CN1162509C - Prepn of luminous oxide film - Google Patents
Prepn of luminous oxide film Download PDFInfo
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- CN1162509C CN1162509C CNB021164509A CN02116450A CN1162509C CN 1162509 C CN1162509 C CN 1162509C CN B021164509 A CNB021164509 A CN B021164509A CN 02116450 A CN02116450 A CN 02116450A CN 1162509 C CN1162509 C CN 1162509C
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- film
- citric acid
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- hours
- emitting film
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Abstract
The present invention belongs to a preparation method of a luminous film. The chemical expression of the luminous film is R2(1-x)O3: A2x, wherein x is greater than 0 and is smaller than or equal to 0.05; RE is Y, La, Gd, Lu, Ga, In; a is Eu, Sm, Tm, Tb, Dy, Er. Metallic oxides are selected as main raw materials; polyethyleneglycol is selected as a surface active agent for preventing metallic ions from agglomerating; citric acid is selected as a complexation agent of metallic ions. Simultaneously, the viscosity of a filming solution is regulated according to the quantity of the citric acid and the polyethyleneglycol to make the thickness of the film controlled within an ideal range. A quartz plate or a single crystal silicon plate is selected as a substrate; the film is plated by an impregnating method. The obtained film is dried for 2 hours, and then is put in a programmed temperature rise furnace to be heated and sintered to 900 to 1000 DEG C. the particle size of the prepared luminous film is homogenized to 10 to 50 nm; the prepared luminous film is compact and has no dehiscence. The technology has the advantages of simple device, easy acquirement of the raw materials, low cost and no toxicity.
Description
Technical field: the preparation method who the invention belongs to light-emitting film.
Background technology: light-emitting film is a kind of important functional material, plays crucial effect in cathode tube, electroluminescent and field emission display.Compare with traditional display screen of making by luminescent powder, light-emitting film contrast gradient, thermal conduction, homogeneity, and aspect such as tack of substrate, outgas speed all demonstrate stronger superiority.Therefore the good light-emitting film of processability has very significant meaning.The preparation method of existing light-emitting film comprises induced with laser deposition (PLD) and metal organic chemical vapor deposition (MOCVD) etc.All there is relatively limitation such as costliness of technology more complicated, equipment in these methods except its distinct advantages.For example, people such as the S.L.Jones of the U.S. are at Appl.Phys.Lett., and 1997, Vol.71, No.3 delivers one piece and relevantly adopts pulse laser induced method to deposit Y on monocrystalline silicon piece on the P404
2O
3: the article of Eu light-emitting film, except that used KrF laser equipment relatively the costliness, technology is more complicated also in this article, and its process is earlier commercially available Y
2O
3: the Ag of Eu luminescent powder and 10wt%
2O mixes and is pressed into diameter is 1 inch thin slice, and thin slice is made target at 1400 ℃ of sintering 48h, and with the laser bombardment target of the 248nm film forming on the monocrystalline silicon piece that is deposited on 800 ℃ then that makes it to volatilize, film also needs at last at 1300 ℃ of different times of annealing.Mainly uses in the MOCVD film-forming process to cost an arm and a leg and deleterious organometallics is starting raw material, and its equipment costliness more.Human mocvd methods such as G.A.Hirata have prepared (Y
0.92Eu
0.08)
2O
3Light-emitting film is auspiciously seen J.Appl.Phys., 2001, Vol.90, No.8, P3919.
Summary of the invention: an object of the present invention is to provide a kind of light-emitting film; Another purpose provides a kind of method for preparing light-emitting film.It is main raw material that the present invention selects cheap and nontoxic metal oxide, selecting polyoxyethylene glycol is the tensio-active agent that prevents the reunion of metal ion, selecting citric acid is the complexing agent of metal ion, the viscosity of utilizing the amount of citric acid, polyoxyethylene glycol to regulate coated solution simultaneously, the gauge control that makes film is within the ideal scope.
Its chemical expression of light-emitting film of the present invention's preparation is:
R
2(1-x)O
3：A
2x
0＜x≤0.05 wherein; R=Y, La, Gd, Lu, Ga, In; A=Eu, Sm, Tm, Tb, Dy, Er.
It is 99.99% Eu that raw material used in the present invention is selected purity for use
2O
3, Sm
2O
3, Tb
4O
7, Dy
2O
3, Er
2O
3, Y
2O
3, Tm
2O
3, La
2O
3, Gd
2O
3, Lu
2O
3, Ga
2O
3, In
2O
3, solvent is water and ethanol, HNO
3Or HCl is used for the dissolved oxygen raw material, and complexing agent is analytically pure citric acid, and tensio-active agent is a polyoxyethylene glycol, molecular weight=10000.
Preparation process is under the condition of room temperature or heating, by stoichiometry will above-mentioned one or both oxide raw materials with nitric acid or dissolving with hydrochloric acid, adding contains the water and the alcoholic acid mixing solutions H of citric acid
2O/C
2H
5The OH volume ratio is 1: 9, and keeping the mol ratio of citric acid and metallic cation is 2: 1, adds polyoxyethylene glycol 2-6g again, and selecting quartz plate or monocrystalline silicon piece is substrate, adopts the method plated film of dipping; The film that obtains was put in the 100-120 ℃ of baking oven dry 2 hours, be put in the temperature programming stove heat-up rate with 60-70 ℃/h then and be warming up to 500 ℃ and kept 2-3 hour, heat-up rate with 100-300 ℃/h sinters to temperature 900-1000 ℃ again, or finally at volume ratio 5H
2%+95N
2Formed light-emitting film in 4 hours in 900-1000 ℃ of sintering under the reducing atmosphere of %.
Even, the fine and close nothing cracking in the light-emitting film surface of the present invention's preparation, film size of particles is evenly at 10-50nm, and controllable thickness is at 100-300nm.Processing unit is simple, raw material is easy to get, cost is low and nontoxic.
Embodiment is as follows:
Embodiment 1:Y
1.96O
3: Eu
0.04Light-emitting film
Under the room temperature, with 0.98mmol Y
2O
3Oxide compound Eu with the dopant ion of 0.02mmol
2O
3With the dense HNO of 2ml
3With 2ml deionized water heating for dissolving, after the cooling two kinds of solution are mixed, adding the 30ml volume ratio is the mixing solutions of 9: 1 second alcohol and waters, under stirring condition, add 1.68g citric acid and 2g polyoxyethylene glycol, after stirring 1h, use the pickling process plated film on the silica glass substrate that cleans up, pull rate is 0.2cm/s.Film at 100 ℃ of dry 2h, is put in the temperature programming stove heat-up rate with 60 ℃/h then and is heated to 500 ℃ and kept 2 hours, sinter to 900 ℃ and keep 4h with the heat-up rate of 100 ℃/h again.Even, the fine and close nothing cracking in gained transparent film surface, monofilm thickness is 100nm, average particle size 10nm.Under the UV-irradiation, film glows.
Embodiment 2:Gd
1.98O
3: Dy
0.02Light-emitting film
Under the room temperature, with 0.99mmolGd
2O
3With 0.01mmol Dy
2O
3The mixture dense HNO of 2ml
3With 2ml deionized water heating for dissolving, adding the 30ml volume ratio is the mixing solutions of 9: 1 second alcohol and waters, add 1.68g citric acid and 3g polyoxyethylene glycol stirring 1h under stirring condition after, use the pickling process plated film on the monocrystalline silicon piece substrate that cleans up, pull rate is 0.2cm/s.Film at 110 ℃ of dry 2h, is put in the temperature programming stove heat-up rate with 70 ℃/h then and is heated to 500 ℃ and kept 3 hours, sinter to 950 ℃ and keep 4h with the heat-up rate of 200 ℃/h again.The surperficial even compact of film does not have cracking, and monofilm thickness is 150nm, average particle size 15nm.Under the UV-irradiation, film jaundice light.
Embodiment 3:Lu
1.98O
3: Sm
0.02Light-emitting film
Under the room temperature, with 0.99mmolLu
2O
3With 0.01mmol Sm
2O
3The mixture dense HNO of 2ml
3With 2ml deionized water heating for dissolving, adding the 30ml volume ratio is the mixing solutions of 9: 1 second alcohol and waters, adds 1.68 citric acids, 4g polyoxyethylene glycol under stirring condition, behind the stirring 1h, use the pickling process plated film on the quartz plate substrate that cleans up, pull rate is 0.2cm/s.Film at 120 ℃ of dry 2h, is put in the temperature programming stove heat-up rate with 65 ℃/h then and is heated to 500 ℃ and kept 3 hours, sinter to 1000 ℃ and keep 4h with the heat-up rate of 300 ℃/h again.。The surperficial even compact of film does not have cracking, and monofilm thickness is 160nm, average particle size 20nm.Under the UV-irradiation, film sends out light orange red.
Embodiment 4:La
1.96O
3: Er
0.04Light-emitting film
Under the room temperature, with 0.98mmolLa
2O
3With 0.02mmol Er
2O
3Mixture 2mlHNO
3With 2ml deionized water heating for dissolving, it is the mixing solutions of 9: 1 second alcohol and waters that the cooling back adds the 30ml volume ratio, adds 1.68g citric acid, 5g polyoxyethylene glycol under stirring condition, and process is with embodiment 1.The surperficial even compact of film does not have cracking, and monofilm thickness is 200nm, average particle size 30nm.Under the UV-irradiation, the film green light.
Embodiment 5:Ga
1.98O
3: Tm
0.02Light-emitting film
Under the room temperature, with 0.99mmolGa
2O
3With 0.01mmol Tm
2O
3With dense HCl of 2ml and 2ml deionized water heating for dissolving, it is the mixing solutions of 9: 1 second alcohol and waters that the cooling back adds the 30ml volume ratio, adds 1.68g citric acid, 6g polyoxyethylene glycol under stirring condition, and process is with embodiment 2.The surperficial even compact of film does not have cracking, and monofilm thickness is 230nm, average particle size 50nm.Under the UV-irradiation, the film blue light-emitting.
Embodiment 6:In
1.90O
3: Tb
0.10Light-emitting film
Under the room temperature, with 0.95mmolIn
2O
3And 0.025mmolTb
4O
7With the dense HNO of 2ml
3With 2ml deionized water heating for dissolving, it is the mixing solutions of 9: 1 second alcohol and waters that the cooling back adds the 30ml volume ratio, adds 1.68g citric acid, 5g polyoxyethylene glycol under stirring condition, and process is with embodiment 4, finally at 5H
2%+95N
2Under % (volume ratio) reducing atmosphere in 1000 ℃ of sintering 4 hours.The surperficial even compact of film does not have cracking, and monofilm thickness is 200nm, average particle size 30nm.Under the UV-irradiation, the film green light.
Claims (2)
1. the preparation method of a light-emitting film, it is characterized in that selecting for use purity is 99.99% Eu
2O
3, Sm
2O
3, Dy
2O
3, Er
2O
3, Y
2O
3, Tm
2O
3, La
2O
3, Gd
2O
3, Lu
2O
3, Tb
4O
7, Ga
2O
3, In
2O
3One or both oxide compounds wherein are starting raw material; Solvent is water and ethanol; HNO
3Or HCl is used for the dissolved oxygen raw material; Complexing agent is analytically pure citric acid; Tensio-active agent is a polyoxyethylene glycol, molecular weight=10000; The chemical expression of prepared light-emitting film is: R2 (1-x) O3: A2x, wherein 0＜x≤0.05; R=Y, La, Gd, Lu, Ga or In; A=Eu, Sm, Tm, Tb, Dy or Er.
Preparation process: by stoichiometry with a kind of matrix oxide compound R2O3 and a kind of activator oxide compound A2O3 raw material with nitric acid or dissolving with hydrochloric acid, adding the water and the alcoholic acid mixing solutions H2O/C2H5OH volume ratio that contain citric acid is 1: 9, keeping the mol ratio of citric acid and metallic cation is 2: 1, add 2-6g polyoxyethylene glycol/mol R2O3 again, stirring mixes solution, selecting quartz plate or monocrystalline silicon piece is substrate, adopts the method plated film of dipping; The film that obtains was put in the 100-120 ℃ of baking oven dry 2 hours, be put in the temperature programming stove heat-up rate with 60-70 ℃/h then and be warming up to 500 ℃ and kept 3 hours, heat-up rate with 100-300 ℃/h sinters to temperature 900-1000 ℃ again, or finally forms light-emitting film in 4 hours in 900-1000 ℃ of sintering under the reducing atmosphere of volume ratio 5H2%+95N2%.
2. the preparation method of light-emitting film as claimed in claim 1 is characterized in that the thickness of film and the size of particle regulate by the amount that adds citric acid and polyoxyethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021164509A CN1162509C (en) | 2002-04-05 | 2002-04-05 | Prepn of luminous oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021164509A CN1162509C (en) | 2002-04-05 | 2002-04-05 | Prepn of luminous oxide film |
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| Publication Number | Publication Date |
|---|---|
| CN1374365A CN1374365A (en) | 2002-10-16 |
| CN1162509C true CN1162509C (en) | 2004-08-18 |
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ID=4744110
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021164509A Expired - Fee Related CN1162509C (en) | 2002-04-05 | 2002-04-05 | Prepn of luminous oxide film |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320566C (en) * | 2004-12-04 | 2007-06-06 | 西南师范大学 | Process for preparing adjustable viscosity magnetic liquid |
| CN102382644B (en) * | 2010-08-27 | 2013-08-07 | 海洋王照明科技股份有限公司 | Rare earth oxide luminescent material and preparation method thereof |
| CN105295913A (en) * | 2015-12-10 | 2016-02-03 | 济南大学 | Yellow monodispersible spherical rare earth oxide fluorescent powder and preparation method thereof |
| CN109852381A (en) * | 2019-01-23 | 2019-06-07 | 北京镓族科技有限公司 | A kind of gallium oxide film of Yb and Er codope and preparation method thereof |
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2002
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| Publication number | Publication date |
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