CN103788950A - Rare earth lanthanum aluminate luminescent material and preparation method thereof - Google Patents
Rare earth lanthanum aluminate luminescent material and preparation method thereof Download PDFInfo
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- CN103788950A CN103788950A CN201210428392.2A CN201210428392A CN103788950A CN 103788950 A CN103788950 A CN 103788950A CN 201210428392 A CN201210428392 A CN 201210428392A CN 103788950 A CN103788950 A CN 103788950A
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Abstract
A rare earth aluminum aluminate luminescent material has the following general chemical formula: La1-x-yReyAlO3:Tmx@Mz. Re is at least one of Y, Gd and Lu; M is at least one of Ag, Au, Pt, Pd and Cu metal nanoparticles; Tm is doped in La1-x-yReyAlO3; @ refers to coating, and La1-x-yReyAlO3:Tmx coats M; x is greater than 0 and no more than 0.2; y is greater than 0 and no more than 0.1; and z represents a molar ratio of M and Al, and is greater than 0 and no more than 1.5*10<-2>. The invention also provides a preparation method of the rare earth lanthanum aluminate luminescent material. According to the rare earth lanthanum aluminate luminescent material and the preparation method thereof, the metal nanoparticles are introduced to greatly improve the luminescence efficiency of the rare earth lanthanum aluminate luminescent material in the same excitation conditions, the wavelength of emission light has not changed, and the purity and brightness of the emitted light are at high levels after excitation. The invention can be applied to field emission devices.
Description
Technical field
The present invention relates to luminescent material technical field, particularly relate to rare earth lanthanum aluminate light-emitting material and preparation method thereof.
Background technology
The sixties in 20th century, Ken Shoulder has proposed the imagination based on field emission cathode array (Field Emissive Arrays, FEAs) electron beam micro device, utilizes FEAs Design and manufacture flat pannel display and light source device.The principle of work of this novel feds with and traditional cathode tube (Cathode-Ray Tube, CRT) similar, by luminous picture or the lighting use of being embodied as of beam bombardment red, green, blue three-color phosphor, this kind of device all has potential advantage at aspects such as brightness, visual angle, time of response, operating temperature range, energy consumptions.
One of key factor of the feds of excellent is preparation high-performance fluorescent material.The fluorescent material that feds adopts is at present mainly used for sulfide series, oxide compound series and the oxysulfide series phosphor powder of conventional cathode ray tube and projection TV teletron.It is higher that sulfide series and oxysulfide series phosphor powder have luminosity, and there is the characteristic of certain electroconductibility, but easily decompose under the bombardment of large beam deflection, emit elemental sulfur and " poison " negative electrode needle point, and generate other throw outs and cover phosphor surface, reduce the luminous efficiency of fluorescent material.Oxide compound, aluminate fluorescent powder stability are good, but also have the not high enough shortcoming of luminous efficiency.
Summary of the invention
Based on this, be necessary to provide rare earth lanthanum aluminate light-emitting material that a kind of luminous efficiency is higher and preparation method thereof.
A kind of rare earth lanthanum aluminate light-emitting material, has following chemical general formula: La
1-x-yre
yalO
3: Tm
x@M
zdescribed Re is at least one in yttrium (Y), gadolinium (Gd) and lutetium (Lu), described M is at least one in silver (Ag), gold (Au), platinum (Pt), palladium (Pd) and copper (Cu) metal nanoparticle, and described thulium (Tm) is entrained in La
1-x-yre
yalO
3in ,@represents to be coated, described La
1-x-yre
yalO
3: Tm
xcoated described M, 0<x≤0.2,0<y≤0.1, z be M with Al mole ratio, 0<z≤1.5 × 10
-2.
Therein in an embodiment, 0.01≤x≤0.1.
Therein in an embodiment, 0.005≤y≤0.05.
Therein in an embodiment, 1 × 10
-5≤ z≤5 × 10
-3.
A preparation method for rare earth lanthanum aluminate light-emitting material, comprising:
At least one metal salt solution in Ag, Au, Pt, Pd and Cu is mixed and reacted with auxiliary agent and reductive agent, make the colloidal sol that contains M; Described M is selected from least one in Ag, Au, Pt, Pd and Cu metal nanoparticle;
According to M and Al mole ratio y, in the colloidal sol that contains M described in alumina aerogels is dissolved to, at 50 ℃ ~ 75 ℃ temperature, stir 0.5 hour ~ 3 hours, ultrasonic, dry, after grinding, at 600 ℃ ~ 1200 ℃, calcine 0.5 hour ~ 4 hours, obtain the alumina aerogels of coated M, 0<y≤0.1; And
According to La
1-x-yre
yalO
3: Tm
x@M
zstoichiometric ratio, take the compound of La, compound, the compound of Tm and the alumina aerogels of described coated M of Re, grind and be placed in reducing atmosphere, and be warming up to 1200 ℃ ~ 1500 ℃ processing 2 hours ~ 10 hours, furnace cooling is cooled to room temperature, and obtaining chemical general formula is La
1-x-yre
yalO
3: Tm
x@M
zrare earth aluminate based luminescent material, described Re is at least one in Y, Gd and Lu element, described M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, described Tm is entrained in La
1-x-yre
yalO
3in ,@represents to be coated, described La
1-x-yre
yalO
3: Tm
xcoated described M, 0<x≤0.2, z be M with Al mole ratio, 0<z≤1.5 × 10
-2.
In an embodiment, in described metal salt solution, the concentration of metal ion is 1 × 10 therein
-4mol/L ~ 2 × 10
-2mol/L.
Therein in an embodiment, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate and sodium laurylsulfonate, and the concentration of the addition of described auxiliary agent in the colloidal sol of the described M of containing is 1 × 10
-4g/mL ~ 5 × 10
-2g/mL.
In an embodiment, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate and sodium borohydride therein, and the mol ratio of the addition of described reductive agent and the metal ion of described metal salt solution is 0.5:1 ~ 10:1.
In an embodiment, described reducing atmosphere is nitrogen (N therein
2) and hydrogen (H
2) mixed atmosphere, carbon dust atmosphere (C), carbon monoxide atmosphere (CO) and hydrogen atmosphere at least one.
In an embodiment, the compound of described La is lanthanum trioxide, lanthanum nitrate, Phosbloc or lanthanum oxalate therein; The compound of described Re is oxide compound, nitrate, carbonate or the oxalate of Re; The compound of described Tm is trioxide, thulium nitrate, thulium carbonate or thulium oxalate
Above-mentioned rare earth lanthanum aluminate light-emitting material, by having introduced metal nanoparticle, the luminous efficiency of rare earth lanthanum aluminate light-emitting material under same shooting conditions is greatly improved, and radiative wavelength does not change.This rare earth lanthanum aluminate light-emitting material has good luminescent properties, after being stimulated radiative purity of color and brightness all higher, can be applied in feds.
Accompanying drawing explanation
Fig. 1 is the rare earth lanthanum aluminate light-emitting material preparation method's of an embodiment schema;
Fig. 2 is the cathodoluminescence spectrum comparison diagram under the rare earth lanthanum aluminate light-emitting material prepared of embodiment 2 and traditional luminescent material 3kv voltage.
Embodiment
Below in conjunction with embodiment and accompanying drawing, rare earth lanthanum aluminate light-emitting material and preparation method thereof is described in further detail.
The rare earth lanthanum aluminate light-emitting material of one embodiment is a kind of fluorescent material, has following chemical general formula: La
1-x-yre
yalO
3: Tm
x@M
z, Re is at least one in Y, Gd and Lu element, and M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, and Tm is entrained in La
1-x-yre
yalO
3in ,@represents to be coated, La
1-x-yre
yalO
3: Tm
xcoated M, 0<x≤0.2,0 < y≤0.1, z be M with Al mole ratio, 0<z≤1.5 × 10
-2.
In other embodiment, the span of x can be 0.01≤x≤0.1.
In other embodiment, the span of y can be 0.005≤y≤0.05.
In other embodiment, the span of z can be 1 × 10
-5≤ z≤5 × 10
-3.
Above-mentioned rare earth lanthanum aluminate light-emitting material, by having introduced metal nanoparticle, the luminous efficiency of rare earth lanthanum aluminate light-emitting material under same shooting conditions is greatly improved, and radiative wavelength does not change.This rare earth lanthanum aluminate light-emitting material has good luminescent properties, after being stimulated radiative purity of color and brightness all higher, can be applied in feds.
Refer to Fig. 1, the preparation method of the rare earth lanthanum aluminate light-emitting material of an embodiment, comprising:
S101, mixes at least one the metal salt solution in Ag, Au, Pt, Pd and Cu react with auxiliary agent and reductive agent, makes the colloidal sol that contains M; M is selected from least one in Ag, Au, Pt, Pd and Cu metal nanoparticle.
In the present embodiment, metal salt solution concentration flexible configuration according to actual needs, can be 1 × 10
-4mol/L ~ 2 × 10
-2mol/L.Auxiliary agent can be at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate and sodium laurylsulfonate, and the concentration of the addition of auxiliary agent in the colloidal sol that contains M is 1 × 10
-4g/mL～5 × 10
-2g/mL.Reductive agent can be at least one in hydrazine hydrate, xitix, Trisodium Citrate and sodium borohydride, and the mol ratio of the metal ion in addition and the metal salt solution of reductive agent is 0.5:1 ~ 1 0:1.Obtain under the prerequisite of metal nanometer particle colloid in assurance, for energy efficient, the reaction times of this reaction can be 10 minutes ~ 45 minutes.
S102, according to M and Al mole ratio y, alumina aerogels is dissolved in the colloidal sol that contains M, at 50 ℃ ~ 75 ℃ temperature, stir 0.5 hour ~ 3 hours, ultrasonic, dry, after grinding, at 600 ℃ ~ 1200 ℃, calcine 0.5 hour ~ 4 hours, obtain the alumina aerogels of coated M, 0<y≤0.1.
In the present embodiment, ultrasonic can be ultrasonic 10min left and right under the power of 500W.Dry can be to be to carry out under 60 ℃ ~ 150 ℃ conditions in temperature.In this process, alumina aerogels has the network structure of porous, and density is low, and specific surface area is large, can be high temperature resistant, therefore can be combined with metal nanoparticle, and can obtain the alumina aerogels of coated M.
S103, according to La
1-x-yre
yalO
3: Tm
x@M
zstoichiometric ratio, take the compound of La, compound, the compound of Tm and the alumina aerogels of coated M of Re, grind and be placed in reducing atmosphere, and be warming up to 1200 ℃ ~ 1500 ℃ processing 2 hours ~ 10 hours, furnace cooling is cooled to room temperature, and obtaining chemical general formula is La
1-x-yre
yalO
3: Tm
x@M
zrare earth aluminate based luminescent material, Re is at least one in Y, Gd and Lu element, M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, Tm is entrained in La
1-x-yre
yalO
3in ,@represents to be coated, La
1-x-yre
yalO
3: Tm
xcoated M, 0<x≤0.2, z be M with Al mole ratio, 0<z≤1.5 × 10
-2.
In the present embodiment, reducing atmosphere can be at least one in mixed atmosphere, carbon dust atmosphere, carbon monoxide atmosphere and the hydrogen atmosphere of nitrogen and hydrogen.In weakly reducing atmosphere, the metal ion of high valence state can be reduced into the metal ion of lower valency, or protection metal ion is not oxidized.The compound of La can be lanthanum trioxide, lanthanum nitrate, Phosbloc or lanthanum oxalate.The compound of Re can be oxide compound, nitrate, carbonate or the oxalate of Re.The compound of Tm can be trioxide, thulium nitrate, thulium carbonate or thulium oxalate.
The preparation method of above-mentioned rare earth lanthanum aluminate light-emitting material, first prepare metal nanoparticle, then adopt alumina aerogels adsorbing metal nanoparticle, obtain being coated with the alumina aerogels of metal nanoparticle, and then prepare the lanthanum aluminate light-emitting material of clad metal nano particle take the alumina aerogels that is coated with metal nanoparticle as raw material.Strengthen light-emitting phosphor by clad metal nano particle.And preparation method's technique of above-mentioned rare earth lanthanum aluminate light-emitting material is simple, equipment requirements is low, pollution-free, be easy to control, be suitable for suitability for industrialized production.
Describe below in conjunction with specific embodiment.
Embodiment 1
High temperature solid-state method is prepared La
0.895y
0.1alO
3: Tm
0.005@Pt
5 × 10-3
Take 51.8mg 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 5 minutes, and then drip 2.6mL5 × 10 in chloroplatinic acid aqueous solution
-2the hydrazine hydrate solution of mol/L, continues reaction 40 minutes afterwards, and obtaining 20mLPt content is 5 × 10
-3the Pt nanoparticle sol of mol/L.
Take alumina aerogels 0.6117g, being dissolved into 12mLPt content is 5 × 10
-3in the Pt nanoparticle sol of mol/L, at 50 ℃, stir 3 hours, then ultrasonic 10 minutes, then be dried at 60 ℃, dried sample is ground evenly, at 600 ℃, precalcining 4 hours, obtains the alumina aerogels that contains metal nanoparticle.
Take the Phosbloc (La of 1.0243g
2(CO
3)
3), the yttrium carbonate (Y of 0.1105g
2(CO
3)
3), the alumina aerogels that contains metallics Pt of 0.2549g and the thulium carbonate (Tm of 0.0065g
2(CO
3)
3), be placed in agate mortar and be fully ground to and mix.Then by powder transfer in corundum crucible, the N that is 95% in volume fraction in tube furnace
2with the volume fraction H that is 5%
2the lower 1200 ℃ of thermal reductions of weakly reducing atmosphere 10 hours of mixed gas, be cooled to room temperature, can obtain the luminescent material La of coated Pt nanoparticle
0.895y
0.1alO
3: Tm
0.005@Pt
5 × 10-3.
High temperature solid-state method is prepared La
0.89y
0.01alO
3: Tm
0.1@Ag
2.5 × 10-4
Take 0.68mg Silver Nitrate (AgNO
3) be dissolved in the deionized water of 18.4mL; After Silver Nitrate dissolves completely, take 2mg Trisodium Citrate and be dissolved in silver nitrate aqueous solution under the environment of magnetic agitation.Take 1.14mg sodium borohydride molten in 10mL deionized water, obtaining 10mL concentration is 1.5 × 10
-3the 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
-3the sodium borohydride aqueous solution of mol/L.Continue afterwards reaction 10 minutes, obtaining 20mLAg content is 2 × 10
-4the Ag nanoparticle sol of mol/L.
Take alumina aerogels 0.6117g, being dissolved into 15mLAg content is 2 × 10
-4in the Ag nanoparticle sol of mol/L, at 60 ℃, stir 2 hours, then ultrasonic 10 minutes, then be dried at 80 ℃, dried sample is ground evenly, at 800 ℃, precalcining 2 hours, obtains the alumina aerogels that contains Ag nanoparticle.
Then take the lanthanum trioxide (La of 0.7249g
2o
3), the yttrium oxide (Y of 0.0028g
2o
3) and the alumina aerogels that contains Ag nanoparticle of 0.2549g and the trioxide (Tm of 0.0965g
2o
3) be placed in agate mortar and be fully ground to and mix.Then by powder transfer in corundum crucible, the N that is 95% in volume fraction in tube furnace
2with the volume fraction H that is 5%
2the lower 1500 ℃ of thermal reductions of weakly reducing atmosphere of mixed gas 2 hours, are cooled to room temperature, can obtain the luminescent material La0.89Y of coated Ag nanoparticle
0.01alO
3: Tm
0.1@Ag
2.5 × 10-4, the luminescent material of this coated Ag nanoparticle is at the luminous lower blue light-emitting of low-voltage cathode ray.
As shown in Figure 2, the luminescent material La of the clad metal nano particle Ag preparing for the present embodiment
0.89y
0.01alO
3: Tm
0.1@Ag
2.5 × 10-4with the luminescent material La of clad metal nano particle not
0.89y
0.01alO
3: Tm
0.1cathodoluminescence spectrum comparison diagram under 3kv voltage.Wherein curve 1 is the luminescent material La of clad metal nano particle Ag
0.89y
0.01alO
3: Tm
0.1, Ag
2.5 × 10-4luminescent spectrum curve, curve 2 is luminescent material La of not clad metal nano particle
0.89y
0.01alO
3: Tm
0.1luminescent spectrum curve.As can be seen from Figure 2,, at the emission peak at 455nm place, after coated Ag nanoparticle, the luminous intensity of luminescent material has strengthened 42% before not being coated.
Embodiment 3
High temperature solid-state method is prepared La
0.92gd
0.05alO
3: Tm
0.03@Au
1.5 × 10-2:
Take 82.4mg hydrochloro-auric acid (AuCl
3hCl4H
2o) be dissolved in the deionized water of 10mL.After hydrochloro-auric acid dissolves completely, take 28mg Trisodium Citrate and 12mg 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, stirring reaction adds 5mL1 × 10 after 5 minutes again in aqueous solution of chloraurate
-2the aqueous ascorbic acid of mol/L, continues reaction 30 minutes afterwards, and obtaining 20mLAu content is the Au nanoparticle sol of mol/L.
Take 0.6117g alumina aerogels, being dissolved into 18mLAu content is 1 × 10
-2in the Au nanoparticle sol of mol/L, at 75 ℃, stir 0.5 hour, then ultrasonic 10 minutes, then be dried at 150 ℃, dried sample is ground evenly, at 1200 ℃, precalcining 0.5 hour, obtains the alumina aerogels that contains Au nanoparticle.
Then take the Lanthanum trichloride (LaCl of 2.2564g
3), the Gadolinium trichloride (GdCl of 0.1318g
3), the thulium chloride (TmCl of 0.0806g
3)
Then take the lanthanum trioxide (La of 1.4986g
2o
3), the yttrium oxide (Gd of 0.0906g
2o
3), the trioxide (Tm of 0.0579g
2o
3) and the 0.5098g alumina aerogels that contains Au nanoparticle, be placed in agate mortar and be fully ground to and mix.Then by powder transfer in corundum crucible, in retort furnace, adopt carbon reducing agent, 1300 ℃ of thermal reductions 4 hours, are cooled to room temperature, can obtain the luminescent material La of coated Au nanoparticle
0.92gd
0.05alO
3: Tm
0.03@Au
1.5 × 10-2.
Embodiment 4
High temperature solid-state method is prepared La
0.985lu
0.005alO
3: Tm
0.01@Pd
1 × 10-5:
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 10mL deionized water, obtaining concentration is 1 × 10
-3the sodium borohydride reduction liquid of mol/L.Under the environment of magnetic agitation, in palladium chloride aqueous solution, add fast 10mL1 × 10
-3the sodium borohydride aqueous solution of mol/L, continues reaction 20 minutes afterwards, and obtaining 20mLPd content is 5 × 10
-5the Pd nanoparticle sol of mol/L.
Take 0.3058g alumina aerogels, being dissolved into 1.2mLPd content is 5 × 10
-5in the Pd nanoparticle sol of mol/L, at 65 ℃, stir 1.5 hours, then ultrasonic 10 minutes, then be dried at 120 ℃, dried sample is ground evenly, at 1100 ℃, precalcining 2 hours, obtains the alumina aerogels that contains Pd nanoparticle.
Then take the lanthanum nitrate (La (NO of 3.2011g
3)
3), the lutecium nitrate (Lu (NO of 0.0180g
3)
3), the thulium nitrate (Tm (NO of 0.0355g
3)
3) and the 0.5098g alumina aerogels that contains Pd nanoparticle, be placed in agate mortar and be fully ground to and mix.Then by powder transfer in corundum crucible, in the N that is 95% in volume fraction in tube furnace
2with the volume fraction H that is 5%
2the lower 1300 ℃ of thermal reductions of weakly reducing atmosphere 5 hours of mixed gas, be cooled to room temperature, can obtain the luminescent material La of coated Pd nanoparticle
0.985lu
0.005alO
3: Tm
0.01@Pd
1 × 10-5.
Embodiment 5
High temperature solid-state method is prepared La
0.75y
0.02gd
0.03alO
3: Tm
0.20@Cu
5 × 10-4
The preparation of Cu nanoparticle sol: take 2mg cupric nitrate (Cu (NO
3)
2) be dissolved in the ethanol of 16mL, after dissolving completely, stir while add 12mg 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 10 minutes, and obtaining 20mLCu content is 5 × 10
-4the Cu nanometer particle colloid of mol/L.
Take 0.6117g alumina aerogels, being dissolved into 12mLCu content is 5 × 10
-4in the Cu nanometer particle colloid of mol/L, at 70 ℃, stir 1 hour, then ultrasonic 10 minutes, then be dried at 70 ℃, dried sample is ground evenly, at 800 ℃, precalcining 2 hours, obtains the alumina aerogels that contains Cu nanoparticle.
Take the lanthanum trioxide (La of 1.2219g
2o
3), the yttrium oxide (Y of 0.0226g
2o
3), the gadolinium sesquioxide (Gd of 0.0544g
2o
3), the trioxide (Tm of 0.3859g
2o
3) and the 0.5098g alumina aerogels that contains metallics Cu, be placed in agate mortar and be fully ground to and mix.Then by powder transfer in corundum crucible, the N that is 95% in volume fraction in tube furnace
2with the volume fraction H that is 5%
2the lower 1250 ℃ of thermal reductions of weakly reducing atmosphere 6 hours of mixed gas, be cooled to room temperature, can obtain the luminescent material La of coated Cu nanoparticle
0.75y
0.02gd
0.03alO
3: Tm
0.20@Cu
5 × 10-4.
Embodiment 6
High temperature solid-state method is prepared La
0.99alO
3: Tm
0.01@(Ag
0.5/ Au
0.5)
1.25 × 10-3
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 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 2mL1.5 × 10 that add in above-mentioned mixing solutions
-2the sodium borohydride aqueous solution of mol/L, continues reaction 20 minutes afterwards, and obtaining the total metal concentration of 30mL is 1 × 10
-3the Ag/Au nanoparticle sol of mol/L.
Take alumina aerogels 0.6117g, being dissolved into the total metal concentration of 15mL is 1 × 10
-3in the Ag/Au nanoparticle sol of mol/L, at 60 ℃, stir 2 hours, then ultrasonic 10 minutes, then be dried at 80 ℃, dried sample is ground evenly, at 1000 ℃, precalcining 4 hours, obtains the alumina aerogels that contains Ag/Au nanoparticle.
Take the lanthanum trioxide (La of 0.8063g
2o
3), the trioxide (Tm of 0.0096g
2o
3) and the 0.2549g alumina aerogels that contains Ag/Au nanoparticle, be placed in agate mortar and be fully ground to and mix.Then by powder transfer in corundum crucible, under the common reducing atmosphere of building of carbon dust and CO, 1350 ℃ of thermal reductions 5 hours, are cooled to room temperature, can obtain clad alloy Ag
0.5/ Au
0.5the luminescent material La of nanoparticle
0.99alO
3: Tm
0.01@(Ag
0.5/ Au
0.5)
1.25× 10
-3, this luminescent material is at the luminous lower blue light-emitting of low-voltage cathode ray.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a rare earth lanthanum aluminate light-emitting material, is characterized in that, has following chemical general formula: La
1-x-yre
yalO
3: Tm
x@M
z, described Re is at least one in Y, Gd and Lu element, and described M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, and described Tm is entrained in La
1-x-yre
yalO
3in ,@represents to be coated, described La
1-x-yre
yalO
3: Tm
xcoated described M, 0<x≤0.2,0<y≤0.1, z be M with Al mole ratio, 0<z≤1.5 × 10
-2.
2. rare earth lanthanum aluminate light-emitting material according to claim 1, is characterized in that, 0.01≤x≤0.1.
3. rare earth lanthanum aluminate light-emitting material according to claim 1, is characterized in that, 0.005≤y≤0.05.
4. rare earth lanthanum aluminate light-emitting material according to claim 1, is characterized in that, 1 × 10
-5≤ z≤5 × 10
-3.
5. a preparation method for rare earth lanthanum aluminate light-emitting material, is characterized in that, comprising:
At least one metal salt solution in Ag, Au, Pt, Pd and Cu is mixed and reacted with auxiliary agent and reductive agent, make the colloidal sol that contains M; Described M is selected from least one in Ag, Au, Pt, Pd and Cu metal nanoparticle;
According to M and Al mole ratio y, in the colloidal sol that contains M described in alumina aerogels is dissolved to, at 50 ℃ ~ 75 ℃ temperature, stir 0.5 hour ~ 3 hours, ultrasonic, dry, after grinding, at 600 ℃ ~ 1200 ℃, calcine 0.5 hour ~ 4 hours, obtain the alumina aerogels of coated M, 0<y≤0.1; And
According to La
1-x-yre
yalO
3: Tm
x@M
zstoichiometric ratio, take the compound of La, compound, the compound of Tm and the alumina aerogels of described coated M of Re, grind and be placed in reducing atmosphere, and be warming up to 1200 ℃ ~ 1500 ℃ processing 2 hours ~ 10 hours, furnace cooling is cooled to room temperature, and obtaining chemical general formula is La
1-x-yre
yalO
3: Tm
x@M
zrare earth aluminate based luminescent material, described Re is at least one in Y, Gd and Lu element, described M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, described Tm is entrained in La
1-x-yre
yalO
3in ,@represents to be coated, described La
1-x-yre
yalO
3: Tm
xcoated described M, 0<x≤0.2, z be M with Al mole ratio, 0<z≤1.5 × 10
-2.
6. the preparation method of rare earth lanthanum aluminate light-emitting material according to claim 5, is characterized in that, in described metal salt solution, the concentration of metal ion is 1 × 10
-4mol/L ~ 2 × 10
-2mol/L.
7. the preparation method of rare earth lanthanum aluminate light-emitting material according to claim 5, 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, and the concentration of the addition of described auxiliary agent in the colloidal sol of the described M of containing is 1 × 10
-4g/mL ~ 5 × 10
-2g/mL.
8. the preparation method of rare earth lanthanum aluminate light-emitting material according to claim 5, it is characterized in that, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate and sodium borohydride, and the mol ratio of the addition of described reductive agent and the metal ion of described metal salt solution is 0.5:1 ~ 1 0:1.
9. the preparation method of rare earth lanthanum aluminate light-emitting material according to claim 5, is characterized in that, described reducing atmosphere is at least one in mixed atmosphere, carbon dust atmosphere, carbon monoxide atmosphere and the hydrogen atmosphere of nitrogen and hydrogen.
10. the preparation method of rare earth lanthanum aluminate light-emitting material according to claim 5, is characterized in that, the compound of described La is lanthanum trioxide, lanthanum nitrate, Phosbloc or lanthanum oxalate; The compound of described Re is oxide compound, nitrate, carbonate or the oxalate of Re; The compound of described Tm is trioxide, thulium nitrate, thulium carbonate or thulium oxalate.
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