WO2013143104A1 - 掺杂金属纳米粒子发光材料及其制备方法 - Google Patents
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Definitions
- the invention relates to a luminescent material, in particular to a doped metal nanoparticle luminescent material and a preparation method thereof.
- the preparation of high-performance luminescent materials is one of the key factors in the manufacture of excellent performance field emission devices.
- the sulphide and sulphur oxide-based luminescent materials have high luminescence brightness and certain conductivity, but are easily decomposed under the bombardment of large beam electron beams, and the elemental sulfur is released. "Poisoning" the cathode tip and generating other deposits covering the phosphor surface, reducing the luminous efficiency of the phosphor.
- Oxide and silicate-based luminescent materials have good stability, but the luminous efficiency is not high enough.
- One of the problems to be solved by the present invention is to provide a doped metal nanoparticle luminescent material which can improve the luminous efficiency of a field emitter.
- a doped metal nanoparticle luminescent material having the chemical formula: A 5-x (PO 4 ) 2 SiO 4 :xRE@M y ; wherein @ represents cladding, M is a core, M is a metal nanoparticle, M is selected One of Ag, Au, Pt, Pd and Cu; RE is one or two of Eu, Gd, Tb, Tm, Sm, Ce, Dy and Mn ions; A is Ca, Sr, Ba, Mg One or two of Li, Na, and K elements; x is a stoichiometric coefficient, x is 0 ⁇ x ⁇ 1; y is the molar ratio of M to Si, and y is 0 ⁇ y ⁇ 0.01; preferably, the value of x is 0.001 ⁇ x ⁇ 0.5; the value of y is 1 ⁇ 10 -5 ⁇ y ⁇ 5 ⁇ 10 -3 .
- the second problem to be solved by the present invention is to provide a method for preparing the above-mentioned doped metal nanoparticle luminescent material, comprising the following steps:
- PVP polyvinylpyrrolidone
- step S4 in the air atmosphere or reducing atmosphere, the mixed powder obtained in step S4 is calcined at 800 ⁇ 1600 ° C for 0.5 ⁇ 15h, then cooled to room temperature, the calcined material is taken out, and the metal nanoparticle luminescent material is obtained after grinding.
- the chemical formula of the doped metal nanoparticle luminescent material is A 5-x (PO 4 ) 2 SiO 4 : xRE@M y ;
- M is the core
- M is a metal nanoparticle
- M is selected from Ag, Au, Pt, One of Pd and Cu
- RE is one or two of Eu, Gd, Tb, Tm, Sm, Ce, Dy and Mn ions
- A is Ca, Sr One or two of Ba, Mg, Li, Na, and K elements
- x is a stoichiometric coefficient, x is 0 ⁇ x ⁇ 1
- y is M and Si The molar ratio of y is 0 ⁇ y ⁇ 0.01.
- step S1 the sol of M is obtained by the following method:
- the salt solution containing M, the auxiliary agent for stabilizing dispersion and the reducing agent are stirred and mixed to obtain a sol of M; the molar concentration of the sol of M is 5 ⁇ 10 -4 mol/L to 5 ⁇ 10 - 2 mol/L.
- the salt raw material of M is AgNO 3 , AuCl 3 ⁇ HCl ⁇ 4H 2 O , H 2 PtCl 6 ⁇ 6H 2 O , PdCl 2 ⁇ 2H 2 O and Cu(NO 3 ) 2 At least one
- the auxiliary agent is at least one of polyvinylpyrrolidone, sodium citrate, cetyltrimethylammonium bromide, sodium lauryl sulfate and sodium dodecylsulfonate, and the amount of the auxiliary agent is added.
- the content in the finally obtained M sol is 1 ⁇ 10 -4 g/mL to 5 ⁇ 10 -2 g/mL;
- the reducing agent is at least one of hydrazine hydrate, ascorbic acid, sodium citrate or sodium borohydride, and the molar ratio of the reducing agent to M is 3.6:1 ⁇ 18:1.
- the concentration of the PVP aqueous solution is 0.005 g / mL ⁇ 0.1g / mL.
- the source compound of the A is selected from the group consisting of oxides, carbonates or oxalates of A; the soluble phosphate is NH 4 H 2 PO 4 Or (NH 4 ) 2 HPO 4 ; the source compound of the RE is selected from the group consisting of an oxide, a carbonate or an oxalate.
- the reducing atmosphere is a mixed atmosphere of N 2 and H 2 in a volume ratio of 95:5.
- x has a value of 0.001 ⁇ x ⁇ 0.5; and y has a value of 1 ⁇ 10 -5 ⁇ y ⁇ 5 ⁇ 10 -3 .
- the doped metal nanoparticle luminescent material provided by the invention has high luminous efficiency under electron beam excitation and can be suitably applied to a field emission light source device.
- the preparation method of the doped metal nanoparticle luminescent material has the advantages of simple process, high product quality and low cost, and can be widely applied in the manufacture of luminescent materials.
- 1 is a flow chart of a preparation process of a doped metal nanoparticle luminescent material
- Example 2 is a doped Ag nanoparticle luminescent material prepared by the method of Example 7 (Sr 4.7 Li 0.15 (PO 4 ) 2 SiO 4 : 0.05 Gd, 3 + 0.1 Tb 3 + @Ag 1 ⁇ 10 -5 ) and Comparative Example 1 Comparison of luminescence spectra of luminescent materials (Sr 4.7 Li 0.15 (PO 4 ) 2 SiO 4 :0.05Gd 3+ , 0.1Tb 3+ ) without added nano-Ag particles; wherein curve 1 represents the ratio 1 Luminescence curve of undoped metal nanoparticle luminescent material (Sr 4.7 Li 0.15 (PO 4 ) 2 SiO 4 :0.05Gd 3+ , 0.1Tb 3+ ), curve 2 shows doped Ag nanoparticles prepared in Example 7 A luminescence curve of a luminescent material (Sr 4.7 Li 0.15 (PO 4 ) 2 SiO 4 : 0.05 Gd 3+ , 0.1 Tb 3 + @Ag 1 ⁇ 10 -5 ).
- a doped metal nanoparticle luminescent material provided by the specific embodiment of the present invention has the chemical formula: A 5-x (PO 4 ) 2 SiO 4 : xRE@M y ; wherein @ represents cladding, M is core, M
- M is selected from one of Ag, Au, Pt, Pd, and Cu
- RE is one or both of Eu, Gd, Tb, Tm, Sm, Ce, Dy, and Mn ions
- x is a stoichiometric coefficient, x is 0 ⁇ x ⁇ 1
- y is the molar ratio of M to Si, y
- the value is 0 ⁇ y ⁇ 0.01; preferably, the value of x is 0.001 ⁇ x ⁇ 0.5; the value of y is 1 ⁇ 10 -5 ⁇ y ⁇ 5 ⁇ 10 -3 .
- the preparation method of the above doped metal nanoparticle luminescent material comprises the following steps:
- a M-containing salt solution, an auxiliary agent for stabilizing dispersion, and a reducing agent are mixed to prepare a sol containing M, specifically:
- the auxiliary agent is at least one of polyvinylpyrrolidone, sodium citrate, cetyltrimethylammonium bromide, sodium lauryl sulfate and sodium dodecylsulfonate, and the amount of the auxiliary agent is added.
- the content in the finally obtained M sol is 1 ⁇ 10 -4 g/mL to 5 ⁇ 10 -2 g/mL;
- the reducing agent is at least one of hydrazine hydrate, ascorbic acid, sodium citrate and sodium borohydride.
- the molar ratio of the reducing agent to M is 3.6:1 to 18:1, and the reducing agent is prepared or diluted to a concentration of 1 mol/ An aqueous solution of L ⁇ 1 ⁇ 10 -4 mol / L;
- the salt containing M is at least one of AgNO 3 , AuCl 3 ⁇ HCl ⁇ 4H 2 O , H 2 PtCl 6 ⁇ 6H 2 O , PdCl 2 .2H 2 O and Cu(NO 3 ) 2 , and the solvent is water. Or ethanol; wherein the M is at least one of Ag, Au, Pt, Pd, and Cu nanoparticles.
- the sol containing M is added to the aqueous solution of PVP, and after the surface treatment of the M nanoparticles, the SiO 2 nanospheres are coated by the St ⁇ ber method to obtain SiO 2 @ M y nanospheres, specifically:
- anhydrous ethanol and ammonia water are sequentially added to the surface-treated M, and the mixture is uniformly stirred; then, tetraethyl orthosilicate is added under stirring, and after reacting for 3 to 10 hours, it is separated and dried to obtain SiO 2 @M y nanometer.
- the volume ratio of anhydrous ethanol, deionized water, ammonia water and ethyl orthosilicate is 10:18 ⁇ 30:3 ⁇ 8:1 ⁇ 1.5.
- the mixed powder obtained in the step S2 is calcined at 800 to 1600 ° C for 0.5 to 15 h, and then cooled to room temperature, and taken out.
- the calcined material is doped to obtain a doped metal nanoparticle luminescent material, and the chemical formula of the doped metal nanoparticle luminescent material is A 5-x ( PO 4 ) 2 SiO 4 : xRE@M y ;
- M is the core
- M is a metal nanoparticle
- M is selected from Ag, Au, Pt, One of Pd and Cu
- RE is one or two of Eu, Gd, Tb, Tm, Sm, Ce, Dy and Mn ions
- A is Ca, Sr One or two of Ba, Mg, Li, Na, and K elements
- x is a stoichiometric coefficient, x is 0 ⁇ x ⁇ 1
- y is M and Si The molar ratio of y is 0 ⁇ y ⁇ 0.01.
- the source compound of the A is selected from the group consisting of oxides, carbonates or oxalates of A; the soluble phosphate is NH 4 H 2 PO 4 Or (NH 4 ) 2 HPO 4 ; the source compound of the RE is selected from the group consisting of an oxide, a carbonate or an oxalate.
- the reducing atmosphere is a mixed atmosphere of N 2 and H 2 in a volume ratio of 95:5.
- x has a value of 0.001 ⁇ x ⁇ 0.5; and y has a value of 1 ⁇ 10 -5 ⁇ y ⁇ 5 ⁇ 10 -3 .
- the doped metal nanoparticle luminescent material provided by the invention has high luminous efficiency under electron beam excitation and can be suitably applied to a field emission light source device.
- the preparation method of the doped metal nanoparticle luminescent material has the advantages of simple process, high product quality and low cost, and can be widely applied in the manufacture of luminescent materials.
- Pd nanoparticles doped Ba 4.8 Na 0.1 (PO 4 ) 2 SiO 4 :0.1Eu 2+ luminescent material, ie Ba 4.8 Na 0.1 (PO 4 ) 2 SiO 4 :0.1Eu 2+ @Pd 1 ⁇ 10 -2
- the mixture was calcined at 1100 ° C for 6 h and cooled to room temperature to obtain Ba 4.8 Na 0.1 (PO 4 ) 2 SiO 4 :0.1Eu 2+ luminescent material doped with Pd nanoparticles, ie Ba 4.8 Na 0.1 (PO 4 ) 2 SiO 4 : 0.1Eu 2+ @Pd 1 ⁇ 10 -2 .
- the reducing atmosphere was calcined at 1050 °C for 5 h and cooled to room temperature to obtain Sr 4.7 Li 0.15 (PO 4 ) 2 SiO 4 :0.05Gd 3+ , 0.1Tb 3+ luminescent material doped with Ag nanoparticles, ie Sr 4.7 Li 0.15 (PO 4 ) 2 SiO 4 : 0.05Gd 3+ , 0.1Tb 3+ @Ag 1 ⁇ 10 -5 .
- Example 2 is a doped Ag nanoparticle luminescent material prepared by the method of Example 7 (Sr 4.7 Li 0.15 (PO 4 ) 2 SiO 4 : 0.05Gd 3+ , 0.1Tb 3+ @Ag 1 ⁇ 10 -5 ) and Comparative Example 1 Comparison of luminescence spectra of luminescent materials (Sr 4.7 Li 0.15 (PO 4 ) 2 SiO 4 : 0.05 Gd, 0.1 Tb ) without added nano-Ag particles; wherein curve 1 represents the undoped metal prepared by the ratio 1 Luminescence curve of nanoparticle luminescent material (Sr 4.7 Li 0.15 (PO 4 ) 2 SiO 4 :0.05Gd 3+ , 0.1Tb 3+ ), curve 2 shows doped Ag nanoparticle luminescent material prepared in Example 7 (Sr 4.7 Lu 0.15 (PO 4 ) 2 SiO 4 : 0.05Gd 3+ , 0.1Tb 3+ @Ag 1 ⁇ 10 -5 ).
- the emission peak at 545 nm is doped with Ag under 5kV electron beam excitation.
- the luminescence intensity of the luminescent material after the nanoparticle is 45% higher than that of the luminescent material of the undoped Ag nanoparticle.
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Abstract
Description
Claims (10)
- 一种掺杂金属纳米粒子发光材料,其特征在于,其化学式为: A5-x(PO4)2SiO4:xRE@M y ;其中, @ 表示包覆, M 为内核, M 为金属纳米粒子, M 选自 Ag 、 Au 、 Pt 、 Pd 及 Cu 中的一种; RE 为 Eu 、 Gd 、 Tb 、 Tm 、 Sm 、 Ce 、 Dy 及 Mn 离子中的一种或两种; A 为 Ca 、 Sr 、 Ba 、 Mg 、 Li 、 Na 及 K 元素中的一种或两种; x 为化学计量系数, x 的取值为 0<x≤1 ; y 为 M 与 Si 的摩尔之比, y 的取值为 0<y≤0.01 。
- 根据权利要求 1 所述的种掺杂金属纳米粒子发光材料,其特征在于, x 的取值为 0.001≤x≤0.5 ; y 的取值为 1 ×10-5≤y≤5×10-3 。
- 一种掺杂金属纳米粒子发光材料的制备方法,其特征在于,包括如下步骤:S1 、室温下,称取 PVP 溶于去离子水中,配制成 PVP 水溶液;然后加入 M 的溶胶至 PVP 水溶液,磁力搅拌 2~24h ,得经表面处理后的 M 的溶胶溶液;S2 、随后向表面处理过的 M 的溶胶溶液中依次加入无水乙醇和氨水,搅拌均匀;接着,在搅拌下加入正硅酸乙酯,反应 3~10h 后,分离干燥,制得 SiO2 @My 纳米球;其中,无水乙醇、去离子水、氨水、正硅酸乙酯的体积比为 10:18~30:3~8:1~1.5 ;S3 、按照化学式 A5-x(PO4)2SiO4:xRE@M y 中各元素的化学计量比,称取 A 的源化合物、易溶性磷酸盐、 RE 的源化合物及步骤 S2 制得的 SiO2 @My 纳米球,研磨、均匀混合,获得混合粉体;S4 、在空气气氛或还原气氛中,将步骤 S3 获得的混合粉体在 800~1600℃ 下保温煅烧 0.5~15h ,然后冷却至室温,取出煅烧物,研磨后即得掺杂金属纳米粒子发光材料,该掺杂金属纳米粒子发光材料的化学式为 A5-x(PO4)2SiO4:xRE@M y ;上述步骤中, @ 表示包覆, M 为内核, M 为金属纳米粒子, M 选自 Ag 、 Au 、 Pt 、 Pd 及 Cu 中的一种; RE 为 Eu 、 Gd 、 Tb 、 Tm 、 Sm 、 Ce 、 Dy 及 Mn 离子中的一种或两种; A 为 Ca 、 Sr 、 Ba 、 Mg 、 Li 、 Na 及 K 元素中的一种或两种; x 为化学计量系数, x 的取值为 0<x≤1 ; y 为 M 与 Si 的摩尔之比, y 的取值为 0<y≤0.01 。
- 根据权利要求 3 所述的掺杂金属纳米粒子发光材料的制备方法,其特征在于,步骤 S1 中, M 的溶胶是采用如下方法制得的:将含 M 的盐溶液、起稳定分散作用的助剂和还原剂混合,搅拌反应后,制得含 M 的溶胶; M 的溶胶的摩尔浓度为 5×10-4mol/L ~ 5×10-2mol/L 。
- 根据权利要求 4 所述的掺杂金属纳米粒子发光材料的制备方法,其特征在于,所述 含 M 的盐溶液中, M 的盐原料为 AgNO3 、 AuCl3·HCl·4H2O 、H2PtCl6·6H2O 、 PdCl2·2H2O 及 Cu(NO3)2 中的至少一种。
- 根据权利要求 4 所述的掺杂金属纳米粒子发光材料的制备方法,其特征在于,所述助剂为聚乙烯砒咯烷酮、柠檬酸钠、十六烷基三甲基溴化铵、十二烷基硫酸钠及十二烷基磺酸钠中的至少一种,助剂的添加量在最终得到的 M 溶胶中的含量为 1×10-4g/mL ~ 5×10-2g/mL ;还原剂为水合肼、抗坏血酸、柠檬酸钠及硼氢化钠中的至少一种,还原剂的添加量与 M 的摩尔比为 3.6:1 ~ 18:1 。
- 根据权利要求 3 所述的掺杂金属纳米粒子发光材料的制备方法,其特征在于,步骤 S1 中, PVP 水溶液的浓度为 0.005g /mL ~ 0.1g /mL 。
- 根据权利要求 3 所述的掺杂金属纳米粒子发光材料的制备方法,其特征在于,步骤 S3 中,所述 A 的源化合物选自 A 的氧化物、碳酸盐或草酸盐;所述易溶性磷酸盐为 NH4H2PO4 或 (NH4)2HPO4 ;所述 RE 的源化合物选自氧化物、碳酸盐或草酸盐。
- 根据权利要求 3 所述的掺杂金属纳米粒子发光材料的制备方法,其特征在于,步骤 S4 中,所述还原气氛为体积比为 95:5 的 N2 和 H2 的混合气氛。
- 根据权利要求 3 至 9 任一所述的种掺杂金属纳米粒子发光材料的制备方法,其特征在于, x 的取值为 0.001≤x≤0.5 ; y 的取值为 1 ×10-5≤y≤5×10-3 。
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PCT/CN2012/073261 WO2013143104A1 (zh) | 2012-03-29 | 2012-03-29 | 掺杂金属纳米粒子发光材料及其制备方法 |
JP2015502043A JP2015514830A (ja) | 2012-03-29 | 2012-03-29 | 金属ナノ粒子ドープ発光材料及びその調製方法 |
US14/372,743 US20140374658A1 (en) | 2012-03-29 | 2012-03-29 | Luminescent materials doped with metal nano particles and preparation methods therefor |
CN201280066461.8A CN104039924A (zh) | 2012-03-29 | 2012-03-29 | 掺杂金属纳米粒子发光材料及其制备方法 |
EP12872469.7A EP2832818B1 (en) | 2012-03-29 | 2012-03-29 | Luminescent materials doped with metal nano particles and preparation methods therefor |
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PCT/CN2012/073261 WO2013143104A1 (zh) | 2012-03-29 | 2012-03-29 | 掺杂金属纳米粒子发光材料及其制备方法 |
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US (1) | US20140374658A1 (zh) |
EP (1) | EP2832818B1 (zh) |
JP (1) | JP2015514830A (zh) |
CN (1) | CN104039924A (zh) |
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CN108251112A (zh) * | 2018-03-17 | 2018-07-06 | 青岛科技大学 | 一种新型的光谱可调的自激活荧光粉 |
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CN111205831B (zh) * | 2020-01-17 | 2021-10-12 | 江苏大学 | 一种分频液的纳米流体及其制备方法和应用 |
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CN101284990A (zh) * | 2008-06-05 | 2008-10-15 | 复旦大学 | 一种碱土金属磷硅酸盐白色光发射荧光粉及其制造方法 |
CN102382646A (zh) * | 2010-08-31 | 2012-03-21 | 海洋王照明科技股份有限公司 | 一种硅酸钇钠绿光发光材料及其制备方法 |
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CN102191054B (zh) * | 2010-03-11 | 2013-10-09 | 海洋王照明科技股份有限公司 | 硅酸盐发光材料及其制备方法 |
EP2565251B1 (en) * | 2010-04-30 | 2014-09-17 | Ocean's King Lighting Science&Technology Co., Ltd. | A rare earth-aluminium/gallate based fluorescent material and manufacturing method thereof |
EP2565252B1 (en) * | 2010-04-30 | 2014-07-02 | Ocean's King Lighting Science&Technology Co., Ltd. | Aluminate fluorescent materials and preparation methods thereof |
CN102906219B (zh) * | 2010-06-18 | 2014-05-21 | 海洋王照明科技股份有限公司 | 卤硅酸盐发光材料及其制备方法和应用 |
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- 2012-03-29 US US14/372,743 patent/US20140374658A1/en not_active Abandoned
- 2012-03-29 EP EP12872469.7A patent/EP2832818B1/en not_active Not-in-force
- 2012-03-29 CN CN201280066461.8A patent/CN104039924A/zh active Pending
- 2012-03-29 WO PCT/CN2012/073261 patent/WO2013143104A1/zh active Application Filing
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CN101284990A (zh) * | 2008-06-05 | 2008-10-15 | 复旦大学 | 一种碱土金属磷硅酸盐白色光发射荧光粉及其制造方法 |
CN102382646A (zh) * | 2010-08-31 | 2012-03-21 | 海洋王照明科技股份有限公司 | 一种硅酸钇钠绿光发光材料及其制备方法 |
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Cited By (2)
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CN108251112A (zh) * | 2018-03-17 | 2018-07-06 | 青岛科技大学 | 一种新型的光谱可调的自激活荧光粉 |
CN108251112B (zh) * | 2018-03-17 | 2020-07-28 | 青岛科技大学 | 一种新型的光谱可调的自激活荧光粉 |
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EP2832818A1 (en) | 2015-02-04 |
EP2832818A4 (en) | 2015-12-09 |
EP2832818B1 (en) | 2016-10-12 |
US20140374658A1 (en) | 2014-12-25 |
CN104039924A (zh) | 2014-09-10 |
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