WO2012019359A1 - 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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WO2012019359A1
WO2012019359A1 PCT/CN2010/075972 CN2010075972W WO2012019359A1 WO 2012019359 A1 WO2012019359 A1 WO 2012019359A1 CN 2010075972 W CN2010075972 W CN 2010075972W WO 2012019359 A1 WO2012019359 A1 WO 2012019359A1
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source compound
silicate phosphor
preparing
metal nanoparticle
precursor
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PCT/CN2010/075972
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English (en)
French (fr)
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周明杰
马文波
廖秋荣
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海洋王照明科技股份有限公司
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Priority to US13/806,375 priority Critical patent/US9074136B2/en
Priority to EP20100855780 priority patent/EP2604671A4/en
Priority to JP2013523453A priority patent/JP5649730B2/ja
Priority to PCT/CN2010/075972 priority patent/WO2012019359A1/zh
Priority to CN201080067332.1A priority patent/CN102933688B/zh
Publication of WO2012019359A1 publication Critical patent/WO2012019359A1/zh

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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
    • C09K11/77742—Silicates
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less

Definitions

  • the invention belongs to the technical field of luminescent materials, and in particular relates to a silicate phosphor and a preparation method thereof.
  • White LED Light Emitting Diodes
  • white LED has the advantages of low power consumption, long life and environmental protection. With the improvement of luminous efficiency and the reduction of production cost, white LED is expected to become a new generation of illumination light after incandescent, fluorescent and high-intensity discharge lamps.
  • Solid-state light source white light LEDs replace traditional vacuum light sources as transistors replace traditional vacuum electron tubes. Destructive technological innovations will cause a revolution in the field of lighting.
  • the most common method for achieving LED white light is to form a white LED by combining a blue LED chip and a yellow-emitting phosphor that can be effectively excited by blue light.
  • this method can achieve high luminous efficiency, it lacks red light in its emission wavelength and cannot obtain warm white light and high color rendering white LED.
  • Another way to implement white LEDs is to use a blue LED chip with green and red phosphors to achieve a white LED with high color rendering and low color temperature.
  • green phosphors and nitride red phosphors have low luminance and high cost.
  • the main disadvantage is that the half-height width is narrow, and the existing luminescent material having a wide emission spectrum has low luminous efficiency.
  • the present invention provides a silicate phosphor powder doped with metal nanoparticles, which has high luminous efficiency, performance and structural stability.
  • a silicate phosphor having the chemical formula: M 2 a M 3 b Si c O [a+3(b+x)/2+2c] :xCe 3+ , yM 0 , wherein 2.8 ⁇ a ⁇ 3.2 , 1.8 ⁇ b ⁇ 2.1, 2.9 ⁇ c ⁇ 3.3, 0.01 ⁇ x ⁇ 0.2, 1 ⁇ 10 -4 ⁇ y ⁇ 1 ⁇ 10 -2 , M 2 is a combination of at least one of Sr, Ba, Mg and Ca M 3 is Sc or a combination of Sc and Y; M 0 represents a metal nanoparticle selected from one of Ag, Au, Pt, Pd or Cu nanoparticles.
  • the source compound of M 2 , M 3 is weighed according to the stoichiometric ratio of the corresponding element in the chemical formula M 2 a M 3 b Si c O [a+3(b+x)/2+2c] :xCe 3+ , yM 0
  • Source compound, source compound of Si, source compound of Ce, and M 0 metal nanoparticle sol wherein 2.8 ⁇ a ⁇ 3.2, 1.8 ⁇ b ⁇ 2.1, 2.9 ⁇ c ⁇ 3.3, 0.01 ⁇ x ⁇ 0.2, 1 ⁇ 10 -4 ⁇ y ⁇ 1 ⁇ 10 -2
  • M 2 is a combination of at least one of Sr, Ba, Mg and Ca
  • M 3 is Sc or a combination of Sc and Y
  • M 0 represents a metal nanoparticle selected from Ag One of Au, Pt, Pd or Cu nanoparticles;
  • the pre-fired precursor is calcined in a reducing atmosphere to obtain the silicate phosphor.
  • the phosphor of the present invention has a higher luminous efficiency by doping the metal nanoparticles
  • the phosphor of the present invention has a broad emission spectrum, and the phosphor powder and the red-emitting phosphor are coated on the blue LED chip to obtain white light with high color rendering and low color temperature;
  • the phosphors can be obtained by the solid phase method by adding the corresponding reactants in proportion, thereby making the preparation process simple, the cost is low, and the invention has broad application prospects.
  • FIG. 1 is a flow chart of a process for preparing a silicate phosphor according to the present invention
  • Example 3 is an excitation spectrum diagram of a silicate phosphor prepared in Example 1 of the present invention at a monitoring wavelength of 505 nm;
  • This embodiment provides a silicate phosphor having a chemical formula of M 2 a M 3 b Si c O [a+3(b+x)/2+2c] :xCe 3+ , yM 0 , wherein 2.8 ⁇ a ⁇ 3.2, 1.8 ⁇ b ⁇ 2.1, 2.9 ⁇ c ⁇ 3.3, 0.01 ⁇ x ⁇ 0.2, 1 ⁇ 10 -4 ⁇ y ⁇ 1 ⁇ 10 -2 , and M 2 is at least one of Sr, Ba, and Mg Combination with Ca; M 3 is Sc or a combination of Sc and Y; M 0 represents a metal nanoparticle selected from one of Ag, Au, Pt, Pd or Cu nanoparticles.
  • This embodiment utilizes a plasma generated on the surface of a metal nanoparticle by incorporating metal nanoparticles into a silicate phosphor (Surface) Plasmon, SP) Resonance effect to increase the luminous intensity of the phosphor.
  • the surface plasmon generated on the surface of metal nanoparticles is a wave propagating along the interface between the metal and the medium, the amplitude of which decays exponentially with the distance from the interface.
  • 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 phosphor and Enhance its spontaneous emission rate. Moreover, by utilizing the coupling effect of the surface plasmon, the internal quantum efficiency of the phosphor can be greatly improved, thereby increasing the luminescence intensity of the silicate phosphor.
  • the above silicate phosphor has strong absorption in the range of 400-500 nm, and is very suitable for excitation of blue LED chips, and can be applied to white LEDs, and has at least the following advantages compared with the prior art:
  • the phosphor of the present invention has a higher luminous efficiency by doping the metal nanoparticles
  • the silicate phosphor of this embodiment has a broad emission spectrum because Ce 3+ is in this silicate.
  • the 4f energy level is cleaved into 2 F 7/2 and 2 F 5/2 , so that the emission peak of Ce 3+ includes a main peak of about 505 nm and a shoulder of about 540, and the emission spectrum is wide; coating on the blue LED chip
  • the silicate phosphor powder and the red-emitting phosphor can obtain white light with high color rendering and low color temperature;
  • the preparation method of the silicate phosphor of the invention is as shown in FIG. 1 , and the preparation process thereof comprises the following steps:
  • the source compound of M 2 , M 3 is weighed Source compound, source compound of Si, source compound of Ce, and M 0 metal nanoparticle sol; wherein 2.8 ⁇ a ⁇ 3.2, 1.8 ⁇ b ⁇ 2.1, 2.9 ⁇ c ⁇ 3.3, 0.01 ⁇ x ⁇ 0.2, 1 ⁇ 10 -4 ⁇ y ⁇ 1 ⁇ 10 -2 , M 2 is a combination of at least one of Sr, Ba, Mg and Ca; M 3 is Sc or a combination of Sc and Y; M 0 represents a metal nanoparticle selected from Ag One of Au, Pt, Pd or Cu nanoparticles;
  • the pre-fired precursor is calcined in a reducing atmosphere to obtain the silicate phosphor.
  • the preparation method of the M 0 metal nanoparticle sol preferably comprises the steps of: dissolving the source compound of M 0 , adding an auxiliary agent and a reducing agent, and after the reaction is completed, adding The surface treatment agent is treated to obtain a M 0 metal nanoparticle sol.
  • a reducing agent solution having a concentration ranging from 1 ⁇ 10 ⁇ 3 mol/L to 0.1 mol/L;
  • the solvent is preferably water and a volatile alcohol, Wherein the volatile alcohol is preferably but not only ethanol;
  • the reducing agent solution in 3) is added to the obtained solution in a molar ratio of reducing agent to M 0 metal ion of 1.2:1 to 4.8:1, and the reaction is carried out for 10 min to 45 min to obtain a solution.
  • reaction liquid prepared in the above 4) was weighed and stirred for 3 h to 24 h by adding a surface treatment agent to obtain a M 0 metal nanoparticle sol.
  • the amount of the auxiliary agent added is preferably 1.5 ⁇ 10 ⁇ 4 g/mL to 2.1 ⁇ 10 ⁇ 3 g/mL in the M 0 metal nanoparticle sol; the molar ratio of the reducing agent added amount to the M 0 metal ion is preferably 1.2:1 to 4.8:1; the amount of the surface treatment agent added is preferably 1.5 ⁇ 10 -4 g / mL to 2.1 ⁇ 10 -3 g / mL in the M 0 metal nanoparticle sol.
  • the source compound of the above M 0 is preferably at least one of silver nitrate, chloroauric acid, chloroplatinic acid, palladium chloride, copper nitrate;
  • the auxiliary agent is preferably polyvinylpyrrolidone (PVP), sodium citrate, ten At least one of hexaalkyltrimethylammonium bromide, sodium lauryl sulfate or sodium dodecylsulfonate;
  • the reducing agent is preferably at least one of hydrazine hydrate, ascorbic acid or sodium borohydride;
  • the surface treatment agent is preferably at least one of polyvinylpyrrolidone and 3-aminopropyltrimethoxysiloxane.
  • the source of the Si compound is preferably, but not limited to four tetraethylorthosilicate; compound of the M source 2 is preferably 2 M nitrates, sulfates, halides at least one substance in; said source compound is preferably 3 M is at least one 3 M nitrate, sulfates, halides; Ce source compound is preferably a Ce nitrate, sulfates, halides At least one of them.
  • the alcohol of the source compound alcohol solution of Si is preferably a volatile alcohol, wherein the volatile alcohol is preferably but not only ethanol; the pH of the mixture is preferably 3-6;
  • the temperature of the water bath heating reaction is preferably 60-95 ° C, and the heating method is not only heated by a water bath, but also a heating method commonly used in the art; the drying temperature is 80-120 ° C.
  • the preferred method of pre-burning the precursor is to first grind the precursor and then perform a pre-firing treatment, thereby improving the pre-treatment effect of the precursor, and the pre-burning temperature is preferably It is 700-1000 ° C, and the time is preferably 3-5 hours.
  • the temperature at which the precursor is calcined in a reducing atmosphere is preferably 1250-1500 ° C, and the time is preferably 2-12 hours; the reducing atmosphere is preferably a mixed atmosphere of nitrogen and hydrogen.
  • the reducing atmosphere is preferably a mixed atmosphere of nitrogen and hydrogen.
  • the volume ratio of N 2 to H 2 in the reducing atmosphere of N 2 and H 2 is preferably, but not limited to, 95:5, and the calcination in the reducing atmosphere is to produce a small amount of +4 valence Ce which is generated during the combustion process.
  • the ions and M 0 ions are reduced to +3 valence Ce ions and M 0 elemental nanoparticles, thereby generating M 2 a M 3 b Si c O [a+3(b+x)/2+2c] :xCe 3+ ,
  • the yM 0 compound effectively ensures the luminescent properties of M 2 a M 3 b Si c O [a+3(b+x)/2+2c] :xCe 3+ , yM 0 .
  • the corresponding reactants are added in proportion to obtain a phosphor by a solid phase method, thereby making the preparation process simple, the cost is low, and the production and application prospects are broad.
  • compositions of the silicate phosphors and their preparation methods, as well as their properties and the like, are exemplified below by way of various examples.
  • the chemical formula is Ca 2.9 Sc 2 Si 3 O 12 :0.1Ce 3+ , 1 ⁇ 10 -3 Ag silicate phosphor
  • the metal nanoparticles were stirred for 12 h; 6 ⁇ 10 -3 mol of tetraethyl orthosilicate was dissolved in 10 ml of ethanol, and then the treated Ag metal nanoparticles and 2.9 mL of 2 mol/L nitric acid were sequentially added while stirring.
  • the precursor was ground and placed in a muffle furnace at 900 ° C for 3 h, and then sintered in a tube furnace at 1300 ° C for 5 h under a 95% N 2 +5% H 2 weak reducing atmosphere. reduction, was cooled to room temperature to obtain Ca 2.9 Sc 2 Si 3 O 12 : 0.1Ce 3+, 1 ⁇ 10 -3 Ag silicate Light powder.
  • FIG. 2 The emission spectrum of the silicate phosphor and the comparatively prepared phosphor under excitation of 460 nm blue light is shown in FIG. 2.
  • curve 1 is an emission spectrum curve of the phosphor prepared in the present embodiment
  • curve 2 is a comparative preparation. Fluorescence emission spectrum curve. It can be seen from the emission spectrum curve that the luminous intensity of the phosphor can be greatly improved by adding metal nanoparticles.
  • the silicate phosphor prepared in this example has an excitation spectrum curve at a monitoring wavelength of 505 nm as shown in FIG. As can be seen from Fig. 3, the silicate phosphor prepared in this example has high luminescence intensity.
  • the silicate phosphor prepared in this example is mixed with Sr 2 Si 5 N 8 :Eu red phosphor, and the emission spectrum curve after encapsulation on the blue LED chip is shown in curve 3 in FIG. 4, and curve 4 in FIG. 4 is YAG yellow.
  • the emission spectrum of the phosphor after the blue LED chip is mounted. 4
  • the color temperature of the white LED of the silicate phosphor prepared in this embodiment and the Sr 2 Si 5 N 8 :Eu red phosphor package is 4860, the color rendering index is 90%, and the luminous efficiency reaches the YAG yellow phosphor package.
  • the white LED light efficiency is 110%; the YAG yellow phosphor package white LED has a color temperature of 6400 and a color rendering index of 78%. It can be seen that the white phosphor LED with high luminous efficiency, high color rendering index and low color temperature is obtained by using the green phosphor of the invention and the red phosphor package.
  • the chemical formula is Ca 2 Sr 0.8 Sc 1.8 Si 2.9 O 11.315 : 0.01Ce 3+ , 1 ⁇ 10 -4 Au silicate phosphor
  • the furnace was heat treated at 700 ° C for 5 h, and then sintered in a tube furnace at 1500 ° C for 2 h under a 95% N 2 +5% H 2 weak reducing atmosphere, and cooled to room temperature to obtain Ca 2 Sr 0.8 Sc 1.8 Si 2.9 O 11.315. : 0.01Ce 3+ , 1 ⁇ 10 -4 Au silicate phosphor.
  • the chemical formula is Ca 1.5 Ba 0.7 Sr 1.0 Sc 1.5 Y 0.6 Si 3.3 O 13.025 : 0.05Ce 3+ , 2 ⁇ 10 -3 Pt silicate phosphor:
  • Eph heat treatment furnace 1000 °C 3h and then sintered in a tube furnace at 1250 °C 12h reduction 95% N 2 + 5% H 2 weak reducing atmosphere, cooled to room temperature, to obtain Ca 1.5 Ba 0.7 Sr 1.0 Sc 1.5 Y 0.6 Si 3.3 O 13.025 : 0.05Ce 3+ , 2 ⁇ 10 -3 Pt phosphor; 6.6 ⁇ 10 -3 mol of tetraethyl orthosilicate was dissolved in 10 ml of ethanol, and then added to the treated one while stirring.
  • Ag metal nanoparticles 1.5 mL of 2 mol/L calcium nitrate solution, 0.7 mL of 2 mol/L lanthanum nitrate solution, 1 mL of 2 mol/L lanthanum nitrate solution, 2 mL of 1 mol/L lanthanum nitrate solution, 2 ml of 0.05 mol /L solution of cerium nitrate, then adjust the pH to 3-4 with nitric acid, then react the solution to a water bath of 85 ° C for 4 hours, dry in an oven at 100 ° C for 3 hours to obtain a precursor, and place the precursor after grinding.
  • the furnace is heat treated at 1000 °C for 3 h in a muffle furnace, and then sintered in a tube furnace at 1250 ° C for 12 h under a weak CO atmosphere. After cooling to room temperature, Ca 1.5 Ba 0.7 Sr 1.0 Sc 1.5 Y 0.6 Si 3.3 O 13.025 : 0.05 Ce 3+ , 2 ⁇ 10 -3 Pt silicate phosphor.
  • the chemical formula is Ca 2.74 Mg 0.06 Sc 2 Si 3.1 O 12.3 : 0.2Ce 3+ , 1 ⁇ 10 -2 Pd silicate phosphor:
  • the barium sulfate solution is then adjusted to pH 3-4 with nitric acid, and then the solution is reacted in a 95 ° C water bath for 3 hours, dried in an oven at 80 ° C for 5 hours to obtain a precursor, and the precursor is ground and placed in a muffle furnace. of annealing at 800 °C 5h, 4h re-sintering reduction at 95% N 2 + 5% H 2 deg.] C in a weakly reducing atmosphere for 1400 tube furnace, To room temperature, to obtain a Ca 2.74 Mg 0.06 Sc 2 Si 3.1 O 12.3: 0.2Ce 3+, 1 ⁇ 10 -2 Pd silicate phosphor.
  • the chemical formula is Ca 1.0 Sr 1.0 Mg 0.9 Sc 1.9 Si 2.95 O 11.77 : 0.08Ce 3+ , 8 ⁇ 10 -4 Cu silicate phosphor:
  • the precursor is ground and placed in a muffle furnace at 750 ° C for 5 h, and then sintered in a tube furnace at 1350 ° C for 8 h under a H 2 weak reducing atmosphere, and cooled to room temperature to obtain Ca 1.0 Sr 1.0 Mg 0.9 Sc. 1.9 Si 2.95 O 11.77 : 0.08Ce 3+ , 8 ⁇ 10 -4 Cu silicate phosphor.
  • the chemical formula is Ca 2.88 Sc 1.94 Y 0.06 Si 3 O 12 : 0.12Ce 3+ , 8 ⁇ 10 -3 Ag silicate phosphor:
  • the precursor was ground and placed in a muffle furnace at 800 ° C for 6 h, and then in a tube furnace at 95% N 2 + 5 %H 2 is reduced in a weak reducing atmosphere at 1450 ° C for 5 h, and cooled to room temperature to obtain Ca 2.88 Sc 1.94 Y 0.0 6 Si 3 O 12 : 0.12Ce 3+ , 8 ⁇ 10 -3 Ag silicate phosphor.
  • the chemical formula is Ca 2.9 Sc 2 Si 3 O 12 : 0.1Ce 3+ silicate phosphor:

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Description

[根据细则37.2由ISA制定的发明名称]　硅酸盐发光材料及其制备方法 技术领域
本发明属于发光材料技术领域，具体涉及一种硅酸盐荧光粉及其制备方法。
背景技术
白光LED（Light Emitting Diodes）具有耗电量小、寿命长、环保等优点。随着发光效率的提高和生产成本的降低，白光LED预计将成为继白炽灯、荧光灯、高强气体放电灯后的新一代照明光源。固态光源白光LED取代传统真空光源如同晶体管取代传统真空电子管一样是破坏性技术创新，将引起照明领域的一场革命。
目前LED白光实现的最常用方法是通过蓝色LED芯片和可被蓝光有效激发的发黄光荧光粉结合组成白光LED。虽然这种方式能获得较高的发光效率，但其发射波长中缺少红光而无法获得暖白光和高显色性的白光LED。实现白光LED的另一种方法就是蓝光LED芯片加上绿色和红色荧光粉，从而获得高显色性低色温的白光LED。但这种绿色荧光粉以及氮化物红色荧光粉的发光亮度较低，而且造价成本高。作为白光LED绿色荧光材料还有主要的缺点是半高宽窄，现有的具有宽的发射光谱发光材料其发光效率较低。
 技术问题
有鉴于此，本发明提供一种硅酸盐荧光粉，该硅酸盐荧光粉掺杂有金属纳米粒子，其发光效率高，性能和结构稳定。
以及，提供一种制备工艺简单、成本低的硅酸盐荧光粉制备方法。
 技术解决方案
本发明解决上述技术问题所采用的技术方案是：
一种硅酸盐荧光粉，其化学式为：M2 aM3 bSicO［a+3(b+x)/2+2c］:xCe3+,yM0，其中，2.8≤a≤3.2，1.8≤b≤2.1，2.9≤c≤3.3，0.01≤x≤0.2，1×10-4≤y≤1×10-2，M2是Sr、Ba、Mg中的至少一种和Ca的组合；M3是Sc或者Sc和Y的组合；M0表示金属纳米粒子，选自Ag、Au、Pt、Pd或Cu纳米粒子中的一种。
以及，一种硅酸盐荧光粉制备方法，其包括如下步骤：
获取M0金属纳米粒子溶胶；
按照化学式M2 aM3 bSicO［a+3(b+x)/2+2c］:xCe3+,yM0中相应元素的化学计量比，称取M2的源化合物、M3的源化合物、Si的源化合物、Ce的源化合物和M0金属纳米粒子溶胶；其中，2.8≤a≤3.2，1.8≤b≤2.1，2.9≤c≤3.3，0.01≤x≤0.2，1×10-4≤y≤1×10-2，M2是Sr、Ba、Mg中的至少一种和Ca的组合；M3是Sc或者Sc和Y的组合；M0表示金属纳米粒子，选自Ag、Au、Pt、Pd或Cu纳米粒子中的一种；
向Si的源化合物的醇溶液中加入M0金属纳米粒子溶胶和M2的源化合物、M3的源化合物和Ce的源化合物的溶液，得到混合液；
将混合液的pH值调至呈酸性，水浴加热反应后，干燥，得到前躯体；
将前躯体预烧；
将预烧后的前躯体在还原气氛中焙烧，得到所述硅酸盐荧光粉。
 有益效果
本发明的硅酸盐荧光粉与现有技术相比，至少具有以下优点：
（1）通过掺杂金属纳米粒子，使本发明的荧光粉有较高的发光效率；
（2）本发明的荧光粉发射光谱较宽，在蓝光LED芯片上包覆该荧光粉体以及发射红光的荧光粉可以获得高显色性低色温的白光；
（3）本发明荧光粉结构、性能非常稳定，它经过水泡、高温加热等处理后，其性能基本不改变；
（4）在该硅酸盐荧光粉制备方法中，按比例添加相应的反应物通过固相法即可获得荧光粉，从而使得制备工艺简单、成本低，具有广阔的生产应用前景。
 附图说明
下面将结合附图及实施例对本发明作进一步说明，附图中：
图1为本发明硅酸盐荧光粉制备工艺流程图；
图2为本发明实施例1制备的硅酸盐荧光粉和对比例制备的荧光粉在460nm蓝光激发下的发射光谱图；其中曲线1是实施例1制备的荧光粉的发射光谱曲线，曲线2是对比例制备的荧光粉的发射光谱曲线；
图3为本发明实施例1制备的硅酸盐荧光粉在监控波长为505nm激发光谱图；
图4为本发明实施例1制备的硅酸盐荧光粉和Sr2Si5N8:Eu红色荧光粉混合与YAG黄色荧光粉分别装在蓝光LED芯片后的发射光谱图；其中曲线3是实施例1制备的荧光粉和Sr2Si5N8:Eu红色荧光粉混合装在蓝光LED芯片后的发射光谱曲线；其中曲线4是YAG黄色荧光粉装在蓝光LED芯片后的发射光谱曲线。
 本发明的实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本实施例提供一种硅酸盐荧光粉，其化学式为：M2 aM3 bSicO［a+3(b+x)/2+2c］:xCe3+,yM0，其中，2.8≤a≤3.2，1.8≤b≤2.1，2.9≤c≤3.3，0.01≤x≤0.2，1×10-4≤y≤1×10-2，M2是Sr、Ba、Mg中的至少一种和Ca的组合；M3是Sc或者Sc和Y的组合；M0表示金属纳米粒子，选自Ag、Au、Pt、Pd或Cu纳米粒子中的一种。
本实施例通过在硅酸盐荧光粉中掺入金属纳米粒子，利用金属纳米粒子表面产生的等离子体（Surface Plasmon，SP）共振效应来提高荧光粉的发光强度。金属纳米粒子表面产生的表面等离子体是一种沿金属和介质界面传播的波，其振幅随离开界面的距离而指数衰减。当在荧光粉中掺杂金属粒子时，表面等离子体激元（Surface plasmon polaritons, SPPs) 的性质、色散关系、激发模式、耦合效应等都将产生重大的变化。SPPs引发的电磁场，不仅仅能够限制光波在亚波长尺寸结构中传播，而且能够产生和操控从光频到微波波段的电磁辐射，实现对光传播的主动操控，增大荧光粉的光学态密度和增强其自发辐射速率。而且，利用表面等离子体的耦合效应，可大大提高荧光粉的内量子效率，从而提高硅酸盐荧光粉的发光强度。
上述硅酸盐荧光粉在400~500nm范围内有强的吸收，非常适合于蓝光LED芯片激发，可应用于白光LED，与现有技术相比，至少具有以下优点：
（1）通过掺杂金属纳米粒子，使本发明的荧光粉有较高的发光效率；
（2）与现有的Eu2+掺杂的硅酸盐绿色荧光粉相比，本实施例硅酸盐荧光粉具有较宽的发射光谱，这是因为Ce3+在这种硅酸盐中4f能级劈裂成2F7/2和2F5/2，从而使得Ce3+的发射峰包括505nm左右的主峰和540左右的肩峰，发射光谱较宽；在蓝光LED芯片上包覆该硅酸盐荧光粉体以及发射红光的荧光粉可以获得高显色性低色温的白光；
（3）本发明荧光粉结构、性能非常稳定，它经过水泡、高温加热等处理后，其性能基本不改变。
以及，本发明硅酸盐荧光粉制备方法，如图1所示，其制备工艺流程包括如下步骤：
S1. 获取M0金属纳米粒子溶胶；
S2. 按照化学式M2 aM3 bSicOa+3(b+x)/2+2c:xCe3+,yM0中相应元素的化学计量比，称取M2的源化合物、M3的源化合物、Si的源化合物、Ce的源化合物和M0金属纳米粒子溶胶；其中，2.8≤a≤3.2，1.8≤b≤2.1，2.9≤c≤3.3，0.01≤x≤0.2，1×10-4≤y≤1×10-2，M2是Sr、Ba、Mg中的至少一种和Ca的组合；M3是Sc或者Sc和Y的组合；M0表示金属纳米粒子，选自Ag、Au、Pt、Pd或Cu纳米粒子中的一种；
S3. 向Si的源化合物的醇溶液中加入M0金属纳米粒子溶胶和M2的源化合物、M3的源化合物和Ce的源化合物的溶液，得到混合液；
S4. 将混合液的pH值调至呈酸性，水浴加热反应后，干燥，得到前躯体；
S5. 将前躯体预烧；
S6. 将预烧后的前躯体在还原气氛中焙烧，得到所述硅酸盐荧光粉。
上述硅酸盐荧光粉制备方法的S1步骤中，所述M0金属纳米粒子溶胶制备方法优选包含步骤为：将M0的源化合物溶解，再加入助剂、还原剂，待反应完毕后，加入表面处理剂处理，得到M0金属纳米粒子溶胶。
该M0金属纳米粒子溶胶制备的更优选方案如下：
1）称取M0的源化合物溶解到溶剂中，配制及稀释成1×10-4mol/L～1×10-2mol/L的溶液，所述溶剂优选为水和易挥发性醇，其中，易挥发性醇优选但不仅仅为乙醇；
2）在磁力搅拌的状态下，将一种或一种以上的助剂溶解到上述1）溶液中；
3）称取相应质量的还原剂物质溶解到溶剂中，配制成浓度范围为1×10-3mol/L～0.1mol/L的还原剂溶液；所述溶剂优选为水和易挥发性醇，其中，易挥发性醇优选但不仅仅为乙醇；
4）在磁力搅拌的环境下，将3）中还原剂溶液按还原剂与M0金属离子的摩尔比为1.2:1～4.8:1加入2）所得到的溶液中，反应10min～45min得到含有M0金属纳米粒子的反应液，该反应液中M0金属纳米粒子浓度为1×10-4mol/L～1×10-2mol/L；
5）量取上述4）制备的反应液，加入表面处理剂搅拌处理3 h~24h，得到M0金属纳米粒子溶胶。
上述助剂添加量为在M0金属纳米粒子溶胶中的含量优选为1.5×10-4g/mL～2.1×10-3g/mL；还原剂添加量与M0金属离子的摩尔比优选为1.2:1～4.8:1；表面处理剂添加量为在M0金属纳米粒子溶胶中的含量优选为1.5×10-4g/mL～2.1×10-3g/mL。
上述M0的源化合物优选为硝酸银、氯金酸、氯铂酸、氯化钯、硝酸铜中的至少一种；助剂优选为聚乙烯砒咯烷酮（PVP）、柠檬酸钠、十六烷基三甲基溴化铵、十二烷基硫酸钠或十二烷基磺酸钠中的至少一种；所述还原剂优选为水合肼、抗坏血酸或硼氢化钠中的至少一种；所述表面处理剂优选为聚乙烯吡咯烷酮、3-氨丙基三甲氧基硅氧烷中的至少一种。
上述硅酸盐荧光粉制备方法的S2步骤中，所述Si的源化合物优选但不仅仅限于四硅酸四乙酯；所述M2的源化合物优选为M2的硝酸盐、硫酸盐、卤化物中的至少一种；所述M3的源化合物优选为M3的硝酸盐、硫酸盐、卤化物中的至少一种；所述Ce的源化合物优选为Ce的硝酸盐、硫酸盐、卤化物中至少的一种。
上述硅酸盐荧光粉制备方法的S3步骤中，所述Si的源化合物醇溶液的醇优选为易挥发性醇，其中，易挥发性醇优选但不仅仅为乙醇；混合液的pH值优选为3-6；所述水浴加热反应的温度优选为60-95℃，该加热方式不仅仅选水浴加热，也可以采用本技术领域常用的加热方式；所述干燥的温度为80-120℃。
上述硅酸盐荧光粉制备方法的S4步骤中，所述前躯体预烧优选方案是先将前躯体研磨，再进行预烧处理，这样可以提高前躯体预处理效果，所述预烧的温度优选为700-1000℃，时间优选为3-5小时。
上述硅酸盐荧光粉制备方法的S5步骤中，所述前躯体在还原气氛中焙烧的温度优选为1250-1500℃，时间优选为2-12小时；该还原气氛优选为氮气与氢气混合还原气氛、CO还原气氛、H2还原气氛中的一种。其中，N2与H2还原气氛中的N2与H2的体积比优选但不仅仅限于为95：5，在该还原气氛中煅烧是为了将在燃烧过程中生成的少量的+4价Ce离子和M0离子还原成+3价Ce离子和M0单质纳米粒子，从而使生成M2 aM3 bSicO［a+3(b+x)/2+2c］:xCe3+,yM0化合物，有效保证M2 aM3 bSicO［a+3(b+x)/2+2c］:xCe3+,yM0的发光性能。
在该硅酸盐荧光粉制备方法中，按比例添加相应的反应物通过固相法即可获得荧光粉，从而使得制备工艺简单、成本低，具有广阔的生产应用前景。
以下通过多个实施例来举例说明硅酸盐荧光粉的不同组成及其制备方法，以及其性能等方面。
实施例1
化学式为Ca2.9Sc2Si3O12:0.1Ce3+,1×10-3Ag硅酸盐荧光粉
称取硝酸银3.4mg和柠檬酸钠35.28mg，溶解于18.4mL的去离子水中，搅拌1.5min，然后缓慢滴入用3.8mg硼氢化钠溶到10mL乙醇中得到的0.01mol/L的硼氢化钠醇溶液1.6mL；继续搅拌反应2min，得到1×10-3mol/L的Ag纳米粒子溶胶；称取0.01g聚乙烯吡咯烷酮（PVP）溶于7mL去离子水中，溶解，然后加入2mL的Ag金属纳米粒子，搅拌12h；量取6×10-3mol的正硅酸四乙酯溶解于10ml乙醇中，然后一边搅拌一边依次加入处理过的Ag金属纳米粒子、2.9mL的2mol/L的硝酸钙溶液、4mL的1mol/L的硝酸钪溶液、4ml的0.05mol/L的硝酸铈溶液，然后用硝酸调节pH值至3-4，然后将溶液至于85℃水浴中反应4小时，在100℃烘箱中干燥12小时后得到前驱体，将前驱体研磨后置于马弗炉中900℃热处理3h，再于管式炉中在95%N2+5%H2弱还原气氛下1300℃烧结5h还原，冷却至室温，即得到Ca2.9Sc2Si3O12: 0.1Ce3+,1×10-3Ag硅酸盐荧光粉。
该硅酸盐荧光粉与对比例制备的荧光粉在460nm蓝光激发下的发射光谱如图2，图2中，曲线1是本实施例制备的荧光粉的发射光谱曲线，曲线2是对比例制备的荧光粉发射光谱曲线。从发射光谱曲线可以看出，通过加入金属纳米粒子可以大幅提高荧光粉的发光强度。
另外，本实施例制备的硅酸盐荧光粉在监控波长为505nm激发光谱曲线见图3。由图3可知，本实施例制备的硅酸盐荧光粉的发光强度高。
将本实施例制备的硅酸盐荧光粉与Sr2Si5N8:Eu红色荧光粉混合，封装于蓝光LED芯片后的发射光谱曲线如图4中曲线3，图4中曲线4为YAG黄色荧光粉装蓝光LED芯片后的发射光谱曲线。由图4可知，本实施例制备的硅酸盐荧光粉与Sr2Si5N8:Eu红色荧光粉封装的白光LED色温为4860，显色指数达到90%，发光效率达到YAG黄色荧光粉封装的白光LED光效的110%；YAG黄色荧光粉封装的白光LED色温为6400，显色指数为78%。可见，利用本发明绿色荧光粉与红色荧光粉封装得到高光效、高显色指数、低色温的白光LED。
实施例2
化学式为Ca2Sr0.8Sc1.8Si2.9O11.315:0.01Ce3+,1×10-4Au硅酸盐荧光粉
称取1.64mg氯金酸溶解到7.5mL的乙醇中，完全溶解后，在搅拌下加入5.6mg柠檬酸钠和2.4mg十六烷基三甲基溴化铵；称取0.76mg硼氢化钠溶解到10mL乙醇中，得到10mL浓度为0.002mol/L的硼氢化钠醇溶液；在磁力搅拌下，往氯金酸的醇溶液中加入2.5mL硼氢化钠醇溶液，继续反应30min，即得Au含量为4×10-4mol/L的Au纳米粒子溶胶，然后称取0.2g 聚乙烯吡咯烷酮溶于5mL去离子水中，溶解，然后加入0.5mL 4×10-4mol/L Au金属纳米粒子，搅拌24h；量取5.8×10-3mol的正硅酸四乙酯溶解于10ml乙醇中，然后一边搅拌一边依次加入处理过的Au金属纳米粒子、2mL的2mol/L的氯化钙溶液、0.8mL的2mol/L的硝酸锶溶液、3.6mL的1mol/L的硝酸钪溶液、0.4ml的0.05mol/L的硝酸铈溶液，然后用硝酸调节pH值至3-4，然后将溶液至于60℃水浴中反应5小时，在120℃烘箱中干燥8小时后得到前驱体，将前驱体研磨后置于马弗炉中700℃热处理5h，再于管式炉中在95%N2+5%H2弱还原气氛下1500℃烧结2h还原，冷却至室温，即可得到Ca2Sr0.8Sc1.8Si2.9O11.315: 0.01Ce3+,1×10-4Au硅酸盐荧光粉。
实施例3
化学式为Ca1.5Ba0.7Sr1.0Sc1.5Y0.6Si3.3O13.025: 0.05Ce3+,2×10-3Pt硅酸盐荧光粉：
称取5.2mg氯铂酸溶解到17mL的乙醇中，完全溶解后，在搅拌下加入8mg柠檬酸钠和1.2mg十二烷基磺酸钠，然后缓慢滴入用0.4mg硼氢化钠溶到10mL乙醇中得到的1×10-3mol/L的硼氢化钠醇溶液0.4mL，反应5min，再加入2.6mL 1×10-2mol/L的水合肼溶液，反应40min，得到Pt含量为5×10-4mol/L的Pt纳米粒子溶胶；称取0.15g 3-氨丙基三甲氧基硅氧烷溶于6mL去离子水中，溶解，然后加入8mL 5×10-4mol/L Pt金属纳米粒子，搅拌18h；量取6.6×10-3mol的正硅酸四乙酯溶解于10ml乙醇中，然后一边搅拌一边依次加入处理过的Pt金属纳米粒子、1.5mL的2mol/L的硫酸锶溶液、0.7mL的2mol/L的硝酸钡钙溶液、1mL的2mol/L的硝酸锶溶液、3mL 1mol/L的氯化钇溶液、2ml的0.05mol/L的硝酸铈溶液，然后用硝酸调节pH值至3-4，然后将溶液至于75℃水浴中反应4小时，在110℃烘箱中干燥3小时后得到前驱体，将前驱体研磨后置于马弗炉中1000℃热处理3h，再于管式炉中在95%N2+5%H2弱还原气氛下1250℃烧结12h还原，冷却至室温，即可得到Ca1.5Ba0.7Sr1.0Sc1.5Y0.6Si3.3O13.025: 0.05Ce3+,2×10-3Pt荧光粉；量取6.6×10-3mol的正硅酸四乙酯溶解于10ml乙醇中，然后一边搅拌一边依次加入处理过的Ag金属纳米粒子、1.5mL的2mol/L的硝酸钙溶液、0.7mL的2mol/L的硝酸钡溶液、1mL 2mol/L的硝酸锶溶液、2mL的1mol/L的硝酸钪溶液、2ml的0.05mol/L的硝酸铈溶液，然后用硝酸调节pH值至3-4，然后将溶液至于85℃水浴中反应4小时，在100℃烘箱中干燥3小时后得到前驱体，将前驱体研磨后置于马弗炉中1000℃热处理3h，再于管式炉中在CO弱还原气氛下1250℃烧结12h还原，冷却至室温，即可得到Ca1.5Ba0.7Sr1.0Sc1.5Y0.6Si3.3O13.025: 0.05Ce3+,2×10-3Pt硅酸盐荧光粉。
实施例4
化学式为Ca2.74Mg0.06Sc2Si3.1O12.3: 0.2Ce3+,1×10-2Pd硅酸盐荧光粉：
称取0.43g氯化钯溶解到15mL的去离子水中，完全溶解后，在搅拌下加入1.1g柠檬酸钠和0.4g十二烷基硫酸钠，然后缓慢滴入用0.038g硼氢化钠溶到10mL乙醇中得到的0.1mol/L的硼氢化钠醇溶液5mL，反应20min，即得Pd含量为5×10-3mol/L的Pd纳米粒子溶胶；称取0.3g 聚乙烯吡咯烷酮溶于5mL去离子水中，溶解，然后加入4mL的5×10-3mol/L Pd金属纳米粒子，搅拌3h；量取6.2×10-3mol的正硅酸四乙酯溶解于10ml乙醇中，然后一边搅拌一边依次加入处理过的Pd金属纳米粒子、2.74mL的2mol/L的硝酸钙溶液、0.6mL的0.2mol/L的硝酸镁溶液、4mL的1mol/L的硝酸钪溶液、2ml的0.2mol/L的硫酸铈溶液，然后用硝酸调节pH值至3-4，然后将溶液至于95℃水浴中反应3小时，在80℃烘箱中干燥5小时后得到前驱体，将前驱体研磨后置于马弗炉中800℃热处理5h，再于管式炉中在95%N2+5%H2弱还原气氛下1400℃烧结4h还原，冷却至室温，即可得到Ca2.74Mg0.06Sc2Si3.1O12.3: 0.2Ce3+,1×10-2Pd硅酸盐荧光粉。
实施例5
化学式为Ca1.0Sr1.0Mg0.9Sc1.9Si2.95O11.77: 0.08Ce3+,8×10-4Cu硅酸盐荧光粉：
称取1.6mg硝酸铜溶解到16mL的乙醇中，完全溶解后，在搅拌下加入12mg聚乙烯吡咯烷酮，然后缓慢滴入0.4mg硼氢化钠溶到10mL乙醇中得到的1×10-3mol/L的硼氢化钠醇溶液4mL，继续搅拌反应2min，得到4×10-4mol/L的Cu纳米粒子溶胶；量取5.9×10-3mol的正硅酸四乙酯溶解于10ml乙醇中，然后一边搅拌一边依次加入处理过的Cu金属纳米粒子、1mL的2mol/L的硝酸钙溶液、1mL 2mol/L的硝酸锶溶液、6mL的0.3mol/L的硝酸镁溶液、3.8mL的1mol/L的硝酸钪溶液、2ml的0.04mol/L的硝酸铈溶液，然后用硝酸调节pH值至3-4，然后将溶液至于85℃水浴中反应3小时，在100℃烘箱中干燥8小时后得到前驱体，将前驱体研磨后置于马弗炉中750℃热处理5h，再于管式炉中在H2弱还原气氛下1350℃烧结8h还原，冷却至室温，即可得到Ca1.0Sr1.0Mg0.9Sc1.9Si2.95O11.77: 0.08Ce3+,8×10-4Cu硅酸盐荧光粉。
实施例6
化学式为Ca2.88Sc1.94Y0.06Si3O12: 0.12Ce3+,8×10-3Ag硅酸盐荧光粉：
称取硝酸银6.8mg和柠檬酸钠70.56mg，溶解于18.4mL的去离子水中，搅拌1.5min，然后缓慢滴入用7.6mg硼氢化钠溶到10mL乙醇中得到的0.01mol/L的硼氢化钠醇溶液3.2mL；继续搅拌反应2min，得到2×10-3mol/L的Ag纳米粒子溶胶；称取0.01g的聚乙烯吡咯烷酮溶于7mL去离子水中，溶解，然后加入8mL Ag金属纳米粒子，搅拌6h；量取6×10-3mol的正硅酸四乙酯溶解于10ml乙醇中，然后一边搅拌一边依次加入处理过的Ag金属纳米粒子、2.88mL的2mol/L的硝酸钙溶液、3.88mL的1mol/L的硝酸钪溶液、2ml的0.06 mol/L的硝酸钇溶液、1.2ml的0.2mol/L的氯化铈溶液，然后用硝酸调节pH值至3-4，然后将溶液至于85℃水浴中反应4小时，在100℃烘箱中干燥6小时后得到前驱体，将前驱体研磨后置于马弗炉中800℃热处理6h，再于管式炉中在95%N2+5%H2弱还原气氛下1450℃烧结5h还原，冷却至室温，即可得到Ca2.88Sc1.94Y0.06Si3O12: 0.12Ce3+,8×10-3Ag硅酸盐荧光粉。
对比例
化学式为Ca2.9Sc2Si3O12: 0.1Ce3+硅酸盐荧光粉：
量取6×10-3mol的正硅酸四乙酯溶解于10ml乙醇中，然后一边搅拌一边加入2.9mL的2mol/L的硝酸钙溶液、4 ml的1mol/L的硝酸钪溶液、4ml的0.05mol/L的硝酸铈溶液，然后用硝酸调节pH值至3-4，然后将溶液至于85℃水浴中反应4小时，在100℃烘箱中干燥12小时后得到前驱体，将前驱体研磨后置于马弗炉中900℃热处理3h，再于管式炉中在95%N2+5%H2弱还原气氛下1300℃烧结5h还原，冷却至室温，即可得到Ca2.9Sc2Si3O12: 0.1Ce3+硅酸盐荧光粉，其在460nm蓝光激发下的发射光谱如图2中曲线2。从发射光谱曲线可以看出，本对比例中硅酸盐荧光粉发光强度弱于实施例1制备的硅酸盐荧光粉发光强度。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种硅酸盐荧光粉，其化学式为：M2 aM3 bSicO［a+3(b+x)/2+2c］:xCe3+,yM0，其中，2.8≤a≤3.2，1.8≤b≤2.1，2.9≤c≤3.3，0.01≤x≤0.2，1×10-4≤y≤1×10-2，M2是Sr、Ba、Mg中的至少一种和Ca的组合；M3是Sc或者Sc和Y的组合；M0表示金属纳米粒子，选自Ag、Au、Pt、Pd或Cu纳米粒子中的一种。
  2. 一种硅酸盐荧光粉制备方法，其包括如下步骤：
    获取M0金属纳米粒子溶胶；
    按照化学式M2 aM3 bSicO［a+3(b+x)/2+2c］:xCe3+,yM0中相应元素的化学计量比，称取M2的源化合物、M3的源化合物、Si的源化合物、Ce的源化合物和M0金属纳米粒子溶胶；其中，2.8≤a≤3.2，1.8≤b≤2.1，2.9≤c≤3.3，0.01≤x≤0.2，1×10-4≤y≤1×10-2，M2是Sr、Ba、Mg中的至少一种和Ca的组合；M3是Sc或者Sc和Y的组合；M0表示金属纳米粒子，选自Ag、Au、Pt、Pd或Cu纳米粒子中的一种；
    向Si的源化合物的醇溶液中加入M0金属纳米粒子溶胶和M2的源化合物、M3的源化合物和Ce的源化合物的溶液，得到混合液；
    将混合液的pH值调至呈酸性，水浴加热反应后，干燥，得到前躯体；
    将前躯体预烧；
    将预烧后的前躯体在还原气氛中焙烧，得到所述硅酸盐荧光粉。
  3. 如权利要求2所述的硅酸盐荧光粉制备方法，其特征在于：
    所述Si的源化合物为四硅酸四乙酯；
    所述M2的源化合物为M2的硝酸盐、硫酸盐、氯化物中的至少一种；
    所述M3的源化合物为M3的硝酸盐、硫酸盐、氯化物中的至少一种；
    所述Ce的源化合物为Ce的硝酸盐、硫酸盐、氯化物中的至少一种。
  4. 如权利要求2所述的硅酸盐荧光粉制备方法，其特征在于：所述M0金属纳米粒子溶胶制备方法包含如下步骤：
    将M0的源化合物溶解，再加入助剂、还原剂，待反应完毕后，加入表面处理剂处理，得到M0金属纳米粒子溶胶；
    所述助剂添加量为在M0金属纳米粒子溶胶中的含量为1.5×10-4g/mL～2.1×10-3g/mL；
    所述还原剂添加量与M0金属离子的摩尔比为1.2:1～4.8:1；
    所述表面处理剂添加量为在M0金属纳米粒子溶胶中的含量为1.5×10-4g/mL～2.1×10-3g/mL。
  5. 如权利要求4所述的硅酸盐荧光粉制备方法，其特征在于：所述M0金属纳米粒子溶胶制备步骤中，
    所述M0的源化合物为硝酸银、氯金酸、氯铂酸、氯化钯、硝酸铜中的至少一种；
    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、十二烷基硫酸钠或十二烷基磺酸钠中的至少一种；
    所述还原剂为水合肼、抗坏血酸或硼氢化钠中的至少一种；
    所述表面处理剂为聚乙烯吡咯烷酮、3-氨丙基三甲氧基硅氧烷中的至少一种。
  6. 如权利要求2所述的硅酸盐荧光粉制备方法，其特征在于：所述混合液制备中，Si的源化合物醇溶液的醇为乙醇。
  7. 如权利要求2所述的硅酸盐荧光粉制备方法，其特征在于：所述前躯体制备步骤中：所述混合液的pH值为3-6；所述水浴加热反应的温度为60-95℃；所述干燥的温度为80-120℃。
  8. 如权利要求7所述的硅酸盐荧光粉制备方法，其特征在于：所述前躯体制备步骤中：所述混合液的pH值用硝酸调节。
  9. 如权利要求2所述的硅酸盐荧光粉制备方法，其特征在于：
    所述前躯体预烧的温度为700-1000℃，时间为3-5小时；
    所述前躯体在还原气氛中焙烧的温度为1250-1500℃，时间为2-12小时。
  10. 如权利要求9所述的硅酸盐荧光粉制备方法，其特征在于：所述还原气氛为氮气与氢气混合气体、CO还原气氛、H2还原气氛中的一种。
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