JP2020105066A - 赤色発光蛍光体、関連方法及び装置 - Google Patents
赤色発光蛍光体、関連方法及び装置 Download PDFInfo
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- JP2020105066A JP2020105066A JP2019213685A JP2019213685A JP2020105066A JP 2020105066 A JP2020105066 A JP 2020105066A JP 2019213685 A JP2019213685 A JP 2019213685A JP 2019213685 A JP2019213685 A JP 2019213685A JP 2020105066 A JP2020105066 A JP 2020105066A
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Classifications
-
- 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
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/617—Silicates
-
- 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
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or alkaline earth metals
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
- F21K9/00—Light sources using semiconductor devices as light-generating elements, e.g. using light-emitting diodes [LED] or lasers
- F21K9/60—Optical arrangements integrated in the light source, e.g. for improving the colour rendering index or the light extraction
- F21K9/64—Optical arrangements integrated in the light source, e.g. for improving the colour rendering index or the light extraction using wavelength conversion means distinct or spaced from the light-generating element, e.g. a remote phosphor layer
-
- 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
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- 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
- 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
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Abstract
Description
効率は、青色(440〜460nm)励起下で85%を超え得る。
式中、
Aは、Li、Na、K、Rb、Cs又はそれらの組合せであり、
Mは、Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd又はそれらの組合せであり
xは、[MFy]イオンの電荷の絶対値であり、
yは、5、6又は7である。
式中、0<z≦0.2である。
本明細書において、「実質的に」とは、粒子の表面の少なくとも約80%、又は特に少なくとも約70%が第1のシェルで覆われていることを意味する。一部の実施形態では、内部コアは、Mn4+イオンを実質的に含まない。一部の実施形態では、Mn4+イオンは、第1のシェルからコアに拡散することがある。一部の実施形態では、0<z≦0.1、さらに具体的には、0<z≦0.06である。
式中、0≦w≦zである。
(A)A2[MF5](式中、AはLi、Na、K、Rb、Cs及びその組合せから選択され、MはAl、Ga、In及びその組合せから選択される)、
(B)A3[MF6](式中、AはLi、Na、K、Rb、Cs及びその組合せから選択され、MはAl、Ga、In及びその組合せから選択される)、
(C)Zn2[MF7](式中、MはAl、Ga、In及びその組合せから選択される)、(D)A[In2F7](式中、AはLi、Na、K、Rb、Cs及びその組合せから選択される)、
(E)A2[MF6](式中、AはLi、Na、K、Rb、Cs及びその組合せから選択され、MはSi、Ge、Sn、Ti、Zr及びその組合せから選択される)、
(F)E[MF6](式中、EはMg、Ca、Sr、Ba、Zn及びその組合せから選択され、MはSi、Ge、Sn、Ti、Zr及びその組合せから選択される)、
(G)Ba0.65Zr0.35F2.70、及び
(H)A3[ZrF7](式中、AはLi、Na、K、Rb、Cs及びその組合せから選択される)。
例えば、下の表1に示されるように、粒径スパンは実施例3及び4について≦1であり、実施例5について≦0.9である。
((Sr1-z(Ca,Ba,Mg,Zn)z)1-(x+w)(Li,Na,K,Rb)wCex)3(Al1-ySiy)O4+y+3(x-w)F1-y-3(x-w)(0<x≦0.10,0≦y≦0.5,0≦z≦0.5,0≦w≦x);(Ca,Ce)3Sc2Si3O12(CaSiG);(Sr,Ca,Ba)3Al1-xSixO4+xF1-x:Ce3+(SASOF));(Ba,Sr,Ca)5(PO4)3(Cl,F,Br,OH):Eu2+,Mn2+;(Ba,Sr,Ca)BPO5:Eu2+,Mn2+;(Sr,Ca)10(PO4)6*νB2O3:Eu2+(0<ν≦1);Sr2Si3O8*2SrCl2:Eu2+;(Ca,Sr,Ba)3MgSi2O8:Eu2+,Mn2+;BaAl8O13:Eu2+;2SrO*0.84P2O5*0.16B2O3:Eu2+;(Ba,Sr,Ca)MgAl10O17:Eu2+,Mn2+;(Ba,Sr,Ca)Al2O4:Eu2+;(Y,Gd,Lu,Sc,La)BO3:Ce3+,Tb3+;ZnS:Cu+,Cl-;ZnS:Cu+,Al3+;ZnS:Ag+,Cl-;ZnS:Ag+,Al3+;(Ba,Sr,Ca)2Si1-ξO4-2ξ:Eu2+(0.2≦ξ≦0.2);(Ba,Sr,Ca)2(Mg,Zn)Si2O7:Eu2+;(Sr,Ca,Ba)(Al,Ga,In)2S4:Eu2+;(Y,Gd,Tb,La,Sm,Pr,Lu)3(Al,Ga)5-αO12-3/2α:Ce3+(0≦α≦0.5);(Ca,Sr)8(Mg,Zn)(SiO4)4Cl2:Eu2+,Mn2+;Na2Gd2B2O7:Ce3+,Tb3+;(Sr,Ca,Ba,Mg,Zn)2P2O7:Eu2+,Mn2+;(Gd,Y,Lu,La)2O3:Eu3+,Bi3+;(Gd,Y,Lu,La)2O2S:Eu3+,Bi3+;(Gd,Y,Lu,La)VO4:Eu3+,Bi3+;(Ca,Sr)S:Eu2+,Ce3+;SrY2S4:Eu2+;CaLa2S4:Ce3+;(Ba,Sr,Ca)MgP2O7:Eu2+,Mn2+;(Y,Lu)2WO6:Eu3+,Mo6+;(Ba,Sr,Ca)βSiγNμ:Eu2+(2β+4γ=3μ);(Ba,Sr,Ca)2Si5-xAlxN8-xOx:Eu2+(0≦x≦2);Ca3(SiO4)Cl2:Eu2+;(Lu,Sc,Y,Tb)2-u-vCevCa1+uLiwMg2-wPw(Si,Ge)3-wO12-u/2(−0.5≦u≦1,0<v≦0.1,かつ0≦w≦0.2);(Y,Lu,Gd)2-φCaφSi4N6+φC1-φ:Ce3+,(0≦φ≦0.5);Eu2+及び/又はCe3+でドープした(Lu,Ca,Li,Mg,Y),α−SiAlON;(Ca,Sr,Ba)SiO2N2:Eu2+,Ce3+;β−SiAlON:Eu2+,3.5MgO*0.5MgF2*GeO2:Mn4+;(Sr,Ca,Ba)AlSiN3:Eu2+;(Sr,Ca,Ba)3SiO5:Eu2+;Ca1-c-fCecEufAl1+cSi1-cN3(0≦c≦0.2,0≦f≦0.2);Ca1-h-rCehEurAl1-h(Mg,Zn)hSiN3(0≦h≦0.2,0≦r≦0.2);Ca1-2s-tCes(Li,Na)sEutAlSiN3(0≦s≦0.2,0≦f≦0.2,s+t>0);及びCa1-σ-χ-φCeσ(Li,Na)χEuφAl1+σ-χSi1-σ+χN3(0≦σ≦0.2,0≦χ≦0.4,0≦φ≦0.2)。
)バックライトを目的とするLEDに使用することができる。子の用途では、LEDカラーポイントは、LCD/カラーフィルターの組合せに通した後の望ましい白色、赤色、緑色、及び青色に基づいて適切に調整される。本明細書に記載されるブレンドのための可能性のある蛍光体のリストは、完全に網羅されているわけではなく、これらのMn4+ドープ蛍光体は、望ましいスペクトルパワー分布を達成するために異なる発光をもつ様々な蛍光体とブレンドされることができる。
実施例1
K2SiF6(100g)(Aldrich)を、1時間ボールミル粉砕し、それに続いて44μmの篩に通して篩分けることによって粗い粒子を除去した。結果として得られる粒子のD50粒径は、19μmであった。
KF(13g)を80ミリリットル(ml)の48%HFに添加した。H2SiF6(35%)(30ml)を、30mlの48%HFに添加した。両方の溶液を個別に撹拌し、次にH2SiF6/HF溶液をKF/HF溶液に添加した。結果として得られるK2SiF6粒子のD50粒径は15μmであった。
実施例3
実施例1で調製したK2SiF6(16g)粒子を、130ミリリットル(ml)の48%HFを含有するビーカーに添加した。懸濁液を10分間撹拌した。KHF2(8g)を、20mlの48%HFを含有するビーカーに撹拌しながら添加した。K2MnF6(2g)を、30mLの48%HFを含有するビーカーに添加し、溶液を5分間撹拌した。撹拌したK2SiF6懸濁液に、K2MnF6溶液を4ml/分で滴下した。K2MnF6溶液を3分間滴下した後に、KHF2溶液をこの同じビーカーに3ml/分の速度で添加した。KHF2の添加が完了すると、懸濁液をさらに10分間撹拌した。撹拌を停止した後、上清をデカントし、結果として得られる蛍光体材料を真空濾過し、酢酸で1回とアセトンで2回すすいだ後、一晩真空乾燥させた。
実施例1で調製したK2SiF6(8g)粒子を、130mlの48%HFを含有するビーカーに添加した。懸濁液を10分間撹拌した。KF(4.5g)を、20mlの48%HFを含有するビーカーに撹拌しながら添加した。本方法は非常に発熱性であるので、KFの溶液を数分間放冷した。K2MnF6(1.5g)を、30mlの48%HFを含有するビーカーに添加し、溶液を5分間撹拌した。K2SiF6粒子の撹拌懸濁液に、K2MnF6溶液を4ml/分で滴下した。K2MnF6溶液を3分間滴下した後に、KF溶液をこの同じビーカーに3ml/分の速度で添加した。KFの添加が完了すると、懸濁液をさらに5分間撹拌した。撹拌を停止した後、上清をデカントし、結果として得られる蛍光体材料を真空濾過し、酢酸で1回とアセトンで2回すすいだ後、一晩真空乾燥させた。
実施例1で調製したK2SiF6(12g)粒子を、130mlの48%HFを含有するビーカーに添加した。懸濁液を10分間撹拌した。KF(8g)を、20mlの48%HFを含有する第2のビーカーに撹拌しながら添加した。本方法は非常に発熱性であるので、KFの溶液を数分間放冷した。K2MnF6(2g)を、30mlの48%HFを含有する第3のビーカーに添加し、溶液を5分間撹拌した。第4のビーカー、4mlの35%H2SiF6に、12mLの48%HFを添加し、撹拌した。K2SiF6粒子の撹拌溶液に、K2MnF6溶液を4ml/分で滴下した。K2MnF6溶液を3分間滴下した後に、KF溶液をこの同じビーカーに3ml/分の速度で添加した。K2MnF6溶液を4分間滴下した後に、H2SiF6溶液を3ml/分の速度で滴下した。H2SiF6の添加が完了すると、懸濁液をさらに5分間撹拌した。撹拌を停止した後、上清をデカントし、結果として得られる蛍光体材料を真空濾過し、酢酸で1回とアセトンで2回すすいだ後、一晩真空乾燥させた。
K2SiF6(8g)粒子を、160mlの48%HFを含有するビーカーに添加した。混合物を30分間撹拌し、次に真空濾過して、溶けていないK2SiF6を除去した。30mlの35%H2SiF6を120mlの48%HFに添加することによって溶液1を調製した。溶液2は、5.47gのKFを12mlのHFに添加することによって調製した。溶液3は、1.5gのK2MnF6を30mlのHFに添加することによって調製した。3つの溶液、溶液1、溶液2及び溶液3を、濾液に滴下した。最初に、溶液3の添加は、溶液1及び溶液2に関して遅れた。Mn4+濃度の低いコアとMn4+に富むシェルを得た。一部の例では、溶液3に対して溶液1及び/又は溶液2の添加期間を延長することによって、Mn4+濃度の低いさらなるシェルが結果として生じた。
Claims (8)
- コア及び第1のシェルを含む粒子集団であって、コアが次の式(II)の化合物を含んでおり、
Ax[MFy] (II)
第1のシェルが次の式(IV)の組成物を含む、粒子集団。
Ax(M1-z、Mnz)Fy] (IV)
式中、
Aは、Li、Na、K、Rb、Cs、NR4又はその組合せであり、
Mは、Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd又はそれらの組合せであり
xは、[MFy]イオンの電荷の絶対値であり、
yは、5、6又は7であり、
0<z≦0.2である。 - 第2のシェルをさらに含み、第2のシェルが、次の式(V)の組成物を含む、請求項1に記載の粒子集団。
Ax[(M1-w、Mnw)Fy] (V)
式中、0≦w≦zである。 - 粒径スパンが1以下の粒度分布を有する、請求項1に記載の粒子集団。
- 粒径スパンが0.9以下の粒度分布を有する、請求項1に記載の粒子集団。
- コアがK2SiF6であり、第1のシェルがK2(Si1-z、Mnz)F6である、請求項1に記載の粒子集団。
- 第2のシェルがK2(Si1-w、Mnw)F6である、請求項2に記載の粒子集団。
- 半導体光源と、光源と放射結合した請求項1に記載の粒子集団とを備える照明装置。
- 半導体光源と、光源と放射結合した請求項1に記載の粒子集団とを備えるブラックライト装置。
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CA2955799A1 (en) | 2016-01-28 |
AU2015294337A1 (en) | 2017-02-09 |
WO2016014392A1 (en) | 2016-01-28 |
JP2017524775A (ja) | 2017-08-31 |
KR102608651B1 (ko) | 2023-11-30 |
JP6928067B2 (ja) | 2021-09-01 |
TWI632223B (zh) | 2018-08-11 |
BR112017001130A2 (pt) | 2018-01-30 |
MX2017001015A (es) | 2017-05-09 |
KR20170033379A (ko) | 2017-03-24 |
US20160024378A1 (en) | 2016-01-28 |
TW201621029A (zh) | 2016-06-16 |
CN106687562A (zh) | 2017-05-17 |
PH12017500251A1 (en) | 2017-07-03 |
AU2015294337B2 (en) | 2018-10-18 |
CN106687562B (zh) | 2020-07-28 |
US9512357B2 (en) | 2016-12-06 |
MY179565A (en) | 2020-11-10 |
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