal, and preferably contains europium and / or cerium as the activator element.
また、もちろん上述の途中で得られるアミド化合物を熱分解反応しない状態でも、少なくともアルカリ土類金属元素と賦活剤元素とを含む共沈窒化物として使用することができる。
また、ここまでアミド化合物を用いて説明したが、イミド化合物を経由しても、同様の共沈窒化物を得ることができる。
かかる上述の方法などにより得られた共沈品を使用する以外は、本発明の蛍光体は公知の手法を用いて製造することが出来る。Of course, even in the state where the amide compound obtained in the above-mentioned process is not subjected to thermal decomposition reaction, it can be used as a coprecipitated nitride containing at least an alkaline earth metal element and an activator element.
Moreover, although demonstrated using the amide compound so far, the same coprecipitation nitride can be obtained also via an imide compound.
Except for using the coprecipitation product obtained by the above-described method, the phosphor of the present invention can be produced using a known method.
以下では、本発明の製造方法を用いて好適に製造される蛍光体のうち、下記式（１）、
Ｍ２Ｍ３Ｍ４Ｘ３：Ｚ （１）
（ただしＭ２は、少なくとも１種のアルカリ土類金属元素を含み、Ｚ元素以外の２価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ３は、３価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ４は、４価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｘは、Ｏ、Ｎ、及びＦからなる群から選ばれる１種または２種以上の元素であり、ＺはＭｎ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、及びＹｂからなる群から選ばれる１種または２種以上の元素である。）で表される蛍光体（以下ＣＡＳＮ蛍光体と略記することがある。）を例にとって説明するが、もちろん本発明は、その要旨を超えない限り、本蛍光体に限定されるものではない。Below, among the phosphors suitably produced using the production method of the present invention, the following formula (1),
M2M3M4X 3 : Z (1)
(However, M2 is at least one element selected from the group consisting of divalent metal elements other than Z element, including at least one alkaline earth metal element, and M3 is a trivalent metal. One or more elements selected from the group consisting of elements, M4 is one or more elements selected from the group consisting of tetravalent metal elements, and X is O, N, And F is one or more elements selected from the group consisting of F, and Z is selected from the group consisting of Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb The present invention will be described with reference to an example of a phosphor represented by the following formula (which may be abbreviated as CASN phosphor). The phosphor is not limited to this.
本発明においては、少なくともＭ２とＺを含む共沈窒化物を原料として使用する。このときのＭ２とＺの組成比が、所望の蛍光体中での組成比になっていない場合、Ｍ２とＺの共沈窒化物以外の他の原料を用いて不足分を補うことができる。例えばＺが不足するのであれば、Ｚの窒化物や酸化物で不足分を補ってもよいし、あるいは他のＭ３やＭ４とＺの共沈窒化物を用いてもよい。また、Ｍ２とＺの組成比を変えた共沈窒化物を２種以上用意しておいて、これらを適当な割合で混合することにより、所望のＭ２とＺの組成比を得ることも出来る。 In the present invention, a coprecipitated nitride containing at least M2 and Z is used as a raw material. If the composition ratio of M2 and Z at this time is not the composition ratio in the desired phosphor, the shortage can be compensated by using other raw materials other than the coprecipitated nitride of M2 and Z. For example, if Z is deficient, the deficiency may be compensated with Z nitride or oxide, or other M3 or M4 and Z coprecipitated nitrides may be used. It is also possible to obtain two or more coprecipitated nitrides having different composition ratios of M2 and Z and to mix them at an appropriate ratio to obtain a desired composition ratio of M2 and Z.
また、Ｍ３としては、Ｂ、Ａｌ、Ｇａ、Ｉｎなどが好ましい。
Ｍ３の原料としては、Ｍ３の窒化物が好ましく、具体的には、ＡｌＮ、ＧａＮ、ＢＮ、ＩｎＮなどが挙げられ、特に好ましくはＡｌＮである。
もちろん、式１の蛍光体に、発光波長制御や耐久性向上などの目的で酸素を敢えて含有させたい場合には、一部の材料を酸化物、例えばＡｌ2Ｏ3などを加えてもよい。また前述のように、Ｍ３の少なくとも一部を共沈窒化物中に共沈させることも可能である。Moreover, as M3, B, Al, Ga, In, etc. are preferable.
As a raw material of M3, a nitride of M3 is preferable, and specifically, AlN, GaN, BN, InN, and the like can be given, and AlN is particularly preferable.
Of course, when the phosphor of Formula 1 is intended to contain oxygen for the purpose of controlling the emission wavelength or improving the durability, an oxide such as Al 2 O 3 may be added as a part of the material. Further, as described above, at least a part of M3 can be coprecipitated in the coprecipitated nitride.
また、Ｍ４としては、Ｓｉ、Ｇｅ、及びＳｎから選ばれる１種または２種以上の元素が好ましい。
このＭ４の原料としては、Ｓｉ３Ｎ４、Ｇｅ３Ｎ４、Ｓｎ３Ｎ４などが好ましく、特に好ましくはＳｉ３Ｎ４である。
また、ＸはＯ、Ｎ、及びＦから選ばれる１種又は２種以上の元素であるが、特に好ましくはＯ及び／又はＮである。これらはＭ２とＺの窒化物共沈品や、Ｍ３の原料、Ｍ４の原料から取り込まれる。Ｆの主な供給源は、後述のフッ化物のフラックスである。Moreover, as M4, 1 type, or 2 or more types of elements chosen from Si, Ge, and Sn are preferable.
As the raw material of the M4, is preferably such as Si 3 N 4, Ge 3 N 4, Sn 3 N 4, particularly preferably Si 3 N 4.
X is one or more elements selected from O, N and F, and particularly preferably O and / or N. These are taken from the M2 and Z nitride co-precipitate, the M3 raw material, and the M4 raw material. The main source of F is a fluoride flux described later.
本発明の製造方法においては、これらの原料を、１２００〜２２００℃の範囲で焼成し、窒化物蛍光体を得る。
このとき、本発明では、必要に応じて、これらの原料の混合物に、焼成温度以下の温度で液相を生成する無機化合物をフラックスとして添加して焼成することができる。このような無機化合物としては、Ｌｉ、Ｎａ、Ｋ、Ｍｇ、Ｃａ、Ｓｒ、及びＢａから選ばれる１種または２種以上の元素のフッ化物、塩化物、ヨウ化物、臭化物、あるいはリン酸塩の１種または２種以上の混合物を挙げることができる。添加した無機化合物は、焼成温度で液相を生成し、金属化合物をぬらして反応を促進する。なかでも、フッ化カルシウムは反応促進効果が高い。無機化合物の添加量は、これらの原料の混合物１００重量部に対して、０．１重量部以上１０重量部以下がよい。０．１重量部より少ないと、反応促進効果が少なく。１０重量部より多いと無機化合物が蛍光体中に残留して輝度を低下させるので好ましくない。蛍光体中への在留が多い場合は、焼成後に無機化合物を溶解する溶剤で洗浄して、無機化合物の含有量を低減させることが好ましい。In the production method of the present invention, these raw materials are baked in the range of 1200 to 2200 ° C. to obtain a nitride phosphor.
At this time, in the present invention, if necessary, an inorganic compound that generates a liquid phase at a temperature lower than the firing temperature can be added to the mixture of these raw materials as a flux and fired. Examples of such inorganic compounds include fluorides, chlorides, iodides, bromides, and phosphates of one or more elements selected from Li, Na, K, Mg, Ca, Sr, and Ba. One type or a mixture of two or more types can be mentioned. The added inorganic compound generates a liquid phase at the firing temperature and wets the metal compound to promote the reaction. Among these, calcium fluoride has a high reaction promoting effect. The addition amount of the inorganic compound is preferably 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the mixture of these raw materials. When the amount is less than 0.1 parts by weight, the reaction promoting effect is small. If the amount is more than 10 parts by weight, the inorganic compound remains in the phosphor and lowers the luminance, which is not preferable. When there are many residences in a fluorescent substance, it is preferable to wash | clean with the solvent which melt | dissolves an inorganic compound after baking, and to reduce content of an inorganic compound.
これらの原料の混合には、例えばボールミル、振動ミル、Ｖ型混合機、撹拌機等の通常工業的に用いられている装置を用いることが出来る。
上記の混合工程を終えた原料の混合物は、粒径数μｍの微粉末が数百μｍから数ｍｍの大きさに凝集した形態をなす（以下、粉体凝集体と略記することがある）。
本発明では、粉体凝集体を嵩密度４０％以下の充填率に保持した状態で焼成する。すなわち、本発明では、粉体に機械的な力を加えることなく、また予め金型などを用いて成形することなく、混合物の粉体凝集体の粒度をそろえたものを、そのままの状態で容器などに嵩密度４０％以下の充填率で充填する。容器としては、これら原料の混合物との反応性が低いことから、窒化ホウ素焼結体が好ましい。必要に応じて、該粉体凝集体を、ふるいなどを用いて、平均粒径５００μｍ以下に造粒して粒度制御することができる。また、スプレードライヤなどを用いて直接的に５００μｍ以下の形状に造粒してもよい。For mixing these raw materials, for example, a generally industrially used apparatus such as a ball mill, a vibration mill, a V-type mixer or a stirrer can be used.
The mixture of raw materials after the above mixing step has a form in which fine powder having a particle size of several μm is aggregated to a size of several hundred μm to several mm (hereinafter, abbreviated as powder aggregate).
In the present invention, the powder aggregate is fired in a state where the bulk density is maintained at a filling rate of 40% or less. That is, in the present invention, the powder powder aggregates having the same particle size without being mechanically applied to the powder or molded in advance using a mold or the like are used as they are. Are filled at a filling rate of 40% or less in bulk density. The container is preferably a boron nitride sintered body because of its low reactivity with a mixture of these raw materials. If necessary, the powder aggregate can be granulated to an average particle size of 500 μm or less using a sieve or the like to control the particle size. Moreover, you may granulate directly in the shape of 500 micrometers or less using a spray dryer etc.
嵩密度を４０％以下の状態に保持したまま焼成するのは、これら原料の混合物の粉末の周りに、自由な空間が保持されたままの状態で焼成すると、焼成後の生成物であるＭ２Ｍ３Ｍ４Ｘ３：Ｚで表される蛍光体が自由な空間に結晶成長することにより結晶同士の接触が少なくなるため、表面欠陥が少ない結晶を合成することが出来るためである。これにより、輝度が高い蛍光体が得られる。嵩密度が４０％を超えると焼成中に部分的に緻密化が起こって、緻密な焼結体となってしまい結晶成長の妨げとなり蛍光体の輝度が低下したり、蛍光体の微細な粉体が得られない。また、粉体凝集体の大きさは５００μｍ以下が、焼成後の粉砕性に優れるため特に好ましい。Firing with the bulk density kept at 40% or less is performed by firing M2M3M4X 3 , which is a product after firing, when the free space is kept around the powder of the mixture of these raw materials. : Because the phosphor represented by Z grows in a free space, the contact between the crystals decreases, so that a crystal with few surface defects can be synthesized. Thereby, a fluorescent substance with high brightness is obtained. If the bulk density exceeds 40%, partial densification occurs during firing, resulting in a dense sintered body that hinders crystal growth and lowers the brightness of the phosphor, or a fine powder of the phosphor. Cannot be obtained. Further, the size of the powder aggregate is particularly preferably 500 μm or less because of excellent grindability after firing.
次に、得られたこれらの原料の混合物を、窒素を含有する不活性雰囲気中において１２００℃以上２２００℃以下の温度範囲で焼成することにより蛍光体を調製する。焼成に用いる炉は、焼成温度が高温であり焼成雰囲気が窒素を含有する不活性雰囲気であることから、金属抵抗加熱方式または黒鉛抵抗加熱方式であり、炉の高温部の材料として炭素を用いた電気炉が好適である。焼成の手法は、常圧焼結法やガス圧焼結法などの外部から機械的な加圧を施さない焼結手法が、嵩密度を高く保ったまま焼成するために好ましい。 Next, a phosphor is prepared by baking the obtained mixture of these raw materials in a temperature range of 1200 ° C. or higher and 2200 ° C. or lower in an inert atmosphere containing nitrogen. The furnace used for firing is a metal resistance heating method or a graphite resistance heating method because the firing temperature is a high temperature and the firing atmosphere is an inert atmosphere containing nitrogen, and carbon is used as the material of the high temperature part of the furnace. An electric furnace is preferred. As the firing method, a sintering method in which mechanical pressure is not applied from the outside, such as an atmospheric pressure sintering method or a gas pressure sintering method, is preferable because firing is performed while maintaining a high bulk density.
窒素を含有する不活性雰囲気として、窒素ガス、窒素とアルゴンの混合ガス、窒素と水素の混合ガス、アンモニアガスなどを挙げることができるが、通常は、窒素ガスが用いられる。ガスの圧力は、０．０５ＭＰａ以上１００ＭＰａ以下の圧力範囲が好ましい。０．０５ＭＰａより低いと原料の窒化ケイ素が分解し、１００ＭＰａより高いと工業的にコストが増大する。好ましくは、０．１ＭＰａ以上１ＭＰａ以下の窒素雰囲気が、生産性に優れる。焼成温度が、１２００℃より低いと反応が十分には進まず、２２００℃以上では粒成長が著しくなるため好ましくない。焼成温度は、好ましくは、１５００℃以上１９００℃以下であり、輝度が高い蛍光体が得られる。 Examples of the inert atmosphere containing nitrogen include nitrogen gas, a mixed gas of nitrogen and argon, a mixed gas of nitrogen and hydrogen, and ammonia gas. Usually, nitrogen gas is used. The gas pressure is preferably in the pressure range of 0.05 MPa or more and 100 MPa or less. If it is lower than 0.05 MPa, the raw material silicon nitride is decomposed, and if it is higher than 100 MPa, the cost is industrially increased. Preferably, a nitrogen atmosphere of 0.1 MPa to 1 MPa is excellent in productivity. If the firing temperature is lower than 1200 ° C., the reaction does not proceed sufficiently, and if it is 2200 ° C. or higher, grain growth becomes remarkable, which is not preferable. The firing temperature is preferably 1500 ° C. or higher and 1900 ° C. or lower, and a phosphor having high luminance is obtained.
焼成して得られた粉体凝集体が固く固着している場合は、例えばボールミル、ジェットミル等の工業的に通常用いられる粉砕機により粉砕する。なかでも、ボールミル粉砕によれば高輝度の蛍光体が得られる。このとき使用するボールおよびポットは、窒化ケイ素焼結体またはサイアロン焼結体製が好ましい。粉砕は平均粒径２０μｍ以下となるまで施すことが好ましい。特に好ましくは平均粒径０．０５μｍ以上５μｍ以下である。平均粒径が２０μｍを超えると粉体の流動性と樹脂への分散性が悪くなり、発光素子と組み合わせて発光装置を形成する際に部位により発光強度が不均一になる。０．０５μｍ以下となると、蛍光体粉体表面の欠陥量が多くなるため蛍光体の組成によっては発光強度が低下する。
粉砕だけで目的の粒径が得られない場合は、分級を組み合わせることができる。分級の手法としては、篩い分け、風力分級、液体中での沈殿法などを用いることができる。When the powder aggregate obtained by firing is firmly fixed, it is pulverized by a pulverizer generally used in industry such as a ball mill and a jet mill. In particular, high brightness phosphors can be obtained by ball milling. The balls and pots used at this time are preferably made of a silicon nitride sintered body or a sialon sintered body. The pulverization is preferably performed until the average particle size becomes 20 μm or less. The average particle size is particularly preferably 0.05 μm or more and 5 μm or less. When the average particle diameter exceeds 20 μm, the fluidity of the powder and the dispersibility in the resin are deteriorated, and the light emission intensity becomes uneven depending on the part when the light emitting device is formed in combination with the light emitting element. When the thickness is 0.05 μm or less, the amount of defects on the surface of the phosphor powder increases, so that the emission intensity decreases depending on the composition of the phosphor.
If the desired particle size cannot be obtained only by grinding, classification can be combined. As a classification method, sieving, air classification, precipitation in a liquid, or the like can be used.
粉砕分級の一方法として酸処理を行ってもよい。焼成して得られた粉体凝集体は、多くの場合、上記式（１）で表される蛍光体の単結晶が微量のガラス相を主体とする粒界相で固く固着した状態となっている。この場合、特定の組成の酸に浸すとガラス相を主体とする粒界相が選択的に溶解して、単結晶が分離する。これにより、それぞれの粒子が単結晶の凝集体ではなく、上記式（１）で表される蛍光体の単結晶１個からなる粒子として得られる。このような粒子は、表面欠陥が少ない単結晶から構成されるため、蛍光体の輝度が特に高くなる。 Acid treatment may be performed as one method of pulverization classification. In many cases, the powder aggregate obtained by firing is in a state where a single crystal of the phosphor represented by the above formula (1) is firmly fixed in a grain boundary phase mainly composed of a small amount of glass phase. Yes. In this case, when immersed in an acid having a specific composition, the grain boundary phase mainly composed of the glass phase is selectively dissolved, and the single crystal is separated. Thereby, each particle is obtained not as a single crystal aggregate but as a particle composed of one single crystal of the phosphor represented by the above formula (1). Since such particles are composed of a single crystal with few surface defects, the luminance of the phosphor is particularly high.
この処理に有効な酸として、フッ化水素酸、硫酸、塩酸、フッ化水素酸と硫酸の混合物を挙げることができる。中でも、フッ化水素酸と硫酸の混合物はガラス相の除去効果が高い。
以上の工程により微細な蛍光体粉末が得られるが、輝度をさらに向上させるには熱処理が効果的である。この場合は、焼成後の粉末、あるいは粉砕や分級により粒度調整された後の粉末を、１０００℃以上で焼成温度以下の温度で熱処理することができる。１０００℃より低い温度では、表面の欠陥除去の効果が少ない。焼成温度以上では粉砕した粉体同志が再度固着するため好ましくない。熱処理に適した雰囲気は、蛍光体の組成により異なるが、窒素、空気、アンモニア、及び水素から選ばれる１種又は２種以上の混合雰囲気中を使用することができ、特に窒素雰囲気が欠陥除去効果に優れるため好ましい。
以上、本発明を式１で表される蛍光体を用いて説明したが、同様の手法により、式（２）、式（３）で示される蛍光体も製造することが出来る。Examples of the acid effective for this treatment include hydrofluoric acid, sulfuric acid, hydrochloric acid, and a mixture of hydrofluoric acid and sulfuric acid. Among them, a mixture of hydrofluoric acid and sulfuric acid has a high glass phase removal effect.
Although fine phosphor powder is obtained by the above steps, heat treatment is effective for further improving the luminance. In this case, the powder after firing or the powder whose particle size has been adjusted by pulverization or classification can be heat-treated at a temperature of 1000 ° C. or higher and lower than the firing temperature. At a temperature lower than 1000 ° C., the effect of removing surface defects is small. Above the firing temperature, the pulverized powders are fixed again, which is not preferable. The atmosphere suitable for the heat treatment varies depending on the composition of the phosphor, but one or two or more mixed atmospheres selected from nitrogen, air, ammonia and hydrogen can be used. It is preferable because it is excellent.
As described above, the present invention has been described using the phosphor represented by Formula 1. However, the phosphors represented by Formula (2) and Formula (3) can also be manufactured by the same method.
以下、本発明を、実施例を用いて説明するが、本発明はその要旨を超えない限り、実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to an Example, unless the summary is exceeded.
太平洋セメント社製Ca3N2/EuN共沈窒化物と、宇部興産社製Si3N4、トクヤマ社製AlNを原料とし、これらをＣａ＋Ｅｕ：Ａｌ：Ｓｉ＝１：１：１（モル比）になるよう、不活性ガスを満たしたグローボックスで、原料を秤量し、粉砕・混合しBN坩堝に充填した。グローボックス内を真空脱気することにより、得られた混合原料／BN坩堝をよく真空脱気した後、０．９２MPaの窒素ガス雰囲気下、１６００℃、２時間、さらに、１８００℃、２時間で焼成してCASN蛍光体を得た。
このとき用いたCa3N2/EuN共沈窒化物は、以下のような手順で作成した。金属Ｃａと金属Ｅｕを所望のモル比とし、その約150倍の体積のある反応容器に入れ、（Ｃａ＋Ｅｕ）1モルに対し、４７モルのアンモニアを加え、１００℃２時間反応させ、カルシウムとユーロピウムの共沈したアミド組成物を得た。この共沈したアミド組成物を窒素雰囲気下、１０００℃で４時間加熱し、Ca3N2/EuN共沈窒化物を得た。Taiheiyo Cement Co 3 N 2 / EuN coprecipitated nitride, Ube Industries Si 3 N 4 , Tokuyama AlN are used as raw materials, and these are Ca + Eu: Al: Si = 1: 1: 1 (molar ratio). In a glow box filled with an inert gas, the raw materials were weighed, ground and mixed, and filled into a BN crucible. By vacuum degassing the inside of the glow box, the resulting mixed raw material / BN crucible was well vacuum degassed, and then in a nitrogen gas atmosphere of 0.92 MPa at 1600 ° C. for 2 hours, further at 1800 ° C. for 2 hours. The CASN phosphor was obtained by firing.
The Ca 3 N 2 / EuN coprecipitated nitride used at this time was prepared by the following procedure. Calcium and europium are prepared by adding 47 mol of ammonia to 1 mol of (Ca + Eu), adding 47 mol of ammonia to the desired molar ratio of metal Ca and metal Eu, and adding 1 mol of (Ca + Eu). A co-precipitated amide composition was obtained. This co-precipitated amide composition was heated at 1000 ° C. for 4 hours under a nitrogen atmosphere to obtain a Ca 3 N 2 / EuN co-precipitated nitride.
（比較例１）
太平洋セメント社製Ca3N2/EuN共沈品の代わりに、市販のCerac社製Ca3N2とレアメタリック社製Eu2O3を使用して、ＥｕとＣａの量を実施例１とあわせた以外は、実施例１同様にして、実施例１と実質的に同じ組成のCASN蛍光体（ＣＡＳＮ：Ｅｕ）を作製した。(Comparative Example 1)
Using commercially available Cerac Ca 3 N 2 and rare metallic Eu 2 O 3 in place of Taiheiyo Cement Co 3N2 / EuN co-precipitated products, except for combining the amounts of Eu and Ca with Example 1 Produced a CASN phosphor (CASN: Eu) having substantially the same composition as in Example 1 in the same manner as in Example 1.
（評価）
実施例１と比較例１の蛍光体の内部量子効率を測定したところ、実施例１のＣＡＳＮ蛍光体の内部量子効率は、９３．４％であり、一方比較例１のＣＡＳＮ蛍光体は８９．９％であった。また、実施例１の蛍光体と比較例１の蛍光体の外観を比較すると、比較例の蛍光体の方が、くすんだ感じであった。
比較例１と比較して内部量子効率は実施例１が高かった。これはCASN蛍光体粉末の体色を比較して、実施例１に‘くすみ’が認められなかった結果とよく一致した。
また、Ｃｕ−Ｋα線によるＸ線回折パターンを測定した結果を、図１に示す。(Evaluation)
When the internal quantum efficiencies of the phosphors of Example 1 and Comparative Example 1 were measured, the internal quantum efficiency of the CASN phosphor of Example 1 was 93.4%, whereas the CASN phosphor of Comparative Example 1 was 89.89. It was 9%. Further, when the appearances of the phosphor of Example 1 and the phosphor of Comparative Example 1 were compared, the phosphor of the Comparative Example was duller.
Compared to Comparative Example 1, the internal quantum efficiency of Example 1 was higher. This was in good agreement with the result in which no dullness was observed in Example 1 by comparing the body color of the CASN phosphor powder.
Moreover, the result of having measured the X-ray-diffraction pattern by a Cu-K alpha ray is shown in FIG.
図１において、上が実施例１のＣＡＳＮ蛍光体の回折パターンであり、下が比較例１のＣＡＳＮ蛍光体の回折パターンである。両者を比べると、実施例１の蛍光体の回折パターンの方が、ピークのカウント数が大きい。この差は、結晶性の差を表していると考えられ、実施例１の蛍光体、すなわち共沈窒化物を原料として使用した方が、結晶性のよい蛍光体を得やすいことが判る。
続いて、発光スペクトルと、ピーク波長、ピーク高さ、及び半値幅について測定した。その結果を表１に示す。In FIG. 1, the top is the diffraction pattern of the CASN phosphor of Example 1, and the bottom is the diffraction pattern of the CASN phosphor of Comparative Example 1. Comparing both, the diffraction pattern of the phosphor of Example 1 has a larger peak count. This difference is considered to represent a difference in crystallinity, and it can be understood that it is easier to obtain a phosphor with good crystallinity when the phosphor of Example 1, that is, a coprecipitated nitride, is used as a raw material.
Subsequently, the emission spectrum, peak wavelength, peak height, and half width were measured. The results are shown in Table 1.
表１中の、「ＣＩＥｘ」，［ＣＩＥｙ］とは、国際照明委員会（ＣＩＥ）が定めるＣＩＥｘｙ色度図上における色度点のｘ座標とｙ座標を意味する。
表１の結果からも分かるように比較例１と実施例１との間において発光スペクトル形状の差を認めることはできなかった。
また、図２として、比較例１と実施例１のCASN蛍光体粉末の走査型電子顕微鏡写真を示す。
実施例１の蛍光体粉末は晶癖が確認でき、また、結晶粒子サイズが揃っていることが観察された。
尚、本実施例では、ＣＡＳＮ蛍光体を例にとって説明したが、ＣＡＳＮ以外の窒化物蛍光体でも本発明と同様の効果が期待できる。特に式（２）で表される蛍光体は、その母体の一般式がＣＡＳＮ＋Ｓｉ３Ｎ４に相当し、比較的近い組成を有することから、ＣＡＳＮ蛍光体同様に、結晶性に優れ、内部量子効率の高い窒化物蛍光体を得ることができると推察される。In Table 1, “CIEx” and [CIEy] mean the x-coordinate and y-coordinate of the chromaticity point on the CIExy chromaticity diagram determined by the International Commission on Illumination (CIE).
As can be seen from the results in Table 1, no difference in emission spectrum shape was observed between Comparative Example 1 and Example 1.
FIG. 2 shows scanning electron micrographs of CASN phosphor powders of Comparative Example 1 and Example 1.
It was observed that the phosphor powder of Example 1 had a crystal habit and that the crystal particle size was uniform.
In the present embodiment, the CASN phosphor is described as an example, but a nitride phosphor other than CASN can be expected to have the same effect as the present invention. In particular, the phosphor represented by the formula (2) has a comparatively close composition because the general formula of the matrix corresponds to CASN + Si 3 N 4, and thus has excellent crystallinity and internal quantum efficiency like the CASN phosphor. It is presumed that a nitride phosphor having a high thickness can be obtained.
本発明により、結晶性に優れ、内部量子効率の高い窒化物蛍光体を提供することができ、本発明の窒化物蛍光体を用いることにより、より高い輝度のＬＥＤを提供することが出来る。
尚、２０１０年１０月２０日に出願された日本特許出願２０１０−２３５９４２号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として取り入れるものである。According to the present invention, a nitride phosphor having excellent crystallinity and high internal quantum efficiency can be provided, and by using the nitride phosphor of the present invention, an LED with higher luminance can be provided.
It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2010-235942 filed on October 20, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.
Claims (9)
Ｍ２Ｍ３Ｍ４Ｘ３：Ｚ （１）
（ただし、Ｍ２は、少なくとも１種のアルカリ土類金属元素を含み、Ｚ元素以外の２価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ３は、３価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ４は、４価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｘは、Ｏ、Ｎ、及びＦからなる群から選ばれる１種または２種以上の元素であり、ＺはＭｎ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、及びＹｂからなる群から選ばれる１種または２種以上の元素である。） The method for producing a nitride phosphor according to claim 1 or 2 , wherein the nitride phosphor is represented by the following formula (1) .
M2M3M4X 3 : Z (1)
(However, M2 is one or more elements selected from the group consisting of divalent metal elements other than Z element, including at least one alkaline earth metal element, and M3 is a trivalent element. One or more elements selected from the group consisting of metal elements, M4 is one or more elements selected from the group consisting of tetravalent metal elements, and X is O, N , And one or more elements selected from the group consisting of F, and Z is a group consisting of Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb. One or more elements selected.)
Ｍ２Ｍ３Ｍ４４Ｘ７：Ｚ （２）
（ただし、Ｍ２は、少なくとも１種のアルカリ土類金属元素を含み、Ｚ元素以外の２価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ３は、３価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ４は、４価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｘは、Ｏ、Ｎ、及びＦからなる群から選ばれる１種または２種以上の元素、ＺはＭｎ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、及びＹｂからなる群から選ばれる１種または２種以上の元素である。） The method for producing a nitride phosphor according to claim 1 or 2 , wherein the nitride phosphor is represented by the following formula (2) .
M2M3M4 4 X 7 : Z (2)
(However, M2 is one or more elements selected from the group consisting of divalent metal elements other than Z element, including at least one alkaline earth metal element, and M3 is a trivalent element. One or more elements selected from the group consisting of metal elements, M4 is one or more elements selected from the group consisting of tetravalent metal elements, and X is O, N , And one or more elements selected from the group consisting of F, Z is selected from the group consisting of Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb One or more elements.)
Ｍ２２Ｍ４５Ｘ８：Ｚ （３）
（ただし、Ｍ２は、少なくとも１種のアルカリ土類金属元素を含み、Ｚ元素以外の２価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｍ４は、４価の金属元素からなる群から選ばれる１種または２種以上の元素であり、Ｘは、Ｏ、Ｎ、及びＦからなる群から選ばれる１種または２種以上の元素であり、ＺはＭｎ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、及びＹｂからなる群から選ばれる１種または２種以上の元素である。） The method for producing a nitride phosphor according to claim 1 or 2 , wherein the nitride phosphor is represented by the following formula (3) .
M2 2 M4 5 X 8 : Z (3)
(However, M2 is one or more elements selected from the group consisting of divalent metal elements other than Z element, including at least one alkaline earth metal element, and M4 is a tetravalent element. One or more elements selected from the group consisting of metal elements, X is one or more elements selected from the group consisting of O, N, and F, and Z is Mn, Ce , Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb, or one or more elements selected from the group consisting of Yb.)
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| PCT/JP2011/074165 WO2012053595A1 (en) | 2010-10-20 | 2011-10-20 | Method for producing nitride fluophor by using coprecipitated material, nitride fluophor, and material therefor |
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| KR20120061343A (en) * | 2010-12-03 | 2012-06-13 | 삼성엘이디 주식회사 | Method for producing phosphor and light emitting device |
| CN105273713A (en) | 2014-07-18 | 2016-01-27 | 三星电子株式会社 | Phosphor and method of preparing same |
| JP6239456B2 (en) * | 2014-07-18 | 2017-11-29 | サムスン エレクトロニクス カンパニー リミテッド | Phosphor and method for producing the same |
| CN106574181B (en) * | 2014-08-07 | 2020-10-16 | 三菱化学株式会社 | Phosphor, light emitting device, image display device, and illumination device |
| WO2019073864A1 (en) * | 2017-10-10 | 2019-04-18 | デンカ株式会社 | Red phosphor and light emission device |
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