CN1613960A - Rare-earth doped tantalic acid salt transparent luminous thin-film and preparation thereof - Google Patents
Rare-earth doped tantalic acid salt transparent luminous thin-film and preparation thereof Download PDFInfo
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- CN1613960A CN1613960A CN 200410066543 CN200410066543A CN1613960A CN 1613960 A CN1613960 A CN 1613960A CN 200410066543 CN200410066543 CN 200410066543 CN 200410066543 A CN200410066543 A CN 200410066543A CN 1613960 A CN1613960 A CN 1613960A
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Abstract
The invention relates to a transparent-shining film of rare-earth choleric acid salt and its production method. The chemical formula is (Ln1-xREx)TaO4(0<x<0.1); Ln=Gd,Lu; RE=Eu,Tb. The process is low cost, simple, and convenience. The film is of transparent, compact and good adhesion. It simplifies conditions of experiment and shortens preparation period. It can be used for the microradiology imaging screen of high space resolution factor and screen of high resolution factor cathode-ray, field emission, plasma display.
Description
Technical field
The present invention relates to a kind of light-emitting film and preparation method thereof, relate to a kind of rare-earth doped tantalic acid salt transparent luminous thin-film and preparation method thereof specifically.
Background technology
Light-emitting film is a kind of important functional material, compare with the display screen that traditional luminescent powder is made, light-emitting film contrast gradient, thermal conduction, homogeneity, and the aspects such as tack of substrate all demonstrate its superiority.In recent years along with the development of X ray micro-imaging technique, adopt the X ray light-emitting film of conventional fluorescent powder preparation, owing to be subjected to the influence of fluorescent powder grain scattering, the spatial resolution of X ray CCD generally can only reach tens microns magnitude, has restricted the further raising of X ray CCD spatial resolution.Use the transparent inorganic thin film scintillation material instead as X ray-visible light transfer medium, and be assigned in CCD and form digital imaging system, its spatial resolution can be brought up to several microns, the performance of aspects such as thermal conduction, homogeneity also can be improved significantly.Therefore under the prerequisite that visible light CCD becomes better and approaching perfection day by day, preparing well behaved radioluminescence film is the key of decision X ray CCD performance index.Rare earth tantalate is because of having the density height, X ray being absorbed characteristics such as strong, that chemical stability is good and the radioresistance injury reinforcing ability is strong, with they matrix as the X ray light-emitting film, suitably mix other rare earth ion as luminescence center, can prepare novel high resolution X-ray imaging screen.For example, people such as A.Koch are at Proc.of Inter.Conf.on Inorg.Scint.andTheir Appl., Sept.22-25, Shanghai, China, 1997, in the article of delivering on the P28, propose with the transparent inorganic thin film scintillation material as X ray-visible light transfer medium, and adopt rheotaxial growth to go out YAG:Ce film scintillation crystal, and successfully having obtained the CT image of spider tooth, spatial resolution reaches 1.59 μ m, also there are many difficulties in the cost height but the film scintillation crystal is not only grown on technology of preparing.People such as A.Garcia-Murillo are at Nucl.Instr.Meth.Phys.Res., A, and 2002, Vol.486, the article of delivering on the P181 is to be raw material with organic alkoxide, adopts colloidal sol-gel technique to prepare Gd
2O
3: Eu and Lu
2O
3: Eu polycrystal film, and studied the blinking characteristic of film, but in preparation process, need to use protective atmosphere, and technology is comparatively loaded down with trivial details during the preparation thick film, and the cycle is also long.People such as S.Y.Seo are at J.Appl.Phys., and 2002, Vol.92, No.9, the article of delivering on the P5248 is to adopt pulsed laser deposition to prepare Gd
2O
3: the Eu film, and the photoluminescence performance of film studied, but used filming equipment costliness, preparation technology is more complicated also.In recent years, many investigators have carried out rear-earth-doped vanadate and phosphoric acid salt (as M.Yu et al., Appl.Phys.A, 2003, Online First), tungstate is (as K.Tanaka et al., J.Appl.Phys., 2001, Vol.90, No.10, P5369), silicate is (as C.Mansuy et al., Chem.Mater., 2003, Vol.15, No.17, P3242) preparation and the performance study of light-emitting film such as grade.Although the existing report of the sol-gel processing of tantalate film preparation only is confined to the research of film piezo-electric, photoelectric property, also do not relate to the luminous field of film.
Summary of the invention
One of purpose of the present invention is to provide a kind of rare-earth doped tantalic acid salt transparent luminous thin-film;
Another object of the present invention is to provide the preparation method of this transparent luminous film.Goal of the invention of the present invention is achieved through the following technical solutions:
The chemical expression of the rare-earth doped tantalic acid salt transparent luminous thin-film that the present invention is prepared is:
(Ln
1-xRE
x)TaO
4
0＜x＜0.1 wherein; Ln=Gd, Lu; RE=Eu, Tb.
The raw materials used purity of the present invention is 99.5% Gd
2O
3, Lu
2O
3, Eu
2O
3, Tb
4O
7, TaCl
5, solvent is a dehydrated alcohol, HNO
3Be used for the dissolved oxygen raw material, tensio-active agent is a polyoxyethylene glycol, and molecular weight is 200.
With the ethanolic soln heating for dissolving of above-mentioned one or both oxide raw materials with nitric acid, TaCl
5Use dissolve with ethanol.Mix by stoichiometry, mixed solution is heated to 78～80 ℃ then, stirring and refluxing added Macrogol 200 after 3～4 hours, continued to reflux 1～2 hour, naturally cooled to room temperature at last, just obtained the required colloidal sol of plated film after ageing in 12～24 hours.Selecting the quartz or the opticglass of cleaning is substrate, adopts the method plated film of spin coating, and film thickness can be regulated by changing speed of rotation.The wet gel film that spin coating is good places IR bake to carry out the thermolysis pre-treatment 2～5 minutes rapidly, is 30～45 minutes with ultraviolet lamp to the time that xerogel thin film carries out the about ultraviolet reinforcement processing of ultraviolet reinforcement processing again.The film of handling through 3～5 times is sent in the program temperature controlling stove, be warming up to 100 ℃ with the speed of 3.5 ℃/min, then the speed with 2 ℃/min continues to be warmed up to 1200 ℃, and insulation 2 hours under this temperature, or finally at volume ratio 5H
2%+95N
2In 1200 ℃ of sintering 4 hours, promptly obtain light-emitting film after naturally cooling to room temperature under the reducing atmosphere of %
Selected light-emitting film substrate material has density height (GdTaO
4, LuTaO
4The density of material is respectively 8.84g/cm
3And 9.75g/cm
3), chemical stability is good, the radioresistance injury reinforcing ability is strong, it is luminous under X ray, negative ray, high energy particle equal excitation that this helps film.
It is raw material that the present invention selects inorganic salt for use; the inorganic salt that adopted are than the easier acquisition of organic alkoxide; more cheap and nontoxic; it is low that colloidal sol-gel technique of the present invention has a synthesis temperature; uniform doping; controllable structure; advantages such as equipment is cheap; therefore the required cost of film preparation is low; technology is simple; convenient; the prepared film homogeneous transparent; fine and close nothing cracking; good with the tack of substrate; and can be doping light emitting ionic or group and provide abundant; various coordination environment; be convenient to modulate the performance of film; pass through thermolysis pre-treatment in the film preparation to the wet gel film; and the ultraviolet reinforcement of xerogel thin film is handled; avoid protective atmosphere required in the film preparation process; thereby simplified experiment condition, accelerated the preparation cycle of thick film.As light-emitting film of new generation, the rare-earth doped tantalic acid salt transparent film has crucial application on high spatial resolution X ray micro-imaging screen, also can be applied on the display screen of high resolution cathode ray, field emission and plasma display simultaneously.
Embodiment:
How further specify the present invention below in conjunction with specific embodiment realizes:
Embodiment 1
Gd
0.9TaO
4: Eu
0.1Preparation
Under the room temperature, with the dense HNO of 2ml
3The dehydrated alcohol that adds 30ml is again the Gd of 0.9mmol
2O
3Dopant ion oxide compound Eu with 0.1mmol
2O
3Add in the ethanolic soln, heated and stirred under 79 ℃ of temperature makes oxide dissolution.TaCl with 20ml dissolve with ethanol 2mmol
5, and join in the above-mentioned settled solution, stirring and refluxing adds the 1ml Macrogol 200 after 3 hours, continue then to reflux 1 hour.Naturally cool to room temperature at last, after ageing in 8 hours, just obtain the required colloidal sol of plated film.Selecting the quartz or the opticglass of cleaning is substrate, adopts the method plated film of spin coating, and film thickness can be regulated by changing speed of rotation.The wet gel film that spin coating is good places IR bake to carry out the thermolysis pre-treatment 2～5 minutes rapidly, with ultraviolet lamp xerogel thin film is carried out ultraviolet reinforcement again and handles about 30 minutes.The film of handling through 3～5 times is sent in the program temperature controlling stove, be warming up to 100 ℃ with the speed of 3.5 ℃/min, then the speed with 2 ℃/min continues to be warmed up to 1200 ℃, and insulation 2 hours under this temperature, promptly obtains light-emitting film after naturally cooling to room temperature.Even, the fine and close nothing cracking of film surface, good with the tack of substrate, under UV-light or x-ray bombardment, film glows.
Embodiment 2
Gd
0.95TaO
4: Tb
0.05Preparation
Under the room temperature, with the dense HNO of 4ml
3The dehydrated alcohol that adds 30ml is again the Gd of 0.95mmol
2O
3Dopant ion oxide compound Tb with 0.025mmol
4O
7Add in the ethanolic soln, heated and stirred under 79 ℃ of temperature makes oxide dissolution.TaCl with 20ml dissolve with ethanol 2mmol
5, and join in the above-mentioned settled solution, stirring and refluxing adds the 1ml Macrogol 200 after 3 hours, continue then to reflux 1 hour.Naturally cool to room temperature at last, after ageing in 8 hours, just obtain the required colloidal sol of plated film.Selecting the quartz or the opticglass of cleaning is substrate, adopts the method plated film of spin coating, and film thickness can be regulated by changing speed of rotation.The wet gel film that spin coating is good places IR bake to carry out the thermolysis pre-treatment 2～5 minutes rapidly, with ultraviolet lamp xerogel thin film is carried out ultraviolet reinforcement again and handles about 30 minutes.The film of handling through 3～5 times is sent in the program temperature controlling stove, be warming up to 100 ℃ with the speed of 3.5 ℃/min, then the speed with 2 ℃/min continues to be warmed up to 1200 ℃, and at 5H
2%+95N
2Sintering is 4 hours under the reducing atmosphere of % (volume ratio), promptly obtains light-emitting film after naturally cooling to room temperature.Even, the fine and close nothing cracking of film surface, good with the tack of substrate, under UV-light or x-ray bombardment, the film green light.
Embodiment 3
Lu
0.9TaO
4: Eu
0.1Preparation
Under the room temperature, with the dense HNO of 2ml
3The dehydrated alcohol that adds 30ml is again the Lu of 0.9mmol
2O
3Dopant ion oxide compound Eu with 0.1mmol
2O
3Add in the ethanolic soln, heated and stirred under 79 ℃ of temperature makes oxide dissolution.TaCl with 20ml dissolve with ethanol 2mmol
5, and join in the above-mentioned settled solution, stirring and refluxing adds the 1ml Macrogol 200 after 3 hours, continue then to reflux 1 hour.Naturally cool to room temperature at last, after ageing in 8 hours, just obtain the required colloidal sol of plated film.Process is with embodiment 1.Even, the fine and close nothing cracking of film surface, good with the tack of substrate, under UV-light or x-ray bombardment, film glows.
Embodiment 4
Lu
0.95TaO
4: Tb
0.05Preparation
Under the room temperature, with the dense HNO of 4ml
3The dehydrated alcohol that adds 30ml is again the Lu of 0.95mmol
2O
3Dopant ion oxide compound Tb with 0.025mmol
4O
7Add in the ethanolic soln, heated and stirred under 79 ℃ of temperature makes oxide dissolution.TaCl with 20ml dissolve with ethanol 2mmol
5, and join in the above-mentioned settled solution, stirring and refluxing adds the 1ml Macrogol 200 after 3 hours, continue then to reflux 1 hour.Naturally cool to room temperature at last, after ageing in 8 hours, just obtain the required colloidal sol of plated film.Process is with embodiment 2.Even, the fine and close nothing cracking of film surface, good with the tack of substrate, under UV-light or x-ray bombardment, the film green light.
Claims (5)
1, a kind of rare-earth doped tantalic acid salt transparent luminous thin-film, its chemical expression is:
(Ln
1-xRE
x)TaO
4
0＜x＜0.1 wherein; Ln=Gd, Lu; RE=Eu, Tb.
2, a kind of rare-earth doped tantalic acid salt transparent luminous thin-film according to claim 1, its preparation method is as follows:
A, with Gd
2O
3, Lu
2O
3, Eu
2O
3, Tb
4O
7In one or both oxide raw materials with the ethanolic soln heating for dissolving of nitric acid, TaCl
5Use dissolve with ethanol, mix, mixed solution is heated to 78～80 ℃ then by stoichiometry, stirring and refluxing added Macrogol 200 after 3～4 hours, continue to reflux 1～2 hour, naturally cool to room temperature at last, after ageing in 12～24 hours, just obtain the required colloidal sol of plated film;
B, quartz or the opticglass selecting to clean are substrate, adopt the method plated film of spin coating, the wet gel film that spin coating is good places IR bake to carry out the thermolysis pre-treatment rapidly, with ultraviolet lamp xerogel thin film being carried out ultraviolet reinforcement again handles, the film of handling through 3～5 times is sent in the program temperature controlling stove, be warming up to 100 ℃ with the speed of 3.5 ℃/min, then the speed with 2 ℃/min continues to be warmed up to 1200 ℃, and under this temperature, be incubated 2 hours, or finally at volume ratio 5H
2%+95N
2In 1200 ℃ of sintering 4 hours, promptly obtain light-emitting film after naturally cooling to room temperature under the reducing atmosphere of %.
3, the preparation method of a kind of rare-earth doped tantalic acid salt transparent luminous thin-film according to claim 2 is characterized in that: raw material Gd in the described A step
2O
3, Lu
2O
3, Eu
2O
3, Tb
4O
7, TaCl
5Purity be 99.5%.
4, the preparation method of a kind of rare-earth doped tantalic acid salt transparent luminous thin-film according to claim 2 is characterized in that: the film thickness in the described B step is regulated by changing speed of rotation.
5, the preparation method of a kind of rare-earth doped tantalic acid salt transparent luminous thin-film according to claim 2, it is characterized in that: carrying out the pretreated time of thermolysis in the described B step is 2～5 minutes, and the time of xerogel thin film being carried out the ultraviolet reinforcement processing is 30～45 minutes.
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|---|---|---|---|
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|---|---|---|---|
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| CN1318537C CN1318537C (en) | 2007-05-30 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445347C (en) * | 2005-09-28 | 2008-12-24 | 同济大学 | Gadolinium tantalate transparent illuminating film and preparing process thereof |
| CN101445727A (en) * | 2008-12-30 | 2009-06-03 | 中国科学院安徽光学精密机械研究所 | Luminescent material doped with niobate, tantalate and the mischcrystal thereof, and crystal growth method thereof for the melt process |
| CN100510203C (en) * | 2007-05-10 | 2009-07-08 | 中国科学院安徽光学精密机械研究所 | Crystal growth way of crystal pulling method for tantalate |
| CN100567450C (en) * | 2007-11-02 | 2009-12-09 | 同济大学 | Tantalic acid gadolinium transparent luminescent thick film and preparation method thereof |
| CN102071462A (en) * | 2011-01-08 | 2011-05-25 | 中国科学院安徽光学精密机械研究所 | Bismuth niobate tantalite luminous material and crystal growth method for same through melt method |
| CN105204114A (en) * | 2015-09-18 | 2015-12-30 | 同济大学 | Photonic crystal wave shifting device for scintillation detection system |
| CN106544022A (en) * | 2016-10-21 | 2017-03-29 | 江苏师范大学 | A kind of Eu3+The tantalates red fluorescence powder of doping, Preparation method and use |
| CN106566548A (en) * | 2016-10-21 | 2017-04-19 | 江苏师范大学 | Green phosphor for white-light LED and preparation method thereof |
| CN106590653A (en) * | 2016-10-21 | 2017-04-26 | 江苏师范大学 | Er<3+>/Yb<3+> co-doped up-conversion luminescent material and preparation method thereof |
| CN112028493A (en) * | 2020-09-17 | 2020-12-04 | 昆明理工大学 | Preparation method and application of high-transparency all-inorganic perovskite quantum dot glass scintillator |
| CN112047636A (en) * | 2020-09-17 | 2020-12-08 | 昆明理工大学 | Preparation method and application of repairable inorganic perovskite quantum dot glass scintillator |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225653A (en) * | 1979-03-26 | 1980-09-30 | E. I. Du Pont De Nemours And Company | X-ray intensifying screen based on rare earth tantalate |
| JPS57168982A (en) * | 1981-04-13 | 1982-10-18 | Nec Corp | Luminescent material |
| US4431922A (en) * | 1981-12-30 | 1984-02-14 | E. I. Du Pont De Nemours And Company | Mixed phosphors comprising both Gd2 O2 S and GdTaO4 and X-ray screens thereof |
| JP2883414B2 (en) * | 1990-06-22 | 1999-04-19 | 日亜化学工業株式会社 | Color plasma display panel |
| FR2721940B1 (en) * | 1994-07-01 | 1997-08-29 | Rhone Poulenc Chimie | USE OF A TANTALATE OF YTTRIUM, LUTECIUM OR GADOLINIUM DOPED IN LOW VOLTAGE LUMINESCENCE |
-
2004
- 2004-09-21 CN CNB200410066543XA patent/CN1318537C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445347C (en) * | 2005-09-28 | 2008-12-24 | 同济大学 | Gadolinium tantalate transparent illuminating film and preparing process thereof |
| CN100510203C (en) * | 2007-05-10 | 2009-07-08 | 中国科学院安徽光学精密机械研究所 | Crystal growth way of crystal pulling method for tantalate |
| CN100567450C (en) * | 2007-11-02 | 2009-12-09 | 同济大学 | Tantalic acid gadolinium transparent luminescent thick film and preparation method thereof |
| CN101445727A (en) * | 2008-12-30 | 2009-06-03 | 中国科学院安徽光学精密机械研究所 | Luminescent material doped with niobate, tantalate and the mischcrystal thereof, and crystal growth method thereof for the melt process |
| CN102071462A (en) * | 2011-01-08 | 2011-05-25 | 中国科学院安徽光学精密机械研究所 | Bismuth niobate tantalite luminous material and crystal growth method for same through melt method |
| CN105204114B (en) * | 2015-09-18 | 2018-08-28 | 同济大学 | A kind of photonic crystal for scintillation detecter system moves wave device |
| CN105204114A (en) * | 2015-09-18 | 2015-12-30 | 同济大学 | Photonic crystal wave shifting device for scintillation detection system |
| CN106544022A (en) * | 2016-10-21 | 2017-03-29 | 江苏师范大学 | A kind of Eu3+The tantalates red fluorescence powder of doping, Preparation method and use |
| CN106566548A (en) * | 2016-10-21 | 2017-04-19 | 江苏师范大学 | Green phosphor for white-light LED and preparation method thereof |
| CN106590653A (en) * | 2016-10-21 | 2017-04-26 | 江苏师范大学 | Er<3+>/Yb<3+> co-doped up-conversion luminescent material and preparation method thereof |
| CN106544022B (en) * | 2016-10-21 | 2019-03-15 | 江苏师范大学 | A kind of Eu3+Tantalates red fluorescence powder, the Preparation method and use of doping |
| CN112028493A (en) * | 2020-09-17 | 2020-12-04 | 昆明理工大学 | Preparation method and application of high-transparency all-inorganic perovskite quantum dot glass scintillator |
| CN112047636A (en) * | 2020-09-17 | 2020-12-08 | 昆明理工大学 | Preparation method and application of repairable inorganic perovskite quantum dot glass scintillator |
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