CN102382649B - 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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- 239000000463 material Substances 0.000 title claims abstract description 114
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 239000000126 substance Substances 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 13
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 12
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 10
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 10
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 10
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 10
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 10
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 39
- 238000001354 calcination Methods 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- -1 polyoxyethylene Polymers 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 230000005284 excitation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 80
- 238000000227 grinding Methods 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 14
- 229910017604 nitric acid Inorganic materials 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 230000001133 acceleration Effects 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 229910052593 corundum Inorganic materials 0.000 description 11
- 239000010431 corundum Substances 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000000975 co-precipitation Methods 0.000 description 7
- 238000003980 solgel method Methods 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000003836 solid-state method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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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 sulfide system and oxide system two classes.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 easily make moist and matrix unstable, under the long-term bombardment of electron beam, can decompose and produce as H
2the gases 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 rare-earth oxide luminescent material of mixing In that a kind of luminous efficiency is high.
Mix a rare-earth oxide luminescent material of In, chemical formula is: Ln
1-xre
xa
1-zin
zo
3; Wherein, Ln is at least one in La, Y, Sc, Lu and Gd; Re is at least one in Tm, Tb, Eu, Sm, Dy and Ce; A is at least one in Al and Ga; The span of described 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 by In, and the luminous efficiency under cathode-ray exciting is improved, and chemical stability is good simultaneously, has very strong application prospect.
In addition, be also necessary to provide the preparation method of the rare-earth oxide luminescent material of at least one above-mentioned In of mixing.
A preparation method for 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 respectively the raw material of Ln, Re, A and In, grind to form mixed powder; Wherein, Ln is at least one in La, Y, Sc, Lu and Gd; Re is at least one in Tm, Tb, Eu, Sm, Dy and Ce; A is at least one in Al and Ga; The span of described x, z is: 0.001≤x≤0.2,0 < z≤0.45;
Described mixed powder is after preheating and calcination processing, cooling, grind, described in obtaining, mix the rare-earth oxide luminescent material of In.
Preferably, described in grind to form the step of mixed powder, also comprise in the mixed powder grinding to form to the raw material of Ln, Re, A and In and add fusing assistant; Described fusing assistant is at least one in boric acid and barium fluoride; The raw material of described Ln, Re, A and In is at least one in corresponding oxide compound, oxyhydroxide, carbonate, oxalate and nitrate; Described preheating temperature is 500～1000 ℃, and the preheating time is 2～10h; Described calcination processing temperature is 1000～1500 ℃, and the calcination processing time is 1～8h.
Preparation method's technique 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, the mixing solutions of the ion that preparation contains Ln, Re, A and In; Wherein, Ln is at least one in La, Y, Sc, Lu and Gd; Re is at least one in Tm, Tb, Eu, Sm, Dy and Ce; A is at least one in Al and Ga; The span of described x, z is: 0.001≤x≤0.2,0 < z≤0.45;
According to the total mole number of metal ion in described mixing solutions, in above-mentioned mixing solutions, add the aqueous solution containing precipitation agent, after mixing, precipitation, washing, drying treatment, obtain solid mixture;
Described solid mixture is carried out after preheating and calcination processing, cooling, grind, described in obtaining, mix the rare-earth oxide luminescent material of In.
Preferably, described precipitation agent is at least one in oxalic acid, volatile salt and bicarbonate of ammonia; Described preheating temperature is 500～1000 ℃, and the described preheating time is 2～10h; Described calcination processing temperature is 1000～1500 ℃, and the described calcination processing time is 1～8h.
Preferably, the mixed solution that contains the ion of Ln, Re, A and In described in is the soluble salt solution such as corresponding nitrate, hydrochloride; The mode that can adopt the low-carbon alcohol such as water or ethanol directly to dissolve soluble salt during concrete preparation, also can adopt relative acid to dissolve the mode of corresponding oxide compound, oxyhydroxide, carbonate.
Preparation method's technique 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, the mixing solutions of the ion that preparation contains Ln, Re, A and In; Wherein, Ln is at least one in La, Y, Sc, Lu and Gd; Re is at least one in Tm, Tb, Eu, Sm, Dy and Ce; A is at least one in Al and Ga; The span of described x, z is: 0.001≤x≤0.2,0 < z≤0.45;
In above-mentioned mixing solutions, add successively complexing agent and stablizer, after water bath processing, obtain precursor sol;
After above-mentioned precursor sol is dry, grind to form powder;
Above-mentioned powder is carried out after preheating, then carry out calcination processing, then cooling, grind, described in obtaining, mix the rare-earth oxide luminescent material of In.
Preferably, in the step of described preparation precursor sol, described complexing agent is citric acid, and the total mole number ratio of described complexing agent mole number and metal ion is 1: 1～1: 4; It is 0.01～0.10g/mL that the addition of described stablizer makes its concentration in described precursor colloidal sol; Described stablizer is the polyoxyethylene glycol of molecular weight 10000.
Preferably, in the step of described preparation precursor sol, the temperature of described water bath processing is 75～95 ℃, and the time of described water bath processing is 2～8h.
Preferably, citric acid can adopt aqueous citric acid solution or citric acid alcoholic solution, as the form of ethanolic soln etc. adds, also can adopt the form of the solids such as citric acid crystal, monohydrate potassium to add.
Preferably, the mixed solution that contains the ion of Ln, Re, A and In described in is the soluble salt solution such as corresponding nitrate, hydrochloride; The mode that can adopt the low-carbon alcohol such as water or ethanol directly to dissolve soluble salt during concrete preparation, also can adopt relative acid to dissolve the mode of corresponding oxide compound, oxyhydroxide, carbonate.
Preferably, described preheating temperature is 500～1000 ℃, and the described preheating time is 2～10h; Described calcination processing temperature is 1000～1500 ℃, and the described calcination processing time is 1～8h.
Preferably, described in mix while containing Tb in the rare-earth oxide luminescent material of In, described calcination processing is carried out in reducing atmosphere; Described reducing atmosphere is nitrogen and hydrogen mixed gas atmosphere, or pure hydrogen atmosphere, or carbon monoxide atmosphere.
Preparation method's technique 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.
[accompanying drawing explanation]
Fig. 1 is the schema that the rare-earth oxide luminescent material of mixing In of an embodiment adopts high temperature solid-state method to prepare;
Fig. 2 is the schema that the rare-earth oxide luminescent material of mixing In of an embodiment adopts coprecipitation method to prepare;
Fig. 3 is the schema that the rare-earth oxide luminescent material of mixing In of an embodiment adopts sol-gel method to prepare;
Fig. 4 is the luminescent spectrum comparison diagram under the rare-earth oxide luminescent material of mixing In of embodiment 2 preparation and cathode-ray exciting that traditional luminescent material is 3kV at acceleration voltage;
Fig. 5 is mixing In and not mixing the luminescent spectrum comparison diagram under the cathode-ray exciting that the rare-earth oxide luminescent material of In is 1.5kV at acceleration voltage of embodiment 5 preparation;
Fig. 6 is the luminescent spectrum comparison diagram under the rare-earth oxide luminescent material of mixing In of embodiment 11 preparation and cathode-ray exciting that traditional luminescent material is 3kV at acceleration voltage;
Fig. 7 is the luminescent spectrum comparison diagram under the rare-earth oxide luminescent material of mixing In of embodiment 11 preparation and cathode-ray exciting that traditional luminescent material is 5kV at acceleration voltage.
[embodiment]
Below in conjunction with drawings and Examples, illustrate rare-earth oxide luminescent material and the three kinds of preparation methods that mix the rare-earth oxide luminescent material of In that mix In.
The rare-earth oxide luminescent material of mixing In of one embodiment, chemical formula is: Ln
1-xre
xa
1-zin
zo
3; Wherein, Ln is at least one in La, Y, Sc, Lu and Gd; Re is at least one in Tm, Tb, Eu, Sm, Dy and Ce; A is at least one in Al and Ga; The span of described 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 by In, and the luminous efficiency under cathode-ray exciting is improved, and chemical stability 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 one in La, Y, Sc, Lu and Gd; Re is at least one in Tm, Tb, Eu, Sm, Dy and Ce; A is at least one in Al and Ga; The span of described x, z is: 0.001≤x≤0.2,0 < z≤0.45.
The raw material of Ln, Re, A and In is at least one in corresponding oxide compound, oxyhydroxide, carbonate, oxalate and nitrate.
S120, said mixture thermal treatment obtain mixing the rare-earth oxide luminescent material of In
Said mixture is added after fusing assistant, first pre-burning 2～10h at 500～1000 ℃, cooling rear grinding, then calcine 1～8h at 1000～1500 ℃, after again grinding, described in obtaining, mix the rare-earth oxide luminescent material of In.
Fusing assistant is at least one in boric acid and 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 is mainly in order to prepare powdery luminescent material; When not being that while specifically needing powdery luminescent material, grinding operation also can omit.
Preparation method's technique 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; The rare-earth oxide luminescent material luminous efficiency of mixing In for preparing is high, good stability, epigranular.
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:
The mixed solution of the ion that S210, preparation contain Ln, Re, A and In
Press chemical formula Ln
1-xre
xa
1-zin
zo
3in the stoichiometric ratio of each element, the mixed solution of the ion that preparation contains Ln, Re, A and In; Wherein, Ln is at least one in La, Y, Sc, Lu and Gd; Re is at least one in Tm, Tb, Eu, Sm, Dy and Ce; A is at least one in Al and Ga; The span of described x, z is: 0.001≤x≤0.2,0 < z≤0.45.
The mixed solution of the ion of the described Ln of containing, Re, A and In is the soluble salt solution such as corresponding nitrate, hydrochloride; The mode that can adopt the low-carbon alcohol such as water or ethanol directly to dissolve soluble salt during concrete preparation, also can adopt relative acid to dissolve the mode of corresponding oxide compound, oxyhydroxide, carbonate.
S220, above-mentioned mixed solution add precipitation agent to obtain solid mixture
Above-mentioned precipitant solution is joined in the mixed solution of ion of the above-mentioned Ln of containing, Re, A and In, after mixing, precipitation, washing, drying treatment, obtain solid mixture; Described precipitation agent is at least one in oxalic acid, volatile salt and bicarbonate of ammonia.
The concentration of above-mentioned precipitant solution and the addition of precipitant solution, determine according to the total amount of substance of metal ion, satisfying the demands, is as the criterion.
S230, said mixture thermal treatment obtain mixing the rare-earth oxide luminescent material of In
By the first pre-burning 2～10h at 500～1000 ℃ of said mixture, cooling rear grinding, then calcine 1～8h at 1000～1500 ℃, after again grinding, described in obtaining, mix the rare-earth oxide luminescent material of In.
Grinding operation is mainly in order to prepare powdery luminescent material; When not being that while specifically needing powdery luminescent material, grinding operation also can omit.
Preparation method's technique 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; The rare-earth oxide luminescent material luminous efficiency of mixing In for preparing is high, good stability, epigranular.
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:
The mixed solution of the ion that S310, preparation contain Ln, Re, A and In
Press chemical formula Ln
1-xre
xa
1-zin
zo
3in the stoichiometric ratio of each element, the mixed solution of the ion that preparation contains Ln, Re, A and In; Wherein, Ln is at least one in La, Y, Sc, Lu and Gd; Re is at least one in Tm, Tb, Eu, Sm, Dy and Ce; A is at least one in Al and Ga; The span of described x, z is: 0.001≤x≤0.2,0 < z≤0.45;
The mixed solution of the ion of the described Ln of containing, Re, A and In is the soluble salt solution such as corresponding nitrate, hydrochloride; The mode that can adopt the low-carbon alcohol such as water or ethanol directly to dissolve soluble salt during concrete preparation, also can adopt relative acid to dissolve the mode of corresponding oxide compound, oxyhydroxide, carbonate.
S320, prepare the precursor sol of above-mentioned mixed solution
Total mole number ratio by citric acid mole number and metal ion is 1: 1～1: 4, complexing agent citric acid is joined in the mixed solution of ion of the above-mentioned Ln of containing, Re, A and In, add stablizer polyoxyethylene glycol, 75～95 ℃ of water-bath 2～8h after mixing, obtain precursor sol again; Wherein, in described precursor sol, Polyethylene glycol is 0.01～0.10g/mL.
Citric acid can adopt aqueous citric acid solution or citric acid alcoholic solution, as the forms such as ethanolic soln add, also can adopt the form of the solids such as citric acid crystal, monohydrate potassium to add.
S330, the dry postheat treatment of precursor sol obtain mixing the rare-earth oxide luminescent material of In
After above-mentioned precursor sol is dry, grind to form powder, first pre-burning 2～10h at 500～1000 ℃, cooling rear grinding, then calcine 1～8h at 1000～1500 ℃, after again grinding, described in obtaining, mix the rare-earth oxide luminescent material of In.
In described calcining step, while containing Tb in the rare-earth oxide luminescent material of the described In of mixing, calcining adopts reducing atmosphere; In the described rare-earth oxide luminescent material of mixing In, during containing Tb, calcining adopts air atmosphere; Described reducing atmosphere is nitrogen and hydrogen mixed gas atmosphere, or pure hydrogen atmosphere, or carbon monoxide atmosphere.
Grinding operation is mainly in order to prepare powdery luminescent material; When not being that while specifically needing powdery luminescent material, grinding operation also can omit.
Preparation method's technique 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 is prepared La
0.99eu
0.1al
0.9in
0.1o
3luminescent material
Take 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%) is placed in agate mortar, grinds evenly.Mixture is put into corundum crucible pre-burning 2h at 500 ℃, be then cooled to room temperature, take out again and fully grind.Finally, it,, in air atmosphere, is calcined to 1h at 1500 ℃, cooling, take out after grinding and obtain powder shaped luminescent material.
Embodiment 2:
High temperature solid-state method is prepared La
0.99tm
0.01al
0.95in
0.05o
3luminescent material
Take 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%) is placed in agate mortar, grinds evenly.Mixture is put into corundum crucible pre-burning 2h at 700 ℃, be then cooled to room temperature, take out again and fully grind.Finally, it,, in air atmosphere, is calcined to 3h at 1400 ℃, cooling, take out after grinding and obtain powder shaped luminescent material.In order to contrast, similarity condition is prepared 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 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 is traditional luminescent material La
0.99tm
0.01alO
3luminescent spectrum.
By Fig. 4, can be drawn, curve 1 is with respect to curve 2, and under the cathode-ray exciting that is 3kV at acceleration voltage, the blue peak luminous intensity of 450～470nm wave band has improved approximately 60%.
Embodiment 3:
High temperature solid-state method is prepared La
0.8dy
0.2al
0.55in
0.45o
3luminescent material
Take 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%) is placed in agate mortar, grinds evenly.Mixture is put into corundum crucible pre-burning 4h at 600 ℃, be then cooled to room temperature, take out again and fully grind.Finally, it,, in air atmosphere, is calcined to 8h at 1000 ℃, cooling, take out after grinding and obtain powder shaped luminescent material.
Embodiment 4:
Coprecipitation method is prepared La
0.95tb
0.05al
0.995in
0.005o
3luminescent material
Take 40.7261g La
2o
3add nitric acid to be configured to the La (NO of 250ml 1mol/L
3)
3solution, take 93.7825g Al (NO
3)
39H
2o adds the Al (NO that water is configured to 250ml 1mol/L
3)
3solution, take 34.7043g In
2o
3add the In (NO that nitric acid is configured to 250ml 1mol/L
3)
3solution, take 4.6731g Tb
4o
7add the Tb (NO that nitric acid is configured to 250ml 0.1mol/L
3)
3solution.Accurately take 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 is placed in beaker, obtains solution A.Total amount of substance according to metal ion, takes 3.9701g H
2c
2o
42H
2o (excessive 5%), soluble in water, obtain solution B.Under magnetic agitation, B solution is added drop-wise in A, fully reaction, precipitation, filters, washs, is dried, and obtains mixture.Mixture is put into corundum crucible pre-burning 4h at 600 ℃, be then cooled to room temperature, take out again and fully grind.Finally, by it in carbon monoxide reducing atmosphere, at 1350 ℃, calcining 2h, cooling, take out after grinding and obtain powder shaped luminescent material.
Embodiment 5:
Coprecipitation method is prepared La
0.98dy
0.02al
0.99in
0.01o
3luminescent material
Take 40.7261g La
2o
3add nitric acid to be configured to the La (NO of 250ml 1mol/L
3)
3solution, take 93.7825g Al (NO
3)
39H
2o adds the Al (NO that water is configured to 250ml 1mol/L
3)
3solution, take 34.7043g In
2o
3add the In (NO that nitric acid is configured to 250ml 1mol/L
3)
3solution, take 4.6624g Dy
2o
3add the Dy (NO that nitric acid is configured to 250ml 0.1mol/L
3)
3solution.Accurately take 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 is placed in beaker, obtains solution A.Total amount of substance according to metal ion, takes 0.8648g (NH
4)
2cO
3and 0.7115NH
4hCO
3(all excessive 20%), soluble in water, obtain solution B.Under magnetic agitation, B solution is added drop-wise in A, fully reaction, precipitation, filters, washs, is dried, and obtains mixture.Mixture is put into corundum crucible pre-burning 4h at 500 ℃, be then cooled to room temperature, take out again and fully grind.Finally, by it in air atmosphere, at 1400 ℃, calcining 2h, cooling, take out after grinding and obtain powder shaped luminescent material.As a comparison, under similarity condition, prepare La
0.98dy
0.02alO
3luminescent material.
Fig. 5 is mixing In and not mixing the luminescent spectrum comparison diagram under the cathode-ray exciting that the rare-earth oxide luminescent material of In is 1.5kV at acceleration voltage of embodiment 5 preparation.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.
By Fig. 5, can be drawn, curve 3 is with respect to curve 4, and under the cathode-ray exciting that is 1.5kV at acceleration voltage, the luminous intensity at 482nm and 574nm place has improved respectively approximately 10% and 18%.
Embodiment 6:
Coprecipitation method is prepared Y
0.8dy
0.2ga
0.55in
0.45o
3luminescent material
Take 28.2262g Y
2o
3add nitric acid to be configured to the Y (NO of 250ml 1mol/L
3)
3solution, take 34.7043g In
2o
3add the In (NO that nitric acid is configured to 250ml 1mol/L
3)
3solution, accurately take the La (NO of 8ml1mol/L
3)
3in (the NO of solution, 4.5ml 1mol/L
3)
3solution is placed in beaker, then adds 1.4066gGa (NO
3)
3, 0.9130g Dy (NO
3)
36H
2o, obtains solution A after dissolving.Total amount of substance according to metal ion, takes 1.5854g (NH
4)
2cO
3(excessive 10%), soluble in water, obtain solution B.Under magnetic agitation, B solution is added drop-wise in A, fully reaction, precipitation, filters, washs, is dried, and obtains mixture.Mixture is put into corundum crucible pre-burning 4h at 700 ℃, be then cooled to room temperature, take out again and fully grind.Finally, by it in air atmosphere, at 1400 ℃, calcining 2h, cooling, take out after grinding and obtain powder shaped luminescent material.
Embodiment 7:
Coprecipitation method is prepared Lu
0.95sc
0.03ce
0.02al
0.95in
0.05o
3luminescent material
Take 47.7415g Lu
2o
3add nitric acid to be configured to the Lu (NO of 250ml 1mol/L
3)
3solution, take 0.6896g Sc
2o
3add nitric acid to be configured to the Sc (NO of 100ml 0.1mol/L
3)
3solution, take 19.5009gAl (OH)
3add the Al (NO that nitric acid is configured to 250ml 1mol/L
3)
3solution, take 75.2082g In (NO
3)
3add the In (NO that water is configured to 250ml 1mol/L
3)
3solution, take 1.7211g CeO
2add the Ce (NO that nitric acid and hydrogen peroxide are configured to 100ml 0.1mol/L
3)
3solution.Take 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 is placed in beaker, obtains solution A.Total amount of substance according to metal ion, takes 1.4050gNH
4hCO
3(excessive 20%), soluble in water, obtain solution B.Under magnetic agitation, A solution is added drop-wise in B, fully reaction, precipitation, filters, washs, is dried, and obtains mixture.Mixture is put into corundum crucible pre-burning 2h at 1000 ℃, be then cooled to room temperature, take out again and fully grind.Finally, by its gas mixture reducing atmosphere at nitrogen and hydrogen (nitrogen and hydrogen volume ratio are 95: 5 or 90: 10), at 1300 ℃, calcining 4h, cooling, take out after grinding and obtain powder shaped luminescent material.
Embodiment 8:
Sol-gel method is prepared La
0.999sm
0.001al
0.7ga
0.2in
0.1o
3
According to above embodiment, obtained certain density nitrate solution.Equally, take 1.7436g Sm
2o
3add nitric acid to be 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 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 is placed in beaker, then adds 5ml water and 20ml ethanolic soln; After 4.2028g monohydrate potassium is dissolved in 20ml ethanol and the 10ml aqueous solution, is joined in above-mentioned solution, then added 7.509g polyoxyethylene glycol; Wherein, citric acid is 1: 1 with the mol ratio of total metal ion, and the concentration of polyoxyethylene glycol (PEG, molecular weight is 10000) is 0.10g/ml.After dissolving mixes, again in 75 ℃ of water-baths, stir 8h, obtain uniform precursor sol.By colloidal sol dry 24h in the air dry oven of 80 ℃, solvent flashing obtains xerogel.After being ground, xerogel obtains mixture.Mixture is put into corundum crucible pre-burning 10h at 500 ℃, be then cooled to room temperature, take out again and fully grind.Finally, by it in air atmosphere, at 1000 ℃, calcining 8h, cooling, take out after grinding and obtain powder shaped luminescent material.
Embodiment 9:
Sol-gel method is prepared La
0.99tm
0.01al
0.9in
0.1o
3
According to above embodiment, obtained certain density nitrate solution.Equally, take 1.9293g Tm
2o
3add nitric acid to be 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 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 is placed in beaker, then adds 5ml water and 10ml ethanolic soln.After 8.4056g monohydrate potassium is dissolved in 20ml ethanol and the 5ml aqueous solution, is joined in above-mentioned solution, then added 3.045g polyoxyethylene glycol; Wherein, citric acid is 2: 1 with the mol ratio of total metal ion, and the concentration of polyoxyethylene glycol (PEG, molecular weight is 10000) is 0.05g/ml.After dissolving mixes, again in 95 ℃ of water-baths, stir 2h, obtain uniform precursor sol.By colloidal sol dry 4h in the air dry oven of 150 ℃, solvent flashing obtains xerogel.After xerogel is ground, obtain mixture, mixture is put into corundum crucible pre-burning 4h at 600 ℃, be then cooled to room temperature, take out again and fully grind.Finally, by it in air atmosphere, at 1300 ℃, calcining 3h, cooling, take out after grinding and obtain powder shaped luminescent material.
Embodiment 10:
Sol-gel method is prepared Gd
0.99tm
0.01al
0.9in
0.1o
3
According to above embodiment, obtained certain density nitrate solution.
According to chemical formula La
0.95tm
0.05al
0.9in
0.1o
3in stoichiometric ratio, accurately take 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 is placed in beaker, then adds 5ml water and 20ml ethanolic soln.After 16.8112g monohydrate potassium is dissolved in 30ml ethanol and the 5ml aqueous solution, is joined in above-mentioned solution, then added 0.7g polyoxyethylene glycol; Wherein, citric acid is 2: 1 with the mol ratio of total metal ion, and the concentration of polyoxyethylene glycol (PEG, molecular weight is 10000) is 0.01g/ml.After dissolving mixes, again in 85 ℃ of water-baths, stir 5h, obtain uniform precursor sol.By colloidal sol dry 8h in the air dry oven of 120 ℃, solvent flashing obtains xerogel.After xerogel is ground, obtain mixture, mixture is put into corundum crucible pre-burning 4h at 600 ℃, be then cooled to room temperature, take out again and fully grind.Finally, by it in air atmosphere, at 1250 ℃, calcining 3h, cooling, take out after grinding and obtain powder shaped luminescent material.
Embodiment 11:
Sol-gel method is prepared La
0.99tm
0.01al
0.9in
0.1o
3
According to above embodiment, obtained certain density nitrate solution.
According to chemical formula La
0.99tm
0.01al
0.9in
0.1o
3in stoichiometric ratio, accurately take 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 is placed in beaker, then adds 5ml water and 20ml ethanolic soln; After 4.2028g monohydrate potassium is dissolved in 20ml ethanol and the 10ml aqueous solution, is joined in above-mentioned solution, then added 2.0021g polyoxyethylene glycol; Wherein, citric acid is 2: 1 with the mol ratio of total metal ion, and the concentration of polyoxyethylene glycol (PEG, molecular weight is 10000) is 0.03g/ml.After dissolving mixes, again in 80 ℃ of water-baths, stir 5h, obtain uniform precursor sol.By colloidal sol dry 8h in the air dry oven of 100 ℃, solvent flashing obtains xerogel.After xerogel is ground, obtain mixture, mixture is put into corundum crucible pre-burning 4h at 800 ℃, be then cooled to room temperature, take out again and fully grind.Finally, by it in air atmosphere, at 1400 ℃, calcining 2h, cooling, take out after grinding and obtain powder shaped luminescent material.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 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 is traditional luminescent material ZnS:Ag, the luminescent spectrum of Cl, curve c is traditional luminescent material LaGaO
3: Tm
3+luminescent spectrum, curve d is traditional luminescent material La
0.99tm
0.01alO
3luminescent spectrum.
By Fig. 6, can be drawn, under the cathode-ray exciting that is 3kV at acceleration voltage, curve a has improved respectively approximately 80%, 162% and 426% with respect to curve b, c and d 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 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 is traditional luminescent material ZnS:Ag, the luminescent spectrum of Cl, curve 3 is traditional luminescent material La
0.99tm
0.01alO
3luminescent spectrum.
By Fig. 7, can be drawn, under the cathode-ray exciting that is 5kV at acceleration voltage, curve 1 has improved respectively approximately 339% and 433% with respect to curve 2 and 3455nm place luminous intensity.
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 (3)
1. 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, the mixing solutions of the ion that preparation contains Ln, Re, A and In; Wherein, Ln is at least one in La, Y, Sc, Lu and Gd; Re is at least one in Tm, Tb, Eu, Sm, Dy and Ce; A is at least one in Al and Ga; The span of described x, z is: 0.001≤x≤0.2,0 < z≤0.45;
In above-mentioned mixing solutions, add successively complexing agent and stablizer, after water bath processing, obtain precursor sol;
After above-mentioned precursor sol is dry, grind to form powder;
Above-mentioned powder is carried out after preheating, then carry out calcination processing, then cooling, grind, described in obtaining, mix the rare-earth oxide luminescent material of In;
Wherein, described preheating temperature is 500～1000 ℃, and the described preheating time is 2～10h; Described calcination processing temperature is 1000～1500 ℃, and the described calcination processing time is 1～8h;
The temperature of described water bath processing is 75～95 ℃, and the time of described water bath processing is 2～8h.
2. the preparation method who mixes the rare-earth oxide luminescent material of In as claimed in claim 1, it is characterized in that, in the step of described preparation precursor sol, described complexing agent is citric acid, and the total mole number of described complexing agent mole number and metal ion is than being 1:1～1:4;
It is 0.01～0.10g/mL that the addition of described stablizer makes its concentration in described precursor colloidal sol; Described stablizer is the polyoxyethylene glycol of molecular weight 10000.
3. the preparation method who mixes the rare-earth oxide luminescent material of In as claimed in claim 1, is characterized in that, described in mix while containing Tb in the rare-earth oxide luminescent material of In, described calcination processing is carried out in reducing atmosphere; Described reducing atmosphere is nitrogen and hydrogen mixed gas atmosphere, or pure hydrogen atmosphere, or carbon monoxide atmosphere.
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| Wancong Lv.White Up-Conversion Luminescence in Rare-Earth-Ion-Doped YAlO3 Nanocrystals.《Journal of Physical Chemistry C》.2008,第112卷第15071-15074页. |
| White Up-Conversion Luminescence in Rare-Earth-Ion-Doped YAlO3 Nanocrystals;Wancong Lv;《Journal of Physical Chemistry C》;20080830;第112卷;第15071-15074页 * |
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