WO2014067433A1 - Poudre de nitrure fluorescente rouge et son procédé de préparation - Google Patents

Poudre de nitrure fluorescente rouge et son procédé de préparation Download PDF

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Publication number
WO2014067433A1
WO2014067433A1 PCT/CN2013/086028 CN2013086028W WO2014067433A1 WO 2014067433 A1 WO2014067433 A1 WO 2014067433A1 CN 2013086028 W CN2013086028 W CN 2013086028W WO 2014067433 A1 WO2014067433 A1 WO 2014067433A1
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WIPO (PCT)
Prior art keywords
red phosphor
nitride red
hours
preparation
hydrogen
Prior art date
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Ceased
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PCT/CN2013/086028
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English (en)
Chinese (zh)
Inventor
何锦华
滕晓明
梁超
符义兵
刘凯
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Jiangsu Bree Optronics Co Ltd
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Jiangsu Bree Optronics Co Ltd
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Publication of WO2014067433A1 publication Critical patent/WO2014067433A1/fr
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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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/77927—Silicon Nitrides or Silicon Oxynitrides

Definitions

  • the invention relates to a nitride red phosphor and a preparation method thereof. Background technique
  • Many organizations have made great progress in the improvement of M 2 Si 5 N 8 : Eu phosphors.
  • Toshiba Corporation introduced the manufacturing method of M 2 Si 5 N 8 :Z in the patent application CN200810145642.5; Osram Co., Ltd.
  • the invention provides a nitride red phosphor and a preparation method thereof.
  • the technical solution of the present invention is:
  • a nitride red phosphor having a chemical structural formula of: L 2 _ x _ y _ z M 5 N 8: Eu x , R y , R′ z , wherein L is at least one of Ca, Sr or Ba M is at least one of Si or Ge, wherein Si is necessary; R is at least one of Na or K; R' is at least one of La, Sm or Sc; 0.001 ⁇ x ⁇ 0.5, 0.0001 ⁇ y ⁇ 0.01, 0.0001 ⁇ z ⁇ 0.01, and y z.
  • the preparation method of the above nitride red phosphor comprises the following steps:
  • step A calcining the material obtained in step A;
  • the material obtained in the step B is pulverized and sieved to obtain a nitride red phosphor.
  • the above preparation method further includes the step D, washing the nitride red phosphor obtained in the step C to a conductivity less than li ⁇ s/cm and drying.
  • the above washing is washed with water after pickling, and the acid used for pickling is one of hydrochloric acid, nitric acid or phosphoric acid, and the concentration of the acid is from 1 to 20% by weight.
  • the calcination is: under normal pressure, in a nitrogen atmosphere or a mixed atmosphere of hydrogen and nitrogen, the calcination is carried out in two stages: the calcination temperature of the first stage is 700-900 ° C, and the calcination time is 4- At 8 hours, the second stage has a calcination temperature of 1400-1800 ° C and a calcination time of 8-15 hours.
  • the volume ratio of hydrogen to nitrogen is (5:95) - (75:25).
  • the raw materials of the L, M, and R' elements are their nitrides, the raw material of the R element is its chloride, and the raw material of the Eu element is its oxide.
  • the above-mentioned nitride phosphor is packaged, that is, the nitride phosphor and YAG are mixed in a certain ratio, and then mixed on a surface of the blue chip according to a certain powder-to-binder ratio, thereby preparing a white LED.
  • the nitride fluorescent powder of the invention has good chemical stability, high luminous efficiency and good aging performance; and the preparation method is simple, easy to operate, pollution-free and low in cost.
  • Fig. 1 is an excitation spectrum diagram of Example 3 and Comparative Example 1.
  • Fig. 2 is an emission spectrum diagram of Example 3 and Comparative Example 1.
  • Fig. 3 is an XRD pattern of Example 3 and Comparative Example 1.
  • Figure 4 is a SEM picture of Example 3.
  • Fig. 5 is a SEM picture of Comparative Example 1.
  • Fig. 6 is an excitation spectrum diagram of Example 7 and Comparative Example 2.
  • Fig. 7 is an emission spectrum chart of Example 7 and Comparative Example 2.
  • Fig. 8 is an excitation spectrum diagram of Example 10 and Comparative Example 3.
  • Fig. 9 is an emission spectrum chart of Example 10 and Comparative Example 3. Detailed ways
  • the phosphors and YAG prepared in all of the examples and the comparative examples were mixed at 0.14:1, and then coated on the surface of the blue chip according to a powder-to-binder ratio of 1:6 to prepare a white LED. After drying, test its initiality.
  • nitride phosphor powder of CaLggSisNgiEuo.ohKo.oos ⁇ mo.oos can be obtained by washing with 4% nitric acid and finally washing with deionized water to a conductivity of 2. ⁇ S /cm and drying.
  • the main peak of emission and the luminous intensity are shown in Table 2, which are higher than Comparative Example 2.
  • the phosphors and YAG prepared in all of the examples and the comparative examples were mixed at 0.2:1, and then coated on the surface of the blue chip in accordance with a powder ratio of 1:5 to prepare a white LED. After drying, the initial performance was tested, and then the aging performance was tested after 168 hours of aging, see Table 2 below:
  • Example 9 Weigh Ba 3 N 2 8.701 lg, Si 3 N 4 8.972g, Eu 2 O 3 2.702g, NaCl O.OOllg, LaN 0.0029g, mix the above materials thoroughly, put them into molybdenum crucible, and then quickly move them into In the tube furnace, it is gradually heated to 900 ° C under the protection of nitrogen-hydrogen mixed atmosphere (hydrogen volume ratio of 25%), kept for 8 hours, then heated to 1600 ° C, kept for 15 hours, ground and sieved. After that, it is washed with 12% phosphoric acid, and finally washed with deionized water until the conductivity is 6.3 s/cm, and dried to obtain B ai . 596 Si 5 N 8 : E U Q. 4 , NaQ.QQ 2 , LaQ.QQ 2 nitride phosphor. The main emission peak and the luminous intensity are shown in Table 3, which are higher than Comparative Example 3.
  • Ba 3 N 2 8.6041 g, Si 3 N 4 8.943 g, Eu 2 0 3 2.692 g, KC1 0.0057 g, LaN 0.0087 g, ScN 0.0012 g were weighed, and the above raw materials were thoroughly mixed and filled into molybdenum crucible, and then It is quickly transferred into the tube furnace, and then gradually heated to 900 ° C under the protection of pure nitrogen, kept for 8 hours, and then heated to 1600 ° C, held for 15 hours, after grinding, sieving, with 4% hydrochloric acid Washing, and finally washing with deionized water to a conductivity of 8.
  • the phosphors and YAG prepared in all of the examples and the comparative examples were mixed at 0.12:1, and then coated on the surface of the blue chip in accordance with a powder ratio of 1:8 to prepare a white LED. After drying, the initial performance was tested, and then the aging performance was tested after 168 hours of aging, see Table 3 below:
  • Bai.596Si5N8 Euo.4, Nao.oo2, Lao.oo2 638 129 85.345 79.753 6.55%
  • Bai.5i8Sro.o8Si5N8 Euo.4, Nao.ooi, S 640 132 86.368 79.859 7.51%

Landscapes

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

Abstract

L'invention porte sur de la poudre de nitrure fluorescente rouge représentée par la formule de structure chimique suivante : L2-x-y-zM5N8:Eux,Ry,R'z, dans laquelle, L représente au moins l'un de Ca, Sr ou Ba; M représente Si et/ou Ge et Si est obligatoire; R représente Na et/ou K; R' représente au moins l'un de La, Sm ou Sc; 0,001 ≤ x ≤ 0,5, 0,0001 ≤ y ≤ 0,01, 0,0001 ≤ z ≤ 0,01 et y = z.
PCT/CN2013/086028 2012-10-30 2013-10-28 Poudre de nitrure fluorescente rouge et son procédé de préparation Ceased WO2014067433A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2012104281880A CN102899038A (zh) 2012-10-30 2012-10-30 一种氮化物红色荧光粉及其制备方法
CN201210428188.0 2012-10-30

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WO2014067433A1 true WO2014067433A1 (fr) 2014-05-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3950884A4 (fr) * 2019-04-03 2022-05-11 National Institute for Materials Science Luminophore, procédé de production associé et élément électroluminescent

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105295903A (zh) * 2015-11-03 2016-02-03 江苏罗化新材料有限公司 一种高显指白光和背光源led用氮化物红色荧光粉的制备方法
CN109370587B (zh) * 2018-09-06 2019-10-29 旭宇光电（深圳）股份有限公司 氮化物近红外荧光材料、含有氮化物近红外荧光材料的发光装置
WO2022134045A1 (fr) * 2020-12-25 2022-06-30 苏州君诺新材科技有限公司 Poudre fluorescente rouge à base d'oxyde d'azote, procédé de préparation associé et dispositif
CN116789088A (zh) * 2023-06-30 2023-09-22 江苏博睿光电股份有限公司 氮化物红色荧光粉及其制备方法、应用

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CN1522291A (zh) * 2002-03-22 2004-08-18 ���ǻ�ѧ��ҵ��ʽ���� 氮化物荧光体,其制造方法及发光装置
EP2009078A1 (fr) * 2007-06-29 2008-12-31 Leuchtstoffwerk Breitungen GmbH Phosphores de nitrure de silicone alcalinoterreux activés Ce3+, Eu2+
CN101831295A (zh) * 2010-04-07 2010-09-15 江苏博睿光电有限公司 一种硅基氮化物红色荧光粉及其制备方法
CN102159665A (zh) * 2008-09-15 2011-08-17 马普科技促进协会 氮化物基荧光体的制备
CN102575161A (zh) * 2009-08-06 2012-07-11 昭和电工株式会社 荧光体及其制造方法以及使用该荧光体的发光装置
KR20130000010A (ko) * 2011-06-16 2013-01-02 한국화학연구원 금속실리콘산질화물계 형광체를 이용한 실리콘질화물계 형광체의 제조 방법

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CN101838533B (zh) * 2009-03-20 2013-07-10 兰州大学 一种led用荧光材料及制备方法
CN101838535B (zh) * 2010-04-07 2013-01-16 江苏博睿光电有限公司 一种稀土荧光粉及其制造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1522291A (zh) * 2002-03-22 2004-08-18 ���ǻ�ѧ��ҵ��ʽ���� 氮化物荧光体,其制造方法及发光装置
EP2009078A1 (fr) * 2007-06-29 2008-12-31 Leuchtstoffwerk Breitungen GmbH Phosphores de nitrure de silicone alcalinoterreux activés Ce3+, Eu2+
CN102159665A (zh) * 2008-09-15 2011-08-17 马普科技促进协会 氮化物基荧光体的制备
CN102575161A (zh) * 2009-08-06 2012-07-11 昭和电工株式会社 荧光体及其制造方法以及使用该荧光体的发光装置
CN101831295A (zh) * 2010-04-07 2010-09-15 江苏博睿光电有限公司 一种硅基氮化物红色荧光粉及其制备方法
KR20130000010A (ko) * 2011-06-16 2013-01-02 한국화학연구원 금속실리콘산질화물계 형광체를 이용한 실리콘질화물계 형광체의 제조 방법

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3950884A4 (fr) * 2019-04-03 2022-05-11 National Institute for Materials Science Luminophore, procédé de production associé et élément électroluminescent
TWI822983B (zh) * 2019-04-03 2023-11-21 國立研究開發法人物質 材料研究機構 螢光體、其製造方法、及發光元件
US11898080B2 (en) 2019-04-03 2024-02-13 National Institute For Materials Science Phosphor, method for producing same and light emitting element

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