# Patent

## Title
Halo-silicate luminescent materials and preparation methods thereof

## Abstract

Halo-silicate luminescent materials and preparation methods thereof are provided. The said luminescent materials are represented by the following general formula: (Ba1-yAy)2-xSiO4:Eux, Dz@ Mn, wherein A is selected from one or two of Sr, Ca, Mg or Zn, D is selected from one of F or Cl, M is selected from at least one of Ag, Au, Pt, Pd or Cu metal nano-particles; @ is coating; (Ba1-yAy)2-xSiO4:Eux, Dz, is shell; 0.001<x≦0.15, 0≦y≦0.5, 0≦z≦0.5, 0<n≦1×10−2. The said luminescent materials have excellent chemical stability and high luminous intensity. Furthermore, the luminescent materials have controlled spherical shape which is beneficial to the coating screen process and the improved displaying effect. The said preparation methods have simple technique, no pollution, manageable process conditions and low equipment requirement, and are beneficial to industry production.

## Background
FIELD OF THE INVENTION
The present invention relates to luminescent materials, more particularly, relates to silicate luminescent materials doped with metal nano-particles. The present invention also relates to a preparation method of silicate luminescent materials.
BACKGROUND OF THE INVENTION
White light LED (light emitting diodes) have attracted an ever-widening attention due to advantages of high efficiency, long lifetime, small size, quick response, no pollution, and energy-saving. At present, one of the primary ways to achieve white light is to combine blue GaN chips with yellow YAG:Ce fluorescent powders. Such method has shortcoming of low color rendering index. However, the main trend and efforts have been directed toward combining near-ultraviolet LED chips and red, green, blue trichromatic powders to produce white light LED, which has high luminous efficiency, tunable color temperature, and high color rendering index. Consequently, LED trichromatic powders that can be efficiently excited by near-ultraviolet are currently studied widely. Therein, luminescent materials which take silicate systems as substrate have raised public concerns due to their features of wide source of raw materials, low-cost, good processing adaptability, moderate synthesis temperature and excellent stability.
Thomas synthesized alkaline-earth metals orthosilicate powders activated by bivalent europium ions. They are a kind of great green powders, compared to YAG fluorescent powders; they have broader excitation spectrum range, better color-purity. Nevertheless, such existing fluorescent powders have problems of low luminous efficiency, bad color rendering, etc.
SUMMARY OF THE INVENTION
Solving the above problems, the present invention provides silicate luminescent materials doped with metal nano-particles which is of low cost and high luminous efficiency, they are represented by general formula of (Ba1-yAy)2-xSiO4:Eux, Dz@ Mn; wherein, A is one or two of Sr, Ca, Mg and Zn, D is any one of F and Cl, M is at least one metal nano-particles of Ag, Au, Pt, Pd and Cu; @ is coating, M nano-particles is a core; (Ba1-yAy)2-x. SiO4:Eux, Dz fluorescent powders are shell; x is in the range of 0.001<x≦0.15, y is in the range of 0≦y≦0.5, z is in the range of 0≦z≦0.5, n is molar ratio of M nano-particles to Si in fluorescent powders, n is in the range of 0≦n≦1×10−2; preferably, x is in the range of 0.005≦x≦0.10; y is in the range of 0.05≦y≦0.2; z is in the range of 0.01≦z≦0.2; n is in the range of 1×10−4≦n≦5×10−3.
The other purpose of the present invention is to provide a preparation method of silicate luminescent materials, comprising:
step S1: adding surface treating agent into M nano-particles colloid, then successively adding ethanol, water, ammonia water and tetra ethoxy silane (where the volume ratio of ethanol, water, ammonia water and tetra ethoxy silane is in the range of 25:8:5:1 to 30:10:7:1), obtaining solution containing nano-sphere of M nano-particles coated in SiO2; wherein, M is at least one nano-particles of Ag, Au, Pt, Pd and Cu;
step S2: regulating pH value of solution containing nano-sphere of M nano-particles coated in SiO2 obtained from step S1 to 5, then adding nitrate solution of Ba, nitrate solution of A and nitrate solution of Eu separately, and adding aqueous nitrate solution of BaD2 or nitrate solution of AD2 according to the stoichiometric ratio of corresponding elements in (Ba1-yAy)2-xSiO4: Eux, Dz, next, adding precipitator, after stirring and reacting for 1 to 8 h, placing precipitates into oven for drying to obtain precursor; wherein, A is one or two of Sr, Ca, Mg and Zn, D is any one of F and Cl; x is in the range of 0.001<x≦0.15, y is in the range of 0≦y≦0.5, z is in the range of 0≦z≦0.5, n is molar ratio of M nano-particles to Si in fluorescent powders, n is in the range of 0<n≦1×10−2;
step S3: heat treating the precursor obtained from step S2 at 600° ̃1000° C. for 2 ̃10 h, and carrying out reducing treatment at 1000° C. ̃1400° C. for 1 ̃8 h in reducing atmosphere, after that, cooling and grinding to obtain said silicate luminescent materials represented by the general formula of (Ba1-yAy)2-xSiO4:Eux, Dz@ Mn; wherein, @ is coating, M nano-particles is a core; (Ba1-yAy)2-x SiO4:Eux, Dz fluorescent powders are shell.
In the step S1 of the above preparation method, said surface treating agent is polyvinyl pyrrolidone, the mass concentration of said surface treating agent in M nano-particles colloid is in the range of 0.005 g/mL to 0.1 g/mL.
In the step S2 of the above preparation method, said precipitator is ammonium bicarbonate, the molar amount of said precipitator is 1.20 to 1.5 times as much as that of luminescent materials (Ba1-yAy)2-xSiO4:Eux, Dz@Mn, that is, the amount of precipitator is excess 20% ̃50%.
In the step S3 of the above preparation method, said reducing atmosphere is at least one of mixed gases of N2 and H2 reducing atmosphere, CO reducing atmosphere and pure H2 reducing atmosphere.
Compared with the prior art, the silicate luminescent materials of the present invention whose shell is formed by coating metal particles improve its internal quantum efficiency; its luminous intensity are increased by adding metal nano particles, in addition, the luminescent materials that exhibit spherical shape have excellent stability, controllable size and morphology, high stacking density, which is favorable for coating screen technique and display; besides, the preparation method of the present invention is simple, low demand in equipment, no pollution, easy to control, and suitable for industrial production.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow chart of preparation method of silicate luminescent material of the present invention;
FIG. 2 is comparison between the spectrums of the luminescent materials prepared in Example 2 of the present invention which are excited at 460 nm. Herein, curve 1 is luminescence spectrum of Ba1.99SiO4:Eu0.01 luminescent material without coating metal nano-particle Ag, curve 2 is luminescence spectrum of Ba1.99SiO4:Eu0.01@Ag1.25×10−3 luminescent material coating metal nano-particle Ag;
FIG. 3 is comparison between the spectrums of the luminescent materials prepared in Example 4 of the present invention which are excited at 460 nm. Herein, curve 1 is luminescence spectrum of Ba1.99SiO4:Eu0.01:F0.1 luminescent material without coating metal nano-particle Ag, curve 2 is luminescence spectrum of Ba1.99SiO4:Eu0.01:F0.1@Ag1.25×10−3 luminescent material coating metal nano-particle Ag.



DETAILED DESCRIPTION OF ILLUSTRATED EMBODIMENTS
Silicate luminescent materials provided in the present invention have general formula of (Ba1-yAy)2-xSiO4:Eux, Dz@ Mn; wherein, A is one or two of Sr, Ca, Mg and Zn, D is any one of F and Cl, M is at least one metal nano-particles of Ag, Au, Pt, Pd and Cu; @ is coating, M nano-particles is a core; (Ba1-yAy)2-x, (SiO4:Eux, Dz fluorescent powders are shell; x is in the range of 0.001<x≦0.15, y is in the range of 0≦y≦0.5, z is in the range of 0≦z≦0.5, n is molar ratio of M nano-particles to Si in fluorescent powders, n is in the range of 0≦n≦1×10−2; preferably, x is in the range of 0.005≦x≦0.10; y is in the range of 0.05≦y≦0.2; z is in the range of 0.01≦z≦0.2; n is in the range of 1×10−4≦n≦5×10−3.
M nano-particles colloid can be prepared before preparing the above silicate luminescent materials, the preparation method comprises:
1) weighing and dissolving compound used as source of M in mixed solvent of ethanol and water to prepare and dilute to achieve a solution containing M ions having molar concentration of 1×10−3 mol/L ̃5×10−2 mol/L; wherein M represents metal nano-particles selecting from one of Ag, Au, Pt, Pd and Cu, compounds used as source of M comprise silver nitrate, chloroauric acid, chloroplatinic acid, palladium and chloride;
2) while magnetically stirring, dissolving assistant agent in solution in the above step 1) to make the mass concentration of assistant agent in the final M nano-particles colloid be in the range of 1×10−4 g/mL to 5×10−2 g/mL; wherein, said assistant agent is at least one of polyvinyl pyrrolidone (PVP), sodium citrate, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl sulfonate;
3) weighing and dissolving reducing agent in mixed solvent of ethanol and water to prepare reducing solution having molar concentration of 1×10−4 mol/L ̃1 mol/L; wherein, said reducing agent is at least one of hydrazine hydrate, ascorbic acid and sodium borohydride;
4) while magnetically stirring, according to the molar ratio of reducing agent to M ions 3.6:1 ̃18:1, adding the reducing solution obtained from the above step 3) into M nano-particles colloid solution containing assistant agent obtained from the above step 2), stirring, allowing the whole system to react for 10 min ̃45 min, then obtaining M nano-particles colloid for later use.
As shown in FIG. 1, the preparation method of the above silicate luminescent materials comprises:
Step S1: adding the obtained M nano-particles colloid into aqueous solution containing surface treating agent, then successively adding ethanol, water, ammonia water and tetra ethoxy silane (where the volume ratio of ethanol, water, ammonia water and tetra ethoxy silane is in the range of 25:8:5:1 to 30:10:7:1), obtaining solution containing nano-sphere of M nano-particles coated in SiO2; wherein, M is at least one nano-particles of Ag, Au, Pt, Pd and Cu;
step S2: regulating pH value of solution containing nano-sphere of M nano-particles coated in SiO2 obtained from step S1 to 5, then adding nitrate solution of Ba, nitrate solution of A and nitrate solution of Eu separately, and adding aqueous nitrate solutions of BaD2 or nitrate solution of AD2 according to the stoichiometric ratio of corresponding elements in (Ba1-yAy)2-x SiO4: Eux, Dz, next, adding precipitator, after stirring and reacting for 1 to 8 h, placing precipitates into oven for drying to obtain precursor; wherein, A is one or two of Sr, Ca, Mg and Zn, D is any one of F and Cl; x is in the range of 0.001<x≦0.15, y is in the range of 0≦y≦0.5, z is in the range of 0≦z≦0.5, n is molar ratio of M nano-particles to Si in fluorescent powders, n is in the range of 0<n≦1×10−2;
step S3: placing the precursor obtained from step S2 into muffle furnace and heat treating at 600° ̃1000° C. for 2 ̃10 h, and then carrying out reducing treatment in reducing atmosphere at 1000° C. ̃1400° C. for 1 ̃8 h, after that, cooling and grinding to obtain said silicate luminescent materials represented by the general formula of (Ba1-yAy)2-xSiO4:Eux, Dz@Mn; wherein, @ is coating, M nano-particles is a core; (Ba1-yAy)2-xSiO4:Eux, Dz fluorescent powders are shell.
In the step S1 of the above preparation method, said surface treating agent is polyvinyl pyrrolidone, the mass concentration of said surface treating agent in M nano-particles colloid is in the range of 0.005 g/mL to 0.1 g/mL.
In the step S2 of the above preparation method, said precipitator is ammonium bicarbonate, the molar amount of said precipitator is 1.20 to 1.5 times as much as that of luminescent materials (Ba1-yAy)2-xSiO4:Eux, Dz@Mn, that is, the amount of precipitator is preferably excess 20% ̃50%, thus ensuring complete precipitation. In this step, white precipitates will be produced after adding ammonium bicarbonate, and then the reaction is conducted while stirring for a certain time, the precipitates are placed into oven for drying after the reaction to obtain precursor.
In the step S3 of the above preparation method, said reducing atmosphere is at least one of mixed gases of N2 and H2 reducing atmosphere, CO reducing atmosphere and pure H2 reducing atmosphere.
The foregoing silicate luminescent materials whose shell is formed by coating metal particles improve its internal quantum efficiency; its luminous intensity are increased by adding metal nano particles, in addition, the luminescent materials that exhibit spherical shape have excellent stability, controllable size and morphology, high stacking density, which is favorable for coating screen technique and display.
The silicate luminescent materials doped with metal nano-particles of the present invention having advantages of excellent stability, better luminescence property can be widely used in the fields of lighting, display and others.
Further description of the present invention will be illustrated, which combined with preferred embodiments in the drawings.
EXAMPLE 1
Preparation of Silicate Luminescent Material (Ba0.9Sr0.1)1.85SiO4:Eu0.15, Cl0.20 @Pt1×10−2 Doped with Platinum (Pt) Nano-Particles
At room temperature, weighing and dissolving 0.30 grams (g) of polyvinyl pyrrolidone (PVP) in 4 milliliters (mL) of deionized water, dissolving, then adding 4 mL of 1×10−2 mol/L platinum metal nano-particles, stirring for 18 hours (h), then adding successively 25 mL of absolute ethanol, 5 mL of ammonium water ammonia water, 1.0 mL of tetra ethoxy silane while stirring; reacting for 6 h, after that, regulating pH of the solution to 5, then adding 21 mL of 0.3 mol/L aqueous solution of Ba(NO3)2, 1.5 mL of 0.5 mol/L aqueous solution of Sr(NO3)2, 3 mL of 0.2 mol/L aqueous solution of Eu(NO3)3, 2 mL of 0.2 mol/L aqueous solution of BaCl2, stirring thoroughly, then dripping slowly 20 mL of 0.5 mol/L NH4HCO3, stirring and reacting for 5 h, then placing precipitates into oven for drying, treating with heat at 600° C. for 10 h, placing into agate mortar and grinding thoroughly to mix well, then transferring powders to corundum crucible, sintering in reducing atmosphere of CO at 1300° C. for 1 h for reduction, cooling to room temperature and (Ba0.9Sr0.1)1.85SiO4: Eu0.15, Cl10.20@Pt1×10−2 luminescent material doped with Pt nano-particles is obtained.
EXAMPLE 2
Preparation of Silicate Luminescent Material Ba1.99SiO4:Eu0.01@Ag1.25×10−3 Doped with Silver (Ag) Nano-Particles
At room temperature, weighing and dissolving 0.1 g of polyvinyl pyrrolidone in 5 mL of deionized water, dissolving, then adding 5 mL of 1×10−3 mol/L silver metal nano-particles, stirring for 12 h, then adding successively 25 mL of absolute ethanol, 6 mL of ammonia water, 1.0 mL of tetra ethoxy silane while stirring; reacting for 3 h, after that, regulating pH of the solution to 5, then adding 26.7 mL of 0.3 mol/L aqueous solution of Ba(NO3)2, 0.4 mL of 0.1 mol/L aqueous solution of Eu(NO3)3, stirring thoroughly, then dripping slowly 10 mL of 1 mol/L NH4HCO3, stirring and reacting for 3 h, then placing precipitates into oven for drying, treating with heat at 800° C. for 4 h, placing into agate mortar and grinding thoroughly to mix well, then transferring powders to corundum crucible, sintering in tube furnace in weak reducing atmosphere of 95% N2 plus 5% H2 at 1200° C. for 4 h for reduction, cooling to room temperature and Ba1.99SiO4:Eu0.01@Ag1.25×10−3 luminescent material doped with Ag nano-particles is obtained.
As shown in FIG. 2, the comparison of spectrums of the luminescent materials Ba1.99SiO4:Eu0.01@Ag1.25×10−3 coating metal nano-particles Ag prepared in the present embodiment with luminescent materials Ba1.99SiO4:Eu0.01 without coating metal nano-particles excited at 460 nm, it can be seen from the emission peak appears at 505 nm that luminous intensity of the luminescent materials coating metal nano-particles was increased by 15% compared to that of the samples without coating metal nano-particles at 505 nm. The luminescent materials of the present embodiment had excellent stability, good color-purity and high luminous efficiency.
EXAMPLE 3
Preparation of Silicate Luminescent Material (Ba0.5Ca0.5)1.999SiO4:Eu0.001, F0.5@Au1×10−4 Doped with Au Nano-Particles
At room temperature, weighing and dissolving 0.15 g of polyvinyl pyrrolidone in 4 mL of deionized water, dissolving, then adding 6 mL of 1×10−4 mol/L Au metal nano-particles, stirring for 12 h, then adding successively 35 mL of absolute ethanol, 10 mL of ammonia water, 1.5 mL of tetra ethoxy silane while stirring; reacting for 4 h, after that, regulating pH of the solution to 5, then adding 6 mL of 1 mol/L solution of Ca(NO3)2, 20 mL of 0.3 mol/L solution of Ba(NO3)2, 6 mL of 0.01 mol/L solution of Eu(NO3)3, 3 mL of 0.5 mol/L solution of BaF2, stirring thoroughly, then dripping slowly 30 mL of 0.5 mol/L NH4HCO3, stirring and reacting for 2 h, then placing precipitates into oven for drying, treating with heat at 1000° C. for 2 h, placing into agate mortar and grinding thoroughly to mix well, then transferring powders to corundum crucible, sintering in tube furnace in reducing atmosphere of H2 at 1300° C. for 8 h for reduction, cooling to room temperature and (Ba0.5Ca0.5)1.999SiO4: Eu0.001, F0.5@Au1×10−4 luminescent material doped with Au nano-particles is obtained.
EXAMPLE 4
Preparation of Silicate Luminescent Material Ba1.99SiO4:Eu0.01:F0.1@Ag1.25×10−3 Doped with Ag Nano-Particles
At room temperature, weighing and dissolving 0.10 g of polyvinyl pyrrolidone in 5 mL of deionized water, dissolving, then adding 5 mL of 1×10−3 mol/L Ag metal nano-particles, stirring for 12 h, then adding successively 25 mL of absolute ethanol, 6 mL of ammonia water, 1.0 mL of tetra ethoxy silane while stirring; reacting for 3 h, after that, regulating pH of the solution to 5, then adding 26 mL of 0.3 mol/L solution of Ba(NO3)2, 0.4 mL of 0.1 mol/L solution of Eu(NO3)3, 2 mL of 0.1 mol/L solution of BaF2, stirring thoroughly, then dripping slowly 10 mL of 1 mol/L NH4HCO3, stirring and reacting for 3 h, then placing precipitates into oven for drying, treating with heat at 800° C. for 2 h, placing into agate mortar and grinding thoroughly to mix well, then transferring powders to corundum crucible, sintering in tube furnace in weak reducing atmosphere of 95% N2 plus 5% H2 at 1200° C. for 4 h for reduction, cooling to room temperature and Ba1.99SiO4:Eu0.01:F0.1@Ag1.25×10−3 luminescent material doped with Ag nano-particles is obtained.
As shown in FIG. 3, the comparison of spectrums of the luminescent materials Ba1.99SiO4:Eu0.01:F0.1@ Ag1.25×10−3 coating metal nano-particles Ag prepared in the present embodiment with luminescent materials Ba1.99SiO4:Eu0.01:F0.1 without coating metal nano-particles excited at 460 nm, it can be seen from the emission peak appears at 505 nm that luminous intensity of the luminescent materials coating metal nano-particles was increased by 12% compared to that of the samples without coating metal nano-particles at 505 nm. The luminescent materials of the present embodiment had excellent stability, good color-purity and high luminous efficiency.
EXAMPLE 5
Preparation of Silicate Luminescent Material (Ba0.8Mg0.2)1.95SiO4:Eu0.05@Ag5×10−3 Doped with Ag Nano-Particles
At room temperature, weighing and dissolving 0.08 g of polyvinyl pyrrolidone in 8 mL of deionized water, dissolving, then adding 2 mL of 1×10−2 mol/L Ag metal nano-particles, stirring for 18 h, then adding successively 20 mL of absolute ethanol, 4 mL of ammonia water, 1.0 mL of tetra ethoxy silane while stirring; reacting for 6 h, after that, regulating pH of the solution to 5, then adding 20.8 mL of 0.3 mol/L solution of Ba(NO3)2, 5.2 mL of 0.3 mol/L solution of Mg(NO3)2, 2 mL of 0.1 mol/L solution of Eu(NO3)3, stirring thoroughly, then dripping slowly 12 mL of 1 mol/L NH4HCO3, stirring and reacting for 8 h, then placing precipitates into oven for drying, treating with heat at 900° C. for 5 h, placing into agate mortar and grinding thoroughly to mix well, then transferring powders to corundum crucible, sintering in tube furnace in weak reducing atmosphere of 95% N2 plus 5% H2 at 1150° C. for 6 h for reduction, cooling to room temperature and (Ba0.8Mg0.2)1.95SiO4:Eu0.05@Ag5×10−3 luminescent material doped with Ag nano-particles is obtained.
EXAMPLE 6
Preparation of Silicate Luminescent Material (Ba0.7Sr0.2Mg0.1)1.9SiO4:Eu0.1, Cl0.01@Cu4×10−4 doped with Cu Nano-Particles
At room temperature, weighing and dissolving 0.18 g of polyvinyl pyrrolidone in 8 mL of deionized water, dissolving, then adding 2 mL of 1×10−3 mol/L Cu metal nano-particles, stirring for 24 h, then adding successively 30 mL of absolute ethanol, 8 mL of ammonia water, 1.2 mL of tetra ethoxy silane while stirring; reacting for 2 h, after that, regulating pH of the solution to 5, then adding 6 mL of 0.3 mol/L solution of Sr(NO3)2, 21.3 mL of 0.3 mol/L solution of Ba(NO3)2, 4.6 mL of 0.2 mol/L solution of Mg(NO3)2, 4.8 mL of 0.1 mol/L solution of Eu(NO3)3, 4.8 mL of 0.01 mol/L solution of SrCl2, stirring thoroughly, then dripping slowly 12 mL of 1 mol/L NH4HCO3, stirring and reacting for 5 h, then placing precipitates into oven for drying, treating with heat at 700° C. for 6 h, placing into agate mortar and grinding thoroughly to mix well, then transferring powders to corundum crucible, sintering in tube furnace in reducing atmosphere of H2 at 1350° C. for 6 h for reduction, cooling to room temperature and (Ba0.7Sr0.2Mg0.1)1.9SiO4: Eu0.1,Cl0.01@Cu5×10−4 luminescent material doped with Cu nano-particles is obtained.
EXAMPLE 7
Preparation of Silicate Luminescent Material (Ba0.95Zn0.05)1.995SiO4:Eu0.00 @Pd3×10−4 Doped with Pd Nano-Particles
At room temperature, weighing and dissolving 0.5 g of PVP in 10 mL of deionized water, dissolving, then adding 4 mL of 3×10−4 mol/L Au metal nano-particles, stirring for 24 h, then adding successively 28 mL of absolute ethanol, 7 mL of ammonia water, 1.0 mL of tetra ethoxy silane while stirring; reacting for 4 h, after that, regulating pH of the solution to 5, then adding 25.3 mL of 0.3 mol/L solution of Ba(NO3)2, 2 mL of 0.2 mol/L solution of Zn(NO3)2, 2 mL of 0.01 mol/L solution of Eu(NO3)3, stirring thoroughly, then dripping slowly 20 mL of 0.5 mol/L NH4HCO3, stirring and reacting for 1 h, then placing precipitates into oven for drying, treating with heat at 600° C. for 8 h, placing into agate mortar and grinding thoroughly to mix well, then transferring powders to corundum crucible, sintering in tube furnace in weak reducing atmosphere of 95% N2 plus 5% H2 at 1400° C. for 3 h for reduction, cooling to room temperature and (Ba0.95Zn0.05)1.995SiO4:Eu0.005@Pd3×10−4 luminescent material doped with Pd nano-particles is obtained.
EXAMPLE 8
Preparation of silicate luminescent material Ba1.95SiO4:Eu0.05@(Ag0.5/Au0.5)2×10−3 doped with (Ag/Au) nano-particles
At room temperature, weighing and dissolving 0.15 g of PVP in 6 mL of deionized water, dissolving, then adding 4 mL of 2×10−3 mol/L Ag0.5/Au0.5 nano-particles, stirring for 15 h, then adding successively 30 mL of absolute ethanol, 7 mL of ammonia water, 1.0 mL of tetra ethoxy silane while stirring; reacting for 6 h, after that, regulating pH of the solution to 5, then adding 26 mL of 0.3 mol/L solution of Ba(NO3)2, 2 mL of 0.1 mol/L solution of Eu(NO3)2, stirring thoroughly, then dripping slowly 25 mL of 0.5 mol/L NH4HCO3, stirring and reacting for 7 h, then placing precipitates into oven for drying, treating with heat at 800° C. for 5 h, placing into agate mortar and grinding thoroughly to mix well, then transferring powders to corundum crucible, sintering in tube furnace in weak reducing atmosphere of 95% N2 plus 5% H2 at 1300° C. for 2 h for reduction, cooling to room temperature and Ba1.99SiO4:Eu0.01@ (Ag0.5/Au0.5)2×10−3 luminescent material doped with (Ag0.5/Au0.5) nano-particles is obtained.
At room temperature, weighing and dissolving 0.15 g of PVP in 6 mL of deionized water, dissolving, then adding 4 mL of 2×10−3 mol/L Ag0.5/Au0.5 nano-particles, stirring for 15 h, then adding successively 30 mL of absolute ethanol, 7 mL of ammonium water, 1.0 mL of tetra ethoxy silane while stirring; reacting for 6 h, after that, regulating pH of the solution to 5, then adding 26 mL of 0.3 mol/L solution of Ba(NO3)2, 2 mL of 0.1 mol/L solution of Eu(NO3)2, stirring thoroughly, then dripping slowly 25 mL of 0.5 mol/L NH4HCO3, stirring and reacting for 7 h, then placing precipitates into oven for drying, treating with heat at 800° C. for 5 h, placing into agate mortar and grinding thoroughly to mix well, then transferring powders to corundum crucible, sintering in tube furnace in weak reducing atmosphere of 95% N2 plus 5% H2 at 1300° C. for 2 h for reduction, cooling to room temperature and Ba1.99SiO4:Eu0.01@ (Ag0.5/Au0.5)2×10−3 luminescent material doped with (Ag0.5/Au0.5) nano-particles is obtained.
While the present invention has been described with reference to particular embodiments, it will be understood that the embodiments are illustrative and that the invention scope is not so limited. Alternative embodiments of the present invention will become apparent to those having ordinary skill in the art to which the present invention pertains. Such alternate embodiments are considered to be encompassed within the spirit and scope of the present invention. Accordingly, the scope of the present invention is described by the appended claims and is supported by the foregoing description.

## Claims

1. Silicate luminescent materials represented by the general formula of (Ba1-yAy)2-xSiO4:Eux, Dz@ Mn, wherein A is one or two of Sr, Ca, Mg and Zn, D is any one of F and Cl, M is at least one metal nano-particles of Ag, Au, Pt, Pd and Cu; @ is coating, M nano-particles is a core; (Ba1-yAy)2-xSiO4:Eux, Dz fluorescent powders are shell; x is in the range of 0.001<x≦0.15, y is in the range of 0≦y≦0.5, z is in the range of 0≦z≦0.5, n is molar ratio of M nano-particles to Si in fluorescent powders, n is in the range of 0<n≦1×10−2.

2. Silicate luminescent materials according to claim 1, wherein
x is in the range of 0.005≦x≦0.10; y is in the range of 0.05≦y≦0.2; z is in the range of 0.01≦z≦0.2; n is in the range of 1×10−4≦n≦5×10−3.

3. A preparation method of silicate luminescent materials, comprising:
step S1: adding surface treating agent into M nano-particles colloid, then successively adding ethanol, water, ammonia water and tetra ethoxy silane, obtaining solution containing nano-sphere of M nano-particles coated in SiO2; wherein, M is at least one nano-particles of Ag, Au, Pt, Pd and Cu;
step S2: regulating pH value of solution containing nano-sphere of M nano-particles coated in SiO2 obtained from step S1 to 5, then adding nitrate solutions of Ba, A and Eu separately, and adding aqueous nitrate solutions of BaD2 or AD2 according to the stoichiometric ratio of corresponding elements in (Ba1-yAy)2-xSiO4:Eux, Dz, next, adding precipitator, after stirring and reacting for 1 to 8 h, placing precipitates into oven for drying to obtain precursor; wherein, A is one or two of Sr, Ca, Mg and Zn, D is any one of F and Cl; x is in the range of 0.001<x≦0.15, y is in the range of 0≦y≦0.5, z is in the range of 0≦z≦0.5, n is molar ratio of M nano-particles to Si in fluorescent powders, n is in the range of 0<n≦1×10−2;
step S3: cooling and grinding the precursor obtained from step S2 after heat treatment and reducing treatment, obtaining said silicate luminescent materials represented by the general formula of (Ba1-yAy)2-xSiO4:Eux, Dz@ Mn; wherein, @ is coating, M nano-particles is a core; (Ba1-yAy)2-xSiO4:Eux, Dz fluorescent powders are shell.

4. The preparation method of silicate luminescent materials according to claim 3, wherein, in said step S1, said surface treating agent is polyvinyl pyrrolidone, the mass concentration of said surface treating agent in M nano-particles colloid is in the range of 0.005 g/mL to 0.1 g/mL.

5. The preparation method of silicate luminescent materials according to claim 3, wherein, in said step S1, the volume ratio of said ethanol, water, ammonia water and tetra ethoxy silane is in the range of 25:8:5:1 to 30:10:7:1.

6. The preparation method of silicate luminescent materials according to claim 3, wherein, in said step S2, said precipitator is ammonium bicarbonate, the molar amount of said precipitator is 1.20 to 1.5 times as much as that of luminescent materials (Ba1-yAy)2-xSiO4:EUx, Dz@ Mn.

7. The preparation method of silicate luminescent materials according to claim 3, wherein, in said step S2, x is in the range of 0.005≦x≦0.10; y is in the range of 0.05≦y≦0.2; z is in the range of 0.01≦z≦0.2; n is in the range of 1×10−4≦n≦5×10−3.

8. The preparation method of silicate luminescent materials according to claim 3, wherein, in said step S3, said heat treatment includes: heat treatment carried out at 600° C. to 1000° C. for 2 to 10 h.

9. The preparation method of silicate luminescent materials according to claim 3, wherein, in said step S3, said reducing treatment includes: reducing treatment carried out at 1000° C. to 1400° C. for 1 to 8 h.

10. The preparation method of silicate luminescent materials according to claim 3, wherein, said reducing treatment is carried out in reducing atmosphere, said reducing atmosphere is at least one of mixed gases of N2 and H2 reducing atmosphere, CO reducing atmosphere, and pure H2 reducing atmosphere.

11. The preparation method of silicate luminescent materials according to claim 4, wherein, in said step S1, the volume ratio of said ethanol, water, ammonia water and tetra ethoxy silane is in the range of 25:8:5:1 to 30:10:7:1.

12. The preparation method of silicate luminescent materials according to claim 6, wherein, in said step S2, x is in the range of 0.005≦x≦0.10; y is in the range of 0.05≦y≦0.2; z is in the range of 0.01≦z≦0.2; n is in the range of 1×10−4≦n≦5×10−3.

13. The preparation method of silicate luminescent materials according to claim 9, wherein, said reducing treatment is carried out in reducing atmosphere, said reducing atmosphere is at least one of mixed gases of N2 and H2 reducing atmosphere, CO reducing atmosphere, and pure H2 reducing atmosphere.