CN104059636B - Metal nano particle-doped ternary sulfide luminescent material and preparation method - Google Patents
Metal nano particle-doped ternary sulfide luminescent material and preparation method Download PDFInfo
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Abstract
The invention belongs to field of light emitting materials, it discloses a kind of metal nano particle-doped ternary sulfide luminescent material and preparation method thereof; The chemical general formula of this luminescent material is Sr
1-xga
2s
4: Eu
x 2+, M
y, wherein, M is at least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and the span of x is 0 & lt; X≤0.2, y is M and (Ln
1-xbi
x)
3gaO
6mole ratio, the span of y is 0 < y≤1 × 10
-2.In metal nano particle-doped ternary sulfide luminescent material of the present invention, introduce M metallics, the luminous efficiency of ternary sulfide luminescent material under same shooting conditions is greatly improved, and radiative wavelength does not change, purity of color and the brightness of launching bright dipping after being stimulated are all higher, can be applied to feds.
Description
Technical field
The present invention relates to field of light emitting materials, particularly relate to a kind of metal nano particle-doped ternary sulfide luminescent material and preparation method.
Background technology
Field Emission Display (FED) is the flat-panel monitor that a kind of new development is got up, its principle of work and traditional cathode tube similar, be imaging by the fluorescent material on beam bombardment display screen.Compared with other flat-panel monitor (FPD), FED all has potential advantage in brightness, visual angle, time of response, operating temperature range, energy consumption etc.Prepare the preparation that one of key factor of premium properties FED is fluorescent material.The SrGa2S4 of Eu doping is a kind of tri compound sulfide, compared with oxide compound, can provide better electron acceleration under the electric field; And relative to some binary sulfides (as SrS, CaS), stable many, but be the focus studied to the raising of its luminous efficiency always.
Summary of the invention
Problem to be solved by this invention is to provide the metal nano particle-doped ternary sulfide luminescent material that a kind of luminous efficiency is higher, can be used for Flied emission.
Technical scheme of the present invention is as follows:
A metal nano particle-doped ternary sulfide luminescent material, its chemical general formula is: Sr
1-xga
2s
4: Eu
x 2+, M
y, wherein, M is metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is the mole number that Eu atom replaces Sr atom, and the span of x is 0<x≤0.2, and y is M and Sr
1-xga
2s
4: Eu
x 2+mole ratio, the span of y is 0 < y≤1 × 10
-2; Sr
1-xga
2s
4: Eu
x 2+for luminescent material, colon is expressed as Eu
2+doping.
Described metal nano particle-doped ternary sulfide luminescent material, preferably, the span of x is 0.001≤x≤0.1, and the span of y is 1 × 10
-5≤ y≤5 × 10
-3.
The invention still further relates to a kind of preparation method of metal nano particle-doped ternary sulfide luminescent material, comprise the steps:
After the salts solution of M, the auxiliary agent playing dissemination and reductive agent hybrid reaction, obtained M nanometer particle colloid solution;
According to Sr
1-xga
2s
4: Eu
x 2+, M
yin each element chemistry metering ratio, measure Sr, the aqueous ethanolic solution of Ga and Eu salt, then add citric acid complexing agent and polyglycol surfactants, stir 2 ~ 6h in 60 ~ 80 DEG C, obtain colloidal sol, measuring described M nanometer particle colloid solution again adds in colloidal sol, stir 2 ~ 12h, obtain precursor sol, precursor sol drying and volatilizing solvent is obtained xerogel, grinding, grinding powder is in 400 ~ 600 DEG C of pre-burnings 2 ~ 10 hours in air atmosphere, and cooling, grinding, obtain precursor powder; Wherein, the mol ratio of citric acid and the total metal ion sum of Sr, Ga and Eu is 1 ~ 5:1; The concentration of polyoxyethylene glycol is 0.05 ~ 0.20g/mL;
Grind described precursor powder even, be placed in process furnace, pass into inert atmosphere subsequently, make to be inert atmosphere in process furnace; Then H is passed into
2s, at 800 ~ 1200 DEG C of calcining 1-8h, is cooled to 500 DEG C to stop H
2s changes rare gas element, under being cooled to normal temperature, stops rare gas element, takes out sample, and namely grinding evenly obtains Sr
1-xga
2s
4: Eu
x 2+, My luminescent material;
In above-mentioned steps, M is metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is the mole number that Eu atom replaces Sr atom, and the span of x is 0<x≤0.2, and y is M and Sr
1-xga
2s
4: Eu
x 2+mole ratio, the span of y is 0 < y≤1 × 10
-2.
The preparation method of described metal nano particle-doped ternary sulfide luminescent material, preferably, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride, and the mol ratio of described reductive agent and M is 0.5:1 ~ 10:1; In actual use, reductive agent needs to be configured to the aqueous solution, and its concentration is 1 × 10
-4mol/L ~ 1mol/L; Auxiliary agent is at least one in polyvinyl pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate, and the content of addition in the M nanometer particle colloid solution finally obtained of auxiliary agent is 1 × 10
-4g/mL ~ 5 × 10
-2g/mL; Auxiliary agent mainly carries out surface modification to M nano particle.
The preparation method of described metal nano particle-doped ternary sulfide luminescent material, preferably, the time of the salts solution of M, auxiliary agent and reductive agent hybrid reaction is 10 ~ 45min.
The preparation method of described metal nano particle-doped ternary sulfide luminescent material, preferably, the molecular weight of described polyoxyethylene glycol is 100-20000, is expressed as polyoxyethylene glycol 100-20000, and lower same, more preferably, the molecular weight of described polyoxyethylene glycol is 2000-10000; Polyoxyethylene glycol is tensio-active agent, and the concentration of polyoxyethylene glycol is 0.05 ~ 0.20g/mL.
The preparation method of described metal nano particle-doped ternary sulfide luminescent material, wherein, Sr, Ga and Eu salt is each self-corresponding nitrate or acetate; Bi salt is corresponding nitrate.
Sr, Ga and Eu salt aqueous ethanolic solution separately adopts following methods to obtain:
Respectively with the oxide compound of Sr, Ga and Eu and carbonate for raw material, be dissolved in nitric acid, then to add volume ratio be in the second alcohol and water of 3 ~ 8:1, the aqueous ethanolic solution of the Sr obtained respectively, Ga and Eu salt; Or respectively with the acetate of Sr, Ga and Eu, nitrate for raw material, being dissolved in volume ratio is in the second alcohol and water of 3 ~ 8:1, the aqueous ethanolic solution of the Sr obtained respectively, Ga and Eu salt.
The preparation method of described metal nano particle-doped ternary sulfide luminescent material, preferably, in precursor powder preparation process, calcining carries out in high temperature box furnace.
The preparation method of described metal nano particle-doped ternary sulfide luminescent material, preferably, the pre-burning of precursor powder and H
2in S calcination process, rare gas element is argon gas, helium etc., preferred argon gas.
The preparation method of described metal nano particle-doped ternary sulfide luminescent material, preferably, the span of x is 0.001≤x≤0.1, and the span of y is 1 × 10
-5≤ y≤5 × 10
-3.
The preparation method of metal nano particle-doped ternary sulfide luminescent material provided by the invention, adopts the material of Sr, Ga and Eu containing metal nanoparticle of sol-gel method preparation, and then as raw material, preparation Sr
1-xga
2s
4: Eu
x 2+, M
yluminescent material, strengthens light-emitting phosphor by metal nano particle-doped.Make ternary sulfide SrGa
2s
4: Eu
2+the luminous efficiency of luminescent material under same shooting conditions is greatly improved, and radiative wavelength does not change.
In above-mentioned metal nano particle-doped ternary sulfide luminescent material, owing to introducing M metal nanoparticle, the luminous efficiency of ternary sulfide luminescent material under same shooting conditions is greatly improved, and radiative wavelength does not change, purity of color and the brightness of launching bright dipping after being stimulated are all higher, can be applied in feds.
The preparation method of metal nano particle-doped ternary sulfide luminescent material of the present invention, processing step is few, relatively simply; Processing condition are not harsh, easily reach, and cost is low; Do not introduce other impurity, the luminescent material quality obtained is high, can be widely used in the preparation of luminescent material.
Accompanying drawing explanation
Fig. 1 is the luminescent spectrum comparison diagram under the obtained luminescent material of the embodiment of the present invention 4 and the cathode-ray exciting of comparative example luminescent material under acceleration voltage is 1KV; Wherein, curve 1 is the Sr being mixed with metal nanoparticle Ag prepared by the present embodiment 4
0.95ga
2s
4:: Eu
0.05 2+, Ag
2.5 × 10the luminescent spectrum of-4 luminescent materials, curve 2 is Sr that comparative example is not mixed with metal nanoparticle Ag
0.95ga
2s
4:: Eu
0.05 2+the luminescent spectrum of luminescent material.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1:Sr
0.9ga
2s
4: Eu
0.1 2+, Pd
1 × 10-5:
The preparation of Pd nano particle colloidal sol: take 0.176mg 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 to be dissolved in 100mL deionized water, obtaining concentration is 1 × 10
-4the sodium borohydride solution of mol/L; Under the condition of magnetic agitation, add the above-mentioned sodium borohydride solution of 10mL in above-mentioned palladium chloride solution fast, reaction 20min, obtaining 20mLPd content is 4 × 10
-5the Pd nano particle colloidal sol of mol/L;
Take 0.7405gSr (CH
3cOO)
2, 2.0698gGa (CH
3cOO)
3with 0.1316gEu (CH
3cOO)
3be placed in container, then add the mixing solutions that 50mL volume ratio is the second alcohol and water of 4:1,11.5272g citric acid and 7.5g polyoxyethylene glycol 100 is added under 80 DEG C of stirring in water bath conditions, stir the colloidal sol obtaining homogeneous transparent for 2 hours, and then the Pd nano particle colloidal sol 1mL added in step one, continue to stir 2h, obtain precursor sol.Precursor sol dry 20h solvent flashing at 70 DEG C is obtained xerogel, then the xerogel grind into powder that will obtain, put into high temperature box furnace calcining at constant temperature 2h at 600 DEG C, grinding obtains precursor powder.
In agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H
2s, at 1200 DEG C of calcining 1h, is cooled to 500 DEG C to stop H
2s changes argon gas, stops argon gas under normal temperature, takes out grinding and evenly namely obtains Sr
0.9ga
2s
4: Eu
0.1 2+, Pd
1 × 10-5 luminescent materials.
Embodiment 2:Sr
0.8ga
2s
4: Eu
0.2 2+, Au
1 × 10-2
Preparation containing Au nanoparticle sol: take 48.4mg hydrochloro-auric acid (AuCl
3hCl4H
2o) be dissolved in the deionized water of 10mL; Under the condition of magnetic agitation, 14mg Trisodium Citrate and 6mg cetyl trimethylammonium bromide are dissolved in above-mentioned chlorauric acid solution; Take 1.9mg sodium borohydride to be dissolved in 10mL deionized water, obtaining concentration is 5 × 10
-3the sodium borohydride solution of mol/L; Take 17.6mg dissolution of ascorbic acid in 10mL deionized water, obtaining concentration is 1 × 10
-2the ascorbic acid solution of mol/L; Under the condition of magnetic agitation, first in above-mentioned chlorauric acid solution, add the above-mentioned sodium borohydride solution of 5mL, after reaction 5min, then add the above-mentioned ascorbic acid solution of 5mL in above-mentioned chlorauric acid solution, continue reaction 20min, obtaining 20mLAu nanoparticle concentration is 5 × 10
-3the colloidal sol of mol/L.
Then 0.3316gSrO is taken, 0.7498gGa
2o
3, 0.1407gEu
2o
3by 2mL concentrated nitric acid and 3mL deionized water heating for dissolving in container, the mixing solutions that 50mL volume ratio is the second alcohol and water of 3:1 is added after cooling, 2.3054g citric acid and 11g Macrogol 200 is added under 80 DEG C of stirring in water bath conditions, stir the colloidal sol obtaining homogeneous transparent for 1 hour, and then the Au nano particle colloidal sol 8mL added in step one, continue to stir 12h, obtain precursor sol.Precursor sol dry 6h solvent flashing at 150 DEG C is obtained xerogel, then the xerogel grind into powder that will obtain, put into high temperature box furnace calcining at constant temperature 4h at 500 DEG C, grinding obtains precursor powder.
In agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H
2s, at 800 DEG C of calcining 8h, is cooled to 500 DEG C to stop H
2s changes argon gas, stops argon gas under normal temperature, takes out grinding and evenly namely obtains Sr
0.8ga
2s
4: Eu
0.2 2+, Au
1 × 10-2 luminescent materials.
Embodiment 3:Sr
0.999ga
2s
4:: Eu
0.001 2+, 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 to 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 20mLPt nanoparticle concentration is 2.5 × 10
-3the colloidal sol of mol/L.
Take 0.5898gSrCO
3, 1.2778gGa
2(CO
3)
3and 0.0010gEu
2(CO
3)
3by 5mL3mol/L dust technology heating for dissolving in container, add the mixing solutions that 50mL volume ratio is the second alcohol and water of 3:1 after cooling, under 65 DEG C of stirring in water bath conditions, add 4.6108g citric acid and 8.25g Macrogol 2000, stir the colloidal sol obtaining homogeneous transparent for 6 hours.And then the Pt nano particle colloidal sol 8mL added in step one, continue to stir 4h, obtain precursor sol.Precursor sol dry 8h solvent flashing at 100 DEG C is obtained xerogel, then the xerogel grind into powder that will obtain, put into high temperature box furnace calcining at constant temperature 6h at 400 DEG C, grinding obtains precursor powder.
In agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H
2s, at 1000 DEG C of calcining 5h, is cooled to 500 DEG C to stop H
2s changes argon gas, stops argon gas under normal temperature, takes out grinding and evenly namely obtains Sr
0.999ga
2s
4:: Eu
0.001 2+, Pt
5 × 10-3 luminescent materials.
Embodiment 4:Sr
0.95ga
2s
4:: Eu
0.05 2+, Ag
2.5 × 10-4:
Preparation containing Ag nanoparticle sol: take 3.4mg Silver Nitrate (AgNO
3) be dissolved in the deionized water of 18.4mL; Under the condition of magnetic agitation, 42mg Trisodium Citrate is dissolved in above-mentioned silver nitrate solution; Take 5.7mg sodium borohydride to be dissolved in 10mL deionized water, obtaining concentration is 1.5 × 10
-2the sodium borohydride solution of mol/L; Under the condition of magnetic agitation, disposablely in above-mentioned silver nitrate solution add the above-mentioned sodium borohydride solution of 1.6mL, continue reaction 10min, obtaining 20mLAg nanoparticle concentration is 1 × 10
-3the colloidal sol of mol/L.
Take 0.8042gSr (NO
3)
2, 2.0459gGa (NO
3)
3with 0.0676gEu (NO
3)
3be placed in container, then add the mixing solutions that 50mL volume ratio is the second alcohol and water of 3:1,6.1478g citric acid and 5g PEG20000 is added under 80 DEG C of stirring in water bath conditions, stir the colloidal sol obtaining homogeneous transparent for 4 hours, and then the Ag nano particle colloidal sol 1mL added in step one, continue to stir 6h, obtain precursor sol.Precursor sol dry 10h solvent flashing at 100 DEG C is obtained xerogel, then the xerogel grind into powder that will obtain, put into high temperature box furnace calcining at constant temperature 5h at 600 DEG C, grinding obtains precursor powder.
In agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H2S, at 900 DEG C of calcining 6h, is cooled to 500 DEG C to stop H2S and changes argon gas, stop argon gas under normal temperature, take out grinding and evenly namely obtain Sr
0.95ga
2s
4:: Eu
0.05 2+, Ag
2.5 × 10-4 luminescent materials.
Fig. 1 is the luminescent spectrum comparison diagram under the obtained luminescent material of the embodiment of the present invention 4 and the cathode-ray exciting of comparative example luminescent material under acceleration voltage is 1KV; Wherein, curve 1 is the Sr being mixed with metal nanoparticle Ag prepared by the present embodiment 4
0.95ga
2s
4:: Eu
0.05 2+, Ag
2.5 × 10the luminescent spectrum of-4 luminescent materials, curve 2 is Sr that comparative example is not mixed with metal nanoparticle Ag
0.95ga
2s
4:: Eu
0.05 2+the luminescent spectrum of luminescent material.
As can be seen from Figure 1, at the emission peak at 531nm place, the luminous intensity of metal nano particle-doped rear luminescent material enhances 26% before not adulterating.
Embodiment 5:Sr
0.99ga
2s
4:: Eu
0.01 2+, Cu
1 × 10-4:
Preparation containing Cu nanoparticle sol: take 1.6mg cupric nitrate (Cu (NO
3)
2) be dissolved in the deionized water of 16mL; Under the condition of magnetic agitation, 2mg polyvinyl pyrrolidone (PVP) is dissolved in above-mentioned copper nitrate solution; Take 0.4mg sodium borohydride to be dissolved in 10mL ethanol, obtaining concentration is 1 × 10
-3the sodium borohydride alcoholic solution of mol/L; Under the condition of magnetic agitation, in above-mentioned copper nitrate solution, slowly instill the above-mentioned sodium borohydride alcoholic solution of 4mL, continue reaction 10min, obtaining 20mLCu nanoparticle concentration is 4 × 10
-4the colloidal sol of mol/L.
Take 0.8380gSr (NO
3)
2, 2.0459gGa (NO
3)
3with 0.0135gEu (NO
3)
3be placed in container, then add the mixing solutions that 50mL volume ratio is the second alcohol and water of 4:1, under 60 DEG C of stirring in water bath conditions, add 4.6108g citric acid and 2.5g PEG 20000, stir the colloidal sol obtaining homogeneous transparent for 3 hours.And then the Cu nanoparticle sol 1mL added in step one, continue to stir 12h, obtain precursor sol.Precursor sol dry 15h solvent flashing at 80 DEG C is obtained xerogel, then the xerogel grind into powder that will obtain, put into high temperature box furnace calcining at constant temperature 5h at 450 DEG C, grinding obtains precursor powder.
In agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H2S, at 1100 DEG C of calcining 3h, is cooled to 500 DEG C to stop H2S and changes argon gas, stop argon gas under normal temperature, take out grinding and evenly namely obtain Sr
0.99ga
2s
4:: Eu
0.01 2+, Cu
1 × 10-4 luminescent materials.
Embodiment 6:Sr
0.92ga
2s
4:: Eu
0.08 2+, (Ag
0.5/ Au
0.5)
1.25 × 10-3:
Preparation containing Ag and Au nanoparticle sol: take 6.2mg hydrochloro-auric acid (AuCl
3hCl4H
2and 2.5mg Silver Nitrate (AgNO O)
3) be dissolved in the deionized water of 28mL, obtain mixing solutions; Under the condition of magnetic agitation, 22mg Trisodium Citrate and 20mg polyvinyl pyrrolidone (PVP) are dissolved in above-mentioned mixing solutions; Take 380mg sodium borohydride to be dissolved in 10mL deionization, obtain the sodium borohydride solution that concentration is 1mol/L; Under the condition of magnetic agitation, disposablely in above-mentioned mixing solutions add the above-mentioned sodium borohydride solution of 0.3mL, continue reaction 20min, obtaining 30mLAg and Au nanoparticle concentration sum is 1 × 10
-3the colloidal sol of mol/L.
Take 0.7788gSr (NO
3)
2, 2.0459gGa (NO
3)
3with 0.1082gEu (NO
3)
3be placed in container, then add the mixing solutions that 50mL volume ratio is the second alcohol and water of 3:1, under 70 DEG C of stirring in water bath conditions, add 3.0739g citric acid and 5.5g Macrogol 4000, stir the colloidal sol obtaining homogeneous transparent for 4 hours.And then the Ag/Au nano particle colloidal sol 5mL added in step one, continue to stir 6h, obtain precursor sol.Precursor sol dry 12h solvent flashing at 100 DEG C is obtained xerogel, then the xerogel grind into powder that will obtain, put into high temperature box furnace calcining at constant temperature 10h at 500 DEG C, grinding obtains precursor powder.
In agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H
2s, at 850 DEG C of calcining 4h, is cooled to 500 DEG C to stop H
2s changes argon gas, stops argon gas under normal temperature, takes out grinding and evenly namely obtains Y
1.95o
2s:Eu
0.05 3+, (Ag
0.5/ Au
0.5)
1.25 × 10-3 luminescent materials.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a preparation method for metal nano particle-doped ternary sulfide luminescent material, is characterized in that, comprise the steps:
By containing after the salts solution of M, the auxiliary agent playing dissemination and reductive agent hybrid reaction, obtain M nanometer particle colloid solution;
According to Sr
1-xga
2s
4: Eu
x 2+, M
yin each element chemistry metering ratio, measure Sr, the aqueous ethanolic solution of Ga and Eu salt, then add citric acid complexing agent and polyglycol surfactants, stir 2 ~ 6h in 60 ~ 80 DEG C, obtain colloidal sol, measuring described M nanometer particle colloid solution again adds in colloidal sol, stir 2 ~ 12h, obtain precursor sol, precursor sol drying and volatilizing solvent is obtained xerogel, grinding, grinding powder is in 400 ~ 600 DEG C of pre-burnings 2 ~ 10 hours in air atmosphere, and cooling, grinding, obtain precursor powder; Wherein, the mol ratio of citric acid and the total metal ion sum of Sr, Ga and Eu is 1 ~ 5:1; The concentration of polyoxyethylene glycol is 0.05 ~ 0.20g/mL;
Grind described precursor powder even, be placed in process furnace, pass into inert atmosphere subsequently, make to be inert atmosphere in process furnace; Then H is passed into
2s, at 800 ~ 1200 DEG C of calcining 1-8h, is cooled to 500 DEG C to stop H
2s changes rare gas element, under being cooled to normal temperature, stops rare gas element, takes out sample, and namely grinding evenly obtains Sr
1-xga
2s
4: Eu
x 2+, M
yluminescent material;
In above-mentioned steps, M is metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is the mol ratio that Eu atom replaces Sr atom, and the span of x is 0<x≤0.2, and y is M and Sr
1-xga
2s
4: Eu
x 2+mole ratio, the span of y is 0 < y≤1 × 10
-2.
2. the preparation method of metal nano particle-doped ternary sulfide luminescent material according to claim 1, it is characterized in that, described auxiliary agent is at least one in polyvinyl pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate; Described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride; The content of addition in the M nanometer particle colloid solution finally obtained of described auxiliary agent is 1 × 10
-4g/mL ~ 5 × 10
-2g/mL, the mol ratio of described reductive agent and M is 0.5:1 ~ 10:1.
3. the preparation method of metal nano particle-doped ternary sulfide luminescent material according to claim 1, is characterized in that, the time containing the salts solution of M, auxiliary agent and reductive agent hybrid reaction is 10 ~ 45min.
4. the preparation method of metal nano particle-doped ternary sulfide luminescent material according to claim 1, is characterized in that, the molecular weight of described polyoxyethylene glycol is 100-20000.
5. the preparation method of metal nano particle-doped ternary sulfide luminescent material according to claim 4, is characterized in that, the molecular weight of described polyoxyethylene glycol is 2000-10000.
6. the preparation method of metal nano particle-doped ternary sulfide luminescent material according to claim 1, is characterized in that, Sr, Ga and Eu salt is each self-corresponding nitrate or acetate.
7. the preparation method of metal nano particle-doped ternary sulfide luminescent material according to claim 1, is characterized in that, in described aqueous ethanolic solution, the volume ratio of ethanol and water is 3 ~ 8:1.
8. the preparation method of metal nano particle-doped ternary sulfide luminescent material according to claim 1, is characterized in that, the span of x is 0.001≤x≤0.1, and the span of y is 1 × 10
-5≤ y≤5 × 10
-3.
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| JP2007224148A (en) * | 2006-02-23 | 2007-09-06 | National Univ Corp Shizuoka Univ | Mixed crystal phosphor and display |
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