JPWO2014030637A1 - β-sialon manufacturing method, β-sialon and light-emitting device - Google Patents
β-sialon manufacturing method, β-sialon and light-emitting device Download PDFInfo
- Publication number
- JPWO2014030637A1 JPWO2014030637A1 JP2014531633A JP2014531633A JPWO2014030637A1 JP WO2014030637 A1 JPWO2014030637 A1 JP WO2014030637A1 JP 2014531633 A JP2014531633 A JP 2014531633A JP 2014531633 A JP2014531633 A JP 2014531633A JP WO2014030637 A1 JPWO2014030637 A1 JP WO2014030637A1
- Authority
- JP
- Japan
- Prior art keywords
- sialon
- blending
- oxide
- light emitting
- producing
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 238000010304 firing Methods 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 38
- 229910001940 europium oxide Inorganic materials 0.000 claims abstract description 13
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000000918 Europium Chemical class 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical class O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 7
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 238000010306 acid treatment Methods 0.000 claims description 11
- 238000002189 fluorescence spectrum Methods 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 1
- 230000003595 spectral effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 239000012071 phase Substances 0.000 description 15
- 229910052693 Europium Inorganic materials 0.000 description 12
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 10
- 230000005284 excitation Effects 0.000 description 9
- 230000007547 defect Effects 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000995 Spectralon Polymers 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0821—Oxynitrides of metals, boron or silicon
- C01B21/0826—Silicon aluminium oxynitrides, i.e. sialons
-
- 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
- C09K11/0838—Aluminates; Silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Led Device Packages (AREA)
Abstract
発光効率を低下させずに、ピーク波長を545nmを超え555nm以下の範囲にすることができるβサイアロンの製造方法、βサイアロン及び発光装置を提供する。原料を配合し混練して均一化する配合工程S1と、配合工程後の原料を焼成してβサイアロンを得る焼成工程S2を行い、一般式:Si6−zAlzOzN8−zで表されるβサイアロンに、Eu2+を固溶したβサイアロンを製造する。その際、配合工程S1では、0.3≦z≦1.0となるように、窒化ケイ素、窒化アルミニウム及び酸化物を配合する一次配合工程S11と、一次配合工程S11後の原料に、βサイアロン粉末、並びに酸化ユーロピウム及びユーロピウム塩のいずれか一方又は両方を配合する二次配合工程S12を行う。また、一次配合工程S11で配合される酸化物には、酸化アルミニウム及び酸化ケイ素のいずれか一方又は両方を使用する。Provided are a β sialon manufacturing method, a β sialon, and a light emitting device capable of making a peak wavelength in a range of more than 545 nm and not more than 555 nm without reducing luminous efficiency. A blending step S1 in which the raw materials are blended, kneaded and homogenized, and a firing step S2 in which the raw materials after the blending step are fired to obtain β sialon are performed, and β sialon represented by the general formula: Β sialon in which Eu 2+ is dissolved is produced. At that time, in the blending step S1, a primary blending step S11 for blending silicon nitride, aluminum nitride and oxide so that 0.3 ≦ z ≦ 1.0, and β sialon as a raw material after the primary blending step S11 are used. A secondary blending step S12 in which one or both of the powder and europium oxide and europium salt is blended is performed. Moreover, any one or both of an aluminum oxide and a silicon oxide are used for the oxide mix | blended by primary compounding process S11.
Description
本発明は、βサイアロンの製造方法、βサイアロン及び発光装置に関する。より詳しくは、βサイアロン(SiAlON)にEu2+を固溶したβサイアロンの製造方法、この方法で製造されたβサイアロン及びこのβサイアロンを用いた発光装置に関する。The present invention relates to a method for producing β sialon, β sialon, and a light emitting device. More specifically, the present invention relates to a method for producing β sialon in which Eu 2+ is dissolved in β sialon (SiAlON), a β sialon produced by this method, and a light emitting device using the β sialon.
βサイアロン(SiAlON)に、発光中心として二価のユーロピウム(Eu2+)を固溶したβサイアロンは、紫外光から青色光の幅広い波長の光で励起されて、緑色光を発することが知られている(特許文献1〜3参照)。例えば、特許文献1の段落0015には、一般式:Si6−ZAlZOZN8−Zで表されるβサイアロン組成について、Zを0.24〜0.42とし、かつ、Eu含有量を0.05〜0.25at%とすることにより、ピーク波長を535nmにしたβサイアロンが開示されている。It is known that β sialon, which is a solid solution of β sialon (SiAlON) with divalent europium (Eu 2+ ) as the emission center, is excited by a wide range of wavelengths from ultraviolet to blue light and emits green light. (See Patent Documents 1 to 3). For example, in paragraph 0015 of Patent Document 1, the β sialon composition represented by the general formula: Si 6-Z Al Z O Z N 8-Z is set such that Z is 0.24 to 0.42 and contains Eu. A β sialon having a peak wavelength of 535 nm by making the amount 0.05 to 0.25 at% is disclosed.
特許文献2には、βサイアロン結晶の格子定数aを0.7605〜0.7610nm、格子定数cを0.2906〜0.2911nm、Eu含有量を0.4〜2質量%、第一遷移金属含有量を5ppm以下にすることにより、高発光効率と、狭帯域発光を実現したβサイアロンが開示されている。特許文献3には、波長700〜800nmの平均拡散反射率が90%以上、蛍光ピーク波長における拡散反射率が85%以上のβサイアロンが開示されている。 Patent Document 2 discloses that β sialon crystal has a lattice constant a of 0.7605 to 0.7610 nm, a lattice constant c of 0.2906 to 0.2911 nm, an Eu content of 0.4 to 2 mass%, and a first transition metal. A β sialon that realizes high luminous efficiency and narrow band emission by making the content 5 ppm or less is disclosed. Patent Document 3 discloses β sialon having an average diffuse reflectance at a wavelength of 700 to 800 nm of 90% or more and a diffuse reflectance at a fluorescence peak wavelength of 85% or more.
前述した特許文献1〜3に記載の従来のβサイアロンは、いずれも波長455nmの光で励起した場合の蛍光スペクトルのピーク波長が540〜545nmである。これに対して、近年、545nmよりも長波長側にピークをもつ蛍光体が求められており、βサイアロンのピーク波長を長波長側にシフトさせるための検討がなされている。 The conventional β sialons described in Patent Documents 1 to 3 described above each have a peak wavelength of a fluorescence spectrum of 540 to 545 nm when excited with light having a wavelength of 455 nm. In contrast, in recent years, a phosphor having a peak on the longer wavelength side than 545 nm has been demanded, and studies have been made to shift the peak wavelength of β sialon to the longer wavelength side.
しかしながら、βサイアロンとして必要な発光効率を維持しながら、ピーク波長を545nmよりも長波長側にすることは難しく、波長455nmの光で励起した場合に、545nmを超え555nm以下の波長にピーク波長を有するβサイアロンは、未だ実現されていない。なお、βサイアロンとして必要な発光効率は、外部量子効率に換算して55%以上である。ここで、「外部量子効率」とは、βサイアロンに照射された励起光の光子数に対する蛍光発光した光子数の比率である。 However, it is difficult to make the peak wavelength longer than 545 nm while maintaining the luminous efficiency necessary for β sialon, and when excited with light having a wavelength of 455 nm, the peak wavelength is increased to a wavelength exceeding 545 nm and not exceeding 555 nm. The β sialon possessed has not been realized yet. Note that the luminous efficiency required for β sialon is 55% or more in terms of external quantum efficiency. Here, “external quantum efficiency” is the ratio of the number of photons emitted by fluorescence to the number of photons of excitation light irradiated to β sialon.
そこで、本発明は、発光効率を低下させずに、ピーク波長を545nmを超え555nm以下の範囲にすることができるβサイアロンの製造方法、βサイアロン及び発光装置を提供することを主目的とする。 Therefore, the main object of the present invention is to provide a β sialon manufacturing method, β sialon, and a light emitting device that can make the peak wavelength in the range of more than 545 nm and less than 555 nm without lowering the luminous efficiency.
本発明者は、前述した課題を解決するため、ピーク波長を長波長側にシフトしたβサイアロンを製造できるように鋭意実験検討を行った結果、単に設計変更によってβサイアロンを製造したのでは、異相生成や粒子間焼結というという新たな課題が生じることがわかった。この粒子間焼結は、蛍光特性低下の原因となる結晶欠陥の生成の原因になっていた。 In order to solve the above-mentioned problems, the present inventor has conducted intensive experimental studies so that β sialon having a peak wavelength shifted to the long wavelength side can be manufactured. It was found that new problems such as generation and inter-particle sintering occur. This inter-particle sintering has been a cause of generation of crystal defects that cause a decrease in fluorescence characteristics.
本発明者は、更に検討を行い、一般式:Si6−zAlzOzN8−zにおけるz値を0.3≦z≦1.0に限定すると共に、特定の方法で製造することによって、発光効率を低下させずに、ピーク波長を545nmよりも長波長側にシフトできることを見出し、本発明に至った。The inventor further studied and limited the z value in the general formula: Si 6-z Al z OzN 8-z to 0.3 ≦ z ≦ 1.0 and by producing it in a specific way, The present inventors have found that the peak wavelength can be shifted to a longer wavelength side than 545 nm without lowering the luminous efficiency, and have reached the present invention.
本発明に係るβサイアロンの製造方法は、原料を配合し混練して均一化する配合工程と、前記配合工程後の原料を焼成してβサイアロンを得る焼成工程とを有し、前記配合工程では、一般式:Si6−zAlzOzN8−z(0.3≦z≦1.0)となるように、窒化ケイ素、窒化アルミニウム及び酸化物を配合する一次配合工程と、前記一次配合工程後の原料に、βサイアロン粉末、並びに酸化ユーロピウム及びユーロピウム塩のいずれか一方又は両方を配合する二次配合工程を行い、前記一次配合工程で配合される酸化物が、酸化アルミニウム及び酸化ケイ素のいずれか一方又は両方であり、一般式:Si6−zAlzOzN8−z(0.3≦z≦1.0)で表されるβサイアロンにEu2+が固溶し、波長455nmの光で励起した場合の蛍光スペクトルのピーク波長が545nmを超え555nm以下であるβサイアロンを得る。
前記二次配合工程では、前記一次配合工程後の原料100質量%に対して、前記βサイアロン粉末を5〜30質量%配合することが好ましい。
前記二次配合工程では、酸化ユーロピウム及びユーロピウム塩のいずれか一方又は両方の合計の配合量を、前記酸化物、前記酸化ユーロピウム及びユーロピウム塩の総配合量に対して、0.33〜0.50とすることが好ましい。
前記焼成工程は、窒素雰囲気下で1820〜2050℃の温度で焼成することが好ましい。
前記焼成工程は、気圧を0.1〜10MPaとすることが好ましい。
本発明のβサイアロンの製造方法は、前記焼成工程後に、粉砕及び分級のいずれか一方又は両方により、平均粒径を30μm以下とする粒度調整工程を行ってもよい。
本発明のβサイアロンの製造方法は、前記焼成工程後又は前記粒度調整工程後のβサイアロンに対して、1300℃以上かつ前記焼成工程時の焼成温度以下の温度条件下に保持する熱処理工程を行ってもよい。
本発明のβサイアロンの製造方法は、前記焼成工程、前記粒度調整工程又は前記熱処理工程後に、βサイアロンを酸溶液に浸漬する浸漬工程と、前記浸漬工程後のβサイアロンの表面に残留する酸溶液を洗浄する洗浄工程とを有する酸処理工程を行ってもよい。The method for producing β sialon according to the present invention includes a blending step of blending raw materials, kneading and homogenizing, and a firing step of firing the raw materials after the blending step to obtain β sialon, , General formula: Si 6-z Al z OzN 8-z (0.3 ≦ z ≦ 1.0) primary blending step of blending silicon nitride, aluminum nitride and oxide, and the primary blending step A secondary blending step of blending β sialon powder and one or both of europium oxide and europium salt into the subsequent raw material is performed, and the oxide blended in the primary blending step is any of aluminum oxide and silicon oxide Eu 2+ is a solid solution in β sialon represented by the general formula: Si 6-z Al z O z N 8-z (0.3 ≦ z ≦ 1.0), and has a wavelength of 455 nm. Excited with light The peak wavelength of the fluorescence spectrum to obtain a β-sialon is less than 555nm exceeds a 545nm in the case of.
In the secondary blending step, it is preferable to blend 5 to 30% by mass of the β sialon powder with respect to 100% by mass of the raw material after the primary blending step.
In the secondary blending step, the total blending amount of either or both of europium oxide and europium salt is 0.33 to 0.50 with respect to the total blending amount of the oxide, europium oxide and europium salt. It is preferable that
The firing process is preferably performed at a temperature of 1820 to 2050 ° C. in a nitrogen atmosphere.
In the firing step, the atmospheric pressure is preferably 0.1 to 10 MPa.
In the method for producing β sialon of the present invention, after the baking step, a particle size adjusting step of adjusting the average particle size to 30 μm or less may be performed by one or both of pulverization and classification.
In the β sialon production method of the present invention, a heat treatment step is performed for maintaining the β sialon after the firing step or after the particle size adjustment step at a temperature of 1300 ° C. or more and not more than a firing temperature at the firing step. May be.
The β sialon production method of the present invention includes an immersion step in which β sialon is immersed in an acid solution after the baking step, the particle size adjustment step, or the heat treatment step, and an acid solution remaining on the surface of the β sialon after the immersion step. You may perform the acid treatment process which has the washing | cleaning process of wash | cleaning.
本発明に係るβサイアロンは、前述したβサイアロンの製造方法で製造されたβサイアロンであって、一般式:Si6−zAlzOzN8−z(0.3≦z≦1.0)で表されるβサイアロンにEu2+が固溶し、波長455nmの光で励起した場合の蛍光スペクトルのピーク波長が545nmを超え555nm以下のものである。
本発明のβサイアロンは、Al含有量が2〜8質量%、Eu含有量が0.3〜1質量%、酸素含有量が0.5〜4質量%であることが好ましい。
本発明のβサイアロンは、粉末X線回折法により測定したβサイアロン以外の結晶相の回折線強度が、βサイアロンの(101)面の回折線強度に対して、1%以下であることが好ましい。The β sialon according to the present invention is a β sialon manufactured by the above-described β sialon manufacturing method, and has a general formula: Si 6-z Al z O z N 8-z (0.3 ≦ z ≦ 1.0 ) Eu 2+ is solid-dissolved in β sialon represented by the following formula, and the peak wavelength of the fluorescence spectrum when excited with light having a wavelength of 455 nm exceeds 545 nm and is 555 nm or less.
The β sialon of the present invention preferably has an Al content of 2 to 8 mass%, an Eu content of 0.3 to 1 mass%, and an oxygen content of 0.5 to 4 mass%.
In the β sialon of the present invention, the diffraction line intensity of the crystal phase other than β sialon measured by powder X-ray diffraction method is preferably 1% or less with respect to the diffraction line intensity of the (101) plane of β sialon. .
本発明に係る発光装置は、発光素子と、前記発光素子の発光面に搭載された蛍光体とを有し、前記蛍光体の一部又は全部に前述したβサイアロンを用いたものである。
本発明の発光装置は、前記発光素子が発光ダイオード(LED)であることが好ましい。The light-emitting device according to the present invention includes a light-emitting element and a phosphor mounted on a light-emitting surface of the light-emitting element, and the β sialon described above is used for part or all of the phosphor.
In the light emitting device of the present invention, the light emitting element is preferably a light emitting diode (LED).
本発明によれば、発光効率としての外部量子効率55%以上を維持しながら、ピーク波長が545nmを超え555nm以下の範囲のβサイアロンを、安定的に製造することができる。 According to the present invention, β sialon having a peak wavelength in the range of more than 545 nm and not more than 555 nm can be stably produced while maintaining the external quantum efficiency of 55% or more as the light emission efficiency.
以下、本発明を実施するための形態について、添付の図面を参照して詳細に説明する。 DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the accompanying drawings.
(第1の実施形態)
[βサイアロン]
本発明の第1の実施形態に係るβサイアロンは、一般式:Si6−zAlzOzN8−z(0.3≦z≦1.0)で表されるβサイアロンに、Eu2+を固溶したものであり、波長455nmの光で励起した場合の蛍光スペクトルのピーク波長が545nmを超え555nm以下である。(First embodiment)
[Β Sialon]
The β sialon according to the first embodiment of the present invention includes Eu 2+ represented by a general formula: Si 6-z Al z O z N 8 -z (0.3 ≦ z ≦ 1.0). The peak wavelength of the fluorescence spectrum when excited with light having a wavelength of 455 nm exceeds 545 nm and is 555 nm or less.
一般式:Si6−zAlzOzN8−zのz値が0.3未満であると、蛍光ピーク波長が545nmよりも低くなる。一方、z値が1.0を超えると、異相生成と粒子間焼結を抑制することが困難となり、発光強度の指標である外部量子効率が55%未満になってしまう。よって、本実施形態のβサイアロンでは、z値を0.3≦z≦1.0に限定する。これにより、蛍光ピーク波長を545nmよりも長波長側にシフトすることができる。When the z value of the general formula: Si 6-z Al z O z N 8-z is less than 0.3, the fluorescence peak wavelength is lower than 545 nm. On the other hand, if the z value exceeds 1.0, it is difficult to suppress heterogeneous phase formation and inter-particle sintering, and the external quantum efficiency, which is an indicator of light emission intensity, is less than 55%. Therefore, in the β sialon of the present embodiment, the z value is limited to 0.3 ≦ z ≦ 1.0. Thereby, the fluorescence peak wavelength can be shifted to a longer wavelength side than 545 nm.
本実施形態のβサイアロンは、全質量あたり、Al含有量が2〜8質量%、Eu含有量が0.3〜1質量%、酸素含有量が0.5〜4質量%であることが好ましい。Al含有量、Eu含有量及び酸素含有量を、前述した範囲にすることにより、βサイアロンの一般式において正確なz値を特定することができる。 The β sialon of the present embodiment preferably has an Al content of 2 to 8 mass%, an Eu content of 0.3 to 1 mass%, and an oxygen content of 0.5 to 4 mass% per total mass. . By setting the Al content, the Eu content, and the oxygen content within the ranges described above, an accurate z value can be specified in the general formula of β sialon.
本実施形態のβサイアロンは、粉末X線回折法により測定したβサイアロン以外の結晶相の回折線強度が、βサイアロンの(101)面の回折線強度に対して、1%以下であることが好ましい。βサイアロン以外の結晶相の回折線強度が1%以下であれば、βサイアロン以外の結晶相の含有量が非常に少なくなり、βサイアロン結晶相を高純度で含んでいることになる。なお、βサイアロン以外の結晶相の回折線強度が1%を超え、不可避的不純物として非晶質やβサイアロン以外の結晶相を含んでいても、特性が低下しない範囲であれば問題はない。 In the β sialon of the present embodiment, the diffraction line intensity of the crystal phase other than β sialon measured by the powder X-ray diffraction method is 1% or less with respect to the diffraction line intensity of the (101) plane of β sialon. preferable. If the diffraction line intensity of the crystal phase other than β sialon is 1% or less, the content of the crystal phase other than β sialon becomes very small, and the β sialon crystal phase is contained in high purity. Note that there is no problem as long as the diffraction line intensity of the crystal phase other than β sialon exceeds 1% and an amorphous or crystal phase other than β sialon is included as an inevitable impurity as long as the characteristics do not deteriorate.
[製造方法]
次に、本発明の実施形態のβサイアロンの製造方法について説明する。図1は本実施形態のβサイアロンの製造方法を示すフローチャート図である。図1に示すように、本実施形態のβサイアロンの製造方法では、原料を配合し混練して均一化する配合工程S1と、配合工程後の原料を焼成してβサイアロンを得る焼成工程S2とを行う。[Production method]
Next, the manufacturing method of (beta) sialon of embodiment of this invention is demonstrated. FIG. 1 is a flowchart showing a method for producing β sialon according to the present embodiment. As shown in FIG. 1, in the manufacturing method of β sialon according to the present embodiment, a blending step S1 for blending raw materials, kneading and homogenizing, and a firing step S2 for firing the raw materials after the blending step to obtain β sialon, I do.
<配合工程S1>
配合工程S1では、2段階で配合を行う。先ず、一次配合工程S11では、一般式:Si6−zAlzOzN8−z(0.3≦z≦1.0)となるように、窒化ケイ素及び酸化ケイ素のいずれか一方又は両方と、窒化アルミニウムと、酸化アルミニウムとを配合する。<Mixing step S1>
In the blending step S1, blending is performed in two stages. First, in the primary blending step S11, either or both of silicon nitride and silicon oxide so as to have a general formula: Si 6−z Al z O z N 8−z (0.3 ≦ z ≦ 1.0) And aluminum nitride and aluminum oxide are blended.
次に、二次配合工程S12において、一次配合工程S11で配合された原料に、βサイアロン粉末と、酸化ユーロピウム及びユーロピウム塩のいずれか一方又は両方を配合する。ここで配合するβサイアロン粉末は、一般式:Si6−zAlzOzN8−z(0.3≦z≦1.0)のものを使用する。Next, in the secondary blending step S12, β sialon powder and any one or both of europium oxide and europium salt are blended with the raw material blended in the primary blending step S11. The β sialon powder to be blended here is one having a general formula: Si 6−z Al z O z N 8−z (0.3 ≦ z ≦ 1.0).
二次配合工程S12におけるβサイアロン粉末の配合比は、一次配合工程後の原料100質量%に対して5〜30質量%とすることが好ましい。βサイアロン粉末の配合量があまりに少ないと、βサイアロン粉末の添加効果が十分得られないことがある。一方、βサイアロン粉末の配合量が多すぎると、βサイアロン粉末の粒成長が過多になり、製造されるβサイアロンの粒子の成長が小さくなる傾向がある。 The blending ratio of β sialon powder in the secondary blending step S12 is preferably 5 to 30% by weight with respect to 100% by weight of the raw material after the primary blending step. If the amount of β sialon powder is too small, the effect of adding β sialon powder may not be sufficiently obtained. On the other hand, when the amount of β sialon powder is too large, the particle growth of β sialon powder becomes excessive, and the growth of the produced β sialon powder tends to be small.
二次配合工程S12における酸化ユーロピウム及びユーロピウム塩のいずれか一方又は両方の配合比(以下、ユーロピウム比率という。)は、酸化物、酸化ユーロピウム及びユーロピウム塩の総配合量に対して、0.33〜0.50となるようにすることが好ましい。 The blending ratio (hereinafter referred to as the europium ratio) of either or both of europium oxide and europium salt in the secondary blending step S12 is 0.33 to the total blending amount of oxide, europium oxide and europium salt. It is preferable to be 0.50.
後述する焼成工程S2の初期段階では、原料中の酸化物が液相を形成し、その液相にSi3N4やAlNが溶解し、βサイアロンが析出される。この生成液相中のユーロピウム比率を上げることで、液相生成温度を低下させて、焼成温度を低くすることができる。この焼成温度の低下により、二次配合工程S12で配合したβサイアロン粉末の分解が抑制され、得られるβサイアロンにおける結晶欠陥の生成を抑制し、蛍光特性の低下を防ぐことが可能となる。In the initial stage of the firing step S2 described later, the oxide in the raw material forms a liquid phase, Si 3 N 4 and AlN are dissolved in the liquid phase, and β sialon is precipitated. By raising the europium ratio in this produced liquid phase, the liquid phase production temperature can be lowered and the firing temperature can be lowered. This reduction in the firing temperature suppresses the decomposition of the β sialon powder blended in the secondary blending step S12, suppresses the generation of crystal defects in the obtained β sialon, and prevents a decrease in fluorescence characteristics.
更に、ユーロピウム比率を上げることで、βサイアロン中へのユーロピウムの固溶も促進され、得られるサイアロンにおける蛍光特性を向上させることができる。ユーロピウム比率が、あまりに低いと液相生成温度を低下させる効果が不十分となり、低温焼成し難くなる。一方、ユーロピウム比率があまりに高いと、液相生成温度を低下させても過剰に液相が生成し、複合酸化物が異相として残存してしまうため、蛍光特性の低下を招くことがある。 Furthermore, by increasing the europium ratio, the solid solution of europium in β sialon is also promoted, and the fluorescence characteristics of the obtained sialon can be improved. If the europium ratio is too low, the effect of lowering the liquid phase formation temperature becomes insufficient, and low-temperature firing becomes difficult. On the other hand, if the europium ratio is too high, the liquid phase is excessively generated even if the liquid phase generation temperature is lowered, and the composite oxide remains as a different phase, which may cause a decrease in fluorescence characteristics.
前述した配合工程S1(一次配合工程S11、二次配合工程S12)における混合方法としては、乾式混合方法、原料各成分と実質的に反応しない不活性溶媒中で湿式混合した後に溶媒を除去する方法がある。混合に用いる装置は、特に限定されるものではなく、V型混合機、ロッキングミキサー、ボールミル、振動ミルなど、公知の装置を用いることができる。 As a mixing method in the blending step S1 (primary blending step S11, secondary blending step S12) described above, a dry mixing method, a method of removing the solvent after wet mixing in an inert solvent that does not substantially react with each component of the raw material. There is. The apparatus used for mixing is not particularly limited, and known apparatuses such as a V-type mixer, a rocking mixer, a ball mill, and a vibration mill can be used.
本実施形態のβサイアロンの製造方法では、配合工程を2段階で行っているため、異相生成を抑制でき、粒子間焼結の発生を抑制できる。具体的には、二次配合工程S12でβサイアロン粉末を添加しているため、後述する焼成工程S2において粒子間の焼結を抑制することができる。これにより結晶欠陥の生成を抑制して、得られるβサイアロンの蛍光特性の低下を抑制することができる。 In the method for producing β sialon of the present embodiment, since the blending process is performed in two stages, the generation of heterogeneous phases can be suppressed and the occurrence of interparticle sintering can be suppressed. Specifically, since β sialon powder is added in the secondary blending step S12, sintering between particles can be suppressed in the firing step S2 described later. Thereby, the production | generation of a crystal defect can be suppressed and the fall of the fluorescence characteristic of (beta) sialon obtained can be suppressed.
<焼成工程S2>
焼成工程S2では、配合工程S1後の原料を焼成してβサイアロンを得る。焼成工程S2において原料を収納する容器には、通常、窒化ホウ素などの焼成時に原料と反応しない材質のものが用いられる。焼成工程S2の条件は、原料の組成などに応じて適宜選択することができるが、焼成工程時の不純物の混入を防ぐために窒素雰囲気下が好ましく、焼成反応の適正化のために1820〜2050℃の範囲内で行うことが好ましい。<Firing step S2>
In the firing step S2, the raw material after the blending step S1 is fired to obtain β sialon. As the container for storing the raw material in the firing step S2, a material that does not react with the raw material during firing, such as boron nitride, is usually used. The conditions for the firing step S2 can be appropriately selected according to the composition of the raw materials, but a nitrogen atmosphere is preferable in order to prevent contamination of impurities during the firing step, and 1820 to 2050 ° C. for optimization of the firing reaction. It is preferable to carry out within the range.
焼成温度は、1900〜1980℃であることがより好ましい。焼成温度が、あまりに低いとβサイアロンの粒成長が進行し難くなる傾向にあり、あまりに高いと粒成長過程で生成する結晶欠陥量が増大し、結晶欠陥が可視光を吸収して蛍光特性を低下させる傾向にあるためである。 The firing temperature is more preferably 1900-1980 ° C. If the firing temperature is too low, the grain growth of β sialon tends to be difficult to proceed. If the firing temperature is too high, the amount of crystal defects generated during the grain growth process increases, and the crystal defects absorb visible light and deteriorate the fluorescence characteristics. This is because it tends to be caused.
焼成工程S2は、気圧が0.1〜10MPaの条件下で行うことが好ましい。焼成時の気圧があまりに低いと、原料窒化物や予め原料中に含有させたβサイアロン粉末の分解が起こることがあり、あまりに高いと装置への負荷が大きくなるからである。焼成工程S2は、焼成工程時の不純物の混入を防ぐために、真空中、又は窒素若しくはアルゴンなどの不活性ガス雰囲気中で行うことが好ましい。 It is preferable to perform baking process S2 on the conditions whose atmospheric | air pressure is 0.1-10 Mpa. This is because if the pressure at the time of firing is too low, the raw material nitride and β sialon powder previously contained in the raw material may be decomposed, and if it is too high, the load on the apparatus increases. The firing step S2 is preferably performed in a vacuum or in an inert gas atmosphere such as nitrogen or argon in order to prevent contamination of impurities during the firing step.
<粒度調整工程>
本実施形態のβサイアロンの製造方法においては、βサイアロン同士の均一性を図るため、焼成工程S2の後に、粉砕及び分級のいずれか一方又は両方により、平均粒径を30μm以下とする粒度調整工程を行うことが好ましい。<Particle size adjustment process>
In the method for producing β sialon according to the present embodiment, in order to achieve uniformity between β sialons, a particle size adjusting step in which the average particle size is 30 μm or less by pulverization and / or classification after the firing step S2. It is preferable to carry out.
粉砕の方法は、特に限定されるものではないが、例えば、焼成されたβサイアロンを、ボールミル、振動ミル及びジェットミルなどの粉砕機を用いて、所定の粒度に粉砕する方法がある。また、分級の方法も、特に限定されるものではないが、例えば、焼成されたβサイアロンのうち、目開き20〜45μm以下の篩を通過したものだけを分離・回収する方法がある。 The pulverization method is not particularly limited. For example, there is a method in which the fired β sialon is pulverized to a predetermined particle size using a pulverizer such as a ball mill, a vibration mill, and a jet mill. Further, the classification method is not particularly limited. For example, among the fired β sialon, there is a method of separating and collecting only those that have passed through a sieve having an opening of 20 to 45 μm or less.
<熱処理工程>
本実施形態のβサイアロンの製造方法においては、焼成工程S2後又は粒度調整工程後のβサイアロンに対して、1300℃以上かつ焼成工程S2における焼成温度以下の温度条件下に保持する熱処理工程を行うことが好ましい。この熱処理工程を行うことにより、βサイアロン中に存在し、可視光発光を阻害する結晶欠陥や第二相を、酸に可溶な状態にすることができる。<Heat treatment process>
In the β sialon manufacturing method of the present embodiment, a heat treatment step is performed for maintaining the β sialon after the firing step S2 or the particle size adjustment step at a temperature of 1300 ° C. or more and not more than the firing temperature in the firing step S2. It is preferable. By performing this heat treatment step, crystal defects and second phase that are present in β sialon and inhibit visible light emission can be made soluble in acid.
ここで、熱処理工程での温度は、あまりに低いと欠陥除去の効果が低くなる傾向にあり、あまりに高くても効果が頭打ちになる傾向にある。また、熱処理工程は、窒素、アンモニア、水素及び希ガスから選択される1種のガス若しくは2種以上の混合ガス雰囲気中、又は真空中で行うことができる。 Here, if the temperature in the heat treatment step is too low, the effect of removing defects tends to be low, and if it is too high, the effect tends to reach its peak. In addition, the heat treatment step can be performed in an atmosphere of one gas selected from nitrogen, ammonia, hydrogen, and a rare gas, or in a mixed gas atmosphere of two or more gases, or in a vacuum.
熱処理工程での温度及び処理時間は、βサイアロンの波長650〜800nmの平均拡散反射率が、熱処理工程前よりも10〜50%低下する条件とすることが好ましい。熱処理工程による平均拡散反射率の低下が10%よりも少ないと、可視光発光阻害因子の状態変化が小さくなり、この処理による特性向上効果が小さくなるからである。また、平均拡散反射率の低下が50%を超えると、正常なβサイアロン結晶の分解を伴うため、好ましくないからである。 The temperature and the treatment time in the heat treatment step are preferably set such that the average diffuse reflectance of β sialon having a wavelength of 650 to 800 nm is reduced by 10 to 50% than before the heat treatment step. This is because if the decrease in average diffuse reflectance due to the heat treatment step is less than 10%, the change in the state of the visible light emission inhibiting factor becomes small, and the effect of improving the characteristics by this treatment becomes small. Moreover, it is not preferable that the decrease in average diffuse reflectance exceeds 50% because it involves decomposition of normal β sialon crystals.
<酸処理工程>
本実施形態のβサイアロンの製造方法においては、焼成工程S2後、粒度調整工程後又は熱処理工程後に、酸処理工程を行うことが好ましい。具体的には、酸処理工程として、βサイアロンを酸溶液に浸漬する浸漬工程と、浸漬工程後のβサイアロンの表面に残留する酸溶液を洗浄する洗浄工程とを行うことが好ましい。酸処理工程は、熱処理工程で変化した発光阻害因子を溶解除去する工程であり、この工程を行うことにより、βサイアロンの蛍光特性を向上させることができる。<Acid treatment process>
In the method for producing β sialon of the present embodiment, it is preferable to perform an acid treatment step after the firing step S2, after the particle size adjustment step, or after the heat treatment step. Specifically, as the acid treatment step, it is preferable to perform an immersion step of immersing β sialon in the acid solution and a cleaning step of cleaning the acid solution remaining on the surface of β sialon after the immersion step. The acid treatment step is a step of dissolving and removing the light emission inhibiting factor changed in the heat treatment step, and by performing this step, the fluorescence characteristics of β sialon can be improved.
酸処理工程で用いられる酸としては、フッ化水素酸、硫酸、リン酸、塩酸及び硝酸のいずれか1種又は2種以上の混合物が挙げられ、これらの酸は水溶液の形態で使用される。浸漬工程の実施方法としては、例えば、熱処理工程後のβサイアロンを、上述の酸を含む水溶液に分散し、数分から数時間程度撹拌して反応させる方法ある。浸漬工程における酸の温度は、特に限定されるものではなく、室温、室温以上に加熱した温度、50〜80℃など、適宜選択することができる。浸漬工程後のβサイアロンは、酸を除去するために、フィルターで酸を分離した後、水洗いする(洗浄工程)。 Examples of the acid used in the acid treatment step include one or a mixture of two or more of hydrofluoric acid, sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid, and these acids are used in the form of an aqueous solution. As an implementation method of the dipping step, for example, there is a method in which β sialon after the heat treatment step is dispersed in the above-mentioned aqueous solution containing the acid and stirred and reacted for about several minutes to several hours. The temperature of the acid in the dipping process is not particularly limited, and can be appropriately selected from room temperature, a temperature heated to room temperature or higher, 50 to 80 ° C, and the like. The β sialon after the dipping process is washed with water after separating the acid with a filter in order to remove the acid (washing process).
以上詳述したように、本実施形態のβサイアロンは、一般式:Si6−zAlzOzN8−zで表されるサイアロンのz値を0.3〜1.0の範囲にすると共に、配合工程を2段階で行い、二次配合工程においてβサイアロン粉末を添加しているため、発光効率を低下させずに、ピーク波長を従来よりも長波長側にシフトさせることができる。その結果、発光効率としての外部量子効率55%以上を維持しながら、ピーク波長が545nmを超え555nm以下の範囲のβサイアロンを実現することができる。As described in detail above, the β sialon of the present embodiment sets the z value of the sialon represented by the general formula: Si 6-z Al z O z N 8-z in the range of 0.3 to 1.0. At the same time, the blending process is performed in two stages, and β sialon powder is added in the secondary blending process, so that the peak wavelength can be shifted to the longer wavelength side than before without lowering the luminous efficiency. As a result, β sialon having a peak wavelength in the range of more than 545 nm and not more than 555 nm can be realized while maintaining the external quantum efficiency of 55% or more as the light emission efficiency.
(第2の実施形態)
次に、本発明の第2の実施形態に係る発光装置について説明する。図2は本実施形態の発光装置の構成を示す模式図である。図2に示すように、本実施形態の発光装置1は、発光素子2と、発光素子の発光面に搭載される蛍光体3とを備え、蛍光体3の一部又は全部に前述した第1の実施形態のβサイアロンが用いられている。(Second Embodiment)
Next, a light emitting device according to a second embodiment of the present invention will be described. FIG. 2 is a schematic diagram showing the configuration of the light emitting device of this embodiment. As shown in FIG. 2, the light-emitting device 1 of the present embodiment includes a light-emitting element 2 and a phosphor 3 mounted on the light-emitting surface of the light-emitting element. The β sialon of the embodiment is used.
発光素子2としては、紫外線発光ダイオード(UV−LED)及び青色発光ダイオード(青色LED)などの各種LED、蛍光体ランプ及びレーザダイオード(LD)などを使用することができ、LEDが好適である。また、蛍光体3としては、前述した第1の実施形態のβサイアロンのみを使用してもよいが、赤色発光蛍光体、橙色発光蛍光体、黄色発光蛍光体、緑色発光蛍光体及び青色発光蛍光体などを組み合わせて使用することができる。これにより、発光装置としての発光色を調整することができる。 As the light emitting element 2, various LEDs such as an ultraviolet light emitting diode (UV-LED) and a blue light emitting diode (blue LED), a phosphor lamp, a laser diode (LD), and the like can be used, and an LED is preferable. Further, as the phosphor 3, only the β sialon of the first embodiment described above may be used, but a red light emitting phosphor, an orange light emitting phosphor, a yellow light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor. Can be used in combination with the body. Thereby, the luminescent color as a light-emitting device can be adjusted.
本実施形態の発光装置1は、リードフレーム4上に発光素子2が搭載され、リードフレーム4上の枠体8の中に蛍光体3を分散させた封止樹脂5により発光素子2を封止している。発光素子2は、ボンディングワイヤ6により他のリードフレーム7に接続されている。 In the light emitting device 1 of this embodiment, the light emitting element 2 is mounted on the lead frame 4, and the light emitting element 2 is sealed with a sealing resin 5 in which the phosphor 3 is dispersed in the frame 8 on the lead frame 4. doing. The light emitting element 2 is connected to another lead frame 7 by a bonding wire 6.
本実施形態の発光装置1は、発光素子2から、励起光として、波長350〜500nmの紫外線から紫、青、緑の可視光を出射し、βサイアロンなどからなる蛍光体3に照射する。励起光の照射によってβサイアロンは、545nmを超え555nm以下の波長域にピークを持つ光を発する。本実施形態の発光装置1に用いられているβサイアロンの発光は、外部量子効率が55%以上であるため、これにより本実施形態の発光装置1は高い発光強度を有する。 The light emitting device 1 of the present embodiment emits visible light of violet, blue, and green from the ultraviolet light having a wavelength of 350 to 500 nm as the excitation light from the light emitting element 2 and irradiates the phosphor 3 made of β sialon or the like. The β sialon emits light having a peak in a wavelength range of more than 545 nm and less than 555 nm by irradiation with excitation light. Since the light emission of β sialon used in the light emitting device 1 of the present embodiment has an external quantum efficiency of 55% or more, the light emitting device 1 of the present embodiment has a high light emission intensity.
以下、本発明の実施例及び比較例を挙げて、本発明の効果について説明する。 Hereinafter, the effects of the present invention will be described with reference to examples and comparative examples of the present invention.
(第1実施例)
第1実施例では、以下に示す方法でβサイアロンを製造し、その特性を評価した。下記表1に、実施例及び比較例のβサイアロンの構成及び評価結果を示す。(First embodiment)
In the first example, β sialon was produced by the following method, and its characteristics were evaluated. Table 1 below shows the configurations and evaluation results of β sialon of the examples and comparative examples.
表1に示すβサイアロンの一般式におけるz値は、原料配合時の値であり、目標値である。なお、表1において、z値の値が同じである実施例1と比較例2で、組成分析値のAl含有量や酸素含有量が異なっているが、これは焼成工程において原料の一部が揮発したり、βサイアロンの結晶に固溶しきれず残存した相がその後の熱処理工程や酸処理工程において、酸処理により除去されたためである。 The z value in the general formula of β sialon shown in Table 1 is a value at the time of blending raw materials and is a target value. In Table 1, the Al content and the oxygen content of the composition analysis values are different between Example 1 and Comparative Example 2 in which the value of z value is the same. This is because the phase that has been volatilized or not completely dissolved in the β sialon crystals has been removed by acid treatment in the subsequent heat treatment step or acid treatment step.
<蛍光スペクトル>
表1に示す蛍光スペクトルのピーク波長は、分光光度計(大塚電子社製 MCPD−7000)を用いて、以下の方法で測定した。先ず、実施例及び比較例の各βサイアロン(以下、試料という。)を、凹型のセルに、その表面が平滑になるように充填し、積分球を取り付けた。次に、この積分球に、発光光源としてのXeランプから波長455nmに分光した青色光を、光ファイバーを用いて導入した。この青色光を励起源として、試料に照射し、分光光度計(大塚電子社製 MCPD−7000)を用いて、試料の蛍光及び反射光のスペクトル測定を行った。得られた蛍光スペクトルからピーク波長を求めた。<Fluorescence spectrum>
The peak wavelength of the fluorescence spectrum shown in Table 1 was measured by the following method using a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). First, each β sialon (hereinafter referred to as a sample) of Examples and Comparative Examples was filled into a concave cell so that the surface thereof was smooth, and an integrating sphere was attached. Next, blue light dispersed at a wavelength of 455 nm from an Xe lamp as a light source was introduced into the integrating sphere using an optical fiber. Using this blue light as an excitation source, the sample was irradiated and the spectrum of the fluorescence and reflected light of the sample was measured using a spectrophotometer (MCPD-7000, manufactured by Otsuka Electronics Co., Ltd.). The peak wavelength was determined from the obtained fluorescence spectrum.
<回折線強度>
表1に示す回折線強度は、粉末X線回折法により(101)面の回折線強度を測定し、βサイアロンの(101)面の回折線強度を100%として算出した値である。なお、表1に示す「異相なし」とは、βサイアロンの(101)面の回折線強度に対して、0.0%であることを示す。<Diffraction line intensity>
The diffraction line intensity shown in Table 1 is a value calculated by measuring the diffraction line intensity of the (101) plane by the powder X-ray diffraction method and setting the diffraction line intensity of the (101) plane of β sialon as 100%. “No heterogeneous phase” shown in Table 1 indicates 0.0% with respect to the diffraction line intensity of the (101) plane of β sialon.
<平均粒子径>
表1に示す平均粒子径は、粒度分布測定装置を用いて、レーザー回折・散乱法による粒子径分布測定により得られた体積基準の積算分率における50%粒子径(D50)である。<Average particle size>
The average particle size shown in Table 1 is a 50% particle size (D50) in a volume-based integrated fraction obtained by particle size distribution measurement by a laser diffraction / scattering method using a particle size distribution measuring device.
<組成分析値におけるAl、Eu及び酸素含有量>
表1に示す組成分析値におけるAl及びEuの値は、実施例及び比較例の各βサイアロンの粉末を、アルカリ融解法により溶解させた後、ICP発光分光分析装置(株式会社リガク製 CIROS−120)により測定したAl含有量及びEu含有量である。表1に示す組成分析値における酸素の値は、酸素窒素分析装置(堀場製作所製 EMGA−920)により測定した酸素含有量である。<Al, Eu and oxygen content in composition analysis value>
The values of Al and Eu in the compositional analysis values shown in Table 1 are obtained by dissolving each β sialon powder of Examples and Comparative Examples by an alkali melting method, and then using an ICP emission spectroscopic analyzer (CIROS-120 manufactured by Rigaku Corporation). The Al content and the Eu content measured by (1). The value of oxygen in the composition analysis values shown in Table 1 is the oxygen content measured by an oxygen nitrogen analyzer (EMGA-920 manufactured by Horiba, Ltd.).
<外部量子効率>
試料部に、反射率が99%の標準反射板(Labsphere社製 スペクトラロン)をセットし、波長455nmに分光した励起光のスペクトルを測定し、450〜465nmの波長範囲のスペクトルから励起光フォトン数(Qex)を算出した。試料部に測定対象のβサイアロンをセットして、波長455nmに分光した青色光をβサイアロンに照射し、得られたスペクトルデータから励起反射光フォトン数(Qref)及び蛍光フォトン数(Qem)を算出した。<External quantum efficiency>
A standard reflector (Spectralon manufactured by Labsphere) with a reflectance of 99% is set on the sample part, the spectrum of the excitation light dispersed at a wavelength of 455 nm is measured, and the number of excitation light photons from the spectrum in the wavelength range of 450 to 465 nm. (Qex) was calculated. Set β sialon to be measured on the sample part, irradiate β sialon with blue light split at a wavelength of 455 nm, and calculate excitation reflected photon number (Qref) and fluorescent photon number (Qem) from the obtained spectrum data did.
励起反射光フォトン数は、励起光フォトン数と同じ波長範囲で、蛍光フォトン数は、465〜800nmの範囲で算出した。得られた3種類のフォトン数から外部量子効率(=Qem/Qex×100)を求めた。 The number of excitation reflected light photons was calculated in the same wavelength range as the number of excitation light photons, and the number of fluorescent photons was calculated in the range of 465 to 800 nm. The external quantum efficiency (= Qem / Qex × 100) was determined from the obtained three types of photons.
[実施例1]
前述した第1の実施形態のβサイアロンの製造方法に従い、一般式:Si6−zAlzOzN8−z(z=0.5)となるように窒化ケイ素と、窒化アルミニウムと、酸化物とを配合して、実施例1のβサイアロンを製造した。[Example 1]
In accordance with the β sialon manufacturing method of the first embodiment described above, silicon nitride, aluminum nitride, and oxidation so as to be a general formula: Si 6−z Al z O z N 8−z (z = 0.5) The β sialon of Example 1 was produced.
<二次配合工程で用いるβサイアロン粉末の製造>
先ず、以下に示す方法及び条件で、二次配合工程で用いるβサイアロン粉末を製造した。原料には、宇部興産株式会社製 α型窒化ケイ素粉末(SN−E10グレード:酸素含有量1.0質量%)を95.43質量%と、トクヤマ株式会社製 窒化アルミニウム粉末(Eグレード:酸素含有量0.9質量%)を3.04質量%と、大明化学株式会社製 酸化アルミニウム粉末(TM−DARグレード)を0.74質量%と、信越化学工業株式会社製 酸化ユーロピウム粉末(RUグレード)を0.79質量%とを用いた。<Manufacture of β sialon powder used in the secondary blending process>
First, β sialon powder used in the secondary blending step was produced by the following method and conditions. As raw materials, 95.43% by mass of α-type silicon nitride powder (SN-E10 grade: oxygen content 1.0% by mass) manufactured by Ube Industries, Ltd. and aluminum nitride powder (E grade: oxygen-containing by Tokuyama Co., Ltd.) 0.94% by mass), 0.74% by mass aluminum oxide powder (TM-DAR grade) manufactured by Daimei Chemical Co., Ltd., and europium oxide powder (RU grade) manufactured by Shin-Etsu Chemical Co., Ltd. Of 0.79% by mass was used.
これらの原料を、V型混合機(筒井理化学器械株式会社製 S−3)により混合した後、凝集物を取り除くために、目開き500μmの篩を通過したものを分離・回収した。回収されたβサイアロン粉末の原料を、蓋付きの円筒型窒化ホウ素製容器(電気化学工業株式会社製 N−1グレード)に充填し、カーボンヒーターの電気炉で0.8MPaの加圧窒素雰囲気中、2000℃で15時間の焼成処理を行ってβサイアロンを得た。 After these raw materials were mixed with a V-type mixer (S-3, manufactured by Tsutsui Rika Kikai Co., Ltd.), the material that passed through a sieve having an opening of 500 μm was separated and collected in order to remove aggregates. The recovered β sialon powder raw material is filled into a cylindrical boron nitride container (N-1 grade, manufactured by Denki Kagaku Kogyo Co., Ltd.) with a lid, and in a pressurized nitrogen atmosphere of 0.8 MPa in an electric furnace of a carbon heater. Then, baking was performed at 2000 ° C. for 15 hours to obtain β sialon.
得られたβサイアロンを、清浄なゴム手袋を着用した人手により解砕した。解砕したβサイアロンを超音速ジェット粉砕器(日本ニューマチック工業社製 PJM−80SP)により粉砕した。粉砕条件は、試料供給速度を50g/分、粉砕エア圧力を0.3MPaとした。得られた粉砕粉末を、二次配合工程において原料として用いるβサイアロン粉末とした。 The obtained β sialon was crushed by a hand wearing clean rubber gloves. The pulverized β sialon was pulverized by a supersonic jet pulverizer (PJM-80SP manufactured by Nippon Pneumatic Industry Co., Ltd.). The pulverization conditions were a sample supply rate of 50 g / min and a pulverization air pressure of 0.3 MPa. The obtained pulverized powder was used as β sialon powder used as a raw material in the secondary blending step.
<βサイアロンの製造方法>
次に、原料として、宇部興産株式会社製 α型窒化ケイ素粉末(SN−E10グレード:酸素含有量1.0質量%)を78.45質量%と、トクヤマ株式会社製 窒化アルミニウム粉末(Eグレード:酸素含有量0.9質量%)を3.51質量%と、大明化学株式会社製 酸化アルミニウム粉末(TM−DARグレード)を3.39質量%と、信越化学工業株式会社製 酸化ユーロピウム粉末(RUグレード)を1.74質量%と、前述した方法及び条件で製造した原料βサイアロン粉末を12.91質量%とを用いた。<Method for producing β sialon>
Next, as a raw material, 78.45% by mass of α-type silicon nitride powder (SN-E10 grade: oxygen content 1.0% by mass) manufactured by Ube Industries, Ltd. and aluminum nitride powder (E grade: manufactured by Tokuyama Co., Ltd.) Oxygen content 0.9% by mass) 3.51% by mass, Daiming Chemical Co., Ltd. aluminum oxide powder (TM-DAR grade) 3.39% by mass, Shin-Etsu Chemical Co., Ltd. Europium oxide powder (RU) Grade) was 1.74% by mass, and 12.91% by mass of the raw material β-sialon powder produced by the method and conditions described above.
これらの原料を、V型混合機(筒井理化学器械株式会社製S−3)により混合した後、目開き500μmの篩を全通させて凝集物を取り除いた。ここでの配合比は、βサイアロンの一般式:Si6−zAlzOzN8−zにおいて、酸化ユーロピウムと原料サイアロンを除いて、z=0.5となるように設計した。また、ユーロピウム比率(表1のEu2O3/酸化物)は、酸化物の割合に対して0.34質量%であった。After these raw materials were mixed with a V-type mixer (S-3 manufactured by Tsutsui Rika Kikai Co., Ltd.), a sieve having an opening of 500 μm was passed through to remove aggregates. The compounding ratio here was designed so that in the general formula of β sialon: Si 6-z Al z O z N 8-z , excluding europium oxide and raw material sialon, z = 0.5. The europium ratio (Eu 2 O 3 / oxide in Table 1) was 0.34% by mass with respect to the ratio of oxide.
引き続き、篩を全通させて回収したβサイアロンの原料に対して焼成工程を行なった。焼成工程では、原料を蓋付きの円筒型窒化ホウ素製容器に充填し、カーボンヒーターの電気炉で0.8MPaの加圧窒素雰囲気中、1900℃で15時間の加熱処理した。この焼成工程によって得られたβサイアロンを、清浄なゴム手袋を着用した人手で解砕した。 Then, the baking process was performed with respect to the raw material of β sialon collected through the sieve. In the firing step, the raw material was filled into a cylindrical boron nitride container with a lid, and was heat-treated at 1900 ° C. for 15 hours in a pressurized nitrogen atmosphere of 0.8 MPa in a carbon heater electric furnace. The β sialon obtained by this baking process was crushed by a hand wearing clean rubber gloves.
解砕後のβサイアロンを、超音速ジェット粉砕器により、試料供給速度が50g/分、粉砕エア圧力が0.5MPaの条件で粉砕処理し、更に粒度分布調整工程として、気流分級機による分級処理を行い、微粉を除去した。その際、分級条件は、試料供給速度を50g/分、分級風量を2.0m/m3、回転数を2000rpmとした。The pulverized β sialon is pulverized with a supersonic jet pulverizer under the conditions of a sample supply rate of 50 g / min and a pulverization air pressure of 0.5 MPa. And fine powder was removed. At that time, the classification conditions were a sample supply speed of 50 g / min, a classification air volume of 2.0 m / m 3 , and a rotation speed of 2000 rpm.
解砕し分級した後のβサイアロンに対して熱処理工程を行なった。熱処理工程では、得られた粉砕粉末を、蓋付きの円筒型窒化ホウ素製容器に充填し、カーボンヒーターの電気炉で大気圧アルゴン雰囲気中、1500℃で8時間の熱処理を行った。熱処理工程前のβサイアロンの色は淡黄色であったが、熱処理工程後のβサイアロン粉末の色は深緑色に変化した。 The β sialon after being crushed and classified was subjected to a heat treatment step. In the heat treatment step, the obtained pulverized powder was filled into a cylindrical boron nitride container with a lid, and heat treatment was performed at 1500 ° C. for 8 hours in an atmospheric pressure argon atmosphere in a carbon heater electric furnace. The color of β sialon before the heat treatment step was light yellow, but the color of β sialon powder after the heat treatment step was changed to dark green.
更に、熱処理工程後のβサイアロンに対して、酸処理工程を行なった。酸処理工程では、50質量%フッ化水素酸と70質量%硝酸とを、質量比で、1:1で混合した混酸(液温80℃)中に、βサイアロンを1時間浸漬した。その後、混酸に浸したβサイアロンを、ろ過し、水洗及び乾燥した。 Further, an acid treatment step was performed on β sialon after the heat treatment step. In the acid treatment step, β sialon was immersed for 1 hour in a mixed acid (liquid temperature 80 ° C.) in which 50 mass% hydrofluoric acid and 70 mass% nitric acid were mixed at a mass ratio of 1: 1. Thereafter, β sialon soaked in the mixed acid was filtered, washed with water and dried.
これにより、一般式:Si6−zAlzOzN8−z(z=0.50)、即ち、Si5.5Al0.5O0.5N7.5で示されるβサイアロンに、Eu2+を固溶した実施例1のβサイアロンが得られた。実施例1のβサイアロンは、Al含有量が2.8質量%、Eu含有量が0.8質量%、酸素含有量が1.589質量%であり、平均粒子径は21.86μmであった。As a result, the general formula: Si 6-z Al z O z N 8-z (z = 0.50), ie, β sialon represented by Si 5.5 Al 0.5 O 0.5 N 7.5 The β sialon of Example 1 in which Eu 2+ was dissolved was obtained. The β sialon of Example 1 had an Al content of 2.8% by mass, an Eu content of 0.8% by mass, an oxygen content of 1.589% by mass, and an average particle size of 21.86 μm. .
実施例1のサイアロンは、波長455nmの光で励起した場合の蛍光スペクトルのピーク波長が552nm、外部量子効率が66%であり、発光効率を低下させずに、ピーク波長を545nmを超え555nm以下の範囲することができた。更に、実施例1のβサイアロンは、粉末X線回折法により測定したβサイアロン以外の結晶相の回折線強度が、βサイアロンの(101)面の回折線強度に対して、0%であり、異相が含まれていないことが確認された。 The sialon of Example 1 has a peak wavelength of 552 nm and an external quantum efficiency of 66% when excited with light having a wavelength of 455 nm, and has a peak wavelength of more than 545 nm and less than 555 nm without lowering the light emission efficiency. Could range. Furthermore, in the β sialon of Example 1, the diffraction line intensity of the crystal phase other than β sialon measured by the powder X-ray diffraction method is 0% with respect to the diffraction line intensity of the (101) plane of β sialon, It was confirmed that no foreign phase was included.
(実施例2)
表1に示すように、z値が0.7になるように原料を配合した以外は、前述した実施例1のβサイアロンと同様の方法及び条件で、実施例2のβサイアロンを製造した。実施例2のβサイアロンは、ピーク波長及び外部量子効率が実施例1のβサイアロンと同じであった。(Example 2)
As shown in Table 1, the β sialon of Example 2 was produced by the same method and conditions as the β sialon of Example 1 described above except that the raw materials were blended so that the z value was 0.7. The β sialon of Example 2 had the same peak wavelength and external quantum efficiency as the β sialon of Example 1.
(実施例3)
表1に示すように、z値が0.3になるように原料を配合した以外は、前述した実施例1のβサイアロンと同様の方法及び条件で、実施例3のβサイアロンを製造した。実施例3のβサイアロンは、実施例1のβサイアロンに比べて、ピーク波長及び外部量子効率が低下したが、いずれも問題ない範囲であった。Example 3
As shown in Table 1, the β sialon of Example 3 was produced in the same manner and conditions as the β sialon of Example 1 described above except that the raw materials were blended so that the z value was 0.3. The β sialon of Example 3 had a lower peak wavelength and external quantum efficiency than the β sialon of Example 1, but both were in the range where there was no problem.
(実施例4)
表1に示すように、z値が1.0になるように原料を配合した以外は、前述した実施例1のβサイアロンと同様の方法及び条件で、実施例4のβサイアロンを製造した。実施例4のβサイアロンは、実施例1のβサイアロンに比べて、ピーク波長が高くなり、外部量子効率が低下したが、いずれも問題ない範囲であった。Example 4
As shown in Table 1, the β sialon of Example 4 was produced in the same manner and conditions as the β sialon of Example 1 described above except that the raw materials were blended so that the z value was 1.0. The β sialon of Example 4 had a higher peak wavelength and a lower external quantum efficiency than the β sialon of Example 1, but both were in the range where there was no problem.
(実施例5)
表1に示すように、z値が0.7、ユーロピウム比率が0.27質量%になるように原料を配合した以外は、前述した実施例1のβサイアロンと同様の方法及び条件で、実施例5のβサイアロンを製造した。実施例5のβサイアロンは、ピーク波長は545nmを超え、外部量子効率は55%に達していた。(Example 5)
As shown in Table 1, it was carried out under the same method and conditions as the β sialon of Example 1 described above, except that the raw materials were blended so that the z value was 0.7 and the europium ratio was 0.27% by mass. The β sialon of Example 5 was produced. The β sialon of Example 5 had a peak wavelength exceeding 545 nm and an external quantum efficiency of 55%.
(比較例1)
表1に示すように、z値が0.2になるように原料を配合した以外は、前述した実施例1のβサイアロンと同様の方法及び条件で、比較例1のβサイアロンを製造した。比較例1のβサイアロンは、ピーク波長が541nmで従来と同等であり、外部量子効率も55%に達しなかった。(Comparative Example 1)
As shown in Table 1, the β sialon of Comparative Example 1 was produced by the same method and conditions as the β sialon of Example 1 described above except that the raw materials were blended so that the z value was 0.2. The β sialon of Comparative Example 1 has a peak wavelength of 541 nm, which is equivalent to the conventional one, and the external quantum efficiency did not reach 55%.
(比較例2)
表1に示すように、原料にサイアロン粉末を用いなかった以外は、前述した実施例1のβサイアロンと同様の方法及び条件で、比較例2のβサイアロンを製造した。比較例2のβサイアロンは、ピーク波長は実施例1のβサイアロンと同じであったが、外部量子効率が44%と、実施例1のβサイアロンに比べて大幅に低いものであった。(Comparative Example 2)
As shown in Table 1, the β sialon of Comparative Example 2 was produced by the same method and conditions as the β sialon of Example 1 described above, except that sialon powder was not used as a raw material. The β sialon of Comparative Example 2 had the same peak wavelength as the β sialon of Example 1, but the external quantum efficiency was 44%, which was significantly lower than the β sialon of Example 1.
(比較例3)
表1に示すように、z値が1.2、ユーロピウム比率が0.41質量%になるように原料を配合した以外は、前述した実施例1のβサイアロンと同様の方法及び条件で、比較例3のβサイアロンを製造した。比較例3のβサイアロンは、ピーク波長が実施例1のβサイアロンよりも更に長波長側にシフトして555nmを超え、外部量子効率が55%に達しなかった。(Comparative Example 3)
As shown in Table 1, a comparison was made in the same method and conditions as in the β sialon of Example 1 described above except that the raw material was blended so that the z value was 1.2 and the europium ratio was 0.41% by mass. The β sialon of Example 3 was produced. The β sialon of Comparative Example 3 had a peak wavelength shifted further to the longer wavelength side than that of Example 1 and exceeded 555 nm, and the external quantum efficiency did not reach 55%.
以上の結果から、z値が0.3〜1.0の範囲から外れる比較例1,3では、ピーク波長が545nm以下又は555nmを超え、更に外部量子効率も55%未満であった。 From the above results, in Comparative Examples 1 and 3 where the z value is out of the range of 0.3 to 1.0, the peak wavelength was 545 nm or less or exceeded 555 nm, and the external quantum efficiency was also less than 55%.
図3は実施例1のβサイアロンの走査型電子顕微鏡(SEM)像であり、図4は比較例2のβサイアロンの走査型電子顕微鏡(SEM)像である。図3及び図4に示すように、原料にサイアロン粉末を用いていない比較例2のβサイアロンは、実施例1のβサイアロンに比べて、粒子サイズが小さかった。これに対して、原料にβサイアロン粉末を添加した実施例1のβサイアロンは、短径が大きく、粒子サイズの揃った柱状粒子からなる構造が得られ、その結果、良好な蛍光特性が得られた。 3 is a scanning electron microscope (SEM) image of β sialon of Example 1, and FIG. 4 is a scanning electron microscope (SEM) image of β sialon of Comparative Example 2. As shown in FIGS. 3 and 4, the β sialon of Comparative Example 2 that does not use sialon powder as a raw material had a smaller particle size than the β sialon of Example 1. On the other hand, the β sialon of Example 1 in which β sialon powder is added to the raw material has a structure composed of columnar particles having a large minor axis and a uniform particle size, and as a result, good fluorescence characteristics are obtained. It was.
(第2実施例)
第2実施例では、前述した実施例及び比較例の各βサイアロンを、シリコーン製の封止樹脂に混入し、青色発光LEDの発光素子表面に搭載した。このLEDを用いて照明装置を作製した。(Second embodiment)
In 2nd Example, each beta sialon of the Example and comparative example which were mentioned above was mixed in silicone sealing resin, and was mounted in the light emitting element surface of blue light emission LED. A lighting device was fabricated using this LED.
その結果、実施例1〜5のβサイアロンを用いた照明装置は、蛍光体の発光波長が従来のβサイアロンよりも長波長側にシフトした発光色を得ることができた。これに対して、比較例1〜3のβサイアロンを用いた照明装置は、蛍光体の発光波長が従来のβサイアロンと同じか、又は発光強度が55%未満であったため、実施例1〜5のβサイアロンを用いた照明装置よりも、暗い発光であった。 As a result, the illuminating device using β sialon of Examples 1 to 5 was able to obtain a luminescent color in which the emission wavelength of the phosphor was shifted to the longer wavelength side than the conventional β sialon. On the other hand, since the illuminating device using β sialon of Comparative Examples 1 to 3 had the same emission wavelength of the phosphor as that of the conventional β sialon or the emission intensity was less than 55%, Examples 1 to 5 It was darker than the lighting device using β sialon.
1 発光装置、2 発光素子、3 蛍光体、4,7 リードフレーム、5 封止樹脂、6 ボンディングワイヤ、8 枠体 DESCRIPTION OF SYMBOLS 1 Light-emitting device, 2 Light-emitting element, 3 Phosphor, 4,7 Lead frame, 5 Sealing resin, 6 Bonding wire, 8 Frame
Claims (13)
前記配合工程後の原料を焼成してβサイアロンを得る焼成工程と、
を有し、
前記配合工程では、
一般式:Si6−zAlzOzN8−z(0.3≦z≦1.0)となるように、窒化ケイ素、窒化アルミニウム及び酸化物を配合する一次配合工程と、
前記一次配合工程後の原料に、βサイアロン粉末、並びに酸化ユーロピウム及びユーロピウム塩のいずれか一方又は両方を配合する二次配合工程を行い、
前記一次配合工程で配合される酸化物が、酸化アルミニウム及び酸化ケイ素のいずれか一方又は両方であり、
一般式:Si6−zAlzOzN8−z(0.3≦z≦1.0)で表されるβサイアロンにEu2+が固溶し、波長455nmの光で励起した場合の蛍光スペクトルのピーク波長が545nmを超え555nm以下であるβサイアロンを得るβサイアロンの製造方法。A blending step of blending and kneading the raw materials, and
A firing step of firing the raw material after the blending step to obtain β sialon;
Have
In the blending step,
A primary blending step of blending silicon nitride, aluminum nitride, and oxide so as to have a general formula: Si 6-z Al z OzN 8-z (0.3 ≦ z ≦ 1.0);
In the raw material after the primary blending step, perform a secondary blending step of blending β sialon powder, and any one or both of europium oxide and europium salt,
The oxide blended in the primary blending step is one or both of aluminum oxide and silicon oxide,
Fluorescence when Eu 2+ is solid-solved in β sialon represented by the general formula: Si 6-z Al z O z N 8-z (0.3 ≦ z ≦ 1.0) and excited by light having a wavelength of 455 nm. A method for producing β sialon, which obtains β sialon having a spectral peak wavelength of more than 545 nm and not more than 555 nm.
βサイアロンを酸溶液に浸漬する浸漬工程と、前記浸漬工程後のβサイアロンの表面に残留する酸溶液を洗浄する洗浄工程とを有する酸処理工程を行う
請求項7に記載のβサイアロンの製造方法。After the firing step, the particle size adjustment step or the heat treatment step,
The method for producing β sialon according to claim 7, wherein an acid treatment step including an immersion step of immersing β sialon in an acid solution and a cleaning step of cleaning an acid solution remaining on the surface of β sialon after the immersion step is performed. .
一般式:Si6−zAlzOzN8−z(0.3≦z≦1.0)で表されるβサイアロンにEu2+が固溶しており、波長455nmの光で励起した場合の蛍光スペクトルのピーク波長が545nmを超え555nm以下であるβサイアロン。A β sialon produced by the method for producing β sialon according to any one of claims 1 to 8,
When Eu 2+ is dissolved in β sialon represented by the general formula: Si 6−z Al z O z N 8−z (0.3 ≦ z ≦ 1.0) and excited by light having a wavelength of 455 nm Β sialon having a peak wavelength in the fluorescence spectrum of 545 nm to 555 nm.
前記蛍光体の一部又は全部が請求項9〜11のいずれか一項に記載のβサイアロンである発光装置。A light emitting element, and a phosphor mounted on a light emitting surface of the light emitting element,
The light emitting device according to claim 9, wherein a part or all of the phosphor is β sialon.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012182973 | 2012-08-22 | ||
JP2012182973 | 2012-08-22 | ||
PCT/JP2013/072172 WO2014030637A1 (en) | 2012-08-22 | 2013-08-20 | METHOD FOR PRODUCING β-SIALON, β-SIALON, AND LIGHT-EMITTING DEVICE |
Publications (1)
Publication Number | Publication Date |
---|---|
JPWO2014030637A1 true JPWO2014030637A1 (en) | 2016-07-28 |
Family
ID=50149945
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014531633A Pending JPWO2014030637A1 (en) | 2012-08-22 | 2013-08-20 | β-sialon manufacturing method, β-sialon and light-emitting device |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPWO2014030637A1 (en) |
TW (1) | TW201412943A (en) |
WO (1) | WO2014030637A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102367209B1 (en) * | 2014-03-06 | 2022-02-23 | 카나가와 인스티튜트 오브 인더스트리얼 사이언스 앤 테크놀로지 | Transparent fluorescent sialon ceramic and method for producing same |
JP6020756B1 (en) * | 2015-05-29 | 2016-11-02 | 日亜化学工業株式会社 | Method for producing β-sialon phosphor |
JP6222288B2 (en) | 2015-08-07 | 2017-11-01 | 日亜化学工業株式会社 | Method for producing β-sialon phosphor |
EP3343248B1 (en) | 2015-08-28 | 2020-02-26 | National University Corporation Gunma University | Charged particle radiation measuring method and charged particle radiation measuring device |
JP6770353B2 (en) * | 2016-07-01 | 2020-10-14 | デンカ株式会社 | β-type sialone phosphor, and light emitting member and light emitting device using the same |
JP6997548B2 (en) * | 2017-06-30 | 2022-01-17 | デンカ株式会社 | Method for producing active β-type sialone phosphor with Eu |
JP6730370B2 (en) * | 2018-05-16 | 2020-07-29 | デンカ株式会社 | Method for producing β-sialon phosphor |
WO2020105456A1 (en) | 2018-11-19 | 2020-05-28 | デンカ株式会社 | β-TYPE SIALON PHOSPHOR AND LIGHT EMITTING DEVICE |
CN109880621B (en) * | 2019-04-01 | 2021-07-30 | 旭宇光电(深圳)股份有限公司 | Fluorescent material, method for producing same, light-emitting film, light-emitting sheet, light-emitting device, and image display device |
US20220298415A1 (en) * | 2019-08-20 | 2022-09-22 | Denka Company Limited | Beta-sialon phosphor and light emitting device |
KR20220049532A (en) * | 2019-08-20 | 2022-04-21 | 덴카 주식회사 | β-Sialon Phosphor Particles and Light-Emitting Device |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007302757A (en) * | 2006-05-10 | 2007-11-22 | Denki Kagaku Kogyo Kk | alpha-TYPE SIALON PHOSPHOR, METHOD FOR PRODUCING THE SAME AND LIGHTING EQUIPMENT |
JP2008255200A (en) * | 2007-04-03 | 2008-10-23 | National Institute Of Advanced Industrial & Technology | Method for producing multicomponent oxynitride fluorescent substance, and product therefrom |
JP2009096882A (en) * | 2007-10-17 | 2009-05-07 | Denki Kagaku Kogyo Kk | Phosphor and method for producing the same |
WO2011058919A1 (en) * | 2009-11-10 | 2011-05-19 | 電気化学工業株式会社 | β-SIALON, METHOD FOR PRODUCING SAME AND LIGHT-EMITTING DEVICE USING SAME |
-
2013
- 2013-08-20 JP JP2014531633A patent/JPWO2014030637A1/en active Pending
- 2013-08-20 WO PCT/JP2013/072172 patent/WO2014030637A1/en active Application Filing
- 2013-08-22 TW TW102129940A patent/TW201412943A/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007302757A (en) * | 2006-05-10 | 2007-11-22 | Denki Kagaku Kogyo Kk | alpha-TYPE SIALON PHOSPHOR, METHOD FOR PRODUCING THE SAME AND LIGHTING EQUIPMENT |
JP2008255200A (en) * | 2007-04-03 | 2008-10-23 | National Institute Of Advanced Industrial & Technology | Method for producing multicomponent oxynitride fluorescent substance, and product therefrom |
JP2009096882A (en) * | 2007-10-17 | 2009-05-07 | Denki Kagaku Kogyo Kk | Phosphor and method for producing the same |
WO2011058919A1 (en) * | 2009-11-10 | 2011-05-19 | 電気化学工業株式会社 | β-SIALON, METHOD FOR PRODUCING SAME AND LIGHT-EMITTING DEVICE USING SAME |
Also Published As
Publication number | Publication date |
---|---|
TW201412943A (en) | 2014-04-01 |
WO2014030637A1 (en) | 2014-02-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2014030637A1 (en) | METHOD FOR PRODUCING β-SIALON, β-SIALON, AND LIGHT-EMITTING DEVICE | |
EP2500399B1 (en) | Method for producing beta-sialon and light-emitting device using the same | |
JP6572373B1 (en) | Method for producing β-sialon phosphor | |
JP4740379B1 (en) | β-type sialon phosphor, its use and method for producing β-type sialon phosphor | |
EP2365047B1 (en) | ß-SIALON PHOSPHOR, USE THEREOF AND METHOD FOR PRODUCING SAME | |
WO2014077240A1 (en) | Phosphor, light-emitting element and lighting device | |
JP2009096882A (en) | Phosphor and method for producing the same | |
WO2012011444A1 (en) | β-TYPE SIALON, PROCESS FOR PRODUCTION OF β-TYPE SIALON, AND LIGHT-EMITTING DEVICE | |
WO2012046288A1 (en) | β-SIALON PHOSPHOR, METHOD FOR PRODUCING SAME, AND USE OF SAME | |
JP2010241995A (en) | beta-TYPE SIALON PHOSPHOR, METHOD FOR PRODUCING THE SAME AND APPLICATION OF THE SAME | |
JP2018002870A (en) | β TYPE SIALON PHOSPHOR AND METHOD FOR PRODUCING THE SAME AND LIGHT EMITTING DEVICE USING THE SAME | |
WO2012033157A1 (en) | Β-sialon and light-emitting device | |
JP2010275437A (en) | Alpha type sialon phosphor, and light-emitting element using the same | |
TWI485230B (en) | Method for manufacturing β-sialon fluorescent body | |
JP7217709B2 (en) | Red phosphor and light-emitting device | |
WO2017155111A1 (en) | Phosphor, light-emitting element, and light-emitting device | |
TWI450947B (en) | Method for producing β-sialon | |
WO2020105456A1 (en) | β-TYPE SIALON PHOSPHOR AND LIGHT EMITTING DEVICE | |
WO2012032824A1 (en) | Β-sialon, light-emitting device and β-sialon production method | |
TWI833035B (en) | β-SIALON PHOSPHOR AND LIGHT-EMITTING DEVICE | |
JP2018150487A (en) | Production method of phosphor, phosphor, light-emitting element and light-emitting device | |
JP7507018B2 (en) | Method for manufacturing β-type sialon phosphor, method for manufacturing wavelength conversion member, and method for manufacturing light emitting device | |
JP2024094873A (en) | Manufacturing method of phosphor powder | |
JP2023166646A (en) | europium-activated β-type sialon phosphor | |
JP2022064478A (en) | METHOD FOR PRODUCING β SIALON PHOSPHOR |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20151201 |