EP2488602A1 - Procédé d'enrobage d'un luminophore de silicate - Google Patents

Procédé d'enrobage d'un luminophore de silicate

Info

Publication number
EP2488602A1
EP2488602A1 EP10767988A EP10767988A EP2488602A1 EP 2488602 A1 EP2488602 A1 EP 2488602A1 EP 10767988 A EP10767988 A EP 10767988A EP 10767988 A EP10767988 A EP 10767988A EP 2488602 A1 EP2488602 A1 EP 2488602A1
Authority
EP
European Patent Office
Prior art keywords
coating
coating material
phosphor
solution
heat treatment
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Withdrawn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
EP10767988A
Other languages
German (de)
English (en)
Inventor
Alexander Baumgartner
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.)
Osram GmbH
Original Assignee
Osram 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 GmbH filed Critical Osram GmbH
Publication of EP2488602A1 publication Critical patent/EP2488602A1/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Withdrawn legal-status Critical Current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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • C09K11/77342—Silicates

Definitions

  • the invention is based on a method for coating a silicate phosphor according to the preamble of claim 1.
  • the method is particularly applicable for orthosilicates or nitrido-orthosilicates.
  • EP 1 199 757 discloses a coating for phosphors, in particular for orthosilicates.
  • SiO 2 is used.
  • An object of the present invention is to provide a method by which the stability of orthosilicate phosphors can be improved in a simple manner.
  • Luko LEDs are needed, the realization of which require suitable Kon ⁇ version materials both with emission in the red and in the green spectral range. Luko means here luminescence conversion. Together with the emission Wavelength of the semiconductor chip is a possible comprehensive ⁇ sender color space can be displayed.
  • a suitable light ⁇ class of materials are green-emitting (nitrido) orthosilicates AE 2 - x - a RE x Eu a Si0 4 - x N x (AE: Sr, Ca, Ba, Mg, rare earth metals (RE): in particular, Y, La ), since they have an appropriate emission wavelength and a good conversion efficiency ⁇ .
  • a disadvantage of the (nitrido) orthosilicate phosphors is the insufficient stability to external chemical influences such as acidic environment or (air) moisture. This leads to a de ⁇ gradation of the phosphor in the LED during the application and thereby adversely affects the Konversi ⁇ onseffizienz in the green spectral range and thus on the color of the LED.
  • the insufficient chemical stability of (nitrido) orthosilicate phosphors can be significantly improved by means of a surface modification and thus the disadvantageous effects of an intrinsic stabilization to be bypassed.
  • an inorganic hydroxide such as Al (OH) 3, Y (OH) 3 or Mg (OH) 2
  • an inorganic oxide layer such as Al 2 O 3, Y 2 O 3, MgO or be ⁇ Sonders preferably S1O 2, or mixed forms of both substance classes on the surface of the phosphor particle, a complete envelopment of the phosphor core is achieved. It is a barrier effect generated that ei ⁇ nen chemical attack on governing the conversion efficiency particle core significantly prevented, thereby resulting in a significantly reduced degradation of the orthosilicate phosphor.
  • this diffusion barrier is effected by deposition from a solution of the coating precursors, preferably by hydrolysis and subsequent condensation of metal alkoxides or metal alkyls, preferably tetraethoxysilane (TEOS), as described fundamentally in the literature (eg: W. Stöber, A. Fink, E Bohn, J. Colloid Interface Sei. 1968, 26, 62-69). Ergän ⁇ zend this can be ensured by a low rate of addition of the coating precursors low supersaturation in solution, so that the nucleation reduced in a separate phase and deposition on the surface of the phosphor particles is favored.
  • TEOS tetraethoxysilane
  • Figure 1 shows a semiconductor device, as the light source
  • LED for white light
  • FIG. 3 the minimization of the thermal damage of the
  • Figure 4 shows a coated phosphor grain schematically.
  • FIG. 1 The structure of one of the ⁇ -like light source for white light is shown ex ⁇ plicitly in FIG. 1
  • the light source is a semiconductor component (chip 1) of the type InGaN having a peak emission wavelength of 460 nm with a first and second electrical connection 2, 3 which is embedded in an opaque base housing 8 in the region of a recess 9.
  • One of the terminals 3 is connected to the chip 1 via a bonding wire 14.
  • the recess has a wall 17 which serves as a reflector for the blue primary radiation of the chip 1.
  • the recess 9 is filled with egg ⁇ ner potting compound 5, which contains as main components a silicone resin (70 to 95 wt .-%) and phosphor pigments 6 (less than 30 wt .-%). Further small shares attributable inter alia to Aerosil.
  • the luminescent pigments are a mixture of several pigments, in particular orthosilicates or nitrido-orthosilicates.
  • FIG. 2 shows a section of a surface light 20 is shown as a lighting unit. It consists of a common carrier 21, to which a cuboid outer housing 22 is glued. Its upper side is provided with a common cover 23.
  • the cuboid housing has recesses in which individual semiconductor components 24 are housed. They are UV-emitting light-emitting diodes with a peak emission of 380 nm.
  • the conversion into white light takes place by means Kon ⁇ version layers that sit directly in the casting resin of the single LED similar to that in Figure 1 described or layers 25, which are accessible on all of the UV radiation Surfaces are attached. These include the inside surfaces of the side walls of the housing, the cover and the bottom part.
  • the conversion layers 25 consist of three phosphors which emit in the red, green and blue spectral range using the phosphors according to the invention.
  • the conversion layers can consist of one or more phosphors according to the invention, in particular luminous substances which emit in the, green and red spectral range.
  • Phosphor was suspended 20 g of phosphor in 173 ml of ethanol and 14.7 ml of deionized water. For better dispersion, it was sonicated for 5 minutes. The coating is done by slow addition of 2.2 ml TEOS in 22 ml EtOH in a 30 min interval with stirring at 60 ° C. The addition is made up to a total volume of TEOS ⁇ of 14.8 ml. After cooling the suspension, the coated phosphor is separated from the reaction mixture, washed with water and ethanol and dried for 12 hours at 60 ° C. For complete dehydration and densification of the coating is then annealed for 5 h at 350 ° C in air.
  • the (nitrido) -orthosilicate phosphors represented by a coating with inorganic oxide layers, preferably S1O 2 have a significantly improved stability compared to acidic and humid environments compared to uncoated phosphors.
  • the time to constant conductivity of the solution as an indicator of the finished hydrolysis of the phosphor, can be increased by at least a factor of 20 by the coating. Consequently, the hydraulic resistance to lysis of the ⁇ (nitrido) orthosilicates has been significantly improved by the coating described herein.
  • An advantage of the invention described above is that stabilization, in contrast to intrinsic see stabilization without variation of the composition of the phosphor material is possible.
  • a variation of the composition for intrinsic stabilization always leads to mostly undesired changes in the luminescent properties of the orthosilicate phosphors, especially the critical emission wavelength for use in LUKOLEDs.
  • here-described ⁇ ne stabilization is by applying an oxide layer does not affect the luminescence properties. Rather, it is that the composition of (nitrides do-) optimized orthosilicates in terms of their luminescent properties and then can be stabilized by the here be ⁇ overridden method made possible by the method described the Stabili ⁇ tion.
  • M-Sion of the type M2SiO (4-x) Nx: Eu, again with M Ba, Sr, Ca, Mg al ⁇ lein or in a mixture.
  • M2-xRExSi04-xNx Eu phosphor.
  • the rare earth element RE is preferably Y and / or La.
  • FIG. 4 shows a coated phosphor grain schematically.
  • the grain 11 of (Sr, Ba) 2 SiO 4: Eu is surrounded by a protective layer of SiO 2 about 0.2 ⁇ m thick, which was applied by the above method.
  • a method for producing a coating on a silicate phosphor characterized in that the following method steps are used:
  • a method according to claim 2 characterized in that during the deposition by low Zugabege ⁇ speed of the precursor of the Be Anlagenungsmateri- than or equal to 250 mmol / 1 metal cation per stun ⁇ de, preferably no greater than 150 mmol / 1, a low supersaturation is ensured in solution.
  • Table 1 hydrolysis of raw layer ⁇ th / coated orthosilicate phosphors in more acidic suspension.
  • Table 1 Hydrolysis stability of uncoated / coated orthosilicate phosphors in acidic suspension.
  • Table 2 Degradation of orthosilicate phosphors in LED application.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention concerne un procédé pour réaliser un revêtement pour luminophores de silicate. Le procédé comprend les étapes suivantes : préparation d'une solution d'un précurseur de la matière d'enrobage; dépôt de la matière d'enrobage sur des particules de luminophore introduites dans la solution; traitement thermique en atmosphère oxydante à des températures d'au moins 200 °C.
EP10767988A 2009-10-12 2010-10-06 Procédé d'enrobage d'un luminophore de silicate Withdrawn EP2488602A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009049056A DE102009049056A1 (de) 2009-10-12 2009-10-12 Verfahren zur Beschichtung eines Silikat-Leuchtstoffs
PCT/EP2010/064913 WO2011045216A1 (fr) 2009-10-12 2010-10-06 Procédé d'enrobage d'un luminophore de silicate

Publications (1)

Publication Number Publication Date
EP2488602A1 true EP2488602A1 (fr) 2012-08-22

Family

ID=43587106

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10767988A Withdrawn EP2488602A1 (fr) 2009-10-12 2010-10-06 Procédé d'enrobage d'un luminophore de silicate

Country Status (5)

Country Link
US (1) US20120207923A1 (fr)
EP (1) EP2488602A1 (fr)
JP (1) JP2013507498A (fr)
DE (1) DE102009049056A1 (fr)
WO (1) WO2011045216A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10654748B2 (en) 2010-03-29 2020-05-19 Vitro Flat Glass Llc Solar control coatings providing increased absorption or tint
US10654747B2 (en) 2010-03-29 2020-05-19 Vitro Flat Glass Llc Solar control coatings with subcritical copper
US9932267B2 (en) 2010-03-29 2018-04-03 Vitro, S.A.B. De C.V. Solar control coatings with discontinuous metal layer
US8729790B2 (en) 2011-06-03 2014-05-20 Cree, Inc. Coated phosphors and light emitting devices including the same
DE202011106052U1 (de) 2011-09-23 2011-11-09 Osram Ag Lichtquelle mit Leuchtstoff und zugehörige Beleuchtungseinheit.
EP2746360A1 (fr) * 2012-12-24 2014-06-25 General Electric Company Procédé de fabrication de phosphore revêtu d'oxyde de terres rares
DE102014105142B4 (de) * 2014-04-10 2021-09-09 OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung Licht emittierende Vorrichtung und Verfahren zur Herstellung einer Licht emittierenden Vorrichtung
US11078718B2 (en) 2018-02-05 2021-08-03 Vitro Flat Glass Llc Solar control coatings with quadruple metallic layers
US10830933B2 (en) 2018-06-12 2020-11-10 Guardian Glass, LLC Matrix-embedded metamaterial coating, coated article having matrix-embedded metamaterial coating, and/or method of making the same
US10562812B2 (en) 2018-06-12 2020-02-18 Guardian Glass, LLC Coated article having metamaterial-inclusive layer, coating having metamaterial-inclusive layer, and/or method of making the same
DE102018125754A1 (de) * 2018-10-17 2020-04-23 Leuchtstoffwerk Breitungen Gmbh Erdalkalimetallsilikat-Leuchtstoff und Verfahren zum Verbessern der Langzeitstabilität eines Erdalkalimetallsilikat-Leuchtstoffes

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2817599A (en) * 1954-10-25 1957-12-24 Rca Corp Method of coating phosphor particles
US4710674A (en) * 1984-05-07 1987-12-01 Gte Laboratories Incorporated Phosphor particle, fluorescent lamp, and manufacturing method
US4585673A (en) * 1984-05-07 1986-04-29 Gte Laboratories Incorporated Method for coating phosphor particles
US4690832A (en) * 1985-05-01 1987-09-01 Gte Products Corporation Process for providing hydrolysis resistant phosphors
US4965091A (en) * 1987-10-01 1990-10-23 At&T Bell Laboratories Sol gel method for forming thin luminescent films
CA2027031A1 (fr) * 1989-10-18 1991-04-19 Loren A. Haluska Enduits d'hermetisation de substrats en atmosphere inerte
US5113118A (en) * 1991-03-11 1992-05-12 Gte Laboratories Incorporated Phosphors with improved lumen output and lamps made therefrom
TW383508B (en) 1996-07-29 2000-03-01 Nichia Kagaku Kogyo Kk Light emitting device and display
JPH10195428A (ja) * 1997-01-16 1998-07-28 Toshiba Corp 蛍光体粒子、その製造方法およびプラズマディスプレイパネル
US6045650A (en) * 1997-09-16 2000-04-04 Sunsmart, Inc. Hydrophilic materials and their method of preparation
DE10051242A1 (de) 2000-10-17 2002-04-25 Philips Corp Intellectual Pty Lichtemittierende Vorrichtung mit beschichtetem Leuchtstoff
JP2005183245A (ja) * 2003-12-22 2005-07-07 Matsushita Electric Ind Co Ltd プラズマディスプレイ表示装置
JP2006028354A (ja) * 2004-07-16 2006-02-02 Keio Gijuku 蛍光体及び蛍光体の製造方法
KR100966764B1 (ko) * 2006-04-26 2010-06-29 삼성에스디아이 주식회사 플라즈마 디스플레이 패널용 형광체 및 이로부터 형성된형광막을 구비한 플라즈마 디스플레이 패널
JP2008111080A (ja) * 2006-10-31 2008-05-15 Mitsubishi Chemicals Corp 蛍光体表面処理方法、蛍光体、蛍光体含有組成物、発光装置、画像表示装置、および照明装置
KR101414243B1 (ko) * 2007-03-30 2014-07-14 서울반도체 주식회사 황화물 형광체 코팅 방법 및 코팅된 황화물 형광체를채택한 발광 소자
JP5330684B2 (ja) * 2007-12-27 2013-10-30 宇部マテリアルズ株式会社 青色発光蛍光体粒子
DE102008060680A1 (de) * 2008-12-08 2010-06-10 Merck Patent Gmbh Oberflächenmodifizierte Silikat-Leuchtstoffe

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011045216A1 *

Also Published As

Publication number Publication date
DE102009049056A1 (de) 2011-04-14
US20120207923A1 (en) 2012-08-16
WO2011045216A1 (fr) 2011-04-21
JP2013507498A (ja) 2013-03-04

Similar Documents

Publication Publication Date Title
EP2488602A1 (fr) Procédé d'enrobage d'un luminophore de silicate
JP6625582B2 (ja) 発光ダイオード用途に使用するための赤色線放出蛍光体
DE102005061828B4 (de) Wellenlängenkonvertierendes Konvertermaterial, lichtabstrahlendes optisches Bauelement und Verfahren zu dessen Herstellung
DE112006003161B4 (de) Ladungskompensierte Nitridleuchtstoffe und deren Verwendung
EP2209869B1 (fr) Substances luminescentes à surface modifiée
EP2129740B1 (fr) Procédé de production de substances luminescentes à base d'orthosilicates pour diodes électroluminescentes à convertisseur phosphore
EP2519986B1 (fr) Matériau d'enrobage en tant que barrière de diffusion envers des molécules d'eau
DE10051242A1 (de) Lichtemittierende Vorrichtung mit beschichtetem Leuchtstoff
DE102008060680A1 (de) Oberflächenmodifizierte Silikat-Leuchtstoffe
EP2171017A1 (fr) Substance luminescente à oxynitrure thermostable et source lumineuse contenant ce type de substance luminescente
DE102007016229A1 (de) Verfahren zur Herstellung von Leuchtstoffen basierend auf Orthosilikaten für pcLEDs
DE112011103143B4 (de) Sialon-leuchtstoff, verfahren zum herstellen desselben und licht-emittierende vorrichtung, welche denselben verwendet
DE102010031755A1 (de) Aluminat-Leuchtstoffe
WO2007140853A1 (fr) Procédé de fabrication d'une substance luminescente émettrice en ligne
DE10307281A1 (de) Beschichteter Leuchtstoff, lichtemittierende Vorrichtung mit derartigem Leuchtstoff und Verfahren zu seiner Herstellung
EP2625247B1 (fr) Luminophores activés par mn
EP2596681B1 (fr) Substances luminescentes de type carbodiimide
DE102018106695A1 (de) Optoelektronisches Bauelement und Verfahren zur Herstellung eines optoelektronischen Bauelements
EP2619283B1 (fr) Substances fluorescentes à base de silicate
WO2024078931A1 (fr) Luminophore, procédé de fabrication d'un luminophore et composant émetteur de rayonnement

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120305

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: OSRAM GMBH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: OSRAM GMBH

17Q First examination report despatched

Effective date: 20130610

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20150504