CN104119892A - Silicate luminescent material cladding metal nanoparticle and preparation method thereof - Google Patents

Silicate luminescent material cladding metal nanoparticle and preparation method thereof Download PDF

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CN104119892A
CN104119892A CN201310150817.2A CN201310150817A CN104119892A CN 104119892 A CN104119892 A CN 104119892A CN 201310150817 A CN201310150817 A CN 201310150817A CN 104119892 A CN104119892 A CN 104119892A
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周明杰
王荣
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention belongs to the field of luminescent materials, and discloses a silicate luminescent material cladding a metal nanoparticle and a preparation method thereof. The chemical general formula of the luminescent material is Ca1-xSnSiO5:Tbx@My, wherein Ca1-xSnSiO5:Tbx is an outer shell, @ represents cladding, and M is an inner core, M is at least one selected from Ag, Au, Pt, Pd and Cu metal nanoparticles, 0<x<=0. 2, y is the molar ratio of M to Si, and 0<y<=1*10<-2>. According to the provided silicate luminescent material, because of introduction of the M doping metal nanoparticle, doping of the M metal nanoparticle helps to improve the luminescent efficiency of the luminescent material.

Description

Silicate luminescent material of a kind of clad metal nano particle and preparation method thereof
Technical field
The present invention relates to field of light emitting materials, relate in particular to silicate luminescent material of a kind of clad metal nano particle and preparation method thereof.
Background technology
White light LEDs (1ight emitting diodes) has that efficiency is high, the life-span is long, volume is little, respond the advantage such as quick, pollution-free, energy-conservation has obtained paying attention to more and more widely.One of major way of realizing at present white light is blue GaN chip and yellow YAG:Ce phosphor combination generation white light.The shortcoming of the method is that colour rendering index is low.And utilize near ultraviolet LED chip and red, green, blue three primary colors fluorescent powder to be combined into white light LEDs, its luminous efficiency is high, colour temperature is adjustable and colour rendering index is high, has been widely studied, and has become the main flow of current development.The LED three primary colors fluorescent powder that therefore, can effectively be excited by purple light, near-ultraviolet light is just widely studied.Wherein, take that luminescent material that silicate systems is matrix has that raw material sources are abundant, low price, Technological adaptability is extensive, synthesis temperature is moderate, stability is attracting people's sight always compared with high.
The silicate fluorescent powder that terbium ion activates, it is a kind of good green emitting phosphor, but the luminous efficiency of current this fluorescent material need to improve.
Summary of the invention
Problem to be solved by this invention is to provide the silicate luminescent material of the clad metal nano particle that a kind of luminous efficiency is higher.
Technical scheme of the present invention is as follows:
A silicate luminescent material for clad metal nano particle, its chemical general formula is: Ca 1-xsnSiO 5: Tb x@M y; Wherein, Ca 1-xsnSiO 5: Tb xfor shell ,@is coated, and M is kernel, is to adulterate all to belong to nanoparticle; M is selected from least one in Ag, Au, Pt, Pd, Cu, and x is the mole number that Tb atom replaces Ca atom, 0 < x≤0.2, and y is the mol ratio of M and Si, 0 < y≤1 * 10 -2; Ca 1-xsnSiO 5: Tb xfor luminescent material, Tb exists with ionic species, is light emitting ionic center, and colon ": " represents Tb doping.
The silicate luminescent material of described clad metal nano particle, preferably, 0.005≤x≤0.1,1 * 10 -5≤ y≤5 * 10 -3.
The present invention also provides the preparation method of the silicate luminescent material of above-mentioned clad metal nano particle, comprises the steps:
Auxiliary agent and reductive agent hybrid reaction by the salts solution of M, a dissemination, make M nanoparticle sol;
M nanoparticle sol is joined in the polyvinylpyrrolidone aqueous solution, M nanoparticle is carried out to surface treatment 8～18h, then add dehydrated alcohol and ammoniacal liquor, stir, then under agitation add tetraethoxy, after reaction, separated dry, obtain SiO 2@M ynanometer ball; Wherein ,@represents SiO 2coated M; The volume ratio of dehydrated alcohol, ammoniacal liquor, tetraethoxy is 15～40:3～8:1～1.8;
According to Ca 1-xsnSiO 5: Tb x@M ythe stoichiometric ratio of middle element, takes Sn, Ca and Tb each self-corresponding solid chemical compound and SiO 2@M ynanometer ball, mixed grinding is even; Then grinding powder is warming up to 500 ℃～1000 ℃ thermal treatments 2～15 hours, be cooled to room temperature, grind the sample obtaining after thermal treatment, again the sample powder of grinding is placed under 1100 ℃～1500 ℃ reducing atmospheres and is reduced 1～8 hour, furnace cooling is cooled to room temperature, resulting sample is ground to powder, obtains its chemical general formula and be: Ca 1-xsnSiO 5: Tb x@M ythe silicate luminescent material of clad metal nano particle;
Wherein, Ca 1-xsnSiO 5: Tb xfor shell ,@is coated, and M is kernel, be metal nano particle-doped, M is selected from least one in Ag, Au, Pt, Pd, Cu, and x is the mole number that Tb atom replaces Ca atom, 0 < x≤0.2, y is the mol ratio of M and Si, 0 < y≤1 * 10 -2.
The preparation method of the silicate luminescent material of described clad metal nano particle, preferably, the concentration of the salts solution of M is 0.8 * 10 -4mol/L～1 * 10 -2mol/L.
The preparation method of the silicate luminescent material of described clad metal nano particle, preferably, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone (PVP), Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate; The content of the addition of described auxiliary agent in the M nanoparticle sol finally obtaining is 1 * 10 -4g/mL～5 * 10 -2g/mL; Described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride; The mol ratio of the addition of described reductive agent and M ion is 0.5:1～10:1, and in practical application, reductive agent need be prepared or is diluted to concentration is 1 * 10 -4the aqueous solution of mol/L～1mol/L.
The preparation method of the silicate luminescent material of described clad metal nano particle, preferably, auxiliary agent and the reductive agent hybrid reaction 10min～45min of the salts solution of M, a dissemination.
The preparation method of the silicate luminescent material of described clad metal nano particle, preferably, the concentration of the polyvinylpyrrolidone aqueous solution is 0.005g/mL～0.1g/mL.
Above-mentioned SiO 2@M yin the preparation of nanometer ball ball, be to adopt method is prepared SiO 2clad nano ball; Be according to the sol-gel method proposing Deng people is carried out coated Si O 2nanometer ball successively adds dehydrated alcohol, deionized water, ammoniacal liquor, tetraethoxy to prepare SiO in metal nanoparticle colloidal sol 2the nanometer ball of clad metal nano particle.
The preparation method of the silicate luminescent material of described clad metal nano particle, preferably, Ca and Tb solid chemical compound is separately respectively oxide compound, carbonate, nitrate, acetate or the oxalate of Ca and Tb, and the solid chemical compound of Sn is stannic oxide SnO 2.
The preparation method of the silicate luminescent material of described clad metal nano particle, preferably, it is the N of 95:5 that described reducing atmosphere is selected volume ratio 2with H 2mix reducing atmosphere and (be expressed as 95%N 2+ 5%H 2), CO reducing atmosphere, pure H 2at least one in reducing atmosphere.
The preparation method of the silicate luminescent material of described clad metal nano particle, preferably, heat treatment process is to carry out in retort furnace, reduction treatment process is to carry out in tube furnace.
The preparation method of the silicate luminescent material of described clad metal nano particle, preferably, 0.005≤x≤0.1,1 * 10 -5≤ y≤5 * 10 -3.
Silicate luminescent material provided by the invention, metal nano particle-doped owing to having introduced M, by doping M metal nanoparticle, reach the luminous efficiency that improves luminescent material, and prepared Ca 1-xsnSiO 5: Tb x@M yluminescent material stability is better.
Preparation method of the present invention, adopts sol-gel method to make SiO 2@M y, then with SiO 2@M yfor silicon source, adopt high temperature solid-state method, the compound preparation corresponding with Sn, Ca and Tb is coated with the fluorescent material of M metal nanoparticle, i.e. Ca 1-xsnSiO 5: Tb x@M y; This preparation method's technique is simple, equipment requirements is low, pollution-free, be easy to control, be suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is luminescent material and the luminescent spectrum comparison diagram of comparative example luminescent material under wavelength 312nm excites of embodiment 3 preparations; Wherein curve 1 is the Ca of the clad metal nano particle Ag that makes of embodiment 3 0.95snSiO 5: Tb 0.05@Ag 2.5 * 10-4the luminescent spectrum of luminescent material, curve 2 is not Ca of clad metal nano particle of comparative example 0.95snSiO 5: Tb 0.05the luminescent spectrum of luminescent material.
Embodiment
The difference that illustrates silicate luminescent material by a plurality of embodiment below forms and preparation method thereof, with and the aspect such as performance.
Embodiment 1
High temperature solid-state method is prepared Ca 0.999snSiO 5: Tb 0.001@Au 1 * 10-2:
The preparation of Au nanoparticle sol: take 41.2mg hydrochloro-auric acid (AuCl 3hCl4H 2o) be dissolved in the deionized water of 10mL; After hydrochloro-auric acid dissolves completely, take 14mg Trisodium Citrate and 6mg cetyl trimethylammonium bromide, and be dissolved in aqueous solution of chloraurate under the environment of magnetic agitation; Take 3.8mg sodium borohydride and 17.6mg xitix is dissolved into respectively in 10mL deionized water, obtaining 10mL concentration is 1 * 10 -2the sodium borohydride aqueous solution of mol/L and 10mL concentration are 1 * 10 -2the aqueous ascorbic acid of mol/L; Under the environment of magnetic agitation, first in aqueous solution of chloraurate, add 5mL sodium borohydride aqueous solution, after stirring reaction 5min, in aqueous solution of chloraurate, add 5mL1 * 10 again -2the aqueous ascorbic acid of mol/L, continues reaction 30min afterwards, and obtaining 20mLAu content is 5 * 10 -3the Au nanoparticle sol of mol/L.Measuring 10mL is 5 * 10 -3the Au nanoparticle sol of mol/L, toward in Au nanoparticle sol in beaker and add the PVP solution of 2mL0.1g/mL, magnetic agitation 8h, obtains the Au nanoparticle after surface treatment.
SiO 2@Au 1 * 10-2preparation: while stir successively, in above-mentioned Au nanoparticle sol, add 25mL dehydrated alcohol, 5mL ammoniacal liquor, 1.2mL tetraethyl orthosilicate, after reaction 8h, through centrifugal, washing, dry, obtain SiO 2@Au 1 * 10-2nanometer ball, wherein y is 1 * 10 -2.
Ca 0.999snSiO 5: Tb 0.001@Au 1 * 10-2preparation: take Ca (CH 3cOO) 20.6314g, SnO 20.6028g, Tb (CH 3cOO) 3the SiO of 0.0013g and 0.2404g 2@Au nanometer ball, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, 500 ℃ of thermal treatment 15h in retort furnace, again in tube furnace under CO reducing atmosphere 1500 ℃ of reduction 1h, be cooled to room temperature, can obtain the Ca of coated Au nanoparticle 0.999snSiO 5: Tb 0.001@Au 1 * 10-2luminescent material.
Embodiment 2
High temperature solid-state method is prepared Ca 0.98snSiO 5: Tb 0.02@Pt 5 * 10-3:
Preparation containing Pt nanoparticle sol: take 25.9mg Platinic chloride (H 2ptCl 66H 2o) be dissolved in the deionized water of 17mL; Under the condition of magnetic agitation, 400mg Trisodium Citrate and 600mg sodium laurylsulfonate are dissolved in above-mentioned platinum acid chloride solution; Take 1.9mg sodium borohydride and be dissolved in 10mL deionized water, obtaining concentration is 5 * 10 -3the sodium borohydride solution of mol/L; Prepare 10mL concentration is 5 * 10 simultaneously -2the hydrazine hydrate solution of mol/L; Under the condition of magnetic agitation, first in above-mentioned platinum acid chloride solution, drip the above-mentioned sodium borohydride solution of 0.4mL, after reaction 5min, then add the above-mentioned hydrazine hydrate solution of 2.6mL in above-mentioned platinum acid chloride solution, continue reaction 40min, obtaining 20mL Pt nanoparticle concentration is 2.5 * 10 -3the colloidal sol of mol/L; Measure 8mL2.5 * 10 -3the Pt nanoparticle sol of mol/L, in beaker, and adds the PVP solution of 4mL0.02g/mL, and magnetic agitation 18h, obtains the Pt nanoparticle after surface treatment.
SiO 2@Pt 5 * 10-3preparation: while stir successively, in above-mentioned Pt nanoparticle sol, add successively 20mL dehydrated alcohol, 4mL ammoniacal liquor, 1mL tetraethyl orthosilicate.After question response 3h, through centrifugal, washing, dry, obtain SiO 2@Pt 5 * 10-3nanometer ball, wherein y is 5 * 10 -3.
Ca 0.98snSiO 5: Tb 0.02@Pt 5 * 10-3preparation: take CaCO 30.3924g, SnO 20.6028g, Tb 2(CO 3) 3the SiO of 0.0199g and 0.2404g 2@Pt nanometer ball, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, 1000 ℃ of thermal treatment 2h in retort furnace, again in tube furnace under pure H2 reducing atmosphere 1200 ℃ of reduction 5h, be cooled to room temperature, can obtain the Ca of coated Pt nanoparticle 0.98snSiO 5: Tb 0.02@Pt 5 * 10-3luminescent material.
Embodiment 3
High temperature solid-state method is prepared Ca 0.95snSiO 5: Tb 0.05@Ag 2.5 * 10-4:
The preparation of Ag nanoparticle sol: take 3.4mg Silver Nitrate (AgNO 3) be dissolved in the deionized water of 18.4mL; After Silver Nitrate dissolves completely, take 42mg Trisodium Citrate and be dissolved in silver nitrate aqueous solution under the environment of magnetic agitation; Take 5.7mg sodium borohydride molten in 10mL deionized water, obtaining 10mL concentration is 1.5 * 10 -2the sodium borohydride aqueous solution of mol/L; Under the environment of magnetic agitation, toward disposable 1.6mL1.5 * 10 that add in silver nitrate aqueous solution -2the sodium borohydride aqueous solution of mol/L, continues reaction 10min afterwards, and obtaining 20mL Ag content is 1 * 10 -3the Ag nanoparticle sol of mol/L; Measure 1.2mL1 * 10 -3the Ag nanoparticle sol of mol/L, in beaker, then adds 10mL0.01g/mL PVP, and magnetic agitation 12h, obtains the Ag nanoparticle after surface treatment.
SiO 2@Ag 2.5 * 10-4preparation: while stir successively to adding in above-mentioned Ag nanoparticle sol, add successively 30mL dehydrated alcohol, 7.2mL ammoniacal liquor, 1.2mL tetraethyl orthosilicate; After question response 6h, through centrifugal, washing, dry, obtain SiO 2@Ag 2.5 * 10-4nanometer ball, wherein y is 2.5 * 10 -4.
Ca 0.95snSiO 5: Tb 0.05@Ag 2.5 * 10-4preparation: take CaCO 30.3803g, SnO 20.6028g, Tb 4o 7the SiO of 0.0374g and 0.2404g 2@Ag nanometer ball, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, 900 ℃ of thermal treatment 4h in retort furnace, then in tube furnace at 95%N 2+ 5%H 2the lower 1350 ℃ of reduction 4h of reducing atmosphere, are cooled to room temperature, can obtain the Ca of coated Ag nanoparticle 0.95snSiO 5: Tb 0.05@Ag 2.5 * 10-4luminescent material.
Fig. 1 is luminescent material and the luminescent spectrum comparison diagram of comparative example luminescent material under wavelength 312nm excites of embodiment 3 preparations; Wherein curve 1 is the Ca of the clad metal nano particle Ag that makes of embodiment 3 0.95snSiO 5: Tb 0.05@Ag 2.5 * 10-4the luminescent spectrum of luminescent material, curve 2 is not Ca of clad metal nano particle of comparative example 0.95snSiO 5: Tb 0.05the luminescent spectrum of luminescent material.
As can be seen from Figure 1, the emission peak at 544nm place, after clad metal nano particle, the luminous intensity of luminescent material has strengthened 25% before not being coated.
Embodiment 4
High temperature solid-state method is prepared Ca 0.8snSiO 5: Tb 0.20@Pd 1 * 10-5:
The preparation of Pd nanoparticle sol: take 0.22mg Palladous chloride (PdCl 22H 2o) be dissolved in the deionized water of 10mL; After Palladous chloride dissolves completely, take 11.0mg Trisodium Citrate and 4.0mg sodium lauryl sulphate, and be dissolved in palladium chloride aqueous solution under the environment of magnetic agitation; Take 0.38mg sodium borohydride molten in 100mL deionized water, obtaining concentration is 1 * 10 -4the sodium borohydride reduction liquid of mol/L; Under the environment of magnetic agitation, in palladium chloride aqueous solution, add fast 10mL1 * 10 -4sodium borohydride aqueous solution, continue afterwards reaction 20min, obtaining 20mL Pd content is 5 * 10 -5the Pd nanoparticle sol of mol/L; Measure 1.5mL5 * 10 -5the Pd nanoparticle sol of mol/L, in beaker, and adds 8mL0.005g/mL PVP, and magnetic agitation 16h, obtains the Pd nanoparticle after surface treatment.
SiO 2@Pd 1 * 10-5preparation: while stir successively, in above-mentioned Pd nanoparticle sol, add successively 40mL dehydrated alcohol, 8mL ammoniacal liquor, 1.8mL tetraethyl orthosilicate.After question response 5h, through centrifugal, washing, dry, obtain SiO 2@Pd 1 * 10-5nanometer ball, wherein y is 1 * 10 -5.
Ca 0.8snSiO 5: Tb 0.20@Pd 1 * 10-5preparation: take CaC 2o 40.4099g, SnO 20.6028g, Tb 2(C 2o 4) 3the SiO of 0.2327g and 0.2404g 2@Pd nanometer ball, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, 700 ℃ of thermal treatment 8h in retort furnace, then in tube furnace at 95%N 2+ 5%H 2the lower 1100 ℃ of reduction 8h of reducing atmosphere, are cooled to room temperature, can obtain the Ca of coated Pd nanoparticle 0.8snSiO 5: Tb 0.20@Pd 1 * 10-5luminescent material.
Embodiment 5
High temperature solid-state method is prepared Ca 0.9snSiO 5: Tb 0.10@Cu 1 * 10-4:
The preparation of Cu nanoparticle sol: take in the ethanol that 1.6mg cupric nitrate is dissolved into 16mL, after dissolving completely, while stir, add 2mg PVP, then slowly splash into 0.4mg sodium borohydride molten to obtain in 10mL ethanol 1 * 10 -3the sodium borohydride alcoholic solution 4mL of mol/L, continues stirring reaction 10min, obtains 20mL4 * 10 -4the Cu nanoparticle sol of mol/L.Measure 1.5mL4 * 10 -4the Cu nanoparticle sol of mol/L, in beaker, and adds 5mL0.03g/mL PVP, and magnetic agitation 10h, obtains the Cu nanoparticle after surface treatment.
SiO 2@Cu 1 * 10-4preparation: while stir in above-mentioned Cu nanoparticle sol, add successively 15mL dehydrated alcohol, 3mL ammoniacal liquor, 1.4mL tetraethyl orthosilicate.After question response 4h, through centrifugal, washing, dry, obtain SiO 2@Cu 1 * 10-4nanometer ball, wherein y is 1 * 10 -4.
Ca 0.9snSiO 5: Tb 0.10@Cu 1 * 10-4preparation: take Ca (NO 3) 20.5907g, SnO 20.6028g, Tb (NO 3) 3the SiO of 0.1380g and 0.2404g 2@Cu nanometer ball, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, 600 ℃ of thermal treatment 10h in retort furnace, then in tube furnace at 95%N 2+ 5%H 2the lower 1300 ℃ of reduction 6h of reducing atmosphere, are cooled to room temperature, can obtain the Ca of coated Cu nanoparticle 0.9snSiO 5: Tb 0.10@Cu 1 * 10-4luminescent material.
Embodiment 6
High temperature solid-state method is prepared Ca 0.9snSiO 5: Tb 0.005@(Ag 0.5/ Au 0.5) 1.25 * 10-3:
Ag 0.5/ Au 0.5the preparation of nanoparticle sol: take 6.2mg hydrochloro-auric acid (AuCl 3hCl4H 2o) and 2.5mg AgNO 3be dissolved in the deionized water of 28mL; After dissolving completely, take 22mg Trisodium Citrate and 20mgPVP, and under the environment of magnetic agitation, be dissolved in above-mentioned mixing solutions; Take freshly prepd 380mg sodium borohydride molten in 10mL deionized water, obtain the sodium borohydride aqueous solution that 10mL concentration is 1mol/L; Under the environment of magnetic agitation, toward the disposable sodium borohydride aqueous solution that adds 0.3mL1mol/L in above-mentioned mixing solutions, continue afterwards reaction 20min, obtaining the total metal concentration of 30mL is 1 * 10 -3the Ag/Au nanoparticle sol of mol/L; Measure 5mL1 * 10 -3the Ag of mol/L 0.5/ Au 0.5nanoparticle sol, in beaker, and adds 10mL0.1g/mL PVP, and magnetic agitation 12h, obtains the Ag after surface treatment 0.5/ Au 0.5nanoparticle.
SiO 2@(Ag 0.5/ Au 0.5) 1.25 * 10-3preparation: while stir in above-mentioned Ag nanoparticle sol, add successively 30mL dehydrated alcohol, 6mL ammoniacal liquor, 1mL tetraethyl orthosilicate.After question response 5h, through centrifugal, washing, dry, obtain SiO 2@(Ag 0.5/ Au 0.5) 1.25 * 10-3nanometer ball, wherein y is 1.25 * 10 -3.
Ca 0.9snSiO 5: Tb 0.005@(Ag 0.5/ Au 0.5) 1.25 * 10-3preparation: take CaO0.2016g, SnO 20.6028g, Tb 4o 7the SiO of 0.0037g and 0.2404g 2@(Ag 0.5/ Au 0.5) 1.25 * 10-3nanometer ball, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, 900 ℃ of thermal treatment 6h in retort furnace, then in tube furnace at 95%N 2+ 5%H 2the lower 1250 ℃ of sintering 5h reduction of reducing atmosphere, is cooled to room temperature, can obtain coated Ag 0.5/ Au 0.5the Ca of Nanoalloy 0.9snSiO 5: Tb 0.005@(Ag 0.5/ Au 0.5) 1.25 * 10-3luminescent material.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. a silicate luminescent material for clad metal nano particle, is characterized in that, its chemical general formula is: Ca 1-xsnSiO 5: Tb x@M y; Wherein, Ca 1-xsnSiO 5: Tb xfor shell ,@is coated, and M is kernel, be metal nano particle-doped, M is selected from least one in Ag, Au, Pt, Pd, Cu, and x is the mole number that Tb atom replaces Ca atom, 0 < x≤0.2, y is the mol ratio of M and Si, 0 < y≤1 * 10 -2.
2. the silicate luminescent material of clad metal nano particle according to claim 1, is characterized in that, 0.005≤x≤0.1,1 * 10 -5≤ y≤5 * 10 -3.
3. the silicate luminescent material of clad metal nano particle according to claim 1, is characterized in that, comprises a kind of in following luminescent material:
Ca 0.999SnSiO 5:Tb 0.001@Au 1×10ˉ2；Ca 0.98SnSiO 5:Tb 0.02@Pt 5×10ˉ3；Ca 0.95SnSiO 5:Tb 0.05@Ag 2.5×10ˉ4；Ca 0.8SnSiO 5:Tb 0.20@Pd 1×10ˉ5；Ca 0.9SnSiO 5:Tb 0.10@Cu 1×10ˉ4；Ca 0.9SnSiO 5:Tb 0.005@(Ag 0.5/Au 0.5) 1.25×10ˉ3。
4. a preparation method for the silicate luminescent material of clad metal nano particle, is characterized in that, comprises the steps:
Auxiliary agent and reductive agent hybrid reaction by the salts solution of M, a dissemination, make M nanoparticle sol;
M nanoparticle sol is joined in the polyvinylpyrrolidone aqueous solution, M nanoparticle is carried out to surface treatment 8～18h, then add dehydrated alcohol and ammoniacal liquor, stir, then under agitation add tetraethoxy, after reaction, separated dry, obtain SiO 2@M ynanometer ball; Wherein ,@represents SiO 2coated M; The volume ratio of dehydrated alcohol, ammoniacal liquor, tetraethoxy is 15～40:3～8:1～1.8;
According to Ca 1-xsnSiO 5: Tb x@M ythe stoichiometric ratio of middle element, takes Sn, Ca and Tb each self-corresponding solid chemical compound and SiO 2@M ynanometer ball, mixed grinding is even; Then grinding powder is warming up to 500 ℃～1000 ℃ thermal treatments 2～15 hours, be cooled to room temperature, grind the sample obtaining after thermal treatment, again the sample powder of grinding is placed under 1100 ℃～1500 ℃ reducing atmospheres and is reduced 1～8 hour, furnace cooling is cooled to room temperature, resulting sample is ground to powder, obtains its chemical general formula and be: Ca 1-xsnSiO 5: Tb x@M ythe silicate luminescent material of clad metal nano particle;
Wherein, Ca 1-xsnSiO 5: Tb xfor shell ,@is coated, and M is kernel, be metal nano particle-doped, M is selected from least one in Ag, Au, Pt, Pd, Cu, and x is the mole number that Tb atom replaces Ca atom, 0 < x≤0.2, y is the mol ratio of M and Si, 0 < y≤1 * 10 -2.
5. the preparation method of the silicate luminescent material of clad metal nano particle according to claim 4, is characterized in that, the concentration of the salts solution of M is 0.8 * 10 -4mol/L～1 * 10 -2mol/L.
6. the preparation method of the silicate luminescent material of clad metal nano particle according to claim 4, it is characterized in that, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate; The content of the addition of described auxiliary agent in the M nanoparticle sol finally obtaining is 1 * 10 -4g/mL～5 * 10 -2g/mL; Described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride; The mol ratio of the addition of described reductive agent and M ion is 0.5:1～10:1; Auxiliary agent and the reductive agent hybrid reaction 10min～45min of the salts solution of M, a dissemination.
7. the preparation method of the silicate luminescent material of clad metal nano particle according to claim 4, is characterized in that, the concentration of the polyvinylpyrrolidone aqueous solution is 0.005g/mL～0.1g/mL.
8. the preparation method of the silicate luminescent material of clad metal nano particle according to claim 4, it is characterized in that, Ca and Tb solid chemical compound is separately respectively oxide compound, carbonate, nitrate, acetate or the oxalate of Ca and Tb, and the solid chemical compound of Sn is stannic oxide SnO 2.
9. the preparation method of the silicate luminescent material of clad metal nano particle according to claim 4, is characterized in that, it is the N of 95:5 that described reducing atmosphere is selected volume ratio 2with H 2mix reducing atmosphere, CO reducing atmosphere, pure H 2at least one in reducing atmosphere.
10. the preparation method of the silicate luminescent material of clad metal nano particle according to claim 4, is characterized in that, 0.005≤x≤0.1,1 * 10 -5≤ y≤5 * 10 -3.
CN201310150817.2A 2013-04-26 2013-04-26 Silicate luminescent material cladding metal nanoparticle and preparation method thereof Pending CN104119892A (en)

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Application publication date: 20141029