EP1390989A1 - Substance fluorescente a haute efficacite - Google Patents

Substance fluorescente a haute efficacite

Info

Publication number
EP1390989A1
EP1390989A1 EP01947188A EP01947188A EP1390989A1 EP 1390989 A1 EP1390989 A1 EP 1390989A1 EP 01947188 A EP01947188 A EP 01947188A EP 01947188 A EP01947188 A EP 01947188A EP 1390989 A1 EP1390989 A1 EP 1390989A1
Authority
EP
European Patent Office
Prior art keywords
phosphor
phosphors
thiometalate
cation
mixture
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.)
Withdrawn
Application number
EP01947188A
Other languages
German (de)
English (en)
Inventor
Manfred Kobusch
Martin Judenhofer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ams Osram International GmbH
Original Assignee
Osram Opto Semiconductors GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Osram Opto Semiconductors GmbH filed Critical Osram Opto Semiconductors GmbH
Publication of EP1390989A1 publication Critical patent/EP1390989A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • 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
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7784—Chalcogenides
    • C09K11/7786—Chalcogenides with alkaline earth metals
    • 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
    • C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
    • C09K11/7716—Chalcogenides
    • C09K11/7718—Chalcogenides with alkaline earth metals
    • 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
    • C09K11/7729—Chalcogenides
    • C09K11/7731—Chalcogenides with alkaline earth metals

Definitions

  • the invention is based on a phosphor from the class of thiometalates according to the preamble of claim 1, the thiometalate being derived from the general formula AB 2 S 4 : D 2+ , where A at least one divalent cation from the group Ba individually or in Is a combination with Mg and / or Ca, and where B is at least one trivalent cation from the group Al, Ga, Y and where the dopant / activator D is europium and / or cerium. The proportion of divalent cation A is reduced by the proportion t of activator D added. These are in particular thiogallates which have light emission in the green spectral range.
  • the concept according to the invention can also be represented in a different notation if the thiometalates of the original empirical formula AB 2 S 4 are written as a product of the components AS and B 2 S 3 in the form AS » B 2 S 3 .
  • the thiometalate is shown as (AS) « w (B 2 S 3 ).
  • Ba can be used as cation A individually or in combination with Mg, Ca, in particular in combination of all three cations.
  • As an activator as a partial replacement for A, europium and / or cerium can be used. Ga, but also Al or Y, is preferably used as the cation B. The gallium can in particular be partially (up to 10 mol%) replaced by aluminum.
  • Another preferred embodiment is phosphors with the composition (AS) » w (B 2 S 3 )
  • a manufacturing process uses the following steps:
  • pyrolysis of the ground nitrate at 500-700 ° C, preferably at 600 ° C, in an Ar or N 2 atmosphere to produce a finely dispersed metal oxide mixture with the desired composition.
  • Second reaction at 800-1000 ° C, preferably 900-950 ° C, in a flowing H 2 S or CS 2 atmosphere or combinations thereof for 1-6 hours, preferably for 2 hours.
  • the flow rate is preferably 50-500 ml / min, preferably 120 ml / min, and the gas atmosphere preferably consists of H 2 S or CS 2 and Ar or N 2 as carrier gas with 10-50% H 2 S or CS 2 or mixtures thereof, preferably 30% H 2 S or CS 2 or mixtures thereof.
  • the mixture is gradually heated up to the reaction temperature, preferably at the rate 0.5-20 K / min, preferably 10 K / min.
  • steps e) and g) a gradual cooling is carried out after the reaction, preferably at the rate 0.5-20 K / min, preferably 10 K / min.
  • the phosphors according to the invention are particularly suitable for use in UV or blue-emitting LEDs for color conversion.
  • they can be used individually or in combination with other phosphors, in particular in combination with other phosphors according to the invention.
  • Another possible application is plasma displays.
  • the phosphors can be used individually or in combination with other phosphors, in particular in combination with other phosphors according to the invention, in order to convert the short-wave plasma discharge radiation into visible light.
  • Figure 1 shows the emission spectrum of the phosphor
  • FIG. 2 shows the reflection spectrum of the phosphor from FIG. 1.
  • the dried nitrate mixture is ground in a mortar mill for 20 minutes and then pyrolyzed at 600 ° C. for 4 hours under nitrogen using the following reaction equation:
  • the oxide mixture generated is filled into a quartz boat and heated to 900 ° C in a tube furnace under protective gas (argon). After reaching the reaction temperature, hydrogen sulfide is introduced with 120 ml of 30% H 2 S / min in a stream of nitrogen and the oxide mixture is converted into the thiogallate within four hours using the following reaction equation: 1 mol [0.20BaO »0.15CaO» 0 ) 60MgO » 0.025Eu 2 ⁇ 3 » 1, 10Ga 2 ⁇ 3] + 4.325mol H 2 S -> (Ba 0.2 oCa 0, i 5 go , 60 Euo , o 5 ) S »1, Ga 2 S 3 + 4.325mol H 2 O + 0.025mol S
  • a temperature of 870 to 930 ° C has proven to be the optimal conversion temperature for a highly efficient phosphor.
  • reaction product is ground in a mortar mill for 10 minutes and reacted again in a 20% hydrogen sulfide stream at 900 ° C. for three hours.
  • the quantum efficiency increases significantly if w is chosen to be both lower and higher than 1, the emission wavelength remaining unchanged at a maximum emission intensity of 532 nm - 538 nm or 508 nm - 513 nm.
  • the installation of the activator Eu 2+ can be favored in terms of more complete and trouble-free installation in the crystal lattice of the thiometalates. It can also be important to achieve a more favorable sulfur stoichiometry in line with the balance sheet, which can be better adapted to the local atomic cation composition according to the model of coreshell formation. Overall, the changed phosphor composition leads to an increased perfection of the phosphor product and / or to a reduction in QE-reducing non-radiative recombination centers.
  • Figure 1 shows the emission spectrum of the phosphor
  • the emission band lies in the green spectral range between about 460 nm and 620 nm.
  • the emission maximum is 538 nm, the mean wavelength is 544 nm.
  • This phosphor can be excited well by short-wave radiation between 300 and 450 nm. It is particularly advantageous for use with LEDs for color conversion, as a so-called LED converter.
  • the emission radiation of a UV-emitting LED is converted into visible light (here green or blue-green) or white light (mixture of red, green and blue emitting phosphors) using one or more phosphors.
  • a second variant, when using a blue LED is the use of one phosphor or two phosphors (for example yellow- or green- and red-emitting phosphors), so that white light also results here.
  • Technical details on this can be found, for example, in US Pat. No. 5,998,925.
  • These phosphors can be applied as LED converters, for example, in full encapsulation using epoxy resins.
  • the phosphor powder is dispersed in an epoxy resin, placed as a drop on the chip and cured. It is important here that the thiometalates have a similarly non-polar surface as the likewise non-polar resin, which leads to good wetting. Further advantages lie in the fact that mixtures with other phosphors such as YAG: Ce or YAG: Ce -based phosphors work well because the specific weight of the two phosphor classes is similar, so that no segregation occurs due to sedimentation effects with a comparable particle size.
  • the specific weight of typical thiometalates is approximately 4.4 to 4.5 g / cm 3
  • that of YAG: Ce-based phosphors is typically 4.6 to 4.7 g / cm 3 .
  • Sedimentation in the resin can be minimized by average particle sizes ⁇ 5 ⁇ m, especially around 2 + 1 ⁇ m.
  • the particle size is adjusted by grinding, for example in ball mills.

Abstract

L'invention concerne une substance fluorescente de la classe des thiométallates, de préférence des thiogallates. Le thiométallate est préparé selon la formule (AS)<.>w(B2S3), dans laquelle A représente au moins un cation bivalent du groupe Ba, seul ou en combinaison avec Mg ou Ca, et B représente au moins un cation trivalent du groupe Al, Ga, Y. Le facteur w peut être compris dans la plage 0,8 </= w </= 0,98 comme dans la plage 1,02 </= w < 1,2.
EP01947188A 2001-05-29 2001-06-07 Substance fluorescente a haute efficacite Withdrawn EP1390989A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE20108873U DE20108873U1 (de) 2001-05-29 2001-05-29 Hocheffizienter Leuchtstoff
DE20108873U 2001-05-29
PCT/DE2001/002131 WO2002097901A1 (fr) 2001-05-29 2001-06-07 Substance fluorescente a haute efficacite

Publications (1)

Publication Number Publication Date
EP1390989A1 true EP1390989A1 (fr) 2004-02-25

Family

ID=7957390

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01947188A Withdrawn EP1390989A1 (fr) 2001-05-29 2001-06-07 Substance fluorescente a haute efficacite

Country Status (8)

Country Link
US (1) US20040135123A1 (fr)
EP (1) EP1390989A1 (fr)
JP (1) JP2004527638A (fr)
KR (1) KR20030020413A (fr)
CN (1) CN1444776A (fr)
CA (1) CA2448529A1 (fr)
DE (1) DE20108873U1 (fr)
WO (1) WO2002097901A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2826016B1 (fr) * 2001-06-13 2004-07-23 Rhodia Elect & Catalysis Compose a base d'un alcalino-terreux, de soufre et d'aluminium, de gallium ou d'indium, son procede de preparation et son utilisation comme luminophore
US20050211991A1 (en) * 2004-03-26 2005-09-29 Kyocera Corporation Light-emitting apparatus and illuminating apparatus
KR100724591B1 (ko) 2005-09-30 2007-06-04 서울반도체 주식회사 발광 소자 및 이를 포함한 ｌｅｄ 백라이트
US8323529B2 (en) 2006-03-16 2012-12-04 Seoul Semiconductor Co., Ltd. Fluorescent material and light emitting diode using the same
DE102007057812A1 (de) * 2007-11-30 2009-06-25 Schott Ag Lichtemittierende Vorrichtung und Verfahren zu deren Herstellung sowie Lichtkonverter und dessen Verwendung
JP5171326B2 (ja) * 2008-03-13 2013-03-27 住友金属鉱山株式会社 無機ｅｌ用蛍光体の製造方法
JP5164618B2 (ja) * 2008-03-13 2013-03-21 住友金属鉱山株式会社 無機ｅｌ用蛍光体の製造方法
US8456082B2 (en) 2008-12-01 2013-06-04 Ifire Ip Corporation Surface-emission light source with uniform illumination
JP2014167974A (ja) * 2013-02-28 2014-09-11 Toyoda Gosei Co Ltd 蛍光体の選別方法及び発光装置
JP6350123B2 (ja) * 2014-08-28 2018-07-04 堺化学工業株式会社 硫化物蛍光体の製造方法
JP7112355B2 (ja) * 2019-02-28 2022-08-03 デクセリアルズ株式会社 緑色発光蛍光体及びその製造方法、並びに蛍光体シート及び発光装置

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US3639254A (en) * 1969-07-01 1972-02-01 Gte Laboratories Inc Alkaline earth thiogallate phosphors
DE10028266A1 (de) * 2000-06-09 2001-12-13 Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh Hocheffizienter Leuchtstoff
JPH0272592A (ja) * 1988-09-06 1990-03-12 Tosoh Corp 薄膜ｅｌ素子
CA2030350C (fr) * 1989-11-27 1994-08-02 Tetsuo Nakai Comprime solide obtenu par frettage et servant a la fabrication d'outils
JP2858397B2 (ja) * 1994-09-07 1999-02-17 株式会社デンソー エレクトロルミネッセンス素子及びその製造方法
JPH08134440A (ja) * 1994-11-14 1996-05-28 Mitsui Mining & Smelting Co Ltd 薄膜エレクトロルミネッセンス素子
US5834053A (en) * 1994-11-30 1998-11-10 The Regents Of The University Of California Blue light emitting thiogallate phosphor
JP3735949B2 (ja) * 1996-06-28 2006-01-18 株式会社デンソー 青色発光材料、それを用いたｅｌ素子、及びその製造方法
FR2755122B1 (fr) * 1996-10-31 1998-11-27 Rhodia Chimie Sa Compose a base d'un alcalino-terreux, de soufre et d'aluminium, de gallium ou d'indium, son procede de preparation et son utilisation comme luminophore
FR2826016B1 (fr) * 2001-06-13 2004-07-23 Rhodia Elect & Catalysis Compose a base d'un alcalino-terreux, de soufre et d'aluminium, de gallium ou d'indium, son procede de preparation et son utilisation comme luminophore
US7125501B2 (en) * 2003-04-21 2006-10-24 Sarnoff Corporation High efficiency alkaline earth metal thiogallate-based phosphors

Non-Patent Citations (1)

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Title
See references of WO02097901A1 *

Also Published As

Publication number Publication date
CN1444776A (zh) 2003-09-24
JP2004527638A (ja) 2004-09-09
WO2002097901A1 (fr) 2002-12-05
US20040135123A1 (en) 2004-07-15
DE20108873U1 (de) 2001-12-06
KR20030020413A (ko) 2003-03-08
CA2448529A1 (fr) 2002-12-05

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