CN1325602C - 高亮度发射绿光的无机发光材料 - Google Patents

高亮度发射绿光的无机发光材料 Download PDF

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CN1325602C
CN1325602C CNB2004100387152A CN200410038715A CN1325602C CN 1325602 C CN1325602 C CN 1325602C CN B2004100387152 A CNB2004100387152 A CN B2004100387152A CN 200410038715 A CN200410038715 A CN 200410038715A CN 1325602 C CN1325602 C CN 1325602C
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phosphor
vuv
high brightness
emitting phosphor
brightness
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CN1572859A (zh
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周仲年
G·A·马金
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Osram Sylvania Inc
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    • 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
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/778—Borates
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10—Crucibles or containers for supporting the melt
    • 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
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/20—Controlling or regulating
    • C30B15/203—Controlling or regulating the relationship of pull rate (v) to axial thermal gradient (G)
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon

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

Abstract

描述了一种高亮度的发射绿光的无机发光材料。无机发光材料具有的通式为：(Y(1-x-y-z)GdxTbyLaz)BO3，其中0.01≤x≤0.4，0.01≤y≤0.1，和0＜z≤0.2。无机发光材料在VUV激发下显示出增强的亮度，其适合用于等离子体显示板。

Description

高亮度发射绿光的无机发光材料
技术领域
本发明总体上涉及用于等离子体显示板的无机发光材料(phosphor)。更具体地，本发明涉及发射绿光的硼酸盐无机发光材料。
背景技术
为了达到全彩色再现，由象素组成等离子体显示板(PDP)，这些象素发射的光相当于红，绿和蓝三厚色。象素由发射红、绿和蓝的无机发光材料形成，该无机发光材料以糊剂或者油墨的形式沉积在器件的内壁上。然后在高温(大约400℃)下，燃尽粘合剂材料。通过由氙-氖气体放电产生的真空紫外(VUV)辐射(172nm)激发无机发光材料达到三色发射。无机发光材料的发光效率、颜色色度、余辉以及稳定性在PDP的性能中具有重要的作用。用于PDP应用中典型的无机发光材料包括发射红光的(Y，Gd)BO3:Eu无机发光材料(YOB)、发射绿光的Zn2SiO4:Mn无机发光材料以及发射蓝光的BaMgAl10O17:Eu。
传统的发射绿光的Zn2SiO4:Mn无机发光材料苦于长久的衰减时间以及逐渐下降的发光效率，这些对板的性能造成负面影响。一种可能更有效的发射绿色的无机发光材料是钇钆铽硼酸盐，(Y，Cd，Tb)BO3。 Kwon等在J.Luminescence 87-89(2000)1039-1041中描述了Y0.95-xGdxTb0.05BO3无机发光材料系统在VUV区域的发光性能。Ohto的日本专利申请11-071581描述了一种用于等离子体显示板的发射绿光的(Y，Gd，Tb)BO3。(Y，Gd，Tb)BO3无机发光材料在172nm处显示出较高的VUV吸收作用，并且燃尽粘合剂后，它在亮度上经历了较小的减少。
发明内容
已经发现用少量的镧取代钇，在VUV激发下提高了(y，Gd，Tb)BO3无机发光材料的亮度。取代的无机发光材料具有的通式为：
(Y(1-x-y-z)GdxTbyLaz)BO3，
其中0.01≤x≤0.4，0.01≤y≤0.1，和0＜z≤02。
优选0.2≤x≤0.3，0.03≤y≤0.07和0.05≤z≤0.15。更优选0.05≤z≤0.1。在VUV激发下，无机发光材料显示出明亮的绿光发射(CIE彩色座标；x＝0.323，y＝0.610)  然而，在超出特定的范围时，增加镧的量会引起VUV亮度的减少。
附图简述
数字举例说明了作为镧浓度函数的VUV亮度的变化。
具体实施方式
为了更透彻地理解本发明以及其它的和进一步的目的、优点及其性能，参考下列公开的内容以及与上述描述的附图结合的附加权利要求。
给出下列非限定性的实施例。
实施例
制备一些镧取代呈增加的钇钆铽硼酸盐无机发光材料样品。无机发光材料具有通式(Y(1-x-y-z)Gd0.245Tb0.065Laz)BO3。无机发光材料由通过下述步骤形成的稀土氧化物共沉淀物制备而成，即在200ml的浓硝酸中溶解一定量的氧化铽，用300ml的水稀释，然后在搅拌下，加热到80℃-90℃，直到溶液变得澄清。然后再添加200ml的浓HNO3。然后将称量的氧化钇、氧化钆和氧化镧慢慢加入到一部分含铽溶液中。搅拌第二溶液直到变得澄清。如果30分钟内溶液没有变澄清，则再加入50ml浓HNO3。然后加入2升的草酸水溶液(1.7mol草酸比1mol稀土氧化物)，并且用氢氧化铵(400-450ml)将第二溶液的pH值调节到1-2。将该共沉淀物过滤，干燥后，在氧化铝坩锅上在1100℃下加热8小时以形成氧化物。通过以1∶1摩尔比混合煅烧的稀土氧化物共沉淀物和硼酸，并在3％的氢气气氛中，在1060℃下燃烧该混合物3小时而制备硼酸盐无机发光材料。下表给出每摩尔无机发光材料中Y，La，Tb的摩尔量以及在172nm激发下这些材料的VUV亮度。
实施例    Y   La    Tb    Gd ％相对VUV亮度
 1(对照) 0.69  0  0.065  0.245  100
 2 0.64  0.05  0.065  0.245  106
 3 0.59  0.1  0.065  0.245  107.7
 4 0.49  0.2  0.065  0.245  101
 5 0.39  0.3  0.065  0.245  97
 6 0.29  0.4  0.065  0.245  88
 7 0.19  0.5  0.065  0.245  83
 8 0.09  0.6  0.065  0.245  76
可以看出，镧的增加引起无机发光材料相对VUV亮度增加，直至每摩尔无机发光材料含有的La为0.2mol。每摩尔无机发光材料含有0.3molLa时，VUV亮度变得小于不含镧时的对照样的VUV亮度。
尽管上面已经显示或者描述了本发明考虑的优选实施方案，但对于本领域技术人员来说很明显其中可以进行各种变化和修改，而没有背离如附加的权利要求所定义的本发明的范围。

Claims (6)

1.一种具有下述通式的无机发光材料：
(Y(1-x-y-z)GdxTbyLaz)BO3，
其中0.01≤x≤0.4，
0.01≤y≤0 1，和
0＜z≤0.2。
2.权利要求1的无机发光材料，其中0.2≤x≤0.3和0.03≤y≤0.07。
3.权利要求1的无机发光材料，其中0.05≤z≤0.15。
4.权利要求1的无机发光材料，其中0.05≤z≤0.1。
5.权利要求2的无机发光材料，其中0.05≤z≤0.15。
6.权利要求2的无机发光材料，其中0.05≤z≤0.1。
CNB2004100387152A 2003-05-09 2004-05-08 高亮度发射绿光的无机发光材料 Expired - Fee Related CN1325602C (zh)

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US10/435,434 US6805813B1 (en) 2003-05-09 2003-05-09 High brightness green-emitting phosphor
US10/435434 2003-05-09

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JP (1) JP2004331979A (zh)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7288215B2 (en) 2005-03-30 2007-10-30 Osram Sylvania Inc. Method of making narrow-band UVB-emitting phosphors
CN102976388A (zh) * 2011-09-07 2013-03-20 中国石油大学(华东) 一种水热制备稀土硝酸盐的方法
US20140124703A1 (en) * 2012-09-02 2014-05-08 Global Tungsten and Powders Corporation BRIGHTNESS OF CE-TB CONTAINING PHOSPHOR AT REDUCED Tb WEIGHT PERCENTAGE

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1453991A (en) * 1973-03-14 1976-10-27 Philips Electronic Associated Luminescent materials
US4403171A (en) * 1981-01-09 1983-09-06 Hitachi, Ltd. Phosphor, process for preparation thereof and lamp containing the same
EP0358278A1 (en) * 1988-09-07 1990-03-14 Koninklijke Philips Electronics N.V. Luminescent terbium-activated borate, luminescent screen provided with such a borate and low-pressure mercury vapour discharge lamp provided with such a screen
JPH1171581A (ja) * 1997-06-19 1999-03-16 Kasei Optonix Co Ltd 希土類硼酸塩蛍光体及びその製造方法
WO2000014014A2 (fr) * 1998-09-03 2000-03-16 Rhodia Chimie Borate de lanthane, de lutecium, d'yttrium ou de gadolinium comprenant deux dopants et son precurseur, utilisation dans les systemes a plasma ou a rayons x
US6238593B1 (en) * 1996-01-17 2001-05-29 Rhodia Chimie Rare-earth borate and its precursor, preparation processes and use of borate as luminophore
US6469322B1 (en) * 1998-02-06 2002-10-22 General Electric Company Green emitting phosphor for use in UV light emitting diodes

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1453991A (en) * 1973-03-14 1976-10-27 Philips Electronic Associated Luminescent materials
US4403171A (en) * 1981-01-09 1983-09-06 Hitachi, Ltd. Phosphor, process for preparation thereof and lamp containing the same
EP0358278A1 (en) * 1988-09-07 1990-03-14 Koninklijke Philips Electronics N.V. Luminescent terbium-activated borate, luminescent screen provided with such a borate and low-pressure mercury vapour discharge lamp provided with such a screen
US6238593B1 (en) * 1996-01-17 2001-05-29 Rhodia Chimie Rare-earth borate and its precursor, preparation processes and use of borate as luminophore
JPH1171581A (ja) * 1997-06-19 1999-03-16 Kasei Optonix Co Ltd 希土類硼酸塩蛍光体及びその製造方法
US6469322B1 (en) * 1998-02-06 2002-10-22 General Electric Company Green emitting phosphor for use in UV light emitting diodes
WO2000014014A2 (fr) * 1998-09-03 2000-03-16 Rhodia Chimie Borate de lanthane, de lutecium, d'yttrium ou de gadolinium comprenant deux dopants et son precurseur, utilisation dans les systemes a plasma ou a rayons x

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DE602004000427T2 (de) 2006-09-28
KR101093979B1 (ko) 2011-12-15
EP1475428A2 (en) 2004-11-10
KR20040095722A (ko) 2004-11-15
JP2004331979A (ja) 2004-11-25
EP1475428B1 (en) 2006-03-01
CN1572859A (zh) 2005-02-02
EP1475428A3 (en) 2004-12-22
US6805813B1 (en) 2004-10-19
US20040222405A1 (en) 2004-11-11
TW200500447A (en) 2005-01-01

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