CN103881714A - Sodium yttrium silicate green light emitting material and preparation method thereof - Google Patents

Sodium yttrium silicate green light emitting material and preparation method thereof Download PDF

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CN103881714A
CN103881714A CN201210555356.2A CN201210555356A CN103881714A CN 103881714 A CN103881714 A CN 103881714A CN 201210555356 A CN201210555356 A CN 201210555356A CN 103881714 A CN103881714 A CN 103881714A
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luminescent material
yttrium silicate
sodium
silicate green
green luminescent
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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 light emitting materials, and discloses a sodium yttrium silicate green light emitting material and a preparation method thereof, wherein the chemical general formula of the material is Na5Y1-xSi4O12:Tbx@My, wherein M is doped metal nanoparticles and is at least one selected from Ag, Au, Pt, Pd and Cu, @ represents coating, M is adopted as the inner core, Na5Y1-xSi4O12:Tbx is adopted as the outer shell, the x value is more than 0 and is less than or equal to 0.6, and y is a molar ratio of M to Si and is more than 0 and is less than or equal to 1*10<-2>. According to the sodium yttrium silicate green light emitting material, the SiO2@M is adopted as the silicon source, the sodium yttrium silicate green light emitting material prepared from the compounds corresponding to Na, Y and Tb is adopted to coat the metal nanoparticles, and the light emitting efficiency of the green light emitting material is increased through coating of the metal nanoparticles.

Description

Sodium yttrium silicate green luminescent material and preparation method thereof
Technical field
The present invention relates to field of light emitting materials, relate in particular to a kind of sodium yttrium silicate green luminescent material and preparation method thereof.
Background technology
Feds is because its running voltage is low in recent years, power consumption is little, do not need deflector coil, without X-radiation, the advantage such as radioprotective and magneticinterference and receiving much concern, field-transmitting cathode and luminescent material be in conjunction with the field emission light source that can obtain high brightness, high colour developing, can apply and the field such as demonstration, various instruction, general lighting.
One of key factor of preparing premium properties feds is the preparation of high-performance green luminescent material body.The fluorescent material that feds adopts is at present mainly some sulfide series for conventional cathode ray tube and projection TV teletron, oxide compound series and oxysulfide series green luminescent material.Wherein, the Na using in the past 5ySi 4o 12: Tb purity of color is high, but luminous efficiency is not high.
Summary of the invention
The sodium yttrium silicate green luminescent material that provides a kind of luminous efficiency higher is provided problem to be solved by this invention.
Technical scheme of the present invention is as follows:
A kind of sodium yttrium silicate green luminescent material, its chemical general formula is: Na 5y 1-xsi 4o 12: Tb x@M y; Wherein, M is metal nano particle-doped, and M is selected from least one in Ag, Au, Pt, Pd and Cu, and@is coated, taking M as kernel, and Na 5y 1-xsi 4o 12: Tb xfor shell, the value of x is 0 < x≤0.6, y be M with Si mole ratio, the value of y is 0 < y≤1 × 10 -2.
Described sodium yttrium silicate green luminescent material, wherein, the value of x is 0.01≤x≤0.3; The value of y is 1 × 10 -5≤ y≤5 × 10 -3.
Described sodium yttrium silicate green luminescent material, wherein, M is Au and Ag.
The present invention also provides the preparation method of sodium yttrium silicate green luminescent material, comprises the steps:
S1, will be containing making M nanometer particle colloid after salts solution, auxiliary agent and the reductive agent hybrid reaction of M; Wherein, the addition of reductive agent is 0.5:1～10:1 with the mol ratio that contains M ion in the salts solution of M; The content of the addition of described auxiliary agent in the M nanometer particle colloid finally obtaining is 1 × 10 -4g/mL～5 × 10 -2g/mL;
S2, step S1 is made to M nanometer particle colloid join in surface treatment agent and carry out surface treatment, add successively more subsequently ethanol, deionized water and ammoniacal liquor, stir, more then add tetraethoxy, after reaction, separate dryly, obtain the SiO of coated M nanoparticle 2powder; Wherein, dehydrated alcohol: deionized water: ammoniacal liquor: the volume ratio of tetraethoxy is 15 ~ 20:5 ~ 25:3 ~ 10:1 ~ 2.5.
S3, according to chemical general formula Na 5y 1-xsi 4o 12: Tb x@M yin each element chemistry metering ratio, take the source compound of Na, source compound, the source compound of Tb and the SiO of the coated M nanoparticle that step S2 makes of Y 2powder, ground and mixed is even, obtains mixed powder; Described mixing vermicelli are placed in to reduction at reducing atmosphere, 900 ~ 1250 DEG C and process 1 ~ 8h, be cooled to room temperature, obtaining chemical general formula is Na 5y 1-xsi 4o 12: Tb x@M ysodium yttrium silicate green luminescent material;
In above-mentioned steps, M is metal nano particle-doped, and M is selected from least one in Ag, Au, Pt, Pd and Cu, and@is coated, taking M as kernel, and Na 5y 1-xsi 4o 12: Tb xfor shell, the value of x is 0 < x≤0.6, y be M with Si mole ratio, the value of y is 0 < y≤1 × 10 -2.
The preparation method of described sodium yttrium silicate green luminescent material, in step S1, the concentration that contains the salts solution of M is 1 × 10 -4mol/L～1 × 10 -2mol/L.
The preparation method of described sodium yttrium silicate green luminescent material, in step S1, described auxiliary agent is polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate.
The preparation method of described sodium yttrium silicate green luminescent material, in step S1, described reductive agent is hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride.
The preparation method of described sodium yttrium silicate green luminescent material, in step S1, the time of described hybrid reaction is 10min～45min.
The preparation method of described sodium yttrium silicate green luminescent material, in step S2, described surface treatment agent is that concentration is the polyvinylpyrrolidonesolution solution of 0.005g/mL～0.1g/mL.
The preparation method of described sodium yttrium silicate green luminescent material, in step S3, the source compound of the source compound of Na, the source compound of Y and Tb is respectively Na, Y and the each self-corresponding oxide compound of Tb, carbonate, acetate or oxalate.
Sodium yttrium silicate green luminescent material provided by the invention, with SiO 2@M is silicon source, and the yttrium silicate sodium green luminescent material clad metal nano particle that adopts Na, Y and compound corresponding to Tb to prepare, improves yttrium silicate sodium green luminescent material luminous efficiency by clad metal nano particle; In addition, by the metal nano particle-doped stability that strengthens yttrium silicate sodium luminescent material.
Sodium yttrium silicate green luminescent material preparation method of the present invention, technique is simple, equipment requirements is low, pollution-free, be easy to control, be suitable for suitability for industrialized production.
Brief description of the drawings
Fig. 1 is preparation technology's schema of sodium yttrium silicate green luminescent material of the present invention;
Fig. 2 is that sodium yttrium silicate green luminescent material prepared by embodiment 3 is the luminescent spectrum comparison diagram under the cathode-ray exciting under 1.5KV with contrast luminescent material at acceleration voltage; Wherein, curve 1 is sodium yttrium silicate green luminescent material prepared by embodiment 3: the Na of clad metal nano particle Ag 5y 0.9si 4o 12: Tb 0.1@Ag 2.5 × 10-4the luminescent spectrum of luminescent material, curve 2 is contrast luminescent materials: the not Na of clad metal nano particle 5y 0.9si 4o 12: Tb 0.1the luminescent spectrum of luminescent material.
Embodiment
Sodium yttrium silicate green luminescent material provided by the invention, its general molecular formula is: Na 5y 1-xsi 4o 12: Tb x@M y; Wherein, M is metal nano particle-doped, and M is selected from least one in Ag, Au, Pt, Pd and Cu, and@is coated, taking M as kernel, and Na 5y 1-xsi 4o 12: Tb xfor shell, the value of x is 0 < x≤0.6, y be M with Si mole ratio, the value of y is 0 < y≤1 × 10 -2.
In sodium yttrium silicate green luminescent material, the value of x is preferably 0.01≤x≤0.30; The value of y is preferably 1 × 10 -5≤ y≤5 × 10 -3.
In sodium yttrium silicate green luminescent material, M can be the one in Ag, Au, Pt, Pd and Cu metal nanoparticle, also can be wherein two or more, can be that mol ratio is the Ag of 1:1 and Au, also can is that mol ratio is Ag and the Au of 2:3, can also be that mol ratio is Pd and the Pt of 3:7, can also be that mol ratio is Ag, Au and the Pt etc. of 1:4:5; Preferably, M is that mol ratio is Ag and the Au of 1:1.
Sodium yttrium silicate green luminescent material provided by the invention, with SiO 2@M is silicon source, and the yttrium silicate sodium green luminescent material clad metal nano particle that adopts Na, Y and compound corresponding to Tb to prepare, improves yttrium silicate sodium green luminescent material luminous efficiency by clad metal nano particle; In addition, by the metal nano particle-doped stability that strengthens yttrium silicate sodium luminescent material.
Compared to prior art, metal nano particle-doped yttrium silicate sodium luminescent material prepared by the present invention has good stability, and the better advantage of luminescent properties is widely used in the fields such as illumination and demonstration.
The preparation method of above-mentioned silicon sodium yttrium silicate green luminescent material, as shown in Figure 1, comprises the steps:
S1: will make M nanometer particle colloid after the salts solution containing M, the auxiliary agent that plays dissemination and reductive agent hybrid reaction; Wherein, the addition of reductive agent is 3.6:1～18:1 with the mol ratio that contains M ion in the salts solution of M; The content of the addition of described auxiliary agent in the M nanometer particle colloid finally obtaining is 1 × 10 -4g/mL～5 × 10 -2g/mL;
S2, step S1 is made to M nanometer particle colloid join and in surface treatment agent, carry out surface treatment, add successively more subsequently dehydrated alcohol, deionized water and ammoniacal liquor, stir, then under agitation add tetraethoxy, after reaction, separate the dry SiO that obtains being coated with M nanoparticle 2powder; Wherein, dehydrated alcohol: deionized water: ammoniacal liquor: it is 15 ~ 20:5 ~ 25:3 ~ 10:1 ~ 2.5 that the volume of tetraethoxy is counted ratio.
S3, be Na according to chemical general formula 5y 1-xsi 4o 12: Tb x@M yin each element chemistry metering ratio, take the SiO that is coated with M nanoparticle making in the source compound of source compound, Tb of source compound, the Y of Na and step S2 2powder, ground and mixed is even, obtains mixed powder; Described mixing vermicelli are placed in to reduction at reducing atmosphere, 900～1250 DEG C and process 1 ~ 8h, be cooled to room temperature, obtain sample powder, ground sample powder, obtaining chemical general formula is Na 5y 1-xsi 4o 12: Tb x@M ysodium yttrium silicate green luminescent material;
In above-mentioned steps, M is metal nano particle-doped, and M is selected from least one in Ag, Au, Pt, Pd and Cu, and@is coated, taking M as kernel, and Na 5y 1-xsi 4o 12: Tb xfor shell, the value of x is 0 < x≤0.6, y be M with Si mole ratio, the value of y is 0 < y≤1 × 10 -2.
The preparation method of sodium yttrium silicate green luminescent material, in step S1:
M concentration of salt solution flexible configuration according to actual needs, is about 1 × 10 -4mol/L～1 × 10 -2mol/L;
Auxiliary agent plays dissemination, for at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate, the content of the addition of auxiliary agent in the metal nanometer particle colloid finally obtaining is 1 × 10 -4g/mL～5 × 10 -2g/mL;
Reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride; In the present embodiment, one of reductive agent adopts solution state, and preparing or be diluted to concentration by reductive agent is 1 × 10 for reductive agent is prepared or is diluted to concentration -4the aqueous solution of mol/L～1mol/L, the addition of reductive agent and the mol ratio of metal ion are 0.5:1～10:1;
Obtain under the prerequisite of M nanometer particle colloid in guarantee, for energy efficient, the time of hybrid reaction is preferably 10min～45min.
The preparation method of sodium yttrium silicate green luminescent material, in step S2, surface treatment agent is the aqueous solution of polyvinylpyrrolidone (PVP), concentration is 0.005g/mL～0.1g/mL; The present invention adopts
Figure BDA00002618980700051
method coated Si O 2nanometer ball successively adds dehydrated alcohol, deionized water, ammoniacal liquor, tetraethoxy to prepare coated Si O in metal nanometer particle colloid 2nanometer ball.
The preparation method of sodium yttrium silicate green luminescent material, in step S3:
The source compound of the source compound of Na, the source compound of Y and Tb is respectively Na, Y and the each self-corresponding oxide compound of Tb, carbonate, acetate or oxalate;
Reducing atmosphere is 95v%N 2with 5v%H 2reducing atmosphere, CO reducing atmosphere, pure H 2at least one in reducing atmosphere.
Sodium yttrium silicate green luminescent material preparation method of the present invention, technique is simple, equipment requirements is low, pollution-free, be easy to control, be suitable for suitability for industrialized production.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
High temperature solid-state method is prepared Na 5y 0.99si 4o 12: Tb 0.01@Au 1 × 10-2:
The preparation of Au nano particle colloidal 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 nano particle colloidal sol of mol/L; Measuring 20mL is 5 × 10 -3the Au nano particle colloidal sol of mol/L, toward in Au nano particle colloidal sol in beaker and add the PVP solution of 5mL0.1g/mL, magnetic agitation 8h, obtains the Au nano particle after surface treatment.
SiO 2@Au 1 × 10-2preparation: stir while in above-mentioned Au nano particle colloidal sol, add 50mL dehydrated alcohol, 10mL ammoniacal liquor successively, 2.5mL tetraethyl orthosilicate, after reaction 8h, through centrifugal, washing, dry, obtain SiO 2@Au 1 × 10-2powder, wherein y is 1 × 10 -2.
Na 5y 0.99si 4o 12: Tb 0.01@Au 1 × 10-2preparation: take Na 2o0.3099g, Y 2o 30.2235g, Tb 4o 7the SiO of 0.0037g and 0.4808g 2@Au powder, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, in tube furnace, 1000 DEG C of sintering 2h reduction under CO reducing atmosphere, is cooled to room temperature, the Na of the Au nanoparticle that can obtain adulterating 5y 0.99si 4o 12: Tb 0.01@Au 1 × 10-2sodium yttrium silicate green luminescent material.
Embodiment 2
High temperature solid-state method is prepared Na 5y 0.7si 4o 12: Tb 0.3@Pt 5 × 103:
The preparation of Pt nano particle colloidal sol: take 25.9mg Platinic chloride (H 2ptCl 66H 2o) be dissolved in the deionized water of 17mL; After Platinic chloride dissolves completely, take 400mg Trisodium Citrate and 600mg sodium laurylsulfonate, and be dissolved in chloroplatinic acid aqueous solution under the environment of magnetic agitation; Take 1.9mg sodium borohydride and be dissolved in 10mL deionized water, obtaining 10mL concentration is 5 × 10 -3the sodium borohydride aqueous solution of mol/L, prepare 10mL concentration is 5 × 10 simultaneously -2the hydrazine hydrate solution of mol/L; Under the environment of magnetic agitation, first in chloroplatinic acid aqueous solution, drip 0.4mL sodium borohydride aqueous solution, stirring reaction 5min, and then drip 2.6mL5 × 10 in chloroplatinic acid aqueous solution -2the hydrazine hydrate solution of mol/L, continues reaction 40min afterwards, and obtaining 10mLPt content is 2.5 × 10 -3the Pt nano particle colloidal sol of mol/L; Measure 8mL2.5 × 10 -3the Pt nano particle colloidal sol of mol/L, in beaker, and adds the PVP solution of 4mL0.02g/mL, and magnetic agitation 18h, obtains the Pt nano particle after surface treatment.
SiO 2@Pt 5 × 10-3preparation: stir while in above-mentioned Pt nano particle colloidal sol, add successively 20mL dehydrated alcohol, 4mL ammoniacal liquor, 1mL tetraethyl orthosilicate successively.After question response 3h, through centrifugal, washing, dry, obtain SiO 2@Pt 5 × 10-3powder, wherein y is 5 × 10 -3.
Na 5y 0.7si 4o 12: Tb 0.3@Pt 5 × 10-3preparation: take Na 2cO 30.2649g, Y 2(CO 3) 30.1252g, Tb 2(CO 3) 3the SiO of 0.0747g and 0.2404g 2@Pt powder, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, in tube furnace at pure H 2the lower 900 DEG C of sintering 8h reduction of reducing atmosphere, is cooled to room temperature, the Na of the Pt nanoparticle that can obtain adulterating 5y 0.7si 4o 12: Tb 0.3@Pt 5 × 10-3sodium yttrium silicate green luminescent material.
Embodiment 3
High temperature solid-state method is prepared Na 5y 0.9si 4o 12: Tb 0.1@Ag 2.5 × 10-4:
The preparation of Ag nano particle colloidal 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 20mLAg content is 1 × 10 -3the Ag nano particle colloidal sol of mol/L; Measure 1.2mL1 × 10 -3the Ag nano particle colloidal sol of mol/L, in beaker, then adds 10mL0.01g/mL PVP, and magnetic agitation 12h, obtains the Ag nano particle after surface treatment.
SiO 2@Ag 2.5 × 10-4preparation: stir while add successively 30mL dehydrated alcohol, 7.2mL ammoniacal liquor, 1.2mL tetraethyl orthosilicate to adding in above-mentioned Ag nano particle colloidal sol successively; After question response 6h, through centrifugal, washing, dry, obtain SiO 2@Ag 2.5 × 10-4powder, wherein y is 2.5 × 10 -4.
Na 5y 0.9si 4o 12: Tb 0.1@Ag 2.5 × 10-4preparation: take Na 2cO 30.2649g, Y 2o 30.1016g, Tb 4o 7the SiO of 0.0187g and 0.2524g 2siO 2@Au powder, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, in tube furnace at 95%N 2add 5%H 2the lower 1050 DEG C of sintering 6h reduction of weakly reducing atmosphere, is cooled to room temperature, the Na of the Ag nanoparticle that can obtain adulterating 5y 0.9si 4o 12: Tb 0.1@Ag 2.5 × 10-4sodium yttrium silicate green luminescent material.
Fig. 2 is that sodium yttrium silicate green luminescent material prepared by embodiment 3 is the luminescent spectrum comparison diagram under the cathode-ray exciting under 1.5KV with contrast luminescent material at acceleration voltage; Wherein, curve 1 is sodium yttrium silicate green luminescent material prepared by embodiment 3: the Na of clad metal nano particle Ag 5y 0.9si 4o 12: Tb 0.1@Ag 2.5 × 10-4the luminescent spectrum of luminescent material, curve 2 is contrast luminescent materials: the not Na of clad metal nano particle 5y 0.9si 4o 12: Tb 0.1the luminescent spectrum of luminescent material.
As can be seen from Figure 2,, at the emission peak at 544nm place, after clad metal nano particle Ag, the more not coated luminous intensity of luminescent material has strengthened 27%.
Embodiment 4
High temperature solid-state method is prepared Na 5y 0.4si 4o 12: Tb 0.6@Pd 1 × 10-5:
The preparation of Pd nano particle colloidal 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, afterwards continue reaction 20min, obtaining 20mL Pd content is 5 × 10 -5the Pd nano particle colloidal sol of mol/L; Measure 1.5mL5 × 10 -5the Pd nano particle colloidal sol of mol/L, in beaker, and adds 6mL0.005g/mL PVP, and magnetic agitation 16h, obtains the Pd nano particle after surface treatment.
SiO 2@Pd 1 × 10-5preparation: stir while in above-mentioned Pd nano particle colloidal sol, add successively 40mL dehydrated alcohol, 8mL ammoniacal liquor, 1.8mL tetraethyl orthosilicate successively.After question response 5h, through centrifugal, washing, dry, obtain SiO 2@Pd 1 × 10-5powder, wherein y is 1 × 10 -5.
Na 5y 0.4si 4o 12: Tb 0.6@Pd 1 × 10-5preparation: take Na 2c 2o 40.3350g, Y 2(C 2o 4) 30.0884g, Tb 2(C 2o 4) 3the SiO of 0.1746g and 0.2404g 2siO 2@Pd powder, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, in tube furnace at 95%N 2add 5%H 2the lower 1250 DEG C of sintering 1h reduction of weakly reducing atmosphere, is cooled to room temperature, can obtain the Na of doping Pd nanoparticle 5y 0.4si 4o 12: Tb 0.6@Pd 1 × 10-5sodium yttrium silicate green luminescent material.
Embodiment 5
High temperature solid-state method is prepared Na 5y 0.8si 4o 12: Tb 0.2@Cu 1 × 10-4:
The preparation of Cu nano particle colloidal sol: take in the ethanol that 1.6mg cupric nitrate is dissolved into 16mL, after dissolving completely, stir while 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 nanometer particle colloid of mol/L.Measure 1.5mL4 × 10 -4the Cu nano particle colloidal sol of mol/L, in beaker, and adds 3.5mL0.03g/mL PVP, and magnetic agitation 10h, obtains the Cu nano particle after surface treatment.
SiO 2@Cu 1 × 10-4preparation: stir while add successively 15mL dehydrated alcohol, 3mL ammoniacal liquor, 1.4mL tetraethyl orthosilicate in above-mentioned Cu nano particle colloidal sol.After question response 4h, through centrifugal, washing, dry, obtain SiO 2@Cu 1 × 10-4powder, wherein y is 1 × 10 -4.
Na 5y 0.8si 4o 12: Tb 0.2@Cu 1 × 10-4preparation: take NaNO 30.4249g, Y (NO 3) 30.2199g, Tb (NO 3) 3the SiO of 0.0689g and 0.2524g 2siO 2@Cu powder, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, in tube furnace at 95%N 2add 5%H 2the lower 1100 DEG C of sintering 4h reduction of weakly reducing atmosphere, is cooled to room temperature, can obtain the Na of doping Pd nanoparticle 5y 0.8si 4o 12: Tb 0.2@Cu 1 × 10-4sodium yttrium silicate green luminescent material.
Embodiment 6
High temperature solid-state method is prepared Na 5y 0.85si 4o 12: Tb 0.15@(Ag 0.5/ Au 0.5) 1.25 × 10-3:
Ag 0.5/ Au 0.5the preparation of nano particle colloidal sol: take 6.2mg hydrochloro-auric acid (AuCl 3hCl4H 2and 2.5mgAgNO O) 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 nano particle colloidal sol of mol/L; Measure 5mL1 × 10 -3the Ag of mol/L 0.5/ Au 0.5nano particle colloidal sol, in beaker, and adds 10mL0.1g/mL PVP, and magnetic agitation 12h, obtains the Ag after surface treatment 0.5/ Au 0.5nano particle.
SiO 2@(Ag 0.5/ Au 0.5) 1.25 × 10-3preparation: stir while add successively 30mL dehydrated alcohol, 6mL ammoniacal liquor, 1mL tetraethyl orthosilicate in above-mentioned Ag nano particle colloidal sol.After question response 5h, through centrifugal, washing, dry, obtain SiO 2@(Ag 0.5/ Au 0.5) 1.25 × 10-3powder, wherein y is 1.25 × 10 -3.
Na 5y 0.85si 4o 12: Tb 0.15@(Ag 0.5/ Au 0.5) 1.25 × 10-3preparation: take Na 2cO 30.2649g, Y 2o 30.0959g, Tb 4o 7the SiO of 0.0280g and 0.2404g 2@(Ag 0.5/ Au 0.5) 1.25 × 10-3powder, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, in tube furnace, 1000 DEG C of sintering 5h reduction under CO reducing atmosphere, is cooled to room temperature, can obtain the Ag that adulterates 0.5/ Au 0.5the Na of Nanoalloy 5y 0.85si 4o 12: Tb 0.15@(Ag 0.5/ Au 0.5) 1.25 × 10-3sodium yttrium silicate green luminescent material.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.

Claims (10)

1. a sodium yttrium silicate green luminescent material, is characterized in that, its chemical general formula is: Na 5y 1-xsi 4o 12: Tb x@M y; Wherein, M is metal nano particle-doped, and M is selected from least one in Ag, Au, Pt, Pd and Cu, and@is coated, taking M as kernel, and Na 5y 1-xsi 4o 12: Tb xfor shell, the value of x is 0 < x≤0.6, y be M with Si mole ratio, the value of y is 0 < y≤1 × 10 -2.
2. sodium yttrium silicate green luminescent material according to claim 1, is characterized in that, the value of x is 0.01≤x≤0.3; The value of y is 1 × 10 -5≤ y≤5 × 10 -3.
3. sodium yttrium silicate green luminescent material according to claim 1, is characterized in that, M is Au and Ag.
4. a preparation method for sodium yttrium silicate green luminescent material, is characterized in that, comprises the steps:
S1, will be containing making M nanometer particle colloid after salts solution, auxiliary agent and the reductive agent hybrid reaction of M; Wherein, the addition of reductive agent is 0.5:1～10:1 with the mol ratio that contains M ion in the salts solution of M; The content of the addition of described auxiliary agent in the M nanometer particle colloid finally obtaining is 1 × 10 -4g/mL～5 × 10 -2g/mL;
S2, step S1 is made to M nanometer particle colloid join in surface treatment agent and carry out surface treatment, add successively more subsequently ethanol, deionized water and ammoniacal liquor, stir, more then add tetraethoxy, after reaction, separate dryly, obtain the SiO of coated M nanoparticle 2powder; Wherein, dehydrated alcohol: deionized water: ammoniacal liquor: the volume ratio of tetraethoxy is 15 ~ 20:5 ~ 25:3 ~ 10:1 ~ 2.5.
S3, according to chemical general formula Na 5y 1-xsi 4o 12: Tb x@M yin each element chemistry metering ratio, take the source compound of Na, source compound, the source compound of Tb and the SiO of the coated M nanoparticle that step S2 makes of Y 2powder, ground and mixed is even, obtains mixed powder; Described mixing vermicelli are placed in to reduction at reducing atmosphere, 900 ~ 1250 DEG C and process 1 ~ 8h, be cooled to room temperature, obtaining chemical general formula is Na 5y 1-xsi 4o 12: Tb x@M ysodium yttrium silicate green luminescent material;
In above-mentioned steps, M is metal nano particle-doped, and M is selected from least one in Ag, Au, Pt, Pd and Cu, and@is coated, taking M as kernel, and Na 5y 1-xsi 4o 12: Tb xfor shell, the value of x is 0 < x≤0.6, y be M with Si mole ratio, the value of y is 0 < y≤1 × 10 -2.
5. the preparation method of sodium yttrium silicate green luminescent material according to claim 4, is characterized in that, in step S1, the concentration that contains the salts solution of M is 1 × 10 -4mol/L～1 × 10 -2mol/L.
6. the preparation method of sodium yttrium silicate green luminescent material according to claim 4, it is characterized in that, in step S1, described auxiliary agent is polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate.
7. the preparation method of sodium yttrium silicate green luminescent material according to claim 4, is characterized in that, in step S1, described reductive agent is hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride.
8. the preparation method of sodium yttrium silicate green luminescent material according to claim 4, is characterized in that, in step S1, the time of described hybrid reaction is 10min～45min.
9. the preparation method of sodium yttrium silicate green luminescent material according to claim 4, is characterized in that, in step S2, described surface treatment agent is that concentration is the polyvinylpyrrolidonesolution solution of 0.005g/mL～0.1g/mL.
10. the preparation method of sodium yttrium silicate green luminescent material according to claim 4, it is characterized in that, in step S3, the source compound of the source compound of Na, the source compound of Y and Tb is respectively Na, Y and the each self-corresponding oxide compound of Tb, carbonate, acetate or oxalate.
CN201210555356.2A 2012-12-20 2012-12-20 Sodium yttrium silicate green light emitting material and preparation method thereof Pending CN103881714A (en)

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