CN102382649A - Rare earth oxide luminescent material doped with In and preparation method thereof - Google Patents
Rare earth oxide luminescent material doped with In and preparation method thereof Download PDFInfo
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- CN102382649A CN102382649A CN2010102696917A CN201010269691A CN102382649A CN 102382649 A CN102382649 A CN 102382649A CN 2010102696917 A CN2010102696917 A CN 2010102696917A CN 201010269691 A CN201010269691 A CN 201010269691A CN 102382649 A CN102382649 A CN 102382649A
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Abstract
The invention discloses a rare earth oxide luminescent material doped with In, of which the chemical formula is Ln1-xRexA1-zInzO3, wherein the Ln is at least one out of La, Y, Sc, Lu and Gd; the Re is at least one out of Tm, Tb, Eu, Sm, Dy and Ce; the A is at least one out of Al and Ga; and the numeric areas of the x and z are as follows: the x is more than or equal to 0.001 and less than or equal to 0.2, and the z is more than 0 and less than or equal to 0.45. For the rare earth oxide luminescent material doped with In, the In replaces Al or Ga, the luminescent efficiency is improved under the excitation of cathode rays, and simultaneously, the rare earth oxide luminescent material doped with In has good chemical stability and extremely wide application prospect. The invention also provides at least one preparation method of the rare earth oxide luminescent material doped with In.
Description
[technical field]
The present invention relates to luminescent material and preparing technical field thereof, relate in particular to rare earth oxide luminescent material of a kind of In of mixing and preparation method thereof.
[background technology]
Traditional cathode-ray luminescence material mainly contains two types of sulfide system and oxide systems.The sulfide system comprises blue powder ZnS:Ag, Cl, SrGa
2S
4: Ce, green powder SrGa
2S
4: Eu and rouge and powder Y
2O
2S:Eu.Oxide system mainly comprises blue powder Y
2SiO
5: Ce, green powder ZnGa
2O
4: Mn, Y
2SiO
5: Tb, Y
3Al
5O
12: Tb and rouge and powder Y
2O
3: Eu.
Sulfide luminescent material makes moist and the matrix instability easily, under the long-term bombardment of electron beam, can decompose generation like H
2Gases such as S, not only Poisoning cathode causes the decline of emission of cathode electronic capability, also causes the decline of the luminous efficiency of sulfide luminescent material own, shortens its life-span.Traditional rare earth oxide luminescent material is not easy to make moist and the good stability of matrix, but electroconductibility, luminous efficiency are not high.
[summary of the invention]
Based on this, be necessary to design the high rare earth oxide luminescent material of mixing In of a kind of luminous efficiency.
A kind of rare earth oxide luminescent material of mixing In, chemical formula is: Ln
1-xRe
xA
1-zIn
zO
3Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45.
The rare earth oxide luminescent material of the above-mentioned In of mixing partly replaces Al or Ga through In, and the luminous efficiency under cathode-ray exciting is improved, and chemicalstability is good simultaneously, has very strong application prospect.
In addition, also be necessary to provide the preparation method of the rare earth oxide luminescent material of at least a above-mentioned In of mixing.
A kind of preparation method who mixes the rare earth oxide luminescent material of In comprises the steps:
Press chemical formula Ln
1-xRe
xA
1-zIn
zO
3In the stoichiometric ratio of each element, take by weighing the raw material of Ln, Re, A and In respectively, grind to form mixed powder; Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45;
After said mixed powder process pre-burning processing and calcination processing, cool off, grind, obtain the rare earth oxide luminescent material of the said In of mixing.
Preferably, the said step that grinds to form mixed powder also comprises in the mixed powder that the raw material to Ln, Re, A and In grinds to form and adds fusing assistant; Said fusing assistant is at least a in boric acid and the barium fluoride; The raw material of said Ln, Re, A and In is at least a in corresponding oxide compound, oxyhydroxide, carbonate, oxalate and the nitrate salt; Said pre-burning treatment temp is 500～1000 ℃, and the pre-burning treatment time is 2～10h; Said calcination processing temperature is 1000～1500 ℃, and the calcination processing time is 1～8h.
Preparing method's technology of the above-mentioned rare earth oxide luminescent material of mixing In is simple, pollution-free, equipment requirements is low, is beneficial to suitability for industrialized production, can be widely used in the preparation field of luminescent material.
Another kind is mixed the preparation method of the rare earth oxide luminescent material of In, comprises the steps:
Press chemical formula Ln
1-xRe
xA
1-zIn
zO
3In the stoichiometric ratio of each element, preparation contains the ionic mixing solutions of Ln, Re, A and In; Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45;
According to the total mole number of metals ion in the said mixing solutions, in above-mentioned mixing solutions, add the aqueous solution that contains precipitation agent, after mixing, deposition, washing, drying treatment, get solid mixture;
After said solid mixture carried out pre-burning processing and calcination processing, cooling, grind, obtain the rare earth oxide luminescent material of the said In of mixing.
Preferably, said precipitation agent is at least a in oxalic acid, volatile salt and the bicarbonate of ammonia; Said pre-burning treatment temp is 500～1000 ℃, and the said pre-burning treatment time is 2～10h; Said calcination processing temperature is 1000～1500 ℃, and the said calcination processing time is 1～8h.
Preferably, the said ionic mixed solution that contains Ln, Re, A and In is soluble salt solution such as corresponding nitrate salt, hydrochloride; The mode that can adopt low-carbon alcohol such as water or ethanol directly to dissolve soluble salt during concrete the preparation also can adopt relative acid to dissolve the mode of corresponding oxide compound, oxyhydroxide, carbonate.
Preparing method's technology of the above-mentioned rare earth oxide luminescent material of mixing In is simple, pollution-free, equipment requirements is low, is beneficial to suitability for industrialized production, can be widely used in the preparation field of luminescent material.
Another kind is mixed the preparation method of the rare earth oxide luminescent material of In, comprises the steps:
Press chemical formula Ln
1-xRe
xA
1-zIn
zO
3In the stoichiometric ratio of each element, preparation contains the ionic mixing solutions of Ln, Re, A and In; Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45;
In above-mentioned mixing solutions, add complexing agent and stablizer successively, obtain precursor sol after the water bath processing;
With grinding to form powder after the above-mentioned precursor sol drying;
After above-mentioned powder carried out pre-burning and handle, carry out calcination processing again, cooling is then ground, and obtains the rare earth oxide luminescent material of the said In of mixing.
Preferably, in the step of said preparation precursor sol, said complexing agent is a Hydrocerol A, and the total mole number ratio of said complexing agent mole number and metals ion is 1: 1～1: 4; It is 0.01～0.10g/mL that the addition of said stablizer makes its concentration in said precursor colloidal sol; Said stablizer is the polyoxyethylene glycol of molecular weight 10000.
Preferably, in the step of said preparation precursor sol, the temperature of said water bath processing is 75～95 ℃, and the time of said water bath processing is 2～8h.
Preferably, Hydrocerol A can adopt aqueous citric acid solution or Hydrocerol A alcoholic solution, adds like the form of ethanolic soln etc., also can adopt solid forms such as Hydrocerol A crystal, monohydrate potassium to add.
Preferably, the said ionic mixed solution that contains Ln, Re, A and In is soluble salt solution such as corresponding nitrate salt, hydrochloride; The mode that can adopt low-carbon alcohol such as water or ethanol directly to dissolve soluble salt during concrete the preparation also can adopt relative acid to dissolve the mode of corresponding oxide compound, oxyhydroxide, carbonate.
Preferably, said pre-burning treatment temp is 500～1000 ℃, and the said pre-burning treatment time is 2～10h; Said calcination processing temperature is 1000～1500 ℃, and the said calcination processing time is 1～8h.
Preferably, when containing Tb in the rare earth oxide luminescent material of the said In of mixing, said calcination processing is carried out in reducing atmosphere; Said reducing atmosphere is nitrogen and hydrogen mixed gas atmosphere, or pure hydrogen atmosphere, or carbon monoxide atmosphere.
Preparing method's technology of the rare earth oxide luminescent material of the above-mentioned In of mixing is simple, pollution-free, do not introduce other impurity, equipment requirements is low, is beneficial to suitability for industrialized production, can be widely used in the preparation field of luminescent material.
[description of drawings]
Fig. 1 is the schema that the rare earth oxide luminescent material of mixing In of an embodiment adopts the high temperature solid-state method preparation;
Fig. 2 is the schema that the rare earth oxide luminescent material of mixing In of an embodiment adopts the coprecipitation method preparation;
Fig. 3 is the schema that the rare earth oxide luminescent material of mixing In of an embodiment adopts the sol-gel method preparation;
Fig. 4 is the luminescent spectrum comparison diagram under the rare earth oxide luminescent material of mixing In of embodiment 2 preparation and the cathode-ray exciting that traditional luminescent material is 3kV at acceleration voltage;
Fig. 5 is that the rare earth oxide luminescent material of mixing In and not mixing In of embodiment 5 preparation is the luminescent spectrum comparison diagram under the cathode-ray exciting of 1.5kV at acceleration voltage;
Luminescent spectrum comparison diagram under the cathode-ray exciting that Fig. 6 at acceleration voltage is 3kV for the rare earth oxide luminescent material of mixing In and traditional luminescent material of embodiment 11 preparation;
Luminescent spectrum comparison diagram under the cathode-ray exciting that Fig. 7 at acceleration voltage is 5kV for the rare earth oxide luminescent material of mixing In and traditional luminescent material of embodiment 11 preparation.
[embodiment]
Specify the rare earth oxide luminescent material of mixing In and the preparation method of three kinds of rare earth oxide luminescent materials of mixing In below in conjunction with accompanying drawing and embodiment.
The rare earth oxide luminescent material of mixing In of one embodiment, chemical formula is: Ln
1-xRe
xA
1-zIn
zO
3Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45.
The rare earth oxide luminescent material of the above-mentioned In of mixing partly replaces Al or Ga through In, and the luminous efficiency under cathode-ray exciting is improved, and chemicalstability is good simultaneously, has very strong application prospect.
The preparation method of the rare earth oxide luminescent material of three kinds of above-mentioned In of mixing is provided below.
One, high temperature solid-state method
Fig. 1 shows, adopts high temperature solid-state method to prepare the rare earth oxide luminescent material of the above-mentioned In of mixing, comprises the steps:
The mixture of the raw material of S110, preparation Ln, Re, A and In
Press chemical formula Ln
1-xRe
xA
1-zIn
zO
3In the stoichiometric ratio of each element, the raw material of Ln, Re, A and In is provided, grind to form mixture; Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45.
The raw material of Ln, Re, A and In is at least a in corresponding oxide compound, oxyhydroxide, carbonate, oxalate and the nitrate salt.
S120, said mixture thermal treatment obtain mixing the rare earth oxide luminescent material of In
After said mixture added fusing assistant, 500～1000 ℃ of following pre-burning 2～10h earlier, grind the cooling back, at 1000～1500 ℃ of calcining 1～8h down, behind the regrinding, obtains the rare earth oxide luminescent material of the said In of mixing again.
Fusing assistant is at least a in boric acid and the barium fluoride; The addition of fusing assistant is as the criterion satisfying the demands.
The effect of fusing assistant is to make reaction more abundant, reduces temperature of reaction; In other embodiment, also can not add fusing assistant, pre-burning and calcining under comparatively high temps.
Grinding operation mainly is in order to prepare the powdery luminescent material; When not being specific when needing the powdery luminescent material, grinding operation also can omit.
Preparing method's technology of the above-mentioned rare earth oxide luminescent material of mixing In is simple, pollution-free, equipment requirements is low, is beneficial to suitability for industrialized production, can be widely used in the preparation field of luminescent material; Rare earth oxide luminescent material luminous efficiency height, good stability, the epigranular of mixing In that prepare.
Two, coprecipitation method
Fig. 2 shows, adopts coprecipitation method to prepare the rare earth oxide luminescent material of the above-mentioned In of mixing, comprises the steps:
S210, preparation contain the ionic mixed solution of Ln, Re, A and In
Press chemical formula Ln
1-xRe
xA
1-zIn
zO
3In the stoichiometric ratio of each element, preparation contains the ionic mixed solution of Ln, Re, A and In; Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45.
The said ionic mixed solution that contains Ln, Re, A and In is soluble salt solution such as corresponding nitrate salt, hydrochloride; The mode that can adopt low-carbon alcohol such as water or ethanol directly to dissolve soluble salt during concrete the preparation also can adopt relative acid to dissolve the mode of corresponding oxide compound, oxyhydroxide, carbonate.
S220, above-mentioned mixed solution add precipitation agent and obtain solid mixture
Above-mentioned precipitant solution is joined in the ionic mixed solution of the above-mentioned Ln of containing, Re, A and In, after mixing, deposition, washing, drying treatment, obtain solid mixture; Said precipitation agent is at least a in oxalic acid, volatile salt and the bicarbonate of ammonia.
The concentration of above-mentioned precipitant solution and the addition of precipitant solution are decided according to the total amount of substance of metals ion, are as the criterion satisfying the demands.
S230, said mixture thermal treatment obtain mixing the rare earth oxide luminescent material of In
With 500～1000 ℃ of following pre-burning 2～10h of said mixture elder generation, grind the cooling back, calcines 1～8h down at 1000～1500 ℃ again, behind the regrinding, obtains the rare earth oxide luminescent material of the said In of mixing.
Grinding operation mainly is in order to prepare the powdery luminescent material; When not being specific when needing the powdery luminescent material, grinding operation also can omit.
Preparing method's technology of the above-mentioned rare earth oxide luminescent material of mixing In is simple, pollution-free, equipment requirements is low, is beneficial to suitability for industrialized production, can be widely used in the preparation field of luminescent material; Rare earth oxide luminescent material luminous efficiency height, good stability, the epigranular of mixing In that prepare.
Three, sol-gel method
Fig. 3 shows, adopts sol-gel method to prepare the rare earth oxide luminescent material of the above-mentioned In of mixing, comprises the steps:
S310, preparation contain the ionic mixed solution of Ln, Re, A and In
Press chemical formula Ln
1-xRe
xA
1-zIn
zO
3In the stoichiometric ratio of each element, preparation contains the ionic mixed solution of Ln, Re, A and In; Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45;
The said ionic mixed solution that contains Ln, Re, A and In is soluble salt solution such as corresponding nitrate salt, hydrochloride; The mode that can adopt low-carbon alcohol such as water or ethanol directly to dissolve soluble salt during concrete the preparation also can adopt relative acid to dissolve the mode of corresponding oxide compound, oxyhydroxide, carbonate.
The precursor sol of S320, the above-mentioned mixed solution of preparation
Total mole number ratio by Hydrocerol A mole number and metals ion is 1: 1～1: 4; The complexing agent Hydrocerol A is joined in the ionic mixed solution of the above-mentioned Ln of containing, Re, A and In; Add the stablizer polyoxyethylene glycol again, mix 75～95 ℃ of water-bath 2～8h in back, obtain precursor sol; Wherein, polyoxyethylene glycol concentration is 0.01～0.10g/mL in the said precursor sol.
Hydrocerol A can adopt aqueous citric acid solution or Hydrocerol A alcoholic solution, adds like forms such as ethanolic solns, also can adopt solid forms such as Hydrocerol A crystal, monohydrate potassium to add.
S330, the dry post-heat-treated of precursor sol obtain mixing the rare earth oxide luminescent material of In
With grinding to form powder after the above-mentioned precursor sol drying, 500～1000 ℃ of following pre-burning 2～10h grind after the cooling earlier, and calcining 1～8h under 1000～1500 ℃ behind the regrinding, obtains the rare earth oxide luminescent material of the said In of mixing again.
In the said calcining step, when containing Tb in the rare earth oxide luminescent material of the said In of mixing, reducing atmosphere is adopted in calcining; When not containing Tb in the rare earth oxide luminescent material of the said In of mixing, air atmosphere is adopted in calcining; Said reducing atmosphere is nitrogen and hydrogen mixed gas atmosphere, or pure hydrogen atmosphere, or carbon monoxide atmosphere.
Grinding operation mainly is in order to prepare the powdery luminescent material; When not being specific when needing the powdery luminescent material, grinding operation also can omit.
Preparing method's technology of the rare earth oxide luminescent material of the above-mentioned In of mixing is simple, pollution-free, do not introduce other impurity, equipment requirements is low, is beneficial to suitability for industrialized production, can be widely used in the preparation field of luminescent material; The rare earth oxide luminescent material luminous efficiency of mixing In for preparing is high, do not need ball milling, good stability, epigranular.
Embodiment 1:
High temperature solid-state method prepares La
0.99Eu
0.1Al
0.9In
0.1O
3Luminescent material
Take by weighing 1.6128g La
2O
3, 0.0176g Eu
2O
3, 0.4588g Al
2O
3, 0.1388g In
2O
3And 0.0309gH
3BO
3(total amount 5%) places agate mortar, grinds evenly.Mixture is put into corundum crucible at 500 ℃ of following pre-burning 2h, be cooled to room temperature then, take out once more and fully grind.At last, it in air atmosphere, is calcined 1h down for 1500 ℃, cooling, taking-up promptly gets the powder shaped luminescent material after grinding.
Embodiment 2:
High temperature solid-state method prepares La
0.99Tm
0.01Al
0.95In
0.05O
3Luminescent material
Take by weighing 1.6128g La
2O
3, 0.0193g Tm
2O
3, 0.4843g Al
2O
3, 0.0694g In
2O
3And 0.0876gBaF
2(total amount 5%) places agate mortar, grinds evenly.Mixture is put into corundum crucible at 700 ℃ of following pre-burning 2h, be cooled to room temperature then, take out once more and fully grind.At last, it in air atmosphere, is calcined 3h down for 1400 ℃, cooling, taking-up promptly gets the powder shaped luminescent material after grinding.In order to compare, similarity condition prepares La
0.99Tm
0.01AlO
3Luminescent material.
Fig. 4 is the luminescent spectrum comparison diagram under the rare earth oxide luminescent material of mixing In of embodiment 2 preparation and the cathode-ray exciting that traditional luminescent material is 3kV at acceleration voltage.Curve 1 is the La of embodiment 2 preparations
0.99Tm
0.01Al
0.95In
0.05O
3The luminescent spectrum of luminescent material, curve 2 are traditional luminescent material La
0.99Tm
0.01AlO
3Luminescent spectrum.
Can be drawn by Fig. 4, curve 1 is under the cathode-ray exciting of 3kV with respect to curve 2 at acceleration voltage, and the blue peak luminous intensity of 450～470nm wave band has improved about 60%.
Embodiment 3:
High temperature solid-state method prepares La
0.8Dy
0.2Al
0.55In
0.45O
3Luminescent material
Take by weighing 1.3032g La
2O
3, 0.3730g Dy
2O
3, 0.2804g Al
2O
3, 0.6246g In
2O
3And 0.0618gH
3BO
3(total amount 10%) places agate mortar, grinds evenly.Mixture is put into corundum crucible at 600 ℃ of following pre-burning 4h, be cooled to room temperature then, take out once more and fully grind.At last, it in air atmosphere, is calcined 8h down for 1000 ℃, cooling, taking-up promptly gets the powder shaped luminescent material after grinding.
Embodiment 4:
Coprecipitation method prepares La
0.95Tb
0.05Al
0.995In
0.005O
3Luminescent material
Take by weighing 40.7261g La
2O
3Adding nitric acid is configured to the La (NO of 250ml 1mol/L
3)
3Solution, take by weighing 93.7825g Al (NO
3)
39H
2O adds the Al (NO that water is configured to 250ml 1mol/L
3)
3Solution, take by weighing 34.7043g In
2O
3Add the In (NO that nitric acid is configured to 250ml 1mol/L
3)
3Solution, take by weighing 4.6731g Tb
4O
7Add the Tb (NO that nitric acid is configured to 250ml 0.1mol/L
3)
3Solution.Accurately take by weighing the La (NO of 9.5ml 1mol/L
3)
3Al (the NO of solution, 9.95ml 1mol/L
3)
3In (the NO of solution, 0.05ml 1mol/L
3)
3Tb (the NO of solution, 5ml 0.1mol/L
3)
3Solution places beaker, obtains solution A.Total amount of substance according to metals ion takes by weighing 3.9701g H
2C
2O
42H
2O (excessive 5%), soluble in water, obtain solution B.Under the magnetic agitation, the B drips of solution is added among the A, fully reaction, deposition, filtration, washing, drying obtain mixture.Mixture is put into corundum crucible at 600 ℃ of following pre-burning 4h, be cooled to room temperature then, take out once more and fully grind.At last, with it in the carbon monoxide reducing atmosphere, under 1350 ℃, calcining 2h, cooling is taken out and is promptly got the powder shaped luminescent material after grinding.
Embodiment 5:
Coprecipitation method prepares La
0.98Dy
0.02Al
0.99In
0.01O
3Luminescent material
Take by weighing 40.7261g La
2O
3Adding nitric acid is configured to the La (NO of 250ml 1mol/L
3)
3Solution, take by weighing 93.7825g Al (NO
3)
39H
2O adds the Al (NO that water is configured to 250ml 1mol/L
3)
3Solution, take by weighing 34.7043g In
2O
3Add the In (NO that nitric acid is configured to 250ml 1mol/L
3)
3Solution, take by weighing 4.6624g Dy
2O
3Add the Dy (NO that nitric acid is configured to 250ml 0.1mol/L
3)
3Solution.Accurately take by weighing the La (NO of 4.9ml 1mol/L
3)
3Al (the NO of solution, 4.95ml 1mol/L
3)
3In (the NO of solution, 0.05ml 1mol/L
3)
3Dy (the NO of solution, 1ml 0.1mol/L
3)
3Solution places beaker, obtains solution A.Total amount of substance according to metals ion takes by weighing 0.8648g (NH
4)
2CO
3And 0.7115NH
4HCO
3(all excessive 20%), soluble in water, obtain solution B.Under the magnetic agitation, the B drips of solution is added among the A, fully reaction, deposition, filtration, washing, drying obtain mixture.Mixture is put into corundum crucible at 500 ℃ of following pre-burning 4h, be cooled to room temperature then, take out once more and fully grind.At last, with it in air atmosphere, under 1400 ℃, calcining 2h, cooling is taken out and is promptly got the powder shaped luminescent material after grinding.As a comparison, similarity condition prepares La down
0.98Dy
0.02AlO
3Luminescent material.
Fig. 5 is that the rare earth oxide luminescent material of mixing In and not mixing In of embodiment 5 preparation is the luminescent spectrum comparison diagram under the cathode-ray exciting of 1.5kV at acceleration voltage.Curve 3 is luminescent material La of embodiment 5 preparations
0.98Dy
0.02Al
0.99In
0.01O
3Luminescent spectrum, curve 4 is luminescent material La of embodiment 5 preparation
0.98Dy
0.02AlO
3Luminescent spectrum.
Can be drawn by Fig. 5, curve 3 is under the cathode-ray exciting of 1.5kV with respect to curve 4 at acceleration voltage, and the luminous intensity at 482nm and 574nm place has improved about 10% and 18% respectively.
Embodiment 6:
Coprecipitation method prepares Y
0.8Dy
0.2Ga
0.55In
0.45O
3Luminescent material
Take by weighing 28.2262g Y
2O
3Adding nitric acid is configured to the Y (NO of 250ml 1mol/L
3)
3Solution, take by weighing 34.7043g In
2O
3Add the In (NO that nitric acid is configured to 250ml 1mol/L
3)
3Solution, accurately take by weighing the La (NO of 8ml1mol/L
3)
3In (the NO of solution, 4.5ml 1mol/L
3)
3Solution places beaker, adds 1.4066gGa (NO again
3)
3, 0.9130g Dy (NO
3)
36H
2O obtains solution A after the dissolving.Total amount of substance according to metals ion takes by weighing 1.5854g (NH
4)
2CO
3(excessive 10%), soluble in water, obtain solution B.Under the magnetic agitation, the B drips of solution is added among the A, fully reaction, deposition, filtration, washing, drying obtain mixture.Mixture is put into corundum crucible at 700 ℃ of following pre-burning 4h, be cooled to room temperature then, take out once more and fully grind.At last, with it in air atmosphere, under 1400 ℃, calcining 2h, cooling is taken out and is promptly got the powder shaped luminescent material after grinding.
Embodiment 7:
Coprecipitation method prepares Lu
0.95Sc
0.03Ce
0.02Al
0.95In
0.05O
3Luminescent material
Take by weighing 47.7415g Lu
2O
3Adding nitric acid is configured to the Lu (NO of 250ml 1mol/L
3)
3Solution, take by weighing 0.6896g Sc
2O
3Adding nitric acid is configured to the Sc (NO of 100ml 0.1mol/L
3)
3Solution, take by weighing 19.5009gAl (OH)
3Add the Al (NO that nitric acid is configured to 250ml 1mol/L
3)
3Solution, take by weighing 75.2082g In (NO
3)
3Add the In (NO that water is configured to 250ml 1mol/L
3)
3Solution, take by weighing 1.7211g CeO
2Add the Ce (NO that nitric acid and ydrogen peroxide 50 are configured to 100ml 0.1mol/L
3)
3Solution.Take by weighing the Lu (NO of 9.5ml 1mol/L
3)
3Sc (the NO of solution, 3ml 0.1mol/L
3)
3Al (the NO of solution, 9.5ml 1mol/L
3)
3In (the NO of solution, 0.5ml 1mol/L
3)
3Ce (the NO of solution, 2ml 0.1mol/L
3)
3Solution places beaker, obtains solution A.Total amount of substance according to metals ion takes by weighing 1.4050gNH
4HCO
3(excessive 20%), soluble in water, obtain solution B.Under the magnetic agitation, the A drips of solution is added among the B, fully reaction, deposition, filtration, washing, drying obtain mixture.Mixture is put into corundum crucible at 1000 ℃ of following pre-burning 2h, be cooled to room temperature then, take out once more and fully grind.At last, in its gas mixture reducing atmosphere (nitrogen and hydrogen volume ratio are 95: 5 or 90: 10) at nitrogen and hydrogen, under 1300 ℃, calcining 4h, cooling is taken out and is promptly got the powder shaped luminescent material after grinding.
Embodiment 8:
Sol-gel method prepares La
0.999Sm
0.001Al
0.7Ga
0.2In
0.1O
3
Obtained certain density nitrate soln according to above embodiment.Equally, take by weighing 1.7436g Sm
2O
3Adding nitric acid is configured to the Sm (NO of 100ml 0.1mol/L
3)
3Solution.
According to chemical formula La
0.999Sm
0.001Al
0.7Ga
0.2In
0.1O
3In stoichiometric ratio, accurately take by weighing the La (NO of 9.99ml1mol/L
3)
3Sm (the NO of solution, 0.1ml 0.1mol/L
3)
3Al (the NO of solution, 7ml 1mol/L
3)
3Al (the NO of solution, 2ml 1mol/L
3)
3In (the NO of solution, 1ml 1mol/L
3)
3Solution places beaker, adds 5ml water and 20ml ethanolic soln again; After being dissolved in the 4.2028g monohydrate potassium in the 20ml ethanol and the 10ml aqueous solution, it is joined in the above-mentioned solution, add the 7.509g polyoxyethylene glycol again; Wherein, Hydrocerol A is 1: 1 with the mol ratio of total metals ion, and the concentration of polyoxyethylene glycol (PEG, molecular weight are 10000) is 0.10g/ml.Again in 75 ℃ of water-baths, stir 8h behind the dissolving mixing, obtain uniform precursor sol.With colloidal sol dry 24h in 80 ℃ air dry oven, solvent flashing obtains xerogel.With obtaining mixture after the xerogel grinding.Mixture is put into corundum crucible at 500 ℃ of following pre-burning 10h, be cooled to room temperature then, take out once more and fully grind.At last, with it in air atmosphere, under 1000 ℃, calcining 8h, cooling is taken out and is promptly got the powder shaped luminescent material after grinding.
Embodiment 9:
Sol-gel method prepares La
0.99Tm
0.01Al
0.9In
0.1O
3
Obtained certain density nitrate soln according to above embodiment.Equally, take by weighing 1.9293g Tm
2O
3Adding nitric acid is configured to the Tm (NO of 100ml 0.1mol/L
3)
3Solution.
According to chemical formula La
0.99Tm
0.01Al
0.9In
0.1O
3In stoichiometric ratio, accurately take by weighing the La (NO of 9.9ml 1mol/L
3)
3Tm (the NO of solution, 1ml 0.1mol/L
3)
3Al (the NO of solution, 9ml 1mol/L
3)
3In (the NO of solution, 1ml 1mol/L
3)
3Solution places beaker, adds 5ml water and 10ml ethanolic soln again.After being dissolved in the 8.4056g monohydrate potassium in the 20ml ethanol and the 5ml aqueous solution, it is joined in the above-mentioned solution, add the 3.045g polyoxyethylene glycol again; Wherein, Hydrocerol A is 2: 1 with the mol ratio of total metals ion, and the concentration of polyoxyethylene glycol (PEG, molecular weight are 10000) is 0.05g/ml.Again in 95 ℃ of water-baths, stir 2h behind the dissolving mixing, obtain uniform precursor sol.With colloidal sol dry 4h in 150 ℃ air dry oven, solvent flashing obtains xerogel.With obtaining mixture after the xerogel grinding, mixture is put into corundum crucible at 600 ℃ of following pre-burning 4h, be cooled to room temperature then, take out once more and fully grind.At last, with it in air atmosphere, under 1300 ℃, calcining 3h, cooling is taken out and is promptly got the powder shaped luminescent material after grinding.
Embodiment 10:
Sol-gel method prepares Gd
0.99Tm
0.01Al
0.9In
0.1O
3
Obtained certain density nitrate soln according to above embodiment.
According to chemical formula La
0.95Tm
0.05Al
0.9In
0.1O
3In stoichiometric ratio, accurately take by weighing 4.2870gGd (NO
3)
36H
2Tm (the NO of O, 5ml 0.1mol/L
3)
3Al (the NO of solution, 9ml 1mol/L
3)
3In (the NO of solution, 1ml 1mol/L
3)
3Solution places beaker, adds 5ml water and 20ml ethanolic soln again.After being dissolved in the 16.8112g monohydrate potassium in the 30ml ethanol and the 5ml aqueous solution, it is joined in the above-mentioned solution, add the 0.7g polyoxyethylene glycol again; Wherein, Hydrocerol A is 2: 1 with the mol ratio of total metals ion, and the concentration of polyoxyethylene glycol (PEG, molecular weight are 10000) is 0.01g/ml.Again in 85 ℃ of water-baths, stir 5h behind the dissolving mixing, obtain uniform precursor sol.With colloidal sol dry 8h in 120 ℃ air dry oven, solvent flashing obtains xerogel.With obtaining mixture after the xerogel grinding, mixture is put into corundum crucible at 600 ℃ of following pre-burning 4h, be cooled to room temperature then, take out once more and fully grind.At last, with it in air atmosphere, under 1250 ℃, calcining 3h, cooling is taken out and is promptly got the powder shaped luminescent material after grinding.
Embodiment 11:
Sol-gel method prepares La
0.99Tm
0.01Al
0.9In
0.1O
3
Obtained certain density nitrate soln according to above embodiment.
According to chemical formula La
0.99Tm
0.01Al
0.9In
0.1O
3In stoichiometric ratio, accurately take by weighing the La (NO of 4.95ml1mol/L
3)
3Tm (the NO of solution, 0.5ml 0.1mol/L
3)
3Al (the NO of solution, 4.5ml 1mol/L
3)
3In (the NO of solution, 0.5ml 1mol/L
3)
3Solution places beaker, adds 5ml water and 20ml ethanolic soln again; After being dissolved in the 4.2028g monohydrate potassium in the 20ml ethanol and the 10ml aqueous solution, it is joined in the above-mentioned solution, add the 2.0021g polyoxyethylene glycol again; Wherein, Hydrocerol A is 2: 1 with the mol ratio of total metals ion, and the concentration of polyoxyethylene glycol (PEG, molecular weight are 10000) is 0.03g/ml.Again in 80 ℃ of water-baths, stir 5h behind the dissolving mixing, obtain uniform precursor sol.With colloidal sol dry 8h in 100 ℃ air dry oven, solvent flashing obtains xerogel.With obtaining mixture after the xerogel grinding, mixture is put into corundum crucible at 800 ℃ of following pre-burning 4h, be cooled to room temperature then, take out once more and fully grind.At last, with it in air atmosphere, under 1400 ℃, calcining 2h, cooling is taken out and is promptly got the powder shaped luminescent material after grinding.Same preparation La
0.99Tm
0.01AlO
3Luminescent material.
Fig. 6 is the luminescent spectrum comparison diagram under the rare earth oxide luminescent material of mixing In of embodiment 11 preparation and the cathode-ray exciting that traditional luminescent material is 3kV at acceleration voltage.Curve a is the La of embodiment 11 preparations
0.99Tm
0.01Al
0.9In
0.1O
3The luminescent spectrum of luminescent material, curve b are traditional luminescent material ZnS:Ag, and the luminescent spectrum of Cl, curve c are traditional luminescent material LaGaO
3: Tm
3+Luminescent spectrum, curve d is traditional luminescent material La
0.99Tm
0.01AlO
3Luminescent spectrum.
Can be drawn by Fig. 6, be under the cathode-ray exciting of 3kV at acceleration voltage, and curve a has improved about 80%, 162% and 426% with respect to curve b, c and d respectively in the blue peak luminous intensity of 450～470nm wave band.
Fig. 7 is the luminescent spectrum comparison diagram under the rare earth oxide luminescent material of mixing In of embodiment 11 preparation and the cathode-ray exciting that traditional luminescent material is 5kV at acceleration voltage.Curve 1 is the La of embodiment 11 preparations
0.99Tm
0.01Al
0.9In
0.1O
3The luminescent spectrum of luminescent material, curve 2 are traditional luminescent material ZnS:Ag, and the luminescent spectrum of Cl, curve 3 are traditional luminescent material La
0.99Tm
0.01AlO
3Luminescent spectrum.
Can be drawn by Fig. 7, be under the cathode-ray exciting of 5kV at acceleration voltage, and curve 1 has improved about 339% and 433% respectively with respect to curve 2 and 3455nm place luminous intensity.
The above embodiment has only expressed several kinds of embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, 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 accompanying claims.
Claims (10)
1. rare earth oxide luminescent material of mixing In, chemical formula is: Ln
1-xRe
xA
1-zIn
zO
3Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45.
2. a preparation method who mixes the rare earth oxide luminescent material of In is characterized in that, comprises the steps:
Press chemical formula Ln
1-xRe
xA
1-zIn
zO
3In the stoichiometric ratio of each element, take by weighing the raw material of Ln, Re, A and In respectively, grind to form mixed powder; Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45;
After said mixed powder process pre-burning processing and calcination processing, cool off, grind, obtain the rare earth oxide luminescent material of the said In of mixing.
3. the preparation method who mixes the rare earth oxide luminescent material of In as claimed in claim 2 is characterized in that, the said step that grinds to form mixed powder also comprises in the mixed powder that the raw material to Ln, Re, A and In grinds to form and adds fusing assistant; Said fusing assistant is at least a in boric acid and the barium fluoride;
The raw material of said Ln, Re, A and In is at least a in corresponding oxide compound, oxyhydroxide, carbonate, oxalate and the nitrate salt;
Said pre-burning treatment temp is 500～1000 ℃, and the pre-burning treatment time is 2～10h; Said calcination processing temperature is 1000～1500 ℃, and the calcination processing time is 1～8h.
4. a preparation method who mixes the rare earth oxide luminescent material of In is characterized in that, comprises the steps:
Press chemical formula Ln
1-xRe
xA
1-zIn
zO
3In the stoichiometric ratio of each element, preparation contains the ionic mixing solutions of Ln, Re, A and In; Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45;
According to the total mole number of metals ion in the said mixing solutions, in above-mentioned mixing solutions, add the aqueous solution that contains precipitation agent, after mixing, deposition, washing, drying treatment, get solid mixture;
After said solid mixture carried out pre-burning processing and calcination processing, cooling, grind, obtain the rare earth oxide luminescent material of the said In of mixing.
5. the preparation method who mixes the rare earth oxide luminescent material of In as claimed in claim 4 is characterized in that, said precipitation agent is at least a in oxalic acid, volatile salt and the bicarbonate of ammonia;
Said pre-burning treatment temp is 500～1000 ℃, and the said pre-burning treatment time is 2～10h; Said calcination processing temperature is 1000～1500 ℃, and the said calcination processing time is 1～8h.
6. a preparation method who mixes the rare earth oxide luminescent material of In is characterized in that, comprises the steps:
Press chemical formula Ln
1-xRe
xA
1-zIn
zO
3In the stoichiometric ratio of each element, preparation contains the ionic mixing solutions of Ln, Re, A and In; Wherein, Ln is at least a among La, Y, Sc, Lu and the Gd; Re is at least a among Tm, Tb, Eu, Sm, Dy and the Ce; A is at least a among Al and the Ga; The span of said x, z is: 0.001≤x≤0.2,0＜z≤0.45;
In above-mentioned mixing solutions, add complexing agent and stablizer successively, obtain precursor sol after the water bath processing;
With grinding to form powder after the above-mentioned precursor sol drying;
After above-mentioned powder carried out pre-burning and handle, carry out calcination processing again, cooling is then ground, and obtains the rare earth oxide luminescent material of the said In of mixing.
7. the preparation method who mixes the rare earth oxide luminescent material of In as claimed in claim 6; It is characterized in that; In the step of said preparation precursor sol, said complexing agent is a Hydrocerol A, and the total mole number ratio of said complexing agent mole number and metals ion is 1: 1～1: 4;
It is 0.01～0.10g/mL that the addition of said stablizer makes its concentration in said precursor colloidal sol; Said stablizer is the polyoxyethylene glycol of molecular weight 10000.
8. the preparation method who mixes the rare earth oxide luminescent material of In as claimed in claim 6 is characterized in that, in the step of said preparation precursor sol, the temperature of said water bath processing is 75～95 ℃, and the time of said water bath processing is 2～8h.
9. the preparation method who mixes the rare earth oxide luminescent material of In as claimed in claim 6 is characterized in that said pre-burning treatment temp is 500～1000 ℃, and the said pre-burning treatment time is 2～10h; Said calcination processing temperature is 1000～1500 ℃, and the said calcination processing time is 1～8h.
10. like claim 6 or the 9 described preparing methods that mix the rare earth oxide luminescent material of In, it is characterized in that when containing Tb in the rare earth oxide luminescent material of the said In of mixing, said calcination processing is carried out in reducing atmosphere; Said reducing atmosphere is nitrogen and hydrogen mixed gas atmosphere, or pure hydrogen atmosphere, or carbon monoxide atmosphere.
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