WO2012077042A1 - Matériaux luminescents à base d'oxynitrure de silicium émettant dans l'orange-rouge - Google Patents

Matériaux luminescents à base d'oxynitrure de silicium émettant dans l'orange-rouge Download PDF

Info

Publication number
WO2012077042A1
WO2012077042A1 PCT/IB2011/055475 IB2011055475W WO2012077042A1 WO 2012077042 A1 WO2012077042 A1 WO 2012077042A1 IB 2011055475 W IB2011055475 W IB 2011055475W WO 2012077042 A1 WO2012077042 A1 WO 2012077042A1
Authority
WO
WIPO (PCT)
Prior art keywords
systems
lighting
lighting systems
oxonitride
mixtures
Prior art date
Application number
PCT/IB2011/055475
Other languages
English (en)
Inventor
Peter Josef Schmidt
Cora Sieglinde Hecht
Wolfgang Schnick
Original Assignee
Koninklijke Philips Electronics N.V.
Philips Intellectual Property & Standards 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 Koninklijke Philips Electronics N.V., Philips Intellectual Property & Standards Gmbh filed Critical Koninklijke Philips Electronics N.V.
Publication of WO2012077042A1 publication Critical patent/WO2012077042A1/fr

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
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • 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
    • C09K11/77347—Silicon Nitrides or Silicon Oxynitrides

Definitions

  • the present invention is directed to novel luminescent materials for light emitting devices, especially to the field of novel luminescent materials for LEDs.
  • Phosphors comprising silicates, phosphates (for example, apatite) and aluminates as host materials, with transition metals or rare earth metals added as activating materials to the host materials, are widely known.
  • phosphates for example, apatite
  • aluminates as host materials, with transition metals or rare earth metals added as activating materials to the host materials.
  • transition metals or rare earth metals added as activating materials to the host materials
  • M is selected out of the group comprising Ba, Sr or mixtures thereof;
  • RE is selected out of the group comprising rare earth metals or mixtures thereof;
  • additives may also be present in the bulk compositions. These additives particularly include such species known to the art as fluxes. Suitable fluxes include alkaline earth - or alkaline - metal oxides, borates, phosphates and halides such as fluorides, ammonium chloride, Si0 2 and the like and mixtures thereof.
  • LEDs may be built which show improved lighting features, especially thermal stability.
  • the Material can be made in excellent purity due to the availability via a nitrification process (see below) using more-ready available oxygen precursor materials.
  • the material has been found to crystallize in a new host lattice; said new host lattice formation can be explained and derived from the (known) M 2 Si 5 N8 structure by partial or complete removal of SiN 4 building blocks from the M 2 Si 5 N8 structure and introduction of terminal O atoms (see figs. 1 and 2 as described later on).
  • RE is Eu
  • Eu is the dopant material
  • x is 0.005 ⁇ x ⁇ 0.02, i.e. the dopant level is somewhat around 1%. This has been shown to be advantageous for many applications within the present invention.
  • y is 0.2 ⁇ y ⁇ 0.6.
  • the material can be made on a large-scale basis with high purity and good material features.
  • the oxygen-comprising precursor material is a silicate material, e.g. Ba 2 Si0 4> Sr 2 Si0 4 or the like, mixtures thereof, which may also be doped with RE, especially Eu.
  • a silicate material e.g. Ba 2 Si0 4> Sr 2 Si0 4 or the like, mixtures thereof, which may also be doped with RE, especially Eu.
  • oxygen-comprising precursor material can be a oxonitridosilicate, e.g. BaSi 2 0 2 N 2 , SrSi 2 0 2 N 2 or or the like.
  • the oxygen- comprising precursor material is an oxide, e.g. BaO, SrO or mixtures thereof and mixtures of these oxides with REO or RE 2 0 3 (e.g. EuO or Eu 2 0 3 ).
  • a preferred embodiment of the inventive method comprises a reduction step carried out simultaneously or prior to the oxonitride formation step. This has been shown to lead to a inventive material with enhanced purity.
  • the reduction step comprises a carbothermal reduction.
  • a preferred embodiment of the inventive method comprises a first oxonitride formation step from a silicate, e.g. according to the following equation:
  • This material is then converted to the inventive material in a combined oxonitride formation step and reduction step using suitable precursor materials such as carbon and silicone nitride, e.g. according to the following equation:
  • the silicon nitride powder may be substituted by silicon powder in both above reactions.
  • Other silicon sources like silicon diimide may also be used.
  • nitrogen gas also dry ammonia may be used for the oxonitride formation reaction and elemental carbon might be substituted by other sources of carbon like carbohydrates, saturated or non-saturated carbohydrates, and plastics and so on.
  • a yet alternative reaction path to the inventive material comprises the oxonitride formation from a metal oxide, e.g. BaO:Eu or the like, following e.g. the following equation:
  • inventive method is to be understood in its broadest sense and also includes reations where e.g. the dopant is provided as a halogenide (which then also can serve as a flux aid etc.).
  • a suitable reaction scheme is e.g.:
  • the present invention furthermore relates to a light emitting structure, especially a LED, comprising at least one material according to the present invention.
  • the present invention furthermore relates to as system comprising a material according to the present invention and/or materials made according to the inventive methods shown above, being used in one or more of the following applications:
  • Fig. 1 shows a schematic perspective partial view of a structure of a host material according to a first example of the present invention
  • Fig. 2 shows the (known) structure of M 2 S1 5 N 8
  • Fig. 3 shows an emission spectrum of the material of Example I
  • Fig. 4 shows an XRD pattern of the material of Example I
  • Fig. 5 shows an emission spectrum of the material of Example II.
  • Fig. 6 shows an XRD pattern of the material of Example II
  • Figs 3 and 4 refer to the material according to Example I, which was made the following way:
  • the orange Sr 4 Si 9+y 0 4 - 4y N 12 4 y :Eu(2%), y ⁇ 0.2 powder shows emission in the orange - red spectral range with a peak at 623 nm (Fig. 3).
  • the quantum efficiency of the phosphor was determined to be 80.7% (commercial YAG:Ce phosphor U728, Philips Lighting, used as a standard), 50% of the integral room temperature intensity has been reached at 218°C.
  • Fig. 4 shows the XRD pattern of Sr 4 Si 9+y 0 4 _ 4y N 12+4y :Eu(2%), y ⁇ 0.2. It can be seen that this material crystallizes in the structure following Fig. 1, i. e. in a novel structure not described before.
  • EXAMPLE II Ba 4 Si 9 0 4 N 12 :Eu(l%).
  • Figs 5 and 6 refer to the material according to Example II, which was made the following way:
  • Fig. 5 shows the emission spectrum of Ba 4 Si 9 0 4 N 12 :Eu(l%).
  • Lumen equivalent of emission 391 lm/W.
  • Fig. 6 shows the XRD pattern of Ba 4 Sic)0 4 N 12 :Eu(l%). It can be seen that this material crystallizes in the structure following Fig. 1, i. e. in a novel structure not described before.

Landscapes

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

Abstract

Cette invention concerne un nouveau matériau émettant dans le rouge ayant la composition suivante : M4-xSi9+yO4-4yN12+4y:Eux où M = Sr, Ba ; 0,001 ≤ x ≤ 0,1, et 0 ≤ y < 0,8.
PCT/IB2011/055475 2010-12-08 2011-12-06 Matériaux luminescents à base d'oxynitrure de silicium émettant dans l'orange-rouge WO2012077042A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10194210.0 2010-12-08
EP10194210 2010-12-08

Publications (1)

Publication Number Publication Date
WO2012077042A1 true WO2012077042A1 (fr) 2012-06-14

Family

ID=45350449

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2011/055475 WO2012077042A1 (fr) 2010-12-08 2011-12-06 Matériaux luminescents à base d'oxynitrure de silicium émettant dans l'orange-rouge

Country Status (2)

Country Link
TW (1) TW201241155A (fr)
WO (1) WO2012077042A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103305214A (zh) * 2013-06-16 2013-09-18 桂林理工大学 一种可调控颜色的掺杂Eu的荧光粉的制备方法
DE102021132496A1 (de) 2021-12-09 2023-06-15 OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung Leuchtstoff, verfahren zur herstellung eines leuchtstoffs und strahlungsemittierendes bauelement

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6680569B2 (en) 1999-02-18 2004-01-20 Lumileds Lighting U.S. Llc Red-deficiency compensating phosphor light emitting device
WO2005052087A1 (fr) 2003-11-26 2005-06-09 Independent Administrative Institution National Institute For Materials Science Phosphore et appareil emetteur de lumiere utilisant ce phosphore
US20050253500A1 (en) * 2004-05-14 2005-11-17 Dowa Mining Co., Ltd. Phosphor and production method of the same and light source and LED using the phosphor
US20080143246A1 (en) * 2004-09-22 2008-06-19 National Institution For Materials Science Phosphor, Production Method Thereof and Light Emitting Instrument
US20100001303A1 (en) * 2007-02-06 2010-01-07 Koninklijke Philips Electronics N.V. Red emitting oxynitride luminescent materials
EP2163593A1 (fr) * 2008-09-15 2010-03-17 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Production de phosphores à base de nitrure
WO2010057745A1 (fr) * 2008-11-20 2010-05-27 Osram Gesellschaft mit beschränkter Haftung Matériau luminescent sr2s15n8 émettant dans le rouge et source de lumière avec ledit matériau luminescent et procédé de fabrication du matériau luminescent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6680569B2 (en) 1999-02-18 2004-01-20 Lumileds Lighting U.S. Llc Red-deficiency compensating phosphor light emitting device
WO2005052087A1 (fr) 2003-11-26 2005-06-09 Independent Administrative Institution National Institute For Materials Science Phosphore et appareil emetteur de lumiere utilisant ce phosphore
US20050253500A1 (en) * 2004-05-14 2005-11-17 Dowa Mining Co., Ltd. Phosphor and production method of the same and light source and LED using the phosphor
US20080143246A1 (en) * 2004-09-22 2008-06-19 National Institution For Materials Science Phosphor, Production Method Thereof and Light Emitting Instrument
US20100001303A1 (en) * 2007-02-06 2010-01-07 Koninklijke Philips Electronics N.V. Red emitting oxynitride luminescent materials
EP2163593A1 (fr) * 2008-09-15 2010-03-17 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Production de phosphores à base de nitrure
WO2010057745A1 (fr) * 2008-11-20 2010-05-27 Osram Gesellschaft mit beschränkter Haftung Matériau luminescent sr2s15n8 émettant dans le rouge et source de lumière avec ledit matériau luminescent et procédé de fabrication du matériau luminescent

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103305214A (zh) * 2013-06-16 2013-09-18 桂林理工大学 一种可调控颜色的掺杂Eu的荧光粉的制备方法
DE102021132496A1 (de) 2021-12-09 2023-06-15 OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung Leuchtstoff, verfahren zur herstellung eines leuchtstoffs und strahlungsemittierendes bauelement

Also Published As

Publication number Publication date
TW201241155A (en) 2012-10-16

Similar Documents

Publication Publication Date Title
Chiu et al. Ca 2 PO 4 Cl: Eu2+: an intense near-ultraviolet converting blue phosphor for white light-emitting diodes
JP6305370B2 (ja) 赤色発光窒化物系カルシウム安定化蛍光体
JP4565141B2 (ja) 蛍光体と発光器具
JP4362625B2 (ja) 蛍光体の製造方法
KR101810234B1 (ko) 적색 방출 발광 물질
TWI351426B (en) Phosphor, method for production thereof, and light
JP4521227B2 (ja) 窒素を含有する蛍光体の製造方法
JP4782079B2 (ja) アルカリ土類金属シリケート系蛍光体および白色発光素子
KR101172143B1 (ko) 백색 발광다이오드 소자용 시온계 산화질화물 형광체, 그의 제조방법 및 그를 이용한 백색 ｌｅｄ 소자
JP2013539490A (ja) 酸窒化物発光材料及びその調製方法並びにそれによって製造された照明光源
JP2012524141A (ja) 赤色発光の発光材料
JP5741177B2 (ja) Ｃａ含有α型サイアロン蛍光体およびその製造方法
JP2006008721A (ja) 蛍光体と蛍光体を用いた発光器具
JP2013536264A (ja) 蛍光体及び係る蛍光体を有する光源
CN102159665A (zh) 氮化物基荧光体的制备
JP6758291B2 (ja) 蛍光体組成物及びその照明装置
JP2007113019A (ja) 蛍光体の製造方法
JP2014503605A (ja) 窒素化合物発光材料及びその調製方法並びにそれによって製造された照明光源
JP5071714B2 (ja) 蛍光体、その製造方法およびそれを用いた発光器具
WO2012077042A1 (fr) Matériaux luminescents à base d&#39;oxynitrure de silicium émettant dans l&#39;orange-rouge
JP2009167382A (ja) 蛍光材料と発光装置
JP2009138070A (ja) 蛍光体とその製造方法及び蛍光体を用いた発光装置
CN110129041B (zh) 一种绿色氮氧化物荧光材料及其制造方法
JP6028858B2 (ja) 酸窒化物蛍光体粉末
CN114605986B (zh) 紫光激发的含氯硅酸盐蓝青色荧光粉及制备与应用方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11797160

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11797160

Country of ref document: EP

Kind code of ref document: A1