Halo-silicate luminescent materials and preparation methods thereof

Preparation of Silicate Luminescent Material (Ba 0.9 Sr 0.1 ) 1.85 SiO 4 :Eu 0.15 , Cl 0.20 @Pt 1×10 −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(NO 3 ) 2 , 1.5 mL of 0.5 mol/L aqueous solution of Sr(NO 3 ) 2 , 3 mL of 0.2 mol/L aqueous solution of Eu(NO 3 ) 3 , 2 mL of 0.2 mol/L aqueous solution of BaCl 2 , stirring thoroughly, then dripping slowly 20 mL of 0.5 mol/L NH 4 HCO 3 , 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 (Ba 0.9 Sr 0.1 ) 1.85 SiO 4 : Eu 0.15 , Cl 10.20 @Pt 1×10 −2 luminescent material doped with Pt nano-particles is obtained.

Preparation of Silicate Luminescent Material Ba 1.99 SiO 4 :Eu 0.01 @Ag 1.25×10 −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(NO 3 ) 2 , 0.4 mL of 0.1 mol/L aqueous solution of Eu(NO 3 ) 3 , stirring thoroughly, then dripping slowly 10 mL of 1 mol/L NH 4 HCO 3 , 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% N 2 plus 5% H 2 at 1200° C. for 4 h for reduction, cooling to room temperature and Ba 1.99 SiO 4 :Eu 0.01 @Ag 1.25×10 −3 luminescent material doped with Ag nano-particles is obtained.

As shown in FIG. 2 , the comparison of spectrums of the luminescent materials Ba 1.99 SiO 4 :Eu 0.01 @Ag 1.25×10 −3 coating metal nano-particles Ag prepared in the present embodiment with luminescent materials Ba 1.99 SiO 4 :Eu 0.01 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.

Preparation of Silicate Luminescent Material (Ba 0.5 Ca 0.5 ) 1.999 SiO 4 :Eu 0.001 , F 0.5 @Au 1×10 −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(NO 3 ) 2 , 20 mL of 0.3 mol/L solution of Ba(NO 3 ) 2 , 6 mL of 0.01 mol/L solution of Eu(NO 3 ) 3 , 3 mL of 0.5 mol/L solution of BaF 2 , stirring thoroughly, then dripping slowly 30 mL of 0.5 mol/L NH 4 HCO 3 , 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 H 2 at 1300° C. for 8 h for reduction, cooling to room temperature and (Ba 0.5 Ca 0.5 ) 1.999 SiO 4 : Eu 0.001 , F 0.5 @Au 1×10 −4 luminescent material doped with Au nano-particles is obtained.

Preparation of Silicate Luminescent Material Ba 1.99 SiO 4 :Eu 0.01 :F 0.1 @Ag 1.25×10 −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(NO 3 ) 2 , 0.4 mL of 0.1 mol/L solution of Eu(NO 3 ) 3 , 2 mL of 0.1 mol/L solution of BaF 2 , stirring thoroughly, then dripping slowly 10 mL of 1 mol/L NH 4 HCO 3 , 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% N 2 plus 5% H 2 at 1200° C. for 4 h for reduction, cooling to room temperature and Ba 1.99 SiO 4 :Eu 0.01 :F 0.1 @Ag 1.25×10 −3 luminescent material doped with Ag nano-particles is obtained.

As shown in FIG. 3 , the comparison of spectrums of the luminescent materials Ba 1.99 SiO 4 :Eu 0.01 :F 0.1 @ Ag 1.25×10 −3 coating metal nano-particles Ag prepared in the present embodiment with luminescent materials Ba 1.99 SiO 4 :Eu 0.01 :F 0.1 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.

Preparation of Silicate Luminescent Material (Ba 0.8 Mg 0.2 ) 1.95 SiO 4 :Eu 0.05 @Ag 5×10 −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(NO 3 ) 2 , 5.2 mL of 0.3 mol/L solution of Mg(NO 3 ) 2 , 2 mL of 0.1 mol/L solution of Eu(NO 3 ) 3 , stirring thoroughly, then dripping slowly 12 mL of 1 mol/L NH 4 HCO 3 , 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% N 2 plus 5% H 2 at 1150° C. for 6 h for reduction, cooling to room temperature and (Ba 0.8 Mg 0.2 ) 1.95 SiO 4 :Eu 0.05 @Ag 5×10 −3 luminescent material doped with Ag nano-particles is obtained.

Preparation of Silicate Luminescent Material (Ba 0.7 Sr 0.2 Mg 0.1 ) 1.9 SiO 4 :Eu 0.1 , Cl 0.01 @Cu 4×10−4 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(NO 3 ) 2 , 21.3 mL of 0.3 mol/L solution of Ba(NO 3 ) 2 , 4.6 mL of 0.2 mol/L solution of Mg(NO 3 ) 2 , 4.8 mL of 0.1 mol/L solution of Eu(NO 3 ) 3 , 4.8 mL of 0.01 mol/L solution of SrCl 2 , stirring thoroughly, then dripping slowly 12 mL of 1 mol/L NH 4 HCO 3 , 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 H 2 at 1350° C. for 6 h for reduction, cooling to room temperature and (Ba 0.7 Sr 0.2 Mg 0.1 ) 1.9 SiO 4 : Eu 0.1 ,Cl 0.01 @Cu 5×10 −4 luminescent material doped with Cu nano-particles is obtained.

Preparation of Silicate Luminescent Material (Ba 0.95 Zn 0.05 ) 1.995 SiO 4 :Eu 0.00 @Pd 3×10 −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(NO 3 ) 2 , 2 mL of 0.2 mol/L solution of Zn(NO 3 ) 2 , 2 mL of 0.01 mol/L solution of Eu(NO 3 ) 3 , stirring thoroughly, then dripping slowly 20 mL of 0.5 mol/L NH 4 HCO 3 , 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% N 2 plus 5% H 2 at 1400° C. for 3 h for reduction, cooling to room temperature and (Ba 0.95 Zn 0.05 ) 1.995 SiO 4 :Eu 0.005 @Pd 3×10 −4 luminescent material doped with Pd nano-particles is obtained.

Preparation of silicate luminescent material Ba 1.95 SiO 4 :Eu 0.05 @(Ag 0.5 /Au 0.5 ) 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 Ag 0.5 /Au 0.5 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(NO 3 ) 2 , 2 mL of 0.1 mol/L solution of Eu(NO 3 ) 2 , stirring thoroughly, then dripping slowly 25 mL of 0.5 mol/L NH 4 HCO 3 , 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% N 2 plus 5% H 2 at 1300° C. for 2 h for reduction, cooling to room temperature and Ba 1.99 SiO 4 :Eu 0.01 @ (Ag 0.5 /Au 0.5 ) 2×10 −3 luminescent material doped with (Ag 0.5 /Au 0.5 ) 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 Ag 0.5 /Au 0.5 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(NO 3 ) 2 , 2 mL of 0.1 mol/L solution of Eu(NO 3 ) 2 , stirring thoroughly, then dripping slowly 25 mL of 0.5 mol/L NH 4 HCO 3 , 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% N 2 plus 5% H 2 at 1300° C. for 2 h for reduction, cooling to room temperature and Ba 1.99 SiO 4 :Eu 0.01 @ (Ag 0.5 /Au 0.5 ) 2×10 −3 luminescent material doped with (Ag 0.5 /Au 0.5 ) 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.