WO2012083517A1 - 一种铟酸镓发光材料及其制备方法 - Google Patents
一种铟酸镓发光材料及其制备方法 Download PDFInfo
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- WO2012083517A1 WO2012083517A1 PCT/CN2010/080023 CN2010080023W WO2012083517A1 WO 2012083517 A1 WO2012083517 A1 WO 2012083517A1 CN 2010080023 W CN2010080023 W CN 2010080023W WO 2012083517 A1 WO2012083517 A1 WO 2012083517A1
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- luminescent material
- gallium indium
- solution
- agent
- preparing
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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
- C09K11/87—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing platina group metals
- C09K11/873—Chalcogenides
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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
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
- C09K11/621—Chalcogenides
Definitions
- the present invention relates to the field of luminescent materials, and in particular to a gallium indium gallium silicate luminescent material doped with metal nanoparticles.
- the invention also relates to a method for preparing a gallium indium luminescent material. Background technique
- sulfide systems such as blue powder ZnS: Ag, Cl, SrGa 2 S 4 : Ce, green powder SrGa 2 S 4 : Eu and red powder Y 2 0 2 S: Eu
- an oxide system such as blue powder Y 2 Si0 5 :Ce, green powder ZnGa 2 0 4 :Mn, Y 2 Si0 5 :Tb, Y 3 Al 5 0 12 :Tb and red powder Y 2 0 3 : Eu.
- the sulfide series has a relatively high stability.
- the oxide system not only has a lower conductivity than the sulfide series, but also needs to be improved in luminous intensity.
- a surface of the luminescent material is coated with a conductive material such as ln 2 O 3 , SnO 2 , ZnO, etc., and a luminescent material having a certain conductivity is studied.
- the present invention provides a gallium indium silicate luminescent material doped with metal nanoparticles having high conductivity and good chemical stability.
- the chemical formula of the gallium indium luminescent material is: GaIn0 3 :zM; wherein M represents a metal nanoparticle, one or two selected from the group consisting of Ag, Au, Pt or Pd, and the range of ⁇ is 1 x 10 — 5 ⁇ ⁇ ⁇ 0.02.
- Another object of the present invention is to provide a method for preparing the above gallium indium luminescent material, which is prepared as follows:
- Step S1 adding a source compound of In and a source compound of Ga to a mixed solvent of water and ethanol in a volume ratio of 1:1 to 1:4 according to the stoichiometric ratio of the corresponding element in the general formula Galn0 3 a mixed solution containing In ions and Ga ions;
- Step S2 adding a chelating agent and a crosslinking agent to the mixed solution prepared in the step S1, Chelating solution;
- Step S3 adding the surface-treated M nanoparticle sol to the chelating solution prepared in step S2, heating and stirring in a water bath, followed by drying to obtain a precursor having a chemical formula of GaIn0 3 :zM; wherein, M Representing metal nanoparticles, one or two selected from the group consisting of Ag, Au, Pt or Pd, and the range of z is 1 x 10 - 5 ⁇ z ⁇ 0.02;
- Step S4 the precursor obtained in the step S3 is subjected to calcination treatment, cooled, ground, and then subjected to calcination treatment, and then cooled and ground to obtain the gallium indium luminescent material having a chemical formula of GaIn0 3 :zM.
- the source compound of In and the source compound of Ga are each a corresponding nitrate.
- the chelating agent is citric acid monohydrate, and the molar amount of the chelating agent is added to the total metal ions (Ga ions and In ions, ie, trivalent Ga ions and trivalent In ions) in the mixed solution.
- the ratio of the molar amount is 1:1 ⁇ 5:1;
- the crosslinking agent is polyethylene glycol having a molecular weight of 2000-20000, and the ratio of the molar amount of the crosslinking agent added to the molar amount of Galn0 3 is 0 ⁇ 1:100.
- the surface-treated M nanoparticle sol is obtained by the following steps:
- Step S31 the source compound of the M is dissolved in water or a ratio of ethanol and water having a volume ratio of 1:7 to 4:1, and is prepared and diluted to a molar concentration of 2.4 x 10 - 4 ⁇ 3 x lO - 3 mol / a mixed solution of L containing M ions;
- Step S32 sequentially adding an auxiliary agent and a reducing agent solution to the step S31, and stirring to obtain an M nanoparticle sol;
- the auxiliary agent is polyvinylpyrrolidone, sodium citrate, cetyltridecyl bromide At least one of ammonium, sodium lauryl sulfate or sodium dodecyl sulfate; the auxiliary agent is added in an amount such that it is 1.5 10" 4 g in the finally obtained M nanoparticle sol.
- the molar concentration of the reducing agent solution is lxl () - 3 mol / L ⁇ 1 lO" 2 mol / L;
- the reducing agent in the reducing agent solution is hydrated Antimony, ascorbic acid or boron hydride At least one of sodium
- the solvent in the reducing agent solution is water or ethanol in a volume ratio of 9: 1-1 : 1; the molar amount of the reducing agent added and the molar amount of M ions The ratio is 1.2:1 - 4.8:1 ;
- Step S33 the M nanoparticle sol prepared in the step S32 is added to the solution containing the surface treatment agent, and stirred to obtain a surface-treated M nanoparticle sol; wherein the surface treatment agent is polyvinylpyrrolidone;
- the treatment agent is added in an amount of 0.0002 g/mL to 0.1 g/mL.
- the water bath heating and stirring process comprises: heating and stirring in a water bath at 60 to 90 ° C; the drying treatment process comprises: blast drying at 60 to 80 ° C, followed by 80 to: Dry in an oven at 150 °C.
- the calcination treatment comprises: pre-firing treatment at 500 ° C to 900 ° C for 2 to 10 h; the calcination treatment comprises: calcination at 800 1300 ° C for 1 to 8 h.
- the present invention has the following advantages:
- the luminescent material GaIn0 3 :zM obtained by the present invention can increase the luminescent intensity of the luminescent material of the invention by more than 90% compared with the luminescent material Galn0 3 to which no metal ions are added;
- the obtained luminescent material GaIn0 3 :zM does not require ball milling, has the advantages of good stability, uniform particle size, high luminous efficiency, etc., and can be used as a cathode ray excitation illuminating field in the field of field emission display or illumination;
- the preparation method of the luminescent material of the invention is simple in operation, non-polluting, easy to control, low in equipment requirements, and advantageous for industrial production, and can be widely used in the field of preparation of luminescent materials.
- FIG. 1 is a flow chart of a preparation process of a gallium indium silicate luminescent material according to the present invention
- the present invention provides a gallium indium luminescent material having a chemical formula of: GaIn0 3 :zM; wherein M represents a metal nanoparticle selected from one or two of Ag, Au, Pt or Pd, z The value ranges from 1 ⁇ 10 to 5 ⁇ 0.02.
- the invention also provides a preparation method of the above luminescent material; as shown in FIG. 1, the following steps are included: Step ⁇ , preparation of metal nanoparticle sol
- auxiliary agent Dissolving the auxiliary agent in the above 1) solution under the condition of magnetic stirring, and making the auxiliary agent in the finally obtained M nanoparticle sol content of 1.5 ⁇ 10 ⁇ 4 g/mL ⁇ 2.1 ⁇ 10 ⁇ 3 g /mL;
- auxiliary agent is polyvinylpyrrolidone (PVP), sodium citrate, cetyltrimethylammonium bromide, sodium lauryl sulfate or sodium dodecyl sulfate At least one type;
- a surface treatment agent such as polyvinylpyrrolidone (PVP) is added to the M nanoparticle sol of the above 4), and stirred for 3 to 24 hours to prepare a Surface treatment agent treated M nanoparticle sol, spare; wherein, relative The surface treatment agent is added in an amount of 0.0002 g/mL to 0.1 g/mL in total volume.
- PVP polyvinylpyrrolidone
- Step B Preparation of GaIn0 3 :zM
- the source compound of In and the source compound of Ga are added to a mixed solvent of water and ethanol in a volume ratio of 1:1 to 1:4, a mixed solution containing In ions and Ga ions; wherein, the source compound of In and the source compound of Ga are respectively corresponding nitrates;
- the mixed solution prepared in 6) is sequentially added with a chelating agent, such as citric acid monohydrate and a crosslinking agent, such as polyethylene glycol having a molecular weight of 10,000, to obtain a chelating solution; wherein, the molar amount of the chelating agent is added.
- a chelating agent such as citric acid monohydrate
- a crosslinking agent such as polyethylene glycol having a molecular weight of 10,000
- the precursor prepared in 8) is pre-fired at 500 ° C ⁇ 900 ° C for 2 ⁇ 10h, cooled, ground, and then calcined at 800 1300 ° C for l ⁇ 8h, cooled again, grinding,
- the gallium indium luminescent material having a chemical formula of GaIn0 3 :zM was obtained.
- the innovation of the present invention lies in: doping metal nanoparticles in the Galn0 3 luminescent material, and improving the luminescence intensity of the luminescent material by surface plasmon resonance generated on the surface of the metal particles.
- SP Surface Plasmon
- SPPs surface plasmon polaritons
- the electromagnetic field induced by SPPs not only limits the propagation of light waves in the sub-wavelength size structure, but also generates and manipulates electromagnetic radiation from the optical frequency to the microwave band, achieving active control of light propagation, increasing the optical density of the luminescent material and Enhance its spontaneous emission rate. Moreover, using the coupling effect of surface plasmons, The internal quantum efficiency of the luminescent material can be greatly improved, thereby increasing the luminescent intensity of the luminescent material.
- the molecular weight of the polyethylene glycol is from 2,000 to 20,000.
- Example 1 Preparation of GaInO 3 by Sol-Gel Method : 2x l0 - 2 Au
- chloroauric acid AuCl 3 'HCl' 43 ⁇ 40
- chloroauric acid AuCl 3 'HCl' 43 ⁇ 40
- 14 mg of sodium citrate and 6 mg of cetyltridecyl ammonium bromide were weighed.
- chloroauric acid under magnetic stirring weigh 1.9 mg of sodium borohydride and 17.6 mg of ascorbic acid, respectively, and dissolve it into 10 mL of deionized water to obtain 10 mL of sodium borohydride at a concentration of 5 lO" 3 mol/L.
- Aqueous solution and 10mL of lxl (T 2 mol / L aqueous solution of ascorbic acid; under magnetic stirring, first add 0.08mL of sodium borohydride aqueous solution to the aqueous chloroauric acid solution, stir the reaction for 5min, then add to the aqueous chloroauric acid solution 3.12mLl xl (T 2 mol / L aqueous solution of ascorbic acid, and then continue to react for 30min, that is, 20mL of Au content of 5x l (r 3 mol / L of Au nanoparticle sol; 2g of PVP, magnetic stirring for 8h, after surface treatment) Au nanoparticles.
- the wet gel was dried overnight in a blast oven at 60 ° C, and dried at 110 ° C to obtain a precursor; the precursor was placed in a high temperature furnace, calcined at 500 ° C for 2 h, and cooled to room temperature. After grinding, it is placed in a high-temperature box furnace, calcined at 800 for 8 hours, naturally cooled, and then taken out.
- the desired luminescent material GaInO 3 : 2xl0_ 2 Au.
- the wet gel was dried overnight in a blast oven at 70 ° C, and dried at 120 ° C to obtain a precursor; the precursor was placed in a high temperature furnace, calcined at 800 ° C for 4 h, and cooled to room temperature. After grinding, it is placed in a high-temperature box furnace, calcined at 1000 for 3 hours, and naturally cooled. After removal, the desired luminescent material GaInO 3 : lxl0 - 3 Ag is obtained.
- the wet gel was dried overnight in a blast oven at 80 ° C, and dried at 150 ° C to obtain a precursor; the precursor was placed in a high temperature furnace, calcined at 900 ° C for 10 h, and cooled to room temperature. After grinding, it is placed in a high-temperature box furnace, calcined at 1200 for 2 hours, and naturally cooled. After removal, the desired luminescent material GaInO 3 : lx l0_ 4 Pt is obtained.
- Example 4 Preparation of GaInO 3 by Sol-Gel Method : lx l0 - 4 Pd
- the wet gel was dried overnight in a blast oven at 80 ° C, and dried at 120 ° C to obtain a precursor; the precursor was placed in a high temperature furnace, calcined at 800 ° C for 4 h, and cooled to room temperature. After grinding, it is placed in a high-temperature box furnace, calcined at 1300 for 1 hour, and naturally cooled. After removal, the desired luminescent material GaInO 3 : lx l0_ 5 Pd is obtained.
- Example 5 embodiment sol - gel method Preparation GaInO 3: 2x l0- 5 Pt / Au
- the wet gel was dried overnight in a blast oven at 80 ° C, and then dried at 100 ° C to obtain a precursor; the precursor was placed in a high temperature furnace, calcined at 850 ° C for 5 h, and cooled to room temperature. After grinding, it is placed in a high-temperature box furnace, calcined at 1300 for 1 hour, and naturally cooled. After removal, the desired luminescent material Galn0 3 : 2 X 10 - 5 Pt/Au is obtained.
- the wet gel was dried overnight in a blast oven at 75 ° C, and then dried at 80 ° C to obtain a precursor; the precursor was placed in a high temperature furnace, calcined at 600 ° C for 5 h, and cooled to room temperature. After grinding, it is placed in a high-temperature box furnace, calcined at 900 for 4 hours, and naturally cooled. After removal, the desired luminescent material GaInO 3 : 4x l0 - 4 Ag is obtained.
- FIG. 2 is a comparison chart of luminescence spectra of a phosphor prepared in Example 6 of the present invention under a cathode ray excitation at an acceleration voltage of 7.0 Kv; wherein curve a is a metal nanoparticle GaInO 3 : 4 x 10" 4 Ag luminescent material added; Emission spectrum; curve b is the emission spectrum of the luminescent material Galn0 3.
- Fig. 1 after the Ag metal is doped, the luminescence intensity of the luminescent material is increased by 85%; and the integrated area is increased by 97%.
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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PCT/CN2010/080023 WO2012083517A1 (zh) | 2010-12-20 | 2010-12-20 | 一种铟酸镓发光材料及其制备方法 |
US13/881,161 US9068118B2 (en) | 2010-12-20 | 2010-12-20 | Luminescent material of gallium indium oxide and preparation method thereof |
CN201080069661.XA CN103180408B (zh) | 2010-12-20 | 2010-12-20 | 一种铟酸镓发光材料及其制备方法 |
JP2013544996A JP5688473B2 (ja) | 2010-12-20 | 2010-12-20 | インジウム・ガリウム酸化物発光材料、及びその製造方法 |
EP10861149.2A EP2657317B1 (en) | 2010-12-20 | 2010-12-20 | Luminescent material of gallium indium oxide and preparation method thereof |
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PCT/CN2010/080023 WO2012083517A1 (zh) | 2010-12-20 | 2010-12-20 | 一种铟酸镓发光材料及其制备方法 |
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US (1) | US9068118B2 (zh) |
EP (1) | EP2657317B1 (zh) |
JP (1) | JP5688473B2 (zh) |
CN (1) | CN103180408B (zh) |
WO (1) | WO2012083517A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104059659A (zh) * | 2013-03-20 | 2014-09-24 | 海洋王照明科技股份有限公司 | 掺杂金属纳米粒子的钆酸钙绿光发光材料及制备方法 |
JP2015536363A (ja) * | 2012-10-31 | 2015-12-21 | オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド | ケイ酸塩発光材料及びその製造方法 |
CN111569856A (zh) * | 2020-04-03 | 2020-08-25 | 清华-伯克利深圳学院筹备办公室 | In-Ga2O3复合光催化剂及其制备方法和应用 |
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US20130202909A1 (en) * | 2012-02-06 | 2013-08-08 | Lg Chem, Ltd. | Method of producing metal nanoparticles |
WO2021070021A1 (en) * | 2019-10-10 | 2021-04-15 | King Abdullah University Of Science And Technology | InGaZnO (IGZO) BASED SYSTEM FOR GAS DETECTION AT ROOM TEMPERATURE |
Citations (3)
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US5858278A (en) * | 1996-02-29 | 1999-01-12 | Futaba Denshi Kogyo K.K. | Phosphor and method for producing same |
US20080164801A1 (en) * | 2007-01-05 | 2008-07-10 | Samsung Electronics Co., Ltd | Field emission electrode, method of manufacturing the same, and field emission device comprising the same |
CN101262017A (zh) * | 2008-04-14 | 2008-09-10 | 山东大学 | 一种可调制带隙宽度的镓铟氧化物薄膜及其制备方法 |
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US6761837B2 (en) | 2002-06-12 | 2004-07-13 | General Electric Company | Europium-activated phosphors containing oxides of rare-earth and group-IIIB metals and method of making the same |
US7022263B2 (en) * | 2002-06-12 | 2006-04-04 | General Electric Company | Europium-activated phosphors containing oxides of rare-earth and group-IIIB metals and method of making the same |
DE602004002296T2 (de) * | 2003-04-07 | 2007-04-26 | Nanolumens Acquisition, Inc. | Europium-dotierte gallium-indium oxide als rot-emittierende, elektrolumineszente phosphormaterialien |
US20090253072A1 (en) * | 2008-04-01 | 2009-10-08 | Petruska Melissa A | Nanoparticle reversible contrast enhancement material and method |
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- 2010-12-20 EP EP10861149.2A patent/EP2657317B1/en active Active
- 2010-12-20 JP JP2013544996A patent/JP5688473B2/ja not_active Expired - Fee Related
- 2010-12-20 US US13/881,161 patent/US9068118B2/en active Active
- 2010-12-20 WO PCT/CN2010/080023 patent/WO2012083517A1/zh active Application Filing
- 2010-12-20 CN CN201080069661.XA patent/CN103180408B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US5858278A (en) * | 1996-02-29 | 1999-01-12 | Futaba Denshi Kogyo K.K. | Phosphor and method for producing same |
US20080164801A1 (en) * | 2007-01-05 | 2008-07-10 | Samsung Electronics Co., Ltd | Field emission electrode, method of manufacturing the same, and field emission device comprising the same |
CN101262017A (zh) * | 2008-04-14 | 2008-09-10 | 山东大学 | 一种可调制带隙宽度的镓铟氧化物薄膜及其制备方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015536363A (ja) * | 2012-10-31 | 2015-12-21 | オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド | ケイ酸塩発光材料及びその製造方法 |
CN104059659A (zh) * | 2013-03-20 | 2014-09-24 | 海洋王照明科技股份有限公司 | 掺杂金属纳米粒子的钆酸钙绿光发光材料及制备方法 |
CN111569856A (zh) * | 2020-04-03 | 2020-08-25 | 清华-伯克利深圳学院筹备办公室 | In-Ga2O3复合光催化剂及其制备方法和应用 |
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US20130234077A1 (en) | 2013-09-12 |
US9068118B2 (en) | 2015-06-30 |
EP2657317A1 (en) | 2013-10-30 |
JP5688473B2 (ja) | 2015-03-25 |
CN103180408B (zh) | 2014-07-02 |
EP2657317B1 (en) | 2015-06-17 |
CN103180408A (zh) | 2013-06-26 |
EP2657317A4 (en) | 2014-10-08 |
JP2014503645A (ja) | 2014-02-13 |
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