WO2014040220A1 - 硅酸盐发光材料及其制备方法 - Google Patents

硅酸盐发光材料及其制备方法 Download PDF

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WO2014040220A1
WO2014040220A1 PCT/CN2012/081237 CN2012081237W WO2014040220A1 WO 2014040220 A1 WO2014040220 A1 WO 2014040220A1 CN 2012081237 W CN2012081237 W CN 2012081237W WO 2014040220 A1 WO2014040220 A1 WO 2014040220A1
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luminescent material
silicate luminescent
nanoparticles
value range
sol
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PCT/CN2012/081237
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English (en)
French (fr)
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周明杰
王荣
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海洋王照明科技股份有限公司
深圳市海洋王照明工程有限公司
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Application filed by 海洋王照明科技股份有限公司, 深圳市海洋王照明工程有限公司 filed Critical 海洋王照明科技股份有限公司
Priority to EP12884461.0A priority Critical patent/EP2896673A4/en
Priority to PCT/CN2012/081237 priority patent/WO2014040220A1/zh
Priority to US14/427,343 priority patent/US20150267110A1/en
Priority to JP2015530257A priority patent/JP2015531413A/ja
Priority to CN201280075663.9A priority patent/CN104619811A/zh
Publication of WO2014040220A1 publication Critical patent/WO2014040220A1/zh

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Definitions

  • the present invention relates to the field of luminescent materials, and in particular to a silicate luminescent material and a method of preparing the same. Background technique
  • LEDs Light emitting diodes
  • One of the main ways to achieve white light is to use a blue GaN chip in combination with a yellow YAG:Ce phosphor to produce white light.
  • the disadvantage of this method is that the color rendering index is low.
  • the combination of near-ultraviolet LED chips and red, green and blue phosphors into white LEDs has high luminous efficiency, adjustable color temperature and high color rendering index, and has been widely studied and become the mainstream of development. Therefore, LED trichromatic phosphors which are effectively excited by violet light and near-ultraviolet light have been extensively studied.
  • luminescent materials based on silicate system have been widely concerned because of their rich raw materials, low price, wide process adaptability, moderate synthesis temperature and high stability.
  • the divalent europium ion-activated alkaline earth metal orthosilicate luminescent material is a good green luminescent material, and its excitation spectrum is wider and the color purity is better than that of the YAG luminescent material.
  • a luminescent material has a problem of low luminous efficiency and poor color rendering.
  • a silicate luminescent material having the chemical formula: (Ba 1-y A y ) 2-x Si0 4 :Eu x , D z @M n ; wherein @ is a cladding, M is a core, (BanA y Si0 4 :Eu x , D z coating the M to form a shell layer; A is at least one of Sr, Ca, Mg and Zn elements, D is F or C1 element, and M is Ag, Au, Pt, Pd And at least one of the Cu nanoparticles; the value of X ranges from 0.001 ⁇ x ⁇ 0.15, and the range of y 0 ⁇ y ⁇ 0.5, the value range of z is 0 ⁇ z ⁇ 0.5; n is the ratio of M to the molar ratio of Si in the silicate luminescent material, and the value of n ranges from 0 ⁇ 1 ⁇ 1 ( ⁇ 2 .
  • X has a value in the range of 0.005 ⁇ ⁇ ⁇ 0.10.
  • the value of y ranges from 0.05 ⁇ y ⁇ 0.2.
  • z has a value in the range of 0.01 ⁇ z ⁇ 0.2.
  • n has a value in the range of 1 ⁇ 10 ⁇ 4 ⁇ ⁇ ⁇ 5 ⁇ 1 ( ⁇ 3 .
  • the above silicate luminescent material forms a core-shell structure by coating metal nanoparticles, and the ruthenium is a core, and (8& ⁇ 2 ⁇ 0 4 , 0 2 is a shell layer, which improves the internal quantum efficiency of the silicate, and at the same time
  • the surface plasmon effect of the nanoparticles makes the luminescence efficiency of the silicate luminescent material greatly improved under the same excitation conditions, and the wavelength of the emitted light does not change, and has the luminescence of the conventional erbium-doped silicate luminescent material. It has the characteristics of higher efficiency and better color rendering, and has the advantages of holding the stability of the silicate luminescent material.
  • a method for preparing a silicate luminescent material having higher luminous efficiency comprises the following steps:
  • cerium-containing nanoparticle-containing sol wherein the cerium is at least one of Ag, Au, Pt, Pd and Cu elements;
  • a mixed solvent of ethanol and water, ammonia water and ethyl orthosilicate are added to the sol containing M nanoparticles in a ratio of a molar ratio of Si to M, and the mixture is stirred and reacted.
  • M sheath nanoparticles Si0 2, Si0 2 @M n obtained containing sol, and then the sol Si0 2 @M n was separated and dried to give powder of Si0 2 @M n, where @ is coated, 0 ⁇ 1 ⁇ 10" 2 ;
  • the molar ratio of Ba to yttrium (1-y): y and the molar ratio of Ba to A and the molar ratio of Eu to Si are (2-x): X: 1, the Ba raw material, A is weighed. The raw material, the Eu raw material and the Si0 2 @M n powder are mixed, and the obtained mixture is pretreated at 600 ° C to 1000 ° C for 2 to 10 hours, and then reduced in a reducing atmosphere at 1000 ° C to 1400 ° C.
  • a silicate luminescent material of the formula (Ba 1-y A y ) 2-x Si0 4 :Eu x , D z @M n , wherein M is the inner core, (Ba 1 -y A y ) 2-x Si0 4 :Eu x , D z coating the M to form a shell layer; A is an element of Sr, Ca, Mg and Zn At least one of them, D is a F or CI element; 0.001 ⁇ x ⁇ 0.15, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.5.
  • the salt solution of the metal M is AgN0 3 , AuCl 3 -HCl-4H 2 0, H 2 PtCl 6 '6H 2 0, PdCl 2 -2H 2 0 and Cu(N0 3 ) 2 a solution of at least one salt.
  • the adjuvant is polyvinylpyrrolidone, sodium citrate, cetyltridecyl ammonium bromide, sodium lauryl sulfate, and sodium dodecyl sulfate.
  • concentration of the auxiliary agent in the sol containing M nanoparticles is lx lO 4 g / mL ⁇ 5 x lO 2 g / mL;
  • the reducing agent is at least one of hydrazine hydrate, ascorbic acid, sodium citrate and sodium borohydride, and the molar ratio of the amount of the reducing agent added to the metal ion in the salt solution of the metal M is 3.6: 1 ⁇ 18: 1.
  • the method further comprises the step of surface-treating the M nanoparticles by adding a polyvinylpyrrolidone aqueous solution to the sol containing M nanoparticles, wherein the concentration of the aqueous solution of polyvinylpyrrolidone is 0.005 g/mL. ⁇ 0.1g/mL.
  • the Ba raw material is at least one of a carbonate, a hydrochloride, an oxide, a nitrate, an acetate, and an oxalate of Ba;
  • the A raw material is an oxide of A At least one of a nitrate, a carbonate, an acetate, and an oxalate;
  • the Eu material is at least one of an oxide, a nitrate, a carbonate, an acetate, and an oxalate of Eu. .
  • a sol-gel method is used to prepare Si0 2 @M, and then 8 ⁇ ) 2 @1 ⁇ is used as a silicon source, and a high-temperature solid phase method is used to correspond to Sr, A and Eu.
  • the compound is prepared by coating a silicate luminescent material coated with metal nanoparticles, namely ( ⁇ 1 ⁇ ⁇ ⁇ ⁇ ) 2 _ ⁇ 8 ) 4 : ⁇ ⁇ , ⁇ ⁇ @ ⁇ ⁇ , reinforcing silicon by coating metal nanoparticles
  • the luminous efficiency of the acid salt luminescent material has the advantages of simple process equipment, low equipment requirement, no pollution, easy control, and is suitable for industrial production.
  • 1 is a flow chart showing a method of preparing a silicate luminescent material according to an embodiment
  • FIG. 2 is a spectral comparison diagram of the luminescent material prepared in Example 4 under excitation at 460 nm, wherein curve 1 is Ba 1 .99 Si0 4 :Eu coated with metal nanoparticle Ag. . . . 1 : F. . 1 @Ag 2 . 5x l . _ 4 luminescence spectrum of luminescent material, curve 2 is BaL SiO ⁇ Eu m ai luminescent material of uncoated metal nanoparticle Ag Luminescence spectrum.
  • ( ⁇ 1- ⁇ ⁇ ⁇ ) 2- ⁇ 8 ) 4 ⁇ ⁇ , ⁇ ⁇ @ ⁇ ⁇ .
  • @ is a wrap. It is the kernel.
  • Niobium is at least one of the elements of Sr, Ca, Mg and Zn.
  • D is an F or C1 element, and M is at least one of Ag, Au, Pt, Pd, and Cu nanoparticles.
  • the value of X ranges from 0.001 ⁇ x ⁇ 0.15, preferably 0.005 ⁇ x ⁇ 0.10.
  • the value of y ranges from 0 ⁇ y ⁇ 0.5, preferably 0.05 ⁇ y ⁇ 0.2.
  • the value of z ranges from 0 ⁇ z ⁇ 0.5, preferably 0.01 ⁇ z ⁇ 0.2;
  • n is the ratio of M to the molar ratio of Si in the silicate luminescent material, and the value of n ranges from 0 ⁇ ⁇ ⁇ 1 ⁇ 1 ( ⁇ 2 , preferably 1 ⁇ 1 ( ⁇ 4 ⁇ ⁇ ⁇ 5 ⁇ 1 ( ⁇ 3 .
  • the above silicate luminescent material forms a core-shell structure by coating metal nanoparticles, and the ruthenium is a core, and (8& ⁇ 2 ⁇ 0 4 , 0 2 is a shell layer, which improves the internal quantum efficiency of the silicate, and at the same time
  • the surface plasmon effect of the nanoparticles makes the luminescence efficiency of the silicate luminescent material greatly improved under the same excitation conditions, and the wavelength of the emitted light does not change, and has the luminescence of the conventional erbium-doped silicate luminescent material. It has the characteristics of higher efficiency and better color rendering, and has the advantages of holding the stability of the silicate luminescent material.
  • a method for preparing a silicate luminescent material includes the following steps:
  • step S110 a salt solution of a metal ruthenium, an auxiliary agent and a reducing agent are mixed and reacted to obtain a sol containing ruthenium nanoparticles, wherein ruthenium is at least one of Ag, Au, Pt, Pd and Cu elements.
  • the salt solution of the metal M is at least one of AgN0 3 , AuCl 3 -HCl-4H 2 0 , H 2 PtCl 6 -6H 2 0, PdCl 2 '2H 2 0 and Cu(N0 3 ) 2 .
  • a solution of a salt is water or ethanol.
  • the auxiliary agent is at least one of polyvinylpyrrolidone (PVP), sodium citrate, cetyltrimethylammonium bromide, sodium lauryl sulfate, and sodium dodecylsulfonate.
  • PVP polyvinylpyrrolidone
  • the concentration in the range is lxlO- 4 g/mL ⁇ 5xlO-/mL.
  • the reducing agent is at least one of hydrazine hydrate, ascorbic acid, sodium citrate and sodium borohydride, and the molar ratio of the reducing agent added to the metal ion in the salt solution of the metal M is 3.6:1 to 18:1.
  • the method further comprises the step of surface-treating the M nanoparticles by adding a polyvinylpyrrolidone aqueous solution to the sol containing the M nanoparticles, wherein the concentration of the aqueous solution of the polyvinylpyrrolidone is 0.005 g/mL. 0.1 g/mL.
  • Step S120 using a Stober method, adding a mixed solvent of ethanol and water, ammonia water and ethyl orthosilicate to the sol containing M nanoparticles according to a ratio of Si to M molar ratio of n, stirring and mixing, and reacting at M nanoparticles coated with an outer layer of Si0 2, to obtain a sol containing Si0 2 @M n, and then on Si0 2 @M n sol was separated and dried to give powder of Si0 2 @M n, where @ is coated,
  • Step S130 according to the molar ratio of Ba to ytterbium (1-y): y and the molar ratio of Ba to A and the molar ratio of Eu to Si are (2-x): X: 1 ratio, weigh Ba
  • the raw material, the A raw material, the Eu raw material and the Si0 2 @M n powder are mixed, and the obtained mixture is pretreated at 600 ° C to 1000 ° C for 2 to 10 hours, and then in a reducing atmosphere at 1000 ° C to 1400 ° C.
  • the Ba raw material is at least one of a carbonate, a hydrochloride, an oxide, a nitrate, an acetate, and an oxalate of Ba.
  • the material A is at least one of oxides, nitrates, carbonates, acetates and oxalates of A.
  • the raw material is at least one of Eu oxides, nitrates, carbonates, acetates and oxalates.
  • the reducing atmosphere is a mixed gas atmosphere of N 2 and 3 ⁇ 4, a CO reducing atmosphere or a pure 3 ⁇ 4 reducing atmosphere.
  • a sol-gel method is used to prepare Si0 2 @M, and then 8 ⁇ ) 2 @1 ⁇ is used as a silicon source, and a high-temperature solid phase method is used to correspond to Sr, A and Eu.
  • the compound is prepared by coating a silicate luminescent material coated with metal nanoparticles, namely ( ⁇ 1 ⁇ ⁇ ⁇ ⁇ ) 2 _ ⁇ 8 ) 4 : ⁇ ⁇ , ⁇ ⁇ @ ⁇ ⁇ , reinforcing silicon by coating metal nanoparticles
  • the luminous efficiency of the acid salt luminescent material The method of the process tube single, set Low requirements, no pollution, easy to control, suitable for industrial production.
  • the different compositions of the silicate luminescent materials and their preparation methods, as well as their performance and the like, are described below in conjunction with specific examples.
  • Pt nanoparticle sol Weigh 51.8mg of chloroplatinic acid (H 2 PtCl 6 -6H 2 0 ) and dissolve it in 17mL of deionized water; when chloroplatinic acid is completely dissolved, weigh 40.0mg of sodium citrate and 60.0mg Sodium dodecyl sulphate is dissolved in chloroplatinic acid aqueous solution under magnetic stirring; 1.9 mg of sodium borohydride is dissolved in 10 mL of deionized water to obtain 10 mL of boron at a concentration of 5 x 1 (T 3 mol/L).
  • Surfactant treatment Measure 10 mL of 5 ⁇ 10 O 3 mol/L Pt nanoparticle sol in a beaker, and add 4 mL of 0.02 g/mL PVP solution and magnetically stir for 18 hours to obtain Pt nanoparticles with surface treatment. Sol.
  • Surfactant treatment Measure 8 mL of 2.5 ⁇ 10 3 mol/L sol containing Au nanoparticles, add 2 mL of 0.1 g/mL PVP solution to the Au nanoparticle sol and magnetically stir for 8 hours to obtain A sol of surface treated Au nanoparticles.
  • Ba 1 . 99 Si0 4 Eu. . . . 1 @Au. - Preparation of 3 : Weigh 1.2205g of barium oxide (BaO), 0.0070g of cerium oxide (Eu 2 0 3 ) and 0.2524g of the above Si0 2 @Au 5 , the powder is placed in an agate mortar and fully ground until homogeneously mixed, prior to Heat treatment at 800 ° C for 4 hours, then sintering in a tube furnace at 1000 ° C for 4 hours under a weak atmosphere of 95% N 2 + 5% H 2 reduction, cooling to room temperature, to obtain Ba L9 doped with Au nanoparticles.
  • 9Si0 4 Euo.oi@Au 5 xio luminescent material.
  • Pd nanoparticle sol Weigh 0.22 mg of palladium chloride (PdCl 2 '2H 2 0 ) and dissolve it in 19 mL of deionized water. When palladium chloride is completely dissolved, weigh l l.Omg sodium citrate and 4.0 mg. Sodium lauryl sulfate was dissolved in an aqueous solution of palladium chloride under magnetic stirring; 3.8 mg of sodium borohydride was dissolved in 10 mL of deionized water to obtain sodium borohydride at a concentration of lx lO- 2 mol/L.
  • Surfactant treatment Measure 1.5 mL of 5 ⁇ 10 ⁇ 5 mol/L sol containing Pd nanoparticles in a beaker, and add 8 mL of 0.005 g/mL PVP and magnetically stir for 16 hours to obtain Pd nanoparticles with surface treatment. Sol.
  • Preparation of Ag nanoparticle sol Weigh 3.4mg of silver nitrate (AgN0 3 ) and dissolve it into 18.4mL of deionized water. When the silver nitrate is completely dissolved, weigh 42mg of sodium citrate and dissolve it into the silver nitrate aqueous solution under magnetic stirring. Weigh 5.7mg of sodium borohydride dissolved in 10mL of deionized water to obtain 10mL of sodium borohydride aqueous solution with a concentration of 1.5xlO 2 mol / L; in a magnetic stirring environment, add 1.6mL1 to the silver nitrate aqueous solution. 5xlO_ 2 mol/L of sodium borohydride aqueous solution, and then the reaction was continued for 10 minutes to obtain 20 mL of Ag-containing sol containing Ag content of I x 10 3 mol/L.
  • Surfactant treatment Measure 1.2 mL of I l0" 3 mol/L sol containing Ag nanoparticles in a beaker, add 10 mL of 0.01 g/mL PVP, and stir magnetically for 12 hours to obtain Ag with surface treatment. A sol of nanoparticles.
  • Preparation of Si0 2 @Ag 2 .5x io-4 While stirring, sequentially add 30 mL of absolute ethanol, 7.2 mL of ammonia water, and 1.2 mL of tetraethyl orthosilicate to the above sol; after 6 hours of reaction, centrifuge to the solid phase, the solid phase material is washed and dried, to give Si0 2 @Ag 2. 5xl. -4 powder.
  • Ba L99 Si0 4 Euo. oi: Fo.i@Ag 2 .5x io-4 luminescent material and Ba SiO coated with uncoated metal particles prepared by coating the metal nanoparticle Ag prepared in this embodiment.
  • ⁇ Eu ⁇ F i luminescent material at 460nm excitation spectrum comparison chart can be seen from the figure at 505nm emission peak, coated with metal nanoparticles after the luminescent material's luminescence intensity is higher than that of uncoated metal nanoparticles The luminescence is enhanced by 35%.
  • Ag nanoparticle sol Weigh 0.0429g silver nitrate (AgN0 3 ), 0.0733g sodium citrate, 0.05g PVP, respectively, to make 10mL 0.025 mol / L AgN0 3 aqueous solution, lOmL 0.025 mol / L sodium citrate Aqueous solution and 10 mL of 5 mg/mL aqueous PVP solution.
  • Surfactant treatment Measure 5 mL of 1 X 10" 3 mol/L sol containing Ag nanoparticles in a beaker, and add 6 mL of 0.06 g/mL PVP, and magnetically stir for 15 hours to obtain Ag with surface treatment. A sol of nanoparticles.
  • Si0 2 @Ag 5xl Preparation of -4: While stirring, 35 mL of absolute ethanol, 8 mL of aqueous ammonia, and 1.5 mL of tetraethyl orthosilicate were sequentially added to the above sol. After reaction for 2 hours, to the solid phase by centrifugation, washing the solid phase material, and dried, to give Si0 2 @Ag 5xl. -4 powder. (Ba 0 .8Mgo. 2 ) i.95Si0 4 : Eu. . 05 @Ag 5xl.
  • Preparation of -4 Weigh 1.4062g of barium oxalate (BaC 2 0 4 ), 0.1752g of magnesium oxalate (MgC 2 0 4 ), 0.0567g of bismuth oxalate (Eu 2 (C 2 0 4 ) 3 ) and 0.2524g of the above Si0 2 @Ag 5xl.
  • Pd nanoparticle sol Weigh 6.6 mg of palladium chloride (PdCl 2 .2H 2 0 ) and dissolve it into 19 mL In deionized water; when the palladium chloride is completely dissolved, weigh l l.Omg sodium citrate and 4.0 mg sodium lauryl sulfate, and dissolve into palladium chloride aqueous solution under magnetic stirring; weigh 3.8
  • the sodium borohydride is dissolved in 10mL of deionized water to obtain a sodium borohydride reducing solution with a concentration of lx lO- 2 mol/L.
  • Surfactant treatment Measure 1.5 mL of 5x lO_ 5 mol/L sol containing Pd nanoparticles in a beaker, add 8 mL of 0.005g/mL PVP, and stir magnetically for 16 hours to obtain Pd nanometers with surface treatment. The sol of particles.
  • Surfactant treatment Measure 5 mL of I x l0_ 3 mol/L of Ag. . 5 /Au. . 5 nanoparticle sol In a beaker, 10 mL of 0.1 g/mL PVP was added and magnetically stirred for 12 hours to obtain a surface-treated Ag. .5/Au 5 nanoparticle sol.

Abstract

本发明涉及一种硅酸盐发光材料及其制备方法，该硅酸盐发光材料具有如下化学通式：(Ba1-yAy)2-xSiO4：Eux，Dz@Mn；其中，@是包覆，Mn 为内核，（Ba1-yAy）2-xSiO4：Eux，Dz为壳层；A为Sr、Ca、Mg或 Zn中的一种或者两种， D为F或Cl中的任意一种，M为Ag、Au、Pt、Pd和Cu金属纳米粒子中的至少一种；x的取值范围为 0.001<x≤0.15，y的取值范围为 0<y≤0.5，z的取值范围为 0≤z≤0.5；n为 M金属纳米粒子与所述硅酸盐发光材料中 Si的摩尔之比，n 的取值范围为 0<n≤1×10-2。通过包覆金属纳米粒子形成核壳结构，有效的提高了发光材料的内量子效率，同时由于金属纳米粒子的表面等离子体效应，极大的提高了硅酸盐发光材料的发光效率。该硅酸盐发光材料的制备方法具有工艺简单、设备要求低、无污染、易于控制，适于工业化生产的优点。

Description

说明书
发明名称： 硅酸盐发光材料及其制备方法
技术领域
本发明涉及发光材料技术领域， 特别是涉及一种硅酸盐发光材料及其制 备方法。 背景技术
白光 LED( light emitting diodes)具有效率高、寿命长、体积小、响应快速、 无污染、 节能等优点得到了越来越广泛的重视。 实现白光的主要方式之一是 采用蓝色 GaN芯片与黄色 YAG:Ce荧光粉组合产生白光。 该方法的缺点是显 色指数低。 而利用近紫外 LED 芯片与红、 绿、 蓝三基色荧光粉组合成白光 LED, 其发光效率高、 色温可调且显色指数高， 已被广泛研究， 并成为发展 的主流。 因此， 可被紫光、 近紫外光有效激发的 LED三基色荧光粉被广泛研 究。 其中， 以硅酸盐体系为基体的发光材料因其具有原料来源丰富、 价格便 宜、 工艺适应性广泛、 合成温度适中、 稳定性较高等优点一直被广泛关注。
二价铕离子激活的碱土金属正硅酸盐发光材料是一种很好的绿色发光材 料， 与 YAG发光材料相比， 其激发光谱更宽、 色纯度更好。 但目前这种发光 材料存在发光效率低、 显色性较差的问题。 发明内容
基于此， 有必要提供一种发光效率较高的硅酸盐发光材料。
一种硅酸盐发光材料，具有化学通式： (Ba1-yAy)2-xSi04:Eux,Dz@Mn;其中， @是包覆， M为内核， （BanAy) Si04:Eux,Dz包覆所述 M形成壳层； A为 Sr、 Ca、 Mg及 Zn元素中的至少一种， D为 F或 C1元素， M为 Ag、 Au、 Pt、 Pd 和 Cu纳米粒子中的至少一种； X的取值范围为 0.001<x≤0.15, y的取值范围 为 0<y≤0.5 , z的取值范围为 0≤z≤0.5; n为 M与所述硅酸盐发光材料中 Si的 摩尔之比， n的取值范围为 0<η≤1 χ 1(Τ2。
在其中一个实施例中， X的取值范围为 0.005≤χ≤0.10。
在其中一个实施例中， y的取值范围为 0.05≤y≤0.2。
在其中一个实施例中， z的取值范围为 0.01 <z<0.2。
在其中一个实施例中， n的取值范围为 1 χ10·4≤η≤5χ1(Τ3。
上述硅酸盐发光材料，通过包覆金属纳米粒子形成核壳结构， Μ为内核， (8&^ 2^^04 ,02为壳层， 提高了硅酸盐的内量子效率， 同时由于金属纳 米粒子的表面等离子体效应， 使得硅酸盐发光材料在同样激发条件下的发光 效率得到极大的提高， 发射光的波长没有改变， 具有比传统的掺杂铕的硅酸 盐发光材料的发光效率更高、 显色性更好的特点， 同时具备捧杂铕硅酸盐发 光材料稳定性的优点。
此外， 还提供一种发光效率较高的硅酸盐发光材料的制备方法， 包括如 下步骤：
将金属 Μ的盐溶液、 助剂和还原剂混合并反应， 制得含 Μ纳米粒子的 溶胶， 其中， 所述 Μ为 Ag、 Au、 Pt、 Pd和 Cu元素中的至少一种；
使用 Stober法， 按照 Si与 M的摩尔比为 n的比例， 向所述含 M纳米粒 子的溶胶中加入乙醇与水的混合溶剂、氨水和正硅酸乙酯， 搅拌混匀后反应， 在所述 M纳米粒子的外层包覆 Si02, 得到含 Si02@Mn的溶胶， 再对溶胶中 Si02@Mn进行分离干燥处理， 得到 Si02@Mn粉末， 其中， @是包覆， 0<η<1 χ 10"2;
按照 Ba与 Α的摩尔比为 （ 1-y ): y以及 Ba与 A的摩尔量之和与 Eu和 Si的摩尔比为 （ 2-x ) ： X： 1的比例， 称取 Ba原料、 A原料、 Eu原料及所述 Si02@Mn粉末混匀， 得到的混合物于 600°C~1000°C下预处理 2~10小时， 然 后在还原气氛中于 1000 °C~1400°C下还原 1~8小时， 冷却， 得到化学通式为 (Ba1-yAy)2-xSi04:Eux,Dz@Mn 的硅酸盐发光材料， 其中， M 为内核， (Ba1-yAy)2-xSi04:Eux,Dz包覆所述 M形成壳层； A为 Sr、 Ca、 Mg及 Zn元素中 的至少一种， D为 F或 CI元素; 0.001<x<0.15 , 0<y<0.5 , 0≤z≤0.5。
在其中一个实施例中，所述金属 M的盐溶液为 AgN03、 AuCl3-HCl-4H20, H2PtCl6'6H20、 PdCl2-2H20和 Cu(N03)2中的至少一种盐的溶液。
在其中一个实施例中， 所述助剂为聚乙烯砒咯烷酮、 柠檬酸钠、 十六烷 基三曱基溴化铵、 十二烷基硫酸钠和十二烷基橫酸钠中的至少一种， 所述助 剂在所述含 M纳米粒子的溶胶中的浓度为 l x lO_4g/mL~5x lO_2g/mL;
所述还原剂为水合肼、 抗坏血酸、 柠檬酸钠和硼氢化钠中的至少一种， 所述还原剂的添加量与所述金属 M 的盐溶液中的金属离子的摩尔比为 3.6: 1 ~ 18: 1。
在其中一个实施例中，还包括在含 M纳米粒子的溶胶中添加聚乙烯比咯 烷酮水溶液对 M纳米粒子进行表面处理的步骤， 其中， 所述聚乙烯吡咯烷酮 水溶液的浓度为 0.005g/mL~0.1g/mL。
在其中一个实施例中， 所述 Ba原料为 Ba的碳酸盐、 盐酸盐、 氧化物、 硝酸盐、醋酸盐及草酸盐中的至少一种；所述 A原料为 A的氧化物、硝酸盐、 碳酸盐、 醋酸盐及草酸盐中的至少一种； 所述 Eu原料为 Eu的氧化物、 硝酸 盐、 碳酸盐、 醋酸盐及草酸盐中的至少一种。
上述硅酸盐发光材料的制备方法，首先，采用溶胶 -凝胶法制得 Si02@M, 再以 8^)2@1^为硅源， 采用高温固相法， 与 Sr、 A和 Eu对应的化合物制备 包覆有金属纳米粒子的硅酸盐发光材料， 即 (Β 1_γΑγ)2_χ8 )4:Ειιχ,Οζ@Μη, 通过 包覆金属纳米粒子来增强硅酸盐发光材料的发光效率。 该方法工艺筒单、 设 备要求低、 无污染、 易于控制， 适于工业化生产。 附图说明
图 1为一实施方式的硅酸盐发光材料的制备方法的流程图；
图 2为实施例 4制备的发光材料在 460nm激发下的光谱对比图， 其中曲 线 1是包覆金属纳米粒子 Ag的 Ba1.99Si04:Eu。.。1:F。.1@Ag2.5x l。_4发光材料的发 光光谱， 曲线 2是未包覆金属纳米粒子 Ag的 BaL^SiO^Eu m ai发光材料的 发光光谱。 具体实施方式
下面结合附图及具体实施例对硅酸盐发光材料及其制备方法进行进一步 的说明。
一 实 施 方 式 的 硅 酸 盐 发 光材 料 ， 具 有 化 学 通 式 ：
(Β 1-γΑγ)2-χ8 )4:Ειιχ,Οζ@Μη。其中， @是包覆。 Μ为内核。（Β31-γΑγ)2-χ8 )4:Ειιχ,Οζ 包覆 Μ形成壳层。 Α为 Sr、 Ca、 Mg及 Zn元素中的至少一种。 D为 F或 C1 元素， M为 Ag、 Au、 Pt、 Pd和 Cu纳米粒子中的至少一种。 X的取值范围为 0.001<x<0.15 ,优选 0.005≤x≤0.10。 y的取值范围为 0<y≤0.5,优选 0.05≤y≤0.2。 z的取值范围为 0≤z≤0.5, 优选 0.01≤z≤0.2; n为 M与硅酸盐发光材料中 Si 的摩尔之比， n的取值范围为 0<η≤1 χ1(Τ2, 优选 1 χ1(Τ4≤η≤5χ1(Τ3。
上述硅酸盐发光材料，通过包覆金属纳米粒子形成核壳结构， Μ为内核， (8&^ 2^^04 ,02为壳层， 提高了硅酸盐的内量子效率， 同时由于金属纳 米粒子的表面等离子体效应， 使得硅酸盐发光材料在同样激发条件下的发光 效率得到极大的提高， 发射光的波长没有改变， 具有比传统的掺杂铕的硅酸 盐发光材料的发光效率更高、 显色性更好的特点， 同时具备捧杂铕硅酸盐发 光材料稳定性的优点。
此外， 在本实施方式中还提供一种硅酸盐发光材料的制备方法， 如图 1 所示， 包括如下步骤：
步骤 S110, 将金属 Μ的盐溶液、 助剂和还原剂混合并反应， 制得含 Μ 纳米粒子的溶胶， 其中， Μ为 Ag、 Au、 Pt、 Pd和 Cu元素中的至少一种。
在本实施方式中， 金属 M 的盐溶液为 AgN03、 AuCl3-HCl-4H20 , H2PtCl6-6H20, PdCl2'2H20和 Cu(N03)2中的至少一种盐的溶液。 溶剂为水或 乙醇。
助剂为聚乙烯砒咯烷酮（PVP )、 柠檬酸钠、 十六烷基三曱基溴化铵、 十 二烷基硫酸钠和十二烷基磺酸钠中的至少一种。助剂在含 M纳米粒子的溶胶 中的浓度为 lxlO-4g/mL~5xlO- /mL。 还原剂为水合肼、 抗坏血酸、 柠檬酸钠 和硼氢化钠中的至少一种，还原剂的添加量与金属 M的盐溶液中的金属离子 的摩尔比为 3.6:1 ~ 18:1。
此外， 在本实施方式中， 还包括在含 M纳米粒子的溶胶中添加聚乙烯比 咯烷酮水溶液对 M纳米粒子进行表面处理的步骤， 其中， 聚乙烯吡咯烷酮水 溶液的浓度为 0.005g/mL~0.1g/mL。
步骤 S120, 使用 Stober法， 按照 Si与 M的摩尔比为 n的比例， 向含 M 纳米粒子的溶胶中加入乙醇与水的混合溶剂、 氨水和正硅酸乙酯， 搅拌混匀 后反应， 在 M纳米粒子的外层包覆 Si02, 得到含 Si02@Mn的溶胶， 再对溶 胶中 Si02@Mn进行分离干燥处理， 得到 Si02@Mn粉末， 其中， @是包覆，
Figure imgf000007_0001
步骤 S130, 按照 Ba与 Α的摩尔比为（ 1-y ): y以及 Ba与 A的摩尔量之 和与 Eu和 Si的摩尔比为 （2-x ) ： X： 1的比例， 称取 Ba原料、 A原料、 Eu 原料及 Si02@Mn粉末混匀， 得到的混合物于 600°C~1000°C下预处理 2~10小 时， 然后在还原气氛中于 1000 °C~1400°C下还原 1~8小时， 冷却， 得到化学 通式为（BanAy xSi04:Eux,Dz@Mn的硅酸盐发光材料， 其中， M 为内核， (Bai-yAy)2-xSi04:Eux,Dz包覆 M形成壳层； A为 Sr、 Ca、 Mg及 Zn元素中的至 少一种， D为 F或 C1元素； 0.001<x<0.15, 0<y<0.5, 0≤ζ≤0·5。
在本实施方式中， Ba原料为 Ba的碳酸盐、 盐酸盐、 氧化物、 硝酸盐、 醋酸盐及草酸盐中的至少一种。 A原料为 A的氧化物、 硝酸盐、 碳酸盐、 醋 酸盐及草酸盐中的至少一种。 原料为 Eu的氧化物、 硝酸盐、 碳酸盐、 醋酸盐 及草酸盐中的至少一种。
还原气氛为 N2与 ¾的混合气体气氛、 CO还原气氛或纯 ¾还原气氛。 上述硅酸盐发光材料的制备方法，首先，采用溶胶 -凝胶法制得 Si02@M, 再以 8^)2@1^为硅源， 采用高温固相法， 与 Sr、 A和 Eu对应的化合物制备 包覆有金属纳米粒子的硅酸盐发光材料， 即 (Β 1_γΑγ)2_χ8 )4:Ειιχ,Οζ@Μη, 通过 包覆金属纳米粒子来增强硅酸盐发光材料的发光效率。 该方法工艺筒单、 设 备要求低、 无污染、 易于控制， 适于工业化生产。 下面结合具体实施例来说明硅酸盐发光材料的不同组成及其制备方法， 以及其性能等方面的测试。
实施例 1
高温
Figure imgf000008_0001
, 10-2：
Pt纳米粒子溶胶的制备：称取 51.8mg氯铂酸（ H2PtCl6-6H20 )溶解到 17mL 的去离子水中； 当氯铂酸完全溶解后， 称取 40.0mg柠檬酸钠和 60.0mg十二 烷基橫酸钠， 并在磁力搅拌的环境下溶解到氯铂酸水溶液中； 称取 1.9mg硼 氢化钠溶解到 10mL去离子水中， 得到 10mL浓度为 5xl(T3mol/L的硼氢化钠 水溶液， 同时配制 10mL浓度为 5xlO_2mol/L的水合肼溶液； 磁力搅拌的环境 下， 先往氯铂酸水溶液中滴加 0.4mL硼氢化钠水溶液， 搅拌反应 5分钟， 然 后再往氯铂酸水溶液中滴加 2.6mL 5xlO_2mol/L的水合肼溶液，之后继续反应 40分钟， 即得 10mL Pt含量为 5xlO_3mol/L的含 Pt纳米粒子的溶胶。
表面活性剂处理： 量取 10mL 5xlO_3mol/L的含 Pt纳米粒子 溶胶于烧杯 中， 并加入 4mL 0.02g/mL的 PVP溶液， 磁力搅拌 18小时， 得到含有经表面 处理后的 Pt纳米粒子的溶胶。
SiO2@Ptl x l 0-2的制备：一边搅拌一边依次向上述溶胶中加入 25mL无水乙 醇、 5mL氨水， 1.2mL正硅酸四乙酯， 反应 8小时后， 经离心去固相物质、 取固相物质、 洗涤固相物质、 干燥， 得到 Si02@Ptlxl。-2粉末。
Figure imgf000008_0002
的制备： 称取 1.2352g 碳酸钡 (BaC03), 0.1092g碳酸锶 (SrC03)、 0.1452g碳酸铕 (Eu2(C03)3)、 0.0832g氯化 钡 (BaCl2)和 0.2524g上述 Si02@Ptlxl。-2粉末置于玛瑙研钵中充分研磨至混合 均匀， 先于 600°C热处理 10小时， 然后于管式炉中在 CO还原气氛下 1300°C 烧结 1 小时还原， 冷却至室温， 即可得到掺杂 Pt 纳米粒子的 (Ba 9Sr i)L85SiO4:Eu0.15,Cl0.20@Ptl x l 0-2发光材料。
实施例 2 高温固相法制备 Bai 9Si04:Euo.oi@Au5 , ι
Au纳米粒子溶胶的制备： 称取 10.3mg氯金酸（ AuCl3'HC14H20 )溶解 到 16.8mL的去离子水中； 当氯金酸完全溶解后， 称取 14mg柠檬酸钠和 6mg 十六烷基三曱基溴化铵， 并在磁力搅拌的环境下溶解到氯金酸水溶液中； 称 取 1.9mg硼氢化钠和 17.6mg抗坏血酸分别溶解到 10mL去离子水中， 得到 lOmL浓度为 5x lO_3mol/L的硼氢化钠水溶液和 lOmL浓度为 I x l0_2mol/L的抗 坏血酸水溶液； 在磁力搅拌的环境下，先往氯金酸水溶液中加入 0.08mL硼氢 化钠水溶液，搅拌反应 5分钟后再往氯金酸水溶液中加入 3.12mLl x l(T2mol/L 的抗坏血酸水溶液,之后继续反应 30分钟，即得 20mLAu含量为 2.5xl(T3mol/L 的含 Au纳米粒子的溶胶。
表面活性剂处理： 量取 8mL为 2.5xlO_3mol/L的含 Au纳米粒子的溶胶， 往 Au纳米粒子溶胶中于烧杯中并加入 2mL 0.1 g/mL 的 PVP溶液， 磁力搅拌 8小时， 得到含有经表面处理后的 Au纳米粒子的溶胶。
^^ ^的制备： 一边搅拌一边依次向上述溶胶中依次加入 20mL 无水乙醇、 4mL氨水， lmL正硅酸四乙酯。 待反应 3小时后， 经离心去固相 物质、 洗涤固相物质、 干燥， 得到 Si02@Au 。-3粉末。
Ba1.99Si04:Eu。.。1@Au 。-3的制备： 称取 1.2205g 氧化钡 (BaO)、 0.0070g 氧化铕 (Eu203)和 0.2524g上述 Si02@Au5 , 粉末置于玛瑙研钵中充分研磨至 混合均匀， 先于 800°C热处理 4小时， 然后于管式炉中在 95%N2+5%H2弱还 原气氛下 1000 °C烧结 4小时还原， 冷却至室温， 即可得到掺杂 Au纳米粒子 的 BaL99Si04:Euo.oi@Au5xio 发光材料。
实施例 3
高温固相法制备 (Ba0.5Cao.5)L999Si04:Eu0細, F s ?^ , 10-5：
Pd纳米粒子溶胶的制备：称取 0.22mg氯化钯（PdCl2'2H20 )溶解到 19mL 的去离子水中； 当氯化钯完全溶解后， 称取 l l.Omg柠檬酸钠和 4.0mg十二烷 基硫酸钠， 并在磁力搅拌的环境下溶解到氯化钯水溶液中； 称取 3.8mg硼氢 化钠溶到 lOmL去离子水中， 得到浓度为 l x lO-2mol/L的硼氢化钠还原液； 在 磁力搅拌的环境下，往氯化钯水溶液中快速加入 lmL I l0"2mol/L的硼氢化钠 水溶液， 之后继续反应 20分钟， 即得 20mL Pd含量为 5xl(T5mol/L的含 Pd 纳米粒子的溶胶。
表面活性剂处理： 量取 1.5mL 5xlO_5mol/L的含 Pd纳米粒子的溶胶于烧 杯中， 并加入 8mL 0.005g/mL PVP, 并磁力搅拌 16小时， 得到含有经表面处 理后的 Pd纳米粒子的溶胶。
SiOs®?^ ^的制备： 一边搅拌一边依次向上述溶胶中依次加入 40mL 无水乙醇、 8mL氨水， 1.8mL正硅酸四乙酯。 待反应 5小时后， 经离心去固 相物质、 洗涤固相物质、 干燥， 得到 SiC^ ?^ ^^粉末。
(Bao.5Cao.5)i.999Si04:Euo.ooi,Fo.5@Pdi , ιο-s的制备： 称取 0.1958g 硝酸钡 (Ba(N03)2 0.6560g硝酸钙 (Ca(N03)2 0.0014g硝酸铕 (Eu(N03)3 0.1753g 氟化钡 (BaF2)和 0.2526g上述 SiOs ?^ ^^粉末置于玛瑙研钵中充分研磨至 混合均匀， 1000°C热处理 2小时， 然后于管式炉中在 ¾还原气氛下 1300°C 烧结 8 小时还原， 冷却至室温， 即可得到掺杂 Pd 纳米粒子的
Figure imgf000010_0001
, 10-5发光材料。
实施例 4
高温固相法制备 Bai.99Si04:Euo.oi:Fo.i@Ag2.5xio-4:
Ag纳米粒子溶胶的制备： 称取 3.4mg硝酸银 ( AgN03 )溶解到 18.4mL 的去离子水中； 当硝酸银完全溶解后， 称取 42mg柠檬酸钠在磁力搅拌的环 境下溶解到硝酸银水溶液中； 称取 5.7mg硼氢化钠溶到 10mL去离子水中， 得到 10mL浓度为 1.5xlO_2mol/L的硼氢化钠水溶液； 在磁力搅拌的环境下， 往硝酸银水溶液中一次性加入 1.6mL1.5xlO_2mol/L的硼氢化钠水溶液， 之后 继续反应 10分钟， 即得 20mL Ag含量为 I xl0_3mol/L的含 Ag纳米粒子的溶 胶。
表面活性剂处理： 量取 1.2mL I l0"3mol/L的含 Ag纳米粒子的溶胶于烧 杯中， 再加入 10mL 0.01 g/mL PVP, 并磁力搅拌 12小时， 得到含经表面处理 后的 Ag纳米粒子的溶胶。 Si02@Ag2.5x io-4的制备： 一边搅拌一边依次向上述溶胶中加入依次加入 30mL无水乙醇、 7.2mL氨水， 1.2mL正硅酸四乙酯； 待反应 6小时后， 经离 心去固相物质、 洗涤固相物质、 干燥， 得到 Si02@Ag2.5xl。-4粉末。
BaL99Si04:Eu。.。1:F。.1@Ag2.5xl。-4的制备：称取 1.1898g氧化钡 (BaO)、0.0070g 氧化铕 (Eu203)、 0.0350g氟化钡 (BaF2)和 0.2524g上述 Si02@Ag2.5xl。-4粉末置 于玛瑙研钵中充分研磨至混合均匀， 800°C热处理 2小时， 然后于管式炉中在 95%N2+5%H2弱还原气氛下 1250°C烧结 4 小时还原， 冷却至室温， 即得到 BaL99SiO4:Eu0.01:F i@Ag2.5x l0-4发光材料。
如图 2 所示是本实施例制备的 包覆金属纳米粒子 Ag 的 BaL99Si04:Euo.oi:Fo.i@Ag2.5x io-4 发 光 材 料 与 未 包 覆 金 属 粒 子 的 Ba^SiO^Eu ^F i发光材料在 460nm激发下的光谱对比图，从图中可以看出 在 505nm处的发射峰， 包覆金属纳米粒子后发光材料的发光强度较未包覆金 属纳米粒子的样品的发光增强了 35%。
实施例 5
高温固相法制备 (Baa8Mg0.2) L95SiO4:Eu0.05 @Ag5 x i0-4:
Ag纳米粒子溶胶的制备： 分别称取 0.0429g硝酸银 (AgN03)、 0.0733g柠 檬酸钠、 0.05g PVP分别配制成 lOmL 0.025 mol/L的 AgN03水溶液、 lOmL 0.025 mol/L 的柠檬酸钠水溶液和 10mL 5mg/mL 的 PVP 水溶液。 取 2mL AgN03水溶液加入到 30mL去离子水中， 同时加入上述 PVP水溶液 4mL搅 拌， 加热至 100°C , 然后逐滴加入 4mL柠檬酸钠水溶液， 反应 15分钟后， 得 到 40mL I l0"3mol/L的含 Ag纳米粒子的溶胶。
表面活性剂处理： 量取 5mL 1 X 10"3mol/L的含 Ag纳米粒子的溶胶于烧杯 中， 并加入 6mL 0.06g/mL PVP, 并磁力搅拌 15小时， 得到含经表面处理后 的 Ag纳米粒子的溶胶。
Si02@Ag5xl。-4的制备： 一边搅拌一边向上述溶胶中依次加入 35mL无水 乙醇、 8mL氨水、 1.5mL正硅酸四乙酯。 待反应 2小时后， 经离心去固相物 质、 洗涤固相物质、 干燥， 得到 Si02@Ag5xl。-4粉末。 (Ba0.8Mgo.2)i.95Si04: Eu。.05@Ag5xl。-4的制备：称取 1.4062g草酸钡 (BaC204)、 0.1752g 草酸镁 (MgC204)、 0.0567g 草酸铕（Eu2(C204)3)和 0.2524g 上述 Si02@Ag5xl。-4粉末置于玛瑙研钵中充分研磨至混合均匀， 900°C热处理 5 小 时， 然后于管式炉中在 95%N2+5%¾弱还原气氛下 1150°C烧结 6小时还原， 冷却至室温， 即得到 (Baa8Mg 2)i.95SiO4:Eu 05@Ag5xl0-4发光材料。
实施例 6
高温固相法制备 (Ba0.7Sra2Mg i)1.9SiO4:Eu0.1,Cl0.01@Culxl0-4:
Cu纳米粒子溶胶的制备： 称取 1.6mg硝酸铜溶解到 16mL的乙醇中， 完 全溶解后，一边搅拌一边加入 12mgPVP, 然后緩慢滴入用 0.4mg硼氢化钠溶 到 10mL 乙醇中得到的 lxl(T3mol/L的硼氢化钠醇溶液 4mL, 继续搅拌反应 10分钟， 得到 20mL 4χ 10"4mol/L的含 Cu纳米粒子的溶胶。
表面活性剂处理：量取 1.5mL4xlO_4mol/L的 Cu纳米粒子溶胶于烧杯中， 并加入 5mL0.03g/mLPVP, 并磁力搅拌 10小时， 得到含经表面处理后的 Cu 纳米粒子的溶胶。
SiO2@Culxl0-4的制备： 一边搅拌一边向上述溶胶中依次加入 15mL无水 乙醇、 3mL氨水， 1.4mL正硅酸四乙酯。 待反应 4小时后， 经离心去固相物 质、 洗涤固相物质、 干燥， 得到 Si02@Culxl。-4粉末。
(Ba 7Sr 2Mg i)1.9SiO4:Eu 1,Cl 01@Culxl0-4的制备： 称取 1.3537g 乙酸钡 (Ba(CH3COO)2)、 0.3127g 乙 酸锶（Sr(CH3COO)2)、 0.1082g 乙 酸镁 (Mg(CH3COO)2)、 0.1316g 乙酸铕 (Eu(CH3COO) 3), 0.0042g氯化钡 (BaCl2)和 0.2524g上述 Si02@Culxl()-4粉末置于玛瑙研钵中充分研磨至混合均匀， 700 °C 热处理 6小时， 然后于管式炉中在 95%N2+5%¾弱还原气氛下 1350°C烧结 6 小时还原， 冷却至室温， 即得到 ^^^！^^ ^^^ ！^^ ^^ 发 光材料。
实施例 7
高温固相法制备 (Ba0.95Zn0.05)L995SiO4:Eu0.005@Pd3 , 10-4：
Pd纳米粒子溶胶的制备： 称取 6.6mg氯化钯（ PdCl2.2H20 )溶解到 19mL 的去离子水中； 当氯化钯完全溶解后， 称取 l l.Omg柠檬酸钠和 4.0mg十二烷 基硫酸钠， 并在磁力搅拌的环境下溶解到氯化钯水溶液中； 称取 3.8mg硼氢 化钠溶到 10mL去离子水中， 得到浓度为 l x lO-2mol/L的硼氢化钠还原液； 在 磁力搅拌的环境下，往氯化钯水溶液中快速加入 lmL I l0"2mol/L的硼氢化钠 水溶液， 之后继续反应 20分钟， 即得 20mL Pd含量为 1.5x l(T3mol/L的含 Pd 纳米粒子的溶胶。
表面活性剂处理： 量取 1.5mL 5x lO_5mol/L的含 Pd纳米粒子的溶胶于烧 杯中， 并加入 8mL 0.005g/mL PVP, 并磁力搅拌 16小时， 得到含经表面处理 后的 Pd纳米粒子的溶胶。
SiOs®?^ ^^的制备： 一边搅拌一边依次向上述溶胶中依次加入 40mL 无水乙醇、 8mL氨水， 1.8mL正硅酸四乙酯。 待反应 5小时后， 经离心去固 相物质、 洗涤固相物质、 干燥， 得到 Si02@Pd3 x 1 ()-4粉末。
(Bao.95Zno.o5)i.995Si04:Euo.oo5@Pd3 , 10-4的制备： 称取 1 · 1624g氧化钡 (BaO)、 0.0325g氧化锌 (ZnO)、 0.0035g氧化铕 (Eu203)和 0.2524g上述 Si02@Pd3 χ 10-4 粉末置于玛瑙研钵中充分研磨至混合均匀， 600°C热处理 8小时， 然后于管式 炉中在 CO 还原气氛下 1400 °C烧结 3 小时还原， 冷却至室温， 即得到 (Bao.95Zno.05) 1.995 Si04： Euo.005 @Pd3 x 10-4发光材料。
实施例 8
高温固相法制备 Β .958ίΟ4:Ειι 05@(Α8α5/Αιι0.5) 1.25 10-3
Ago.5/Au。.5纳米粒子溶胶的制备： 称取 6.2mg氯金酸（ AuCl3'HC14H20 ) 和 2.5mg AgN03溶解到 28mL的去离子水中； 当完全溶解后， 称取 22mg柠 檬酸钠和 20mgPVP, 并在磁力搅拌的环境下溶解到上述混合溶液中； 称取新 制备的 5.7mg 硼氢化钠溶到 10mL 去离子水中， 得到 10mL 浓度为 1.5x lO"2mol/L的硼氢化钠水溶液； 在磁力搅拌的环境下， 往上述混合溶液中 一次性加入 2mL1.5x lO_2mol/L的硼氢化钠水溶液，之后继续反应 20分钟， 即 得 30mL总金属浓度为 I xl0_3mol/L的含 Ag/Au纳米粒子的溶胶。
表面活性剂处理： 量取 5mL I x l0_3mol/L的含 Ag。.5/Au。.5纳米粒子的溶胶 于烧杯中， 并加入 10mL 0.1g/mL PVP, 并磁力搅拌 12小时， 得到含经表面 处理后的 Ag。.5/Au 5纳米粒子的溶胶。
Si02@(Ago.5/Auo.5) i .25x io-3的制备： 一边搅拌一边向溶胶中依次加入 30mL 无水乙醇、 6mL氨水、 lmL正硅酸四乙酯。 待反应 5小时后， 经离心去固相 物质、 洗涤固相物质、 干燥， 得到 Si02@(Ag 5/Au 5)1.25xl()-3粉末。
BaL95Si04:Euo.o5@(Ago.5/Auo.5)i .25x io-3的制备： 称取 1.1959g (氧化钡) BaO、 0.0352g (氧化铕) Eu203和 0.2524g上述 Si02@(Ag。.5/Au。.5)1.25xl。-3粉末置于玛瑙 研钵中充分研磨至混合均匀， 800 °C热处理 5 小时， 然后于管式炉中在 95%N2+5%H2弱还原气氛下 1300°C烧结 2 小时还原， 冷却至室温， 即得到 (Mgo.1 Sr0.84Eu0.06)3 Si05: F0.丄 0@(Ag0.5/Au0.5) i .25x 10-3发光材料。
细， 但并不能因此而理解为对本发明专利范围的限制。 应当指出的是， 对于 本领域的普通技术人员来说， 在不脱离本发明构思的前提下， 还可以做出若 干变形和改进， 这些都属于本发明的保护范围。 因此， 本发明专利的保护范 围应以所附权利要求为准。

Claims

权利要求书
1 、 一种硅酸盐发光材料， 其特征在于， 具有化学通式： (Ba1-yAy)2-xSi04:Eux,Dz@Mn;其中， @是包覆， M为内核，（Β 1-γΑγ)2-χ8 )4:Ειιχ,Οζ 包覆所述 Μ形成壳层； Α为 Sr、 Ca、 Mg及 Zn元素中的至少一种， D为 F 或 C1元素， M为 Ag、 Au、 Pt、 Pd和 Cu纳米粒子中的至少一种； x的取值 范围为 0.001<x≤0.15 , y的取值范围为 0<y≤0.5, z的取值范围为 0≤z≤0.5; n 为 M与所述硅酸盐发光材料中 Si的摩尔之比， n的取值范围为 0<n≤lxl(T2。
2、 如权利要求 1所述的硅酸盐发光材料， 其特征在于， X的取值范围为 0·005≤χ≤0· 10。
3、 如权利要求 1所述的硅酸盐发光材料， 其特征在于， y的取值范围为
Figure imgf000015_0001
4、 如权利要求 1所述的硅酸盐发光材料， 其特征在于， z的取值范围为
Figure imgf000015_0002
5、 如权利要求 1所述的硅酸盐发光材料， 其特征在于， n的取值范围为
Figure imgf000015_0003
6、 一种硅酸盐发光材料的制备方法， 其特征在于， 包括如下步骤： 将金属 M的盐溶液、 助剂和还原剂混合并反应， 制得含 M纳米粒子的 溶胶， 其中， 所述 M为 Ag、 Au、 Pt、 Pd和 Cu元素中的至少一种；
按照 Si与 M的摩尔比为 n的比例， 向所述含 M纳米粒子的溶胶中加入 乙醇与水的混合溶剂、 氨水和正硅酸乙酯， 搅拌混勾后反应， 在所述 M纳米 粒子的外层包覆 Si02, 得到含 Si02@Mn的溶胶， 再对溶胶中 Si02@Mn进行 分离干燥处理， 得到 Si02@Mn粉末， 其中， @是包覆， 0<η<1 χ 10"2;
按照 Ba与 A的摩尔比为 （ 1-y ): y以及 Ba与 A的摩尔量之和与 Eu和 Si的摩尔比为 （ 2-x ) ： X： 1的比例， 称取 Ba原料、 A原料、 Eu原料及所述 Si02@Mn粉末混匀， 得到的混合物于 600°C~1000°C下预处理 2~10小时， 然 后在还原气氛中于 1000 °C~1400°C下还原 1~8小时， 冷却， 得到化学通式为 (Ba1-yAy)2-xSi04:Eux,Dz@Mn 的硅酸盐发光材料， 其中， M 为内核， (Bai-yAy)2-xSi04:Eux,Dz包覆所述 M形成壳层； A为 Sr、 Ca、 Mg及 Zn元素中 的至少一种， D为 F或 C1元素; 0.001<x<0.15, 0<y<0.5, 0≤z≤0.5。
7、 如权利要求 6所述的硅酸盐发光材料的制备方法， 其特征在于， 所述 金属 M的盐溶液为 AgN03、 AuCl3-HCl-4H20, H2PtCl6-6H20, PdCl2'2H20和 Cu(N03)2中的至少一种盐的溶液。
8、 如权利要求 6所述的硅酸盐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、 十六烷基三曱基溴化铵、 十二烷基硫酸 钠和十二烷基礒 g史钠中的至少一种， 所述助剂在所述含 M纳米粒子的溶胶中 的浓度为 lxl(T4g/mL~5xl(T2g/mL;
所述还原剂为水合肼、 抗坏血酸、 柠檬酸钠和硼氢化钠中的至少一种， 所述还原剂的添加量与所述金属 M 的盐溶液中的金属离子的摩尔比为 3.6: 1 ~ 18: 1。
9、 如权利要求 6所述的硅酸盐发光材料的制备方法， 其特征在于， 还包 括在含 M纳米粒子的溶胶中添加聚乙烯比咯烷酮水溶液对 M纳米粒子进行 表面处理的步骤， 其中， 所述聚乙烯吡咯烷酮水溶液的浓度为 0.005g/mL~0.1g/mL„
10、 如权利要求 6所述的硅酸盐发光材料的制备方法， 其特征在于， 所 述 Ba原料为 Ba的碳酸盐、 盐酸盐、 氧化物、 硝酸盐、 醋酸盐及草酸盐中的 至少一种； 所述 A原料为 A的氧化物、 硝酸盐、 碳酸盐、 醋酸盐及草酸盐中 的至少一种； 所述 Eu原料为 Eu的氧化物、 硝酸盐、 碳酸盐、 醋酸盐及草酸 盐中的至少一种。
PCT/CN2012/081237 2012-09-11 2012-09-11 硅酸盐发光材料及其制备方法 WO2014040220A1 (zh)

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