CN104119909A - Hollow structure aluminate yttrium europium luminescent material and preparation method thereof - Google Patents
Hollow structure aluminate yttrium europium luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of luminescent materials, and discloses a hollow structure aluminate yttrium europium luminescent material and a preparation method thereof; the chemical general formula of the luminescent material is Y1-xAlO3:Eux<3+> @ My; wherein Y1-xAlO3:Eux<3+> is a shell, @ is coating, M is an inner core; M is at least one of metal nanoparticles of Ag, Au, Pt, Pd and Cu, x is greater than 0 and less than or equal to 0.2, y is molar ratio of Y1-xAlO3:Eux<3+>, and y is greater than 0 and less than or equal to 1*10<-2>. By introduction of the M metal nanoparticles, luminescence efficiency of the aluminate yttrium europium luminescent material can be improved greatly in same excitation conditions.
Description
Technical field
The present invention relates to field of light emitting materials, relate in particular to europium-doped yttrium aluminate luminescent material of a kind of hollow structure and preparation method thereof.
Background technology
Field Emission Display (FED) is a kind of flat panel display that has very much development potentiality.The operating voltage of field emission display is lower than the operating voltage of cathode tube (CRT), be conventionally less than 5kV, and working current density is relatively large, generally at 10～100 μ Acm
-2.Therefore, higher to the requirement of the luminescent powder for Field Emission Display, as will be there is better saturation, luminous efficiency under low voltage is higher and under high current density without luminance saturation phenomenon etc.At present, the research of Field Emission Display luminescent powder is mainly concentrated on to two aspects: the one, utilize and improve existing cathode tube luminescent powder; The 2nd, find new luminescent material.Commercial cathodoluminescence powder be take sulfide as main, when being used for fabricating yard emission display screen, because sulphur wherein can react with Microamounts of Mo, silicon or germanium etc. in negative electrode, thereby having weakened its electron emission, and then has affected the performance of whole device.In luminescent material Application Areas, exist potential using value.
Yttrium aluminate europium is a kind of red illuminating material of exploitation in recent years, is mainly used in feds, and still, its luminescent material luminous efficiency is not high at present, haves much room for improvement.
Summary of the invention
Problem to be solved by this invention is to provide the europium-doped yttrium aluminate luminescent material of the hollow structure that a kind of luminous efficiency is higher.
Technical scheme of the present invention is as follows:
An europium-doped yttrium aluminate luminescent material for hollow structure, its chemical general formula is: Y
1-xalO
3: Eu
x 3+@M
y; Wherein, Y
1-xalO
3: Eu
x 3+for shell, M is kernel, and@represents to be coated, and M is metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is Eu
3+the mole number that replaces Y ion, 0 < x≤0.2, y is M and Y
1-xalO
3: Eu
x 3+mol ratio, 0 < y≤1 * 10
-2; Y
1-xalO
3: Eu
x 3+for luminescent material, Eu
3+for light emitting ionic center, colon ": " represents Eu
3+for doping.
The europium-doped yttrium aluminate luminescent material of described hollow structure, preferably, 0.005≤x≤0.1,1 * 10
-5≤ y≤5 * 10
-3.
The present invention also provides the preparation method of the europium-doped yttrium aluminate luminescent material of above-mentioned hollow structure, comprises the steps:
Auxiliary agent and reductive agent hybrid reaction by the salts solution of M, a dissemination, make M nanoparticle sol;
In the ethanol solution of sucrose or glucose, add in described M nanoparticle sol, obtain mixing solutions, and the mixed solution obtaining is proceeded in band teflon-lined reactor, add a cover screw after at 120～200 ℃ reaction, make the solution that contains C@M, the solution that contains C@M described in centrifugation, the solid phase that centrifugation is obtained obtains C@M solid after washing, being dried; Wherein, C is carbon, and@represents that C is coated M, and the mol ratio of M and C is 1 * 10
-6: 1～0.4:1;
According to Y
1-xalO
3: Eu
x 3+@M
yin the stoichiometric ratio of each element, measure respectively each self-corresponding salts solution of Y, Al and Eu, be placed in beaker and form mixed solution, then taking C@M solid phase adds in mixed solution, stir, join subsequently in precipitation agent oxalic acid solution, then after regulating pH to be 3-6 reaction 2～8h by ammoniacal liquor, after filtration, washing, drying treatment, obtain Y
1-xal (C
2o
4)
3: Eu
x 3+@C@M
ypresoma; Wherein, C@M solid phase and Y
1-xalO
3: Eu
x 3+@M
ymol ratio be 0.025:1～10:1;
Presoma is ground, grind powder and be put in retort furnace and in air atmosphere in 600～1000 ℃ of pre-burnings 1～8 hour, carbon is converted into CO
2remove, be cooled to subsequently room temperature, and pre-sintered sample is ground to form to powder, and then in by sample powder in tube furnace 1000～1500 ℃ calcining 1～12h, furnace cooling is cooled to room temperature, resulting calcining sample is ground to powder, obtains the europium-doped yttrium aluminate luminescent material of the hollow structure of clad metal nano particle, the chemical general formula of this luminescent material is: Y
1-xalO
3: Eu
x 3+@M
y; Wherein, Y
1-xalO
3: Eu
x 3+for shell, M is kernel, and@represents to be coated, and M is metal nanoparticle, is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is Eu
3+the mole number that replaces Y ion, 0 < x≤0.2, y is M and Y
1-xalO
3: Eu
x 3+mol ratio, 0 < y≤1 * 10
-2.
The preparation method of the europium-doped yttrium aluminate luminescent material of described hollow structure, preferably, the concentration of the salts solution of M is 0.8 * 10
-4mol/L～1 * 10
-2mol/L.
The preparation method of the europium-doped yttrium aluminate luminescent material of described hollow structure, preferably, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate and 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.
The preparation method of the europium-doped yttrium aluminate luminescent material of described hollow structure, preferably, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate and sodium borohydride; The mol ratio of the addition of described reductive agent and M ion is 0.5:1～10:1; During actual use, also needing reductive agent to prepare or be diluted to concentration is 1 * 10
-4the aqueous solution of mol/L～1mol/L.
The preparation method of the europium-doped yttrium aluminate luminescent material of described hollow structure preferably, is 10min～45min by auxiliary agent and the reductive agent hybrid reaction time of the salts solution of M, a dissemination.
The preparation method of the europium-doped yttrium aluminate luminescent material of described hollow structure, preferably, the solid phase that centrifugation is obtained is washed and is comprised deionized water and washing with alcohol; It is 60～100 ℃ of vacuum-drying 2～10h that solid phase after washing is dried.
The preparation method of the europium-doped yttrium aluminate luminescent material of described hollow structure, preferably, each self-corresponding salts solution of Y, Al and Eu is respectively nitrate solution or the acetate solution of Y, Al and Eu; The salts solution of described Y, Al and Eu is raw material for take oxide compound and the carbonate of Y, Al and Eu, be dissolved in nitric acid to make, or to take acetate solution, the nitrate solution of Y, Al and Eu is raw material.
The preparation method of the europium-doped yttrium aluminate luminescent material of described hollow structure, preferably, the add-on of described oxalic acid is enough to precipitate completely Y, Al and the corresponding total ion molar weight of Eu and excessive 25%.
The preparation method of the europium-doped yttrium aluminate luminescent material of described hollow structure, preferably, 0.005≤x≤0.1,1 * 10
-5≤ y≤5 * 10
-3.
Europium-doped yttrium aluminate luminescent material of the present invention, introduced M metallics, the luminous efficiency of europium-doped yttrium aluminate luminescent material under same shooting conditions is greatly improved, and radiative wavelength does not change, this europium-doped yttrium aluminate luminescent material has good luminescent properties, can be applied in feds.
The present invention first adopts the carbon bead (C) of the coated M nanoparticle of hydrothermal method preparation, and then to take the carbon bead that is coated with M nanoparticle be template, adopts oxalate precipitation method to prepare Y
1-xal (C
2o
4)
3: Eu
x 3+@C@M
yprecursor powder, and then calcining, in calcination process, carbon bead will be converted into CO
2overflow, finally obtain the hollow structure Y of clad metal nano particle
1-xalO
3: Eu
x 3+@M
yluminescent material.
The preparation method of europium-doped yttrium aluminate luminescent material of the present invention, processing step is few, relatively simple; Processing condition are not harsh, easily reach, and cost is low; Do not introduce other impurity, the luminescent material quality obtaining is high, can be widely used in the preparation of luminescent material.
Accompanying drawing explanation
Fig. 1 is luminescent material and the cathodoluminescence spectrum comparison diagram of comparative example luminescent material under 3kv voltage of embodiment 3 preparations; Wherein curve 1 is the Y of the clad metal nano particle Ag that makes of embodiment 3
0.95alO
3: Eu
0.05 3+@Ag
2.5 * 10the luminescent spectrum of-4 luminescent materials, curve 2 is not Y of clad metal nano particle of comparative example
0.95alO
3: Eu
0.05 3+the luminescent spectrum of material.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The hollow structure Y for preparing clad metal nano particle
0.9alO
3: Eu
0.1 3+@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.
The preparation of C@Cu: take 0.1426g sucrose dissolved and prepare the alcoholic solution of sucrose in the dehydrated alcohol of 39.5mL, the above-mentioned colloidal sol of 0.5mL is added in the alcoholic solution of sucrose, obtain mixing solutions, again mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 200 ℃ of reaction 5h, prepare the solution that contains C@Cu, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 2 times, and solid formation is dry at 75 ℃, obtain C@Cu, now the mol ratio of metal nanoparticle Cu and C is 4 * 10
-5: 1,
Take 22.5800g Y
2o
3be dissolved in the Y (NO that nitric acid obtains 100mL2mol/L
3)
3solution; Take 1.0196g Al
2o
3be dissolved in the Al (NO that nitric acid obtains 100mL0.2mol/L
3)
3solution; Take 1.7595g Eu
2o
3be dissolved in the Eu (NO that nitric acid obtains 100mL0.1mol/L
3)
3solution.
According to Y
0.9alO
3: Eu
0.1 3+@Cu
1 * 10-4 stoichiometric ratio, pipettes 1.8mL2mol/L Y (NO
3)
3, 20mL0.2mol/L Al (NO
3)
3and 4mL0.1mol/L Eu (NO
3)
3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes C@Cu120mg and adds in mixed solution, stirs.Under magnetic agitation, above-mentioned mixed solution is added drop-wise in 30mL precipitation agent oxalic acid solution (0.5mol/L), then by ammoniacal liquor, to regulate pH be 3, after reaction 4h, after filtration, deionized water and washing with alcohol, 100 ℃ of vacuum-drying 2h, obtain white mass, i.e. Y
0.9al (C
2o
4)
3: Eu
0.1 3+@C@Cu
1 * 10-4 precursor powders;
Presoma is ground, be put in retort furnace, under air atmosphere in 600 pre-burning 8 hours, grind, carbon is converted into CO
2remove, in agate mortar, grind evenly, and then in tube furnace 1500 ℃ of calcining 1h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains the Y of the hollow structure of clad metal nano particle Cu
0.9alO
3: Eu
0.1 3+@Cu
1 * 10-4 luminescent materials.
Embodiment 2
The hollow structure Y for preparing clad metal nano particle
0.8alO
3: Eu
0.2 3+@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.
The preparation of C@Au: take 0.0057g sucrose dissolved and prepare the alcoholic solution of sucrose in the dehydrated alcohol of 24mL, the above-mentioned colloidal sol of 16mL is added in the alcoholic solution of sucrose, obtain mixing solutions, mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 160 ℃ of reaction 20h, prepare the solution that contains C@Au, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 3 times, and dry at 80 ℃, obtain C@Au, now the mol ratio of metal nanoparticle Au and C is 0.4:1;
According to Y
0.8alO
3: Eu
0.2 3+@Au
1 * 10-2 stoichiometric ratio, pipettes 16mL0.2mol/L Y (CH
3cOO)
3solution, 2mL2mol/L Al (CH
3cOO)
3solution and 0.4mL2mol/LEu (CH
3cOO)
3solution, is placed in 100mL beaker and forms mixed solution, then takes C@Au1.2mg and adds in mixed solution, stirs.Under magnetic agitation, above-mentioned mixed solution is added drop-wise in 25mL precipitation agent oxalic acid solution (0.6mol/L), then by ammoniacal liquor, to regulate pH be 5, after reaction 2h, after filtration, deionized water and washing with alcohol, 60 ℃ of vacuum-drying 8h, obtain white mass, i.e. Y
0.8al (C
2o
4)
3: Eu
0.2 3+@C@Au
1 * 10-2 precursor powders;
Presoma is ground, be put in retort furnace, under air atmosphere in 900 ℃ of pre-burnings 3 hours, grind, carbon is converted into CO
2remove, in agate mortar, grind evenly, and then in tube furnace 1000 ℃ of calcining 12h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains the Y of the hollow structure of clad metal nano particle Au
0.8alO
3: Eu
0.2 3+@Au
1 * 10-2 luminescent materials.
Embodiment 3
The hollow structure Y for preparing clad metal nano particle
0.95alO
3: Eu
0.05 3+@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.
The preparation of C@Ag: take the alcoholic solution for preparing glucose in the dehydrated alcohol that 3.003g glucose is dissolved in 35mL, the above-mentioned colloidal sol of 5mL is added in the alcoholic solution of glucose, obtain mixing solutions, mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 180 ℃ of reaction 24h, prepare the solution that contains C@Ag, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 2 times, and dry at 60 ℃, obtain C@Ag, now the mol ratio of metal nanoparticle Ag and C is 5 * 10
-5: 1;
According to Y
0.95alO
3: Eu
0.05 3+@Ag
2.5 * 10-4 stoichiometric ratio, pipettes 7.6mL0.5mol/L Y (NO
3)
3solution, 4mL1mol/L Al (NO
3)
3solution and 2mL0.1mol/L Eu (NO
3)
3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes C@Ag240mg and adds in mixed solution, stirs.Under magnetic agitation, above-mentioned mixed solution is added drop-wise in 15mL precipitation agent oxalic acid solution (1mol/L), then by ammoniacal liquor, to regulate pH be 4, after reaction 6h, after filtration, deionized water and washing with alcohol, 80 ℃ of vacuum-drying 4h, obtain white mass, i.e. Y
0.95al (C
2o
4)
3: Eu
0.05 3+@C@Ag
2.5 * 10-4 precursor powders;
Presoma is ground, be put in retort furnace, under air atmosphere in 800 ℃ of pre-burnings 4 hours, grind, carbon is converted into CO
2remove, in agate mortar, grind evenly, and then in tube furnace 1200 ℃ of calcining 4h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains the Y of the hollow structure of clad metal nano particle Ag
0.95alO
3: Eu
0.05 3+@Ag
2.5 * 10-4 luminescent materials.
Fig. 1 is luminescent material and the cathodoluminescence spectrum comparison diagram of comparative example luminescent material under 3kv voltage of embodiment 3 preparations; Wherein curve 1 is the Y of the clad metal nano particle Ag that makes of embodiment 3
0.95alO
3: Eu
0.05 3+@Ag
2.5 * 10the luminescent spectrum of-4 luminescent materials, curve 2 is not Y of clad metal nano particle of comparative example
0.95alO
3: Eu
0.05 3+the luminescent spectrum of material.
As can be seen from Figure 1, the emission peak at 590nm place, after clad metal nano particle, the luminous intensity of luminescent material has strengthened 21% before not being coated.
Embodiment 4
The hollow structure Y for preparing clad metal nano particle
0.995alO
3: Eu
0.005 3+@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.
The preparation of C@Pd: take the alcoholic solution that obtains glucose in the dehydrated alcohol that 6.005g glucose is dissolved in 36mL, the above-mentioned colloidal sol of 4mL is added in the alcoholic solution of glucose, obtain mixing solutions, mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 120 ℃ of reaction 36h, prepare the solution that contains C@Pd, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 2 times, and dry at 60 ℃, obtain C@Pd, now the mol ratio of metal nanoparticle Pd and C is 1 * 10
-6: 1;
According to Y
0.995alO
3: Eu
0.005 3+@Pd
1 * 10-5 stoichiometric ratio, pipettes 7.96mL0.5mol/L Y (NO
3)
3solution, 5mL0.8mol/L Al (NO
3)
3solution and 4mL0.005mol/L Eu (NO
3)
3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes C@Pd480mg and adds in mixed solution, stirs.Under magnetic agitation, above-mentioned mixed solution is added drop-wise in 10mL precipitation agent oxalic acid solution (1.5mol/L), then by ammoniacal liquor, to regulate pH be 6, after reaction 3h, after filtration, deionized water and washing with alcohol, 70 ℃ of vacuum-drying 6h, obtain white mass, i.e. Y
0.995al (C
2o
4)
3: Eu
0.005 3+@C@Pd
1 * 10-5 precursor powders;
Presoma is ground, be put in retort furnace, under air atmosphere in 1000 ℃ of pre-burnings 1 hour, grind, carbon is converted into CO
2remove, in agate mortar, grind evenly, and then in tube furnace 1400 ℃ of calcining 3h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains the Y of the hollow structure of clad metal nano particle Pd
0.995alO
3: Eu
0.005 3+@Pd
1 * 10-5 luminescent materials.
Embodiment 5
The hollow structure Y for preparing clad metal nano particle
0.99alO
3: Eu
0.01 3+@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.
The preparation of C@Pt: take the alcoholic solution for preparing glucose in the dehydrated alcohol that 0.0150g glucose is dissolved in 30mL, the above-mentioned colloidal sol of 10mL is added in the alcoholic solution of glucose, obtain mixing solutions, again mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 150 ℃ of reaction 10h, prepare the solution that contains C@Pt, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 2 times, and dry at 70 ℃, obtain C@Pt, now the mol ratio of metal nanoparticle Pt and C is 5 * 10
-3: 1,
Take 17.8910g Y
2(CO
3)
3be dissolved in the Y (NO that nitric acid obtains 100mL1mol/L
3)
3solution; Take 11.6994g Al
2(CO
3)
3be dissolved in the Al (NO that nitric acid obtains 100mL1mol/L
3)
3solution; Take 1.2098g Eu
2(CO
3)
3be dissolved in the Eu (NO that nitric acid obtains 100mL0.05mol/L
3)
3solution.
According to Y
0.99alO
3: Eu
0.01 3+@Pt
5 * 10-3 stoichiometric ratio, pipettes 3.96mL1mol/L Y (NO
3)
3solution, 4mL1mol/L Al (NO
3)
3solution and 8mL0.05mol/L Eu (NO
3)
3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes C@Pt48mg and adds in mixed solution, stirs.Under magnetic agitation, above-mentioned mixed solution is added drop-wise in 15mL precipitation agent oxalic acid solution (1mol/L), then by ammoniacal liquor, to regulate pH be 4, after reaction 3h, after filtration, deionized water and washing with alcohol, 70 ℃ of vacuum-drying 5h, obtain white mass, i.e. Y
0.99al (C
2o
4)
3: Eu
0.01 3+@C@Pt
5 * 10-3 precursor powders;
Presoma is ground, be put in retort furnace, under air atmosphere in 900 ℃ of pre-burnings 3 hours, grind, carbon is converted into CO
2remove, in agate mortar, grind evenly, and then in tube furnace 1100 ℃ of calcining 10h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains the Y of the hollow structure of clad metal nano particle
0.99alO
3: Eu
0.01 3+@Pt
5 * 10-3 luminescent materials.
Embodiment 6
The hollow structure Y for preparing clad metal nano particle
0.92alO
3: Eu
0.08 3+@(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
The preparation of C@(Ag/Au): take 0.7131g sucrose dissolved and prepare the alcoholic solution of sucrose in the dehydrated alcohol of 30mL, the above-mentioned colloidal sol of 10mL is added in the alcoholic solution of above-mentioned sucrose, obtain mixing solutions, above-mentioned mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 140 ℃ of reaction 15h, prepare the solution that contains C@(Ag/Au), this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 2 times, and dry at 80 ℃, obtain C@(Ag/Au), now metal nanoparticle (Ag/Au) is 4 * 10 with the mol ratio of C
-4: 1,
According to Y
0.92alO
3: Eu
0.08 3+@(Ag
0.5/ Au
0.5)
1.25 * 10-3 stoichiometric ratio, pipettes 9.2mL0.4mol/L Y (NO
3)
3solution, 2mL2mol/L Al (NO
3)
3solution and 8mL0.04mol/L Eu (NO
3)
3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes C@(Ag/Au) 150mg and adds in mixed solution, stirs.Under magnetic agitation, above-mentioned mixed solution is added drop-wise in 10mL precipitation agent oxalic acid solution (1.5mol/L), then by ammoniacal liquor, to regulate pH be 4, after reaction 8h, after filtration, deionized water and washing with alcohol, 90 ℃ of vacuum-drying 3h, obtain white mass, i.e. Y
0.92al (C
2o
4)
3: Eu
0.08 3+@C@(Ag
0.5/ Au
0.5)
1.25 * 10-3 precursor powders;
Presoma is ground, be put in retort furnace, under air atmosphere in 700 ℃ of pre-burnings 5 hours, grind, carbon is converted into CO
2remove, in agate mortar, grind evenly, and then in tube furnace 1350 ℃ of calcining 6h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains the Y of the hollow structure of clad metal nano particle (Ag/Au)
0.92alO
3: Eu
0.08 3+@(Ag
0.5/ Au
0.5)
1.25 * 10-3 luminescent materials.
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. an europium-doped yttrium aluminate luminescent material for hollow structure, is characterized in that, its chemical general formula is: Y
1-xalO
3: Eu
x 3+@M
y; Wherein, Y
1-xalO
3: Eu
x 3+for shell, M is kernel, and@represents to be coated, and M is metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is Eu
3+the mole number that replaces Y ion, 0 < x≤0.2, y is M and Y
1-xalO
3: Eu
x 3+mol ratio, 0 < y≤1 * 10
-2.
2. the europium-doped yttrium aluminate luminescent material of hollow structure according to claim 1, is characterized in that, 0.005≤x≤0.1,1 * 10
-5≤ y≤5 * 10
-3.
3. the europium-doped yttrium aluminate luminescent material of hollow structure according to claim 1, is characterized in that, comprises a kind of in following luminescent material:
Y
0.9AlO
3:Eu
0.1 3+@Cu
1×10-4；Y
0.8AlO
3:Eu
0.2 3+@Au
1×10-2；Y
0.95AlO
3:Eu
0.05 3+@Ag
2.5×10-4；Y
0.995AlO
3:Eu
0.005 3+@Pd
1×10-5；Y
0.99AlO
3:Eu
0.01 3+@Pt
5×10-3；Y
0.92AlO
3:Eu
0.08 3+@(Ag
0.5/Au
0.5)
1.25×10-3。
4. a preparation method for the europium-doped yttrium aluminate luminescent material of hollow structure, 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;
In the ethanol solution of sucrose or glucose, add in described M nanoparticle sol, obtain mixing solutions, and the mixed solution obtaining is proceeded in band teflon-lined reactor, add a cover screw after at 120～200 ℃ reaction, make the solution that contains C@M, the solution that contains C@M described in centrifugation, the solid phase that centrifugation is obtained obtains C@M solid after washing, being dried; Wherein, C is carbon, and@represents that C is coated M, and the mol ratio of M and C is 1 * 10
-6: 1～0.4:1;
According to Y
1-xalO
3: Eu
x 3+@M
yin the stoichiometric ratio of each element, measure respectively each self-corresponding salts solution of Y, Al and Eu, be placed in beaker and form mixed solution, then taking C@M solid phase adds in mixed solution, stir, join subsequently in precipitation agent oxalic acid solution, then after regulating pH to be 3-6 reaction 2～8h by ammoniacal liquor, after filtration, washing, drying treatment, obtain Y
1-xal (C
2o
4)
3: Eu
x 3+@C@M
ypresoma; Wherein, C@M solid phase and Y
1-xalO
3: Eu
x 3+@M
ymol ratio be 0.025:1～10:1;
Presoma is ground, grind powder and be put in retort furnace and in air atmosphere in 600～1000 ℃ of pre-burnings 1～8 hour, carbon is converted into CO
2remove, be cooled to subsequently room temperature, and pre-sintered sample is ground to form to powder, and then in by sample powder in tube furnace 1000～1500 ℃ calcining 1～12h, furnace cooling is cooled to room temperature, resulting calcining sample is ground to powder, obtains the europium-doped yttrium aluminate luminescent material of the hollow structure of clad metal nano particle, the chemical general formula of this luminescent material is: Y
1-xalO
3: Eu
x 3+@M
y; Wherein, Y
1-xalO
3: Eu
x 3+for shell, M is kernel, and@represents to be coated, and M is metal nanoparticle, is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is Eu
3+the mole number that replaces Y ion, 0 < x≤0.2, y is M and Y
1-xalO
3: Eu
x 3+mol ratio, 0 < y≤1 * 10
-2.
5. the preparation method of the europium-doped yttrium aluminate luminescent material of hollow structure 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 europium-doped yttrium aluminate luminescent material of hollow structure 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 and 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 and sodium borohydride; The mol ratio of the addition of described reductive agent and M ion is 0.5:1～10:1; By auxiliary agent and the reductive agent hybrid reaction time of the salts solution of M, a dissemination, be 10min～45min.
7. the preparation method of the europium-doped yttrium aluminate luminescent material of hollow structure according to claim 4, is characterized in that, the solid phase that centrifugation is obtained is washed and comprised deionized water and washing with alcohol; It is 60～100 ℃ of vacuum-drying 2～10h that solid phase after washing is dried.
8. the preparation method of the europium-doped yttrium aluminate luminescent material of hollow structure according to claim 4, is characterized in that, each self-corresponding salts solution of Y, Al and Eu is respectively nitrate solution or the acetate solution of Y, Al and Eu.
9. the preparation method of the europium-doped yttrium aluminate luminescent material of hollow structure according to claim 4, is characterized in that, the add-on of described oxalic acid is enough to precipitate completely Y, Al and the corresponding total ion molar weight of Eu and excessive 25%.
10. the preparation method of the europium-doped yttrium aluminate luminescent material of hollow structure according to claim 4, is characterized in that, 0.005≤x≤0.1,1 * 10
-5≤ y≤5 * 10
-3.
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|---|---|---|---|---|
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| CN102329613A (en) * | 2011-07-08 | 2012-01-25 | 浙江理工大学 | Hydro-thermal preparation method for spherical boric acid yttrium doped europium fluorescent powder in hollow structure |
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| CN102477297A (en) * | 2010-11-23 | 2012-05-30 | 海洋王照明科技股份有限公司 | Europium-doped yttrium aluminate luminescent material and preparation method thereof |
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2013
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| WO2011156971A1 (en) * | 2010-06-18 | 2011-12-22 | 海洋王照明科技股份有限公司 | Halosilicate luminescent materials and preparation methods and uses thereof |
| CN102337136A (en) * | 2010-07-21 | 2012-02-01 | 海洋王照明科技股份有限公司 | Metal-nanoparticle-doped oxide luminescent material with hollow structure and preparation method thereof |
| CN102477297A (en) * | 2010-11-23 | 2012-05-30 | 海洋王照明科技股份有限公司 | Europium-doped yttrium aluminate luminescent material and preparation method thereof |
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