CN104085928A - Rare-earth-ion-doped tungstate flicker film and preparation method thereof - Google Patents
Rare-earth-ion-doped tungstate flicker film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a rare-earth-ion-doped tungstate flicker film and a preparation method thereof. The method comprises the following steps: (1) adding a complexing agent into an aqueous solution of tungstate and/or tungstic acid, thereby obtaining a first precursor solution containing tungsten element; (2) adding a complexing agent into an aqueous solution of a Eu salt and a Ln salt, thereby obtaining a second precursor solution containing Eu and Ln; (3) mixing the first precursor solution and the second precursor solution, thereby obtaining transparent precursor sol; (4) forming a precursor film on a substrate through a spin coating or pulling method by adopting the transparent precursor sol; (5) presintering the precursor film; and (6) annealing the precursor film.
Description
Technical field
The invention belongs to wet chemistry method oxide compound flicker film preparing technology field, be specifically related to a kind of novel flicker film that may be used for quiescent imaging.
Background technology
Inorganic scintillation material is a kind of novel optical function material, and it can send ultraviolet or visible ray after the energy that absorbs X-ray, gamma-radiation or other high energy particle.An important detector instrument in high energy physics, nuclear physics and nuclear medicine by scintillation material and photomultiplier (PMT), silicon photo diode (Si-PD) or the ccd detector scintillometer of making that is coupled.The similar light source of effect of this scintillation material, it changes into the energy absorbing the pulsed light that be nanosecond or delicate level fall time.Energy on scintillator material is directly proportional these pulse light intensities to irradiation, and they are converted into corresponding electrical signal after being received by photo-detector, and these electrical signal can show structure or the functional character of measurand after processing and analyzing.Wherein with regard to the emission wavelength of special requirement scintillation material must mate with existing photodetector (Ren Guohao, Wang Shaohua. the demand of nuclear medicine technology to electrodeless scintillation material. material Leader, 16 (2002); S.E.Derenzo, M.J.Weber, et al, Nucl.Instru.and Meth.A505 (2003)).
Due to development and the safety random check etc. of mankind's health protection and development and the requirement of quiescent imaging association area, quiescent imaging has obtained broad research with scintillation material.From early stage alkaline earth salt CaWO
4, BaFCl:Eu
2+, LaOBr:Tm
3+the LaOBr:Tm higher to density gradually, effective atomic number is higher
3+, GdOS:Tb
3+and Lu
2o
3: Eu
3+development.Particularly Lu
2o
3: Eu
3+, because it has the density (9.4g/cm of superelevation
3), large luminous intensity (35000ph/MeV), the advantages such as good are mated with the spectrum sensitivity of ccd detector in transmitting main peak position (610nm), and in x-ray imaging field by extensive concern and research (N.Kalyvas, P.Liaparinos, et al, Appl Phys is (2012) A.106; Xue Li, Min Yu, et al, Journal of Colloid and Interface Science349 (2010)).But due to Lu
2o
3: Eu
3+cost high, fall time is long etc., and feature has limited its application greatly.Therefore, the people such as Zhang Zhijun has synthesized novel flicker Ln with high temperature solid-state method
2wO
6: Eu
3+powder, Lu in this system
2wO
6: Eu
3+theoretical density up to 9.7g/cm
3, be 1.0ms fall time, and luminous intensity under excitation of X-rays is higher than Lu
2o
3: Eu
3+, be potential flash luminous material for quiescent imaging (ZJ Zhang, H Zhang, CJ Duan.J Alloy Compd.466 (2008); Zhang Zhijun, Zhao Jingtai etc. tungstate flash luminous material of a kind of doping with rare-earth ions of excitation of X-rays and preparation method thereof. China, 200610027523.0[P] .2006-11-8.).Quiescent imaging has three kinds of forms conventionally with scintillation material: monocrystalline, crystalline ceramics and film.But, research for such material is only confined to powder at present, and powder exists dispersion inequality, is prone to scattering center in application process, be difficult to be integrated in the shortcomings such as device and cause cannot using in concrete image device, prepare monocrystalline so need badly, crystalline ceramics or film, just may meet this field to having the demand of material of excellent imaging performance.
Summary of the invention
The present invention is intended to overcome the deficiency of existing quiescent imaging material and preparation method thereof, the invention provides rare earth ion doped tungstate flash film and preparation method thereof for a kind of Novel static imaging.
The invention provides the preparation method of a kind of Novel static imaging with rare earth ion doped tungstate flash film, described film consist of Ln
2 (1-x)eu
2xwO
6, wherein 0.01≤x≤0.30, described method comprises:
1) in the mixed solution that contains soluble tungstate salt and/or tungsten aqueous acid or water and alcohol, add complexing agent to mix and obtain the first precursor liquid containing W elements, control the pH value of the first precursor liquid between 7-10;
2) in the mixed solution of the aqueous solution that contains soluble E u salt, solubility Ln salt or water and alcohol, add complexing agent to mix and obtain the second precursor liquid containing Eu, Ln, wherein Ln is at least one in Y, Lu, Gd, La, controls the pH value of the second precursor liquid between 2-4;
3) by step 1) prepare containing the first precursor liquid and step 2 of W elements) after the second precursor liquid that contains Eu, Ln prepared mixes, stirring obtains presoma vitreosol, and in vitreosol, the concentration sum of Eu, Ln is 0.02-2.0mol/L;
4) adopt step 3) in preparation presoma vitreosol on substrate, form precursor film by spin coating or crystal pulling method;
5) described precursor film is carried out to preheating in 400-700 DEG C;
6) described precursor film is obtained to described rare earth ion doped tungstate flash film in 700-1000 DEG C of anneal;
Wherein, when a spin coating or lift, in the time that the precursor film of preheating does not reach specific thickness, repeat in the described precursor film that does not reach specific thickness by step 4) in spin coating or crystal pulling method coating presoma vitreosol and in step 5) in pre-burning under pre-sinter process, until the thickness of described precursor film is to specific thickness, then carry out step 6).
Preferably, step 1) in, soluble tungstate salt can be ammonium tungstate and/or ammonium paratungstate.
Preferably, step 2) in, soluble E u salt can be containing at least one in the nitrate of Eu, acetate, vitriol, chlorate, and solubility Ln salt can be containing at least one in the nitrate of Ln, acetate, vitriol, muriate.
Preferably, step 1) and step 2) in, complexing agent can be citric acid, ethylenediamine tetraacetic acid (EDTA), triethylenetetramine, dimercaprol dimercaptopropanol, 1, at least one in 10-phenanthroline, oxine, thiocarbamide, urea.
Preferably, step 1) in the mol ratio of complexing agent and tungstate ion can be (2-6): 1.
Preferably, step 2) in the mol ratio of complexing agent and Eu, Ln molar weight sum can be (1-4): 1.
Preferably, step 3) in, described stirring can be carried out at 40-100 DEG C, and the rotating speed of stirring can be 200-800 rev/min, and the time can be 30-300 minute.
Preferably, step 4) in, the processing parameter of spin coating can be: first adopt within 300-1000r/ minute, be coated with for the first time, and the Shi Jian≤5s of coating for the first time, then adopt be coated with for the second time for 4000-6000r/ minute, the Shi Jian≤5s of coating for the second time; The processing parameter of crystal pulling method is: the rate of pulling is 0.1-1cm/ second.
Preferably, step 5) in, the processing parameter of preheating can be: temperature rise rate is 0.5-5 DEG C/min, and soaking time is 0.5-2 hour.
Preferably, step 6) in, the processing parameter of anneal can be: temperature rise rate is 4-10 DEG C/min, and soaking time is 0.5-12 hour.
The invention provides rare earth ion doped tungstate flash film prepared by a kind of aforesaid method, the thickness of described film is 1nm-100 μ m, and film grain colony is at 10-500nm.
Beneficial effect of the present invention:
Adopt Pechini legal system for film precursor sol, can ensure the mixing of the existing molecular level of metal ion core, element in the final film forming is evenly distributed, granular size homogeneous and be Nano grade, avoids occurring light scattering phenomenon.Have preparation cost low, the feature such as technique is simple, is conducive to large-scale industrialization and produces;
Thin-film light emitting is even, wherein Lu
2wO
6: Eu
3+flicker thin-film light emitting is higher than the Lu of same thickness
2o
3: Eu
3+film, fall time is compared with Lu
2o
3: Eu
3+short, cost is lower;
This film meets the integrated requirement of quiescent imaging device, solved the difficult problem that powder cannot integrated device;
Under excitation of X-rays, there is strong red emission attribute, launch main peak position (612nm) in ccd detector sensitizing range,
Can be used on the technical field relevant to quiescent imaging, such as X ray medical imaging, safety random check, industrial exploration etc.
Brief description of the drawings
Fig. 1 shows the Lu preparing in two embodiments of the present invention
2wO
6: Eu
3+the XRD figure of film, wherein, the XRD figure that in Fig. 1, (a) prepares film for spin-coating method is composed, and the XRD figure that in Fig. 1, (b) prepares film for crystal pulling method is composed, and illustrates that the sample of preparing is Lu
2wO
6: Eu
3+pure phase;
Fig. 2 shows the Lu preparing in an embodiment of the invention
2wO
6: Eu
3+the stereoscan photograph of thin-membrane section, as seen from the figure, film is made up of a lot of rod-shpaed particles, and the length of rod-shpaed particle is about 200nm left and right, and film thickness is in 1 μ m left and right;
Fig. 3 shows the Lu preparing in an embodiment of the invention
2wO
6: Eu
3+the stereoscan photograph of film surface, as seen from the figure, film is compared with even compact;
Fig. 4 shows the Lu preparing in an embodiment of the invention
2wO
6: Eu
3+the stereoscan photograph of thin-membrane section, as seen from the figure, the film thickness of preparing with crystal pulling method is also in 1 μ m left and right, and compactness is better;
Fig. 5 shows the Lu preparing in an embodiment of the invention
2wO
6: Eu
3+the stereoscan photograph of film surface, as seen from the figure, uniformity of film is better;
Fig. 6 shows the Lu preparing in an embodiment of the invention
2wO
6: Eu
3+the Lu of film and same thickness
2o
3: Eu
3+the excitation of X-rays emmission spectrum that film is tested under the same conditions, as can be seen from the figure, the Lu of same thickness
2wO
6: Eu
3+film is compared with Lu
2o
3: Eu
3+film has higher luminous intensity, and the intensity (612nm) of main peak is about Lu
2o
3: Eu
3+1.3 times;
Fig. 7 shows the Lu preparing in an embodiment of the invention
2wO
6: Eu
3+the burst of ultraviolel decay of luminescence curve of film, has obtained the luminescence decay time t of sample according to two exponential attenuation matchings to extinction curve
1=436.5 μ s (21.39%), t
2=1124 μ s (78.61%), the average attenuation time is t=976.9 μ s;
Fig. 8 shows the Y preparing in an embodiment of the invention
2wO
6: Eu
3+the Lu of film and same thickness
2o
3: Eu
3+the excitation of X-rays emmission spectrum that film is tested under the same conditions, as can be seen from the figure Y
2wO
6: Eu
3+the luminous intensity of film can with the Lu of similar thickness
2o
3: Eu
3+film is comparable.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for the present invention is described, and unrestricted the present invention.
The present invention relates to a kind of novel flicker film that may be used for quiescent imaging and preparation method thereof, belong to wet chemistry method oxide compound flicker film preparing technology field.Described flashing film is that trivalent rare earth is from (Eu
3+) activate tungstate material, chemical formula is Ln
2 (1-x)eu
2xo
6, wherein Ln is at least a kind of element in Lu, Gd, Y, La, and x is active ions Eu
3+molar content ratio (0.01≤x≤0.30).Its feature mainly comprises: adopt Pechini method successfully to prepare the Ln of transparent homogeneous
2wO
6: Eu
3+precursor sol, and under specific program control, adopt spin coating or crystal pulling method to prepare the Ln with good flashing performance
2wO
6: Eu
3+(Ln=Lu, Y, Gd, La) film.Adopt the flicker film prepared of the method under excitation of X-rays, luminous intensity can with the inorganic scintillator Lu of similar thickness
2o
3: Eu
3+(5%) film is comparable, and cost is compared with Lu
2o
3: Eu
3+greatly reduce; Glow peak is positioned at 612nm, be in the spectrum sensitive district of typical ccd detector, can be used in quiescent imaging system, as optical signal converter (converting X ray to 612nm ruddiness), therefore can be used on many technical fields such as X ray computer tomoscan (CT) and XRF intensifying screen or other energetic ray detections.
The present invention relates to rare earth ion doped tungstate flash film and preparation method thereof for a kind of Novel static imaging, belong to wet chemistry method oxide compound flicker film preparing technology field.This film is deposited on crystal form form on crystalline state (or non-crystalline state) substrate of non-conductive (or conduction); Film grain colony is at 10-500nm; Film thickness scope, between several nanometers, tens microns, and can or lift number of times by spin coating and regulates and controls.
The described rare earth ion doped tungstate flash film of preparing, doping with rare-earth ions is Eu
3+, the chemical constitution of tungstate film is Ln
2 (1-x)eu
2xwO
6, wherein Ln is one or more rare earth ions in Y, Lu, Gd, La, doping molar content x meets 0.01≤x≤0.30.
The tungstate flash film of doping with rare-earth ions for described quiescent imaging, is characterized in that described flicker film main emission wavelength under excitation of X-rays is positioned at 612nm, best Eu
3+doping ratio x=0.10.
Described preparation method comprises:
1) adopt the solution of Pechini method preparation containing W ionic complex, it is characterized in that: solute is one or more in ammonium tungstate or ammonium paratungstate or wolframic acid, and solvent is the mixed solution of water or water and ethanol, and complexing agent is citric acid, ethylenediamine tetraacetic acid (EDTA), triethylenetetramine, dimercaprol dimercaptopropanol, 1,10-phenanthroline, oxine, thiocarbamide, one or more in urea.Make tungstate solution by the stoichiometric ratio of final rare earth ion doped tungstate system.The molar ratio R that keeps complexing agent and rare earth ion is at (1-4): between 1, pH between 2-4, stirring at room temperature 1h (more than).
2) adopt the solution of Pechini method configuration containing rare earth ion complex compound, solute Lu (NO
3)
3(Y, Gd, La, Eu) or Lu (AC)
3(Y, Gd, La, Eu) or Lu
2(SO
4)
3(Y, Gd, La, Eu) or LuCl
3one or more in (Y, Gd, La, Eu), solution is the mixed solution of water or water and ethanol, complexing agent is citric acid, ethylenediamine tetraacetic acid (EDTA), triethylenetetramine, dimercaprol dimercaptopropanol, 1,10-phenanthroline, oxine, thiocarbamide, in urea one or more.Make rare earth ion salts solution by the stoichiometric ratio of final rare earth ion doped tungstate system.The molar ratio R that keeps complexing agent and W ion is at (2-6): between 1, pH between 7-10, stirring at room temperature 1h (more than).
3) described step 1) and 2) the solution mixing post-heating prepared is stirred to and forms transparent precursor sol, vitreosol concentration (taking rare earth ion concentration as standard) is 0.02-2.0mol/L.
4) colloidal sol of preparing adopts spin coating or crystal pulling method film forming, and spin coating program is: I shelves 300-1000r/min, spin coating time t≤5s; II shelves are 4000-6000r/min, spin coating time t≤5s; The rate of pulling is 0.1-1cm/s.Crystalline state (or non-crystalline state) material that spin coating or the substrate that lifts employing are conduction (or non-conductive), for example silicon chip.
5) every spin coating or lift and once all need preheating, pre-burning atmosphere is air or oxygen, and when pre-burning, temperature rise rate is 0.5-5 DEG C/min, and holding temperature is 400-700 DEG C, and soaking time is 0.5-2h.Every spin coating or lift once all need to pre-burning in retort furnace or high-temperature annealing furnace.
6) film that prepared by described method finally need carry out anneal, it is characterized in that: annealing atmosphere is air or oxygen, when annealing, temperature rise rate is 4-10 DEG C/min, preferably temperature rise rate is 5-10 DEG C/min, holding temperature is 700-1000 DEG C, preferably 800-1000 DEG C, soaking time is 0.5-12h, preferably 1-6h.
The present invention relates to a kind of rare earth ion (Eu for quiescent imaging
3+) doping tungstate flash film and preparation method thereof, the Ln preparing
(1-x)eu
2xwO
6(0.01≤x≤0.30) flicker film has strong red emission attribute under excitation of X-rays, and has high density (9.7g/cm
3) and X ray assimilated efficiency.Can be used on many technical fields of relevant to quiescent imaging (in X ray computer tomoscan, XRF intensifying screen and other devices relevant with quiescent imaging), as X ray medical imaging, safety random check and anti-terrorism, industrial exploration etc.
The high fusing point (approximately 2000 DEG C) that the rear-earth-doped tungstate material of this class of existing preparation has also belongs to oblique system, causes being difficult to growing single-crystal or preparing crystalline ceramics.The features such as cost prepared by combination film is low, the easy control of form, preparation film even, fine and close, that have certain thickness and luminescent properties excellence has great importance, and will make this material be applied to for reality in concrete image device.
The invention provides a kind of Novel static imaging flicker film and preparation method thereof.Successfully prepared evenly, thickness reaches micron order, has the rare earth (Eu of good luminous performance
3+) doping tungstate flash film.The general formula of this rear-earth-doped tungstate flash film is Ln
2 (1-x)eu
2xwO
6, wherein x is activator Eu
3+the doping content of ion, 0.01≤x≤0.30.Principal character of the present invention is by simply, and Pechini method has successfully been prepared containing rare earth ion Y cheaply
3+, Gd
3+, Lu
3+, La
3+, Eu
3+and W
6+vitreosol, through concentrated, filter after spin coating or pulling film forming, finally pre-burning in temperature programmed control stove, prepares by annealing the Ln with excellent luminescent properties
2 (1-x)eu
2xwO
6(0.01≤x≤0.30) flicker film.
The Ln the present invention relates to
2 (1-x)eu
2xwO
6(0.01≤x≤0.30) flicker film has the following advantages:
Adopt Pechini legal system for film precursor sol, can ensure the mixing of the existing molecular level of metal ion core, element in the final film forming is evenly distributed, granular size homogeneous and be Nano grade, avoids occurring light scattering phenomenon.Have preparation cost low, the feature such as technique is simple, is conducive to large-scale industrialization and produces;
Thin-film light emitting is even, wherein Lu
2wO
6: Eu
3+flicker thin-film light emitting is higher than the Lu of same thickness
2o
3: Eu
3+film, fall time is compared with Lu
2o
3: Eu
3+short, cost is lower;
This film meets the integrated requirement of quiescent imaging device, solved the difficult problem that powder cannot integrated device;
Under excitation of X-rays, have strong red emission attribute, transmitting main peak position (612nm), in ccd detector sensitizing range, can be used on the technical field relevant to quiescent imaging, such as X ray medical imaging, safety random check, industrial exploration etc.
Below further list some exemplary embodiments so that the present invention to be described better.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in and limit the scope of the invention for the present invention is described, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjust and all belong to protection scope of the present invention.In addition, concrete proportioning in following processing parameter, time, temperature etc. are only also exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1
Lu
2o
3(99.99%) 0.358 gram, Eu
2o
3(99.99%) 0.035 gram, with appropriate nitric acid by Lu
2o
3and Eu
2o
3dissolve completely, form nitrate solution; Add wherein a certain amount of citric acid (CA), keep rare earth ion (Ln
3+, Ln=Eu, Lu) with the molar concentration rate C (Ln of citric acid
3+): C (CA)=1:2, regulates pH=3; Take (99.95%) 0.51 gram of ammonium paratungstate, with adding a certain amount of citric acid (CA) after appropriate hot water dissolving, keep the mol ratio n (W of W and citric acid
6+): n (CA)=1:2, regulates pH=7-9.Above-mentioned two kinds of solution Hybrid Heating are stirred to forming C (Ln
3+the vitreosol of)=0.125mol/L.Above-mentioned colloidal sol is pressed to I shelves 800r/min (5s), and II shelves are that the program of 5000r/min (5s) is spin-coated on pretreated silicon chip, after each spin coating completes, need be warming up to 600 DEG C with 1 DEG C/min, pre-burning 30min.After spin coating repeatedly, pre-burning 10 times, be warming up to 900 DEG C of 5 DEG C/min, insulation 1h, lowers the temperature naturally afterwards.Finally prepare the Lu with excellent luminescent properties
2wO
6: Eu
3+(10%) film; The XRD figure spectrum of film is participated in Fig. 1 (a), illustrates that the sample of preparing is Lu
2wO
6: Eu
3+pure phase;
Fig. 2 is Lu prepared by embodiment 1
2wO
6: Eu
3+the stereoscan photograph of thin-membrane section.As seen from the figure, film is made up of a lot of rod-shpaed particles, and the length of rod-shpaed particle is about 200nm left and right, and film thickness is in 1 μ m left and right;
Fig. 3 is Lu prepared by embodiment 1
2wO
6: Eu
3+the stereoscan photograph of film surface.As seen from the figure, film is compared with even compact;
Fig. 6 is Lu prepared by embodiment 1
2wO
6: Eu
3+the Lu of film and same thickness
2o
3: Eu
3+the excitation of X-rays emmission spectrum that film is tested under the same conditions.As can be seen from the figure, the Lu of same thickness
2wO
6: Eu
3+film is compared with Lu
2o
3: Eu
3+film has higher luminous intensity, and the intensity (612nm) of main peak is about Lu
2o
3: Eu
3+1.3 times;
Fig. 7 is Lu prepared by embodiment 1
2wO
6: Eu
3+the burst of ultraviolel decay of luminescence curve of film.Extinction curve has been obtained to the luminescence decay time t of sample according to two exponential attenuation matchings
1=436.5 μ s (21.39%), t
2=1124 μ s (78.61%), the average attenuation time is t=976.9 μ s.
Embodiment 2
Lu
2o
3(99.99%) 0.358 gram, Eu
2o
3(99.99%) 0.035 gram, with appropriate nitric acid by Lu
2o
3and Eu
2o
3dissolve completely, form nitrate solution; Add wherein a certain amount of citric acid (CA), keep rare earth ion (Ln
3+, Ln=Eu, Lu) with the molar concentration rate C (Ln of citric acid
3+): C (CA)=1:2, regulates pH=3; Take (99.95%) 0.51 gram of ammonium paratungstate, with adding a certain amount of citric acid (CA) after appropriate hot water dissolving, keep the molar concentration rate C (W of W and citric acid
6+): C (CA)=1:2, regulates pH=7-9.Above-mentioned two kinds of solution Hybrid Heating are stirred to forming C (Ln
3+the vitreosol of)=0.125mol/L.Pretreated silicon chip is immersed in above-mentioned colloidal sol to the speed with 0.2cm/s after 30s and lifts, be then warming up to 600 DEG C with 1 DEG C/min, pre-burning 30min; Repeatedly lift after pre-burning 10 times, be warming up to 900 DEG C with 5 DEG C/min, after insulation 1h, naturally lower the temperature.Finally prepare the Lu with excellent luminescent properties
2wO
6: Eu
3+(10%) film.The XRD figure spectrum of film is participated in Fig. 1 (b), illustrates that the sample of preparing is Lu
2wO
6: Eu
3+pure phase;
Fig. 4 is Lu prepared by embodiment 2
2wO
6: Eu
3+the stereoscan photograph of thin-membrane section.As seen from the figure, the film thickness of preparing with crystal pulling method is also in 1 μ m left and right, and compactness is better;
Fig. 5 is Lu prepared by embodiment 2
2wO
6: Eu
3+the stereoscan photograph of film surface.As seen from the figure, uniformity of film is better.
Embodiment 3
The method that repeats embodiment 1 by each component concentration of specifying in following table 1 and spin coating program, obtains Lu2WO6:Eu
3+(1%) light-emitting film;
Fig. 8 is Y prepared by embodiment 3
2wO
6: Eu
3+the Lu of film and same thickness
2o
3: Eu
3+the excitation of X-rays emmission spectrum that film is tested under the same conditions.As can be seen from the figure Y
2wO
6: Eu
3+the luminous intensity of film can with the Lu of similar thickness
2o
3: Eu
3+film is comparable.
Embodiment 4
Repeat the method for embodiment 2 by each component concentration of specifying in following table 1 and the program that lifts, obtain Lu
2wO
6: Eu
3+(1%) light-emitting film.
Embodiment 5
The method that repeats embodiment 1 by each component concentration of specifying in following table 1 and spin coating program, obtains Lu
2wO
6: Eu
3+(30%) light-emitting film.
Embodiment 6
Repeat the method for embodiment 2 by each component concentration of specifying in following table 1 and the program that lifts, obtain Lu
2wO
6: Eu
3+(30%) light-emitting film.
Embodiment 7
The method that repeats embodiment 1 by each component concentration of specifying in following table 1 and spin coating program, obtains Y
2wO
6: Eu
3+(1%) light-emitting film.
Embodiment 8
The method that repeats embodiment 1 by each component concentration of specifying in following table 1 and spin coating program, obtains Y
2wO
6: Eu
3+(30%) light-emitting film.
Embodiment 9
The method that repeats embodiment 1 by each component concentration of specifying in following table 1 and spin coating program, obtains La
2wO
6: Eu
3+(1%) light-emitting film.
Embodiment 10
The method that repeats embodiment 1 by each component concentration of specifying in following table 1 and spin coating program, obtains La
2wO
6: Eu
3+(30%) light-emitting film.
Embodiment 11
Repeat to implement 1 method by each component concentration and the spin coating program of specifying in following table 1, obtain Gd
2wO
6: Eu
3+(1%) light-emitting film.
Embodiment 12
The method that repeats embodiment 1 by each component concentration of specifying in following table 1 and spin coating program, obtains Gd
2wO
6: Eu
3+(30%) light-emitting film.
Table 1 Ln
2 (1-x)eu
2xwO
6(0.01≤x≤0.30) series thin film Preparation Example
Claims (11)
1. a preparation method for rare earth ion doped tungstate flash film for Novel static imaging, is characterized in that, described film consist of Ln
2 (1-
x)
eu
2
x wO
6, wherein 0.01≤x≤0.30, described method comprises:
1) in the mixed solution that contains soluble tungstate salt and/or tungsten aqueous acid or water and alcohol, add complexing agent to mix and obtain the first precursor liquid containing W elements, control the pH value of the first precursor liquid between 7-10;
2) in the mixed solution of the aqueous solution that contains soluble E u salt, solubility Ln salt or water and alcohol, add complexing agent to mix and obtain the second precursor liquid containing Eu, Ln, wherein Ln is at least one in Y, Lu, Gd, La, controls the pH value of the second precursor liquid between 2-4;
3) prepared by step 1) containing the first precursor liquid and step 2 of W elements) after the second precursor liquid containing Eu, Ln of preparing mixes, stirring obtains presoma vitreosol, in vitreosol, the concentration sum of Eu, Ln is 0.02-2.0mol/L;
4) adopt the presoma vitreosol of preparing in step 3) on substrate, to form precursor film by spin coating or crystal pulling method;
5) described precursor film is carried out to preheating in 400～700 DEG C;
6) described precursor film is obtained to described rare earth ion doped tungstate flash film in 700-1000 DEG C of anneal;
Wherein, when a spin coating or lift, in the time that the precursor film of preheating does not reach specific thickness, repeat to apply presoma vitreosol pre-burning under pre-sinter process in step 5) by spin coating in step 4) or crystal pulling method in the described precursor film that does not reach specific thickness, until the thickness of described precursor film is to specific thickness, then carry out step 6).
2. preparation method according to claim 1, is characterized in that, in step 1), soluble tungstate salt is ammonium tungstate and/or ammonium paratungstate.
3. preparation method according to claim 1 and 2, it is characterized in that, step 2) in, soluble E u salt is containing at least one in the nitrate of Eu, acetate, vitriol, chlorate, solubility Ln salt is containing at least one in the nitrate of Ln, acetate, vitriol, muriate.
4. according to arbitrary described preparation method in claim 1-3, it is characterized in that, step 1) and step 2) in, complexing agent is citric acid, ethylenediamine tetraacetic acid (EDTA), triethylenetetramine, dimercaprol dimercaptopropanol, 1, at least one in 10-phenanthroline, oxine, thiocarbamide, urea.
5. according to arbitrary described preparation method in claim 1-4, it is characterized in that, in step 1), the mol ratio of complexing agent and tungstate ion is (2-6): 1.
6. according to arbitrary described preparation method in claim 1-5, it is characterized in that step 2) in the mol ratio of complexing agent and Eu, Ln molar weight sum be (1-4): 1.
7. according to arbitrary described preparation method in claim 1-6, it is characterized in that, in step 3), described in be stirred in 40-100 DEG C and carry out, the rotating speed of stirring is 200-800 rev/min, the time is 30-300 minute.
8. according to arbitrary described preparation method in claim 1-7, it is characterized in that, in step 4), the processing parameter of spin coating is: first adopt within 300-1000r/ minute, be coated with for the first time, Shi Jian≤the 5s of coating for the first time, adopt again within 4000-6000r/ minute, be coated with for the second time, for the second time the Shi Jian≤5s of coating; The processing parameter of crystal pulling method is: the rate of pulling is 0.1-1cm/ second.
9. according to arbitrary described preparation method in claim 1-8, it is characterized in that, in step 5), the processing parameter of preheating is: temperature rise rate is 0.5-5 DEG C/min, and soaking time is 0.5-2 hour.
10. according to arbitrary described preparation method in claim 1-9, it is characterized in that, in step 6), the processing parameter of anneal is: temperature rise rate is 4-10 DEG C/min, and soaking time is 0.5-12 hour.
The rare earth ion doped tungstate flash film that in 11. 1 kinds of claim 1-10 prepared by arbitrary described method, is characterized in that, the thickness of described film is 1nm-100 μ m, and film grain colony is at 10-500 nm.
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Cited By (4)
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| CN105385445A (en) * | 2015-10-30 | 2016-03-09 | 北京航空航天大学 | Method for co-doping ions in yttrium tungstate base to obtain white light-emitting fluorescent powder |
| CN108407171A (en) * | 2018-01-19 | 2018-08-17 | 同济大学 | A method of preparing Plastic scintillation body thin film |
| CN109661372A (en) * | 2016-08-30 | 2019-04-19 | 住友电气工业株式会社 | Aqueous solution composition and its manufacturing method, oxide powder and its manufacturing method, carbide powder and its manufacturing method, hard alloy and its manufacturing method |
| CN111085111A (en) * | 2019-12-27 | 2020-05-01 | 天津膜天膜科技股份有限公司 | Rare earth complex acid salt antibacterial agent, antibacterial modified hollow fiber membrane and preparation method thereof |
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| CN1468934A (en) * | 2003-06-16 | 2004-01-21 | 中国科学院长春应用化学研究所 | Prepn of luminous tungstate film |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385445A (en) * | 2015-10-30 | 2016-03-09 | 北京航空航天大学 | Method for co-doping ions in yttrium tungstate base to obtain white light-emitting fluorescent powder |
| CN109661372A (en) * | 2016-08-30 | 2019-04-19 | 住友电气工业株式会社 | Aqueous solution composition and its manufacturing method, oxide powder and its manufacturing method, carbide powder and its manufacturing method, hard alloy and its manufacturing method |
| CN108407171A (en) * | 2018-01-19 | 2018-08-17 | 同济大学 | A method of preparing Plastic scintillation body thin film |
| CN108407171B (en) * | 2018-01-19 | 2019-12-27 | 同济大学 | Method for preparing plastic scintillator film |
| CN111085111A (en) * | 2019-12-27 | 2020-05-01 | 天津膜天膜科技股份有限公司 | Rare earth complex acid salt antibacterial agent, antibacterial modified hollow fiber membrane and preparation method thereof |
| CN111085111B (en) * | 2019-12-27 | 2022-05-17 | 天津膜天膜科技股份有限公司 | Rare earth complex acid salt antibacterial agent, antibacterial modified hollow fiber membrane and preparation method thereof |
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