CN104085928B - Rare earth ion doped tungstate flash film and preparation method thereof - Google Patents
Rare earth ion doped tungstate flash film and preparation method thereof Download PDFInfo
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Abstract
A kind of rare earth ion doped tungstate flash film and preparation method thereof, described method comprises: 1) in tungstate and/or tungsten aqueous acid, adds the first precursor liquid that complexing agent obtains containing W elements; 2) in the aqueous solution of Eu salt, Ln salt, the second precursor liquid that complexing agent obtains containing Eu, Ln is added; 3) presoma vitreosol is obtained after being mixed with the second precursor liquid by the first precursor liquid; 4) presoma vitreosol is adopted on substrate, to form precursor film by spin coating or crystal pulling method; 5) preheating is carried out to described precursor film; 6) anneal is carried out to described precursor film.<b />
Description
Technical field
The invention belongs to wet chemistry method oxide compound flicker technical field of film preparation, 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 absorbing X-ray, gamma-radiation or other high energy particle.The scintillometer made of being coupled with photomultiplier (PMT), silicon photo diode (Si-PD) or ccd detector by scintillation material is an important detector instrument in high energy physics, nuclear physics and nuclear medicine.The similar light source of effect of this scintillation material, it changes into the energy absorbed the pulsed light that fall time is nanosecond or delicate level.The intensity of these pulsed lights is directly proportional to the energy of irradiation on scintillator material, and they are converted into corresponding electrical signal after being received by photo-detector, and these electrical signal are through process and structure or the functional character that can show measurand after analyzing.The emission wavelength wherein just specially requiring scintillation material must mate with existing photodetector (Ren Guohao, Wang Shaohua. medicine imaging technique is to the demand of electrodeless scintillation material. material Leader, 16 (2002); S.E.Derenzo, M.J.Weber, etal, Nucl.Instru.andMeth.A505 (2003)).
Due to the development and safety random check etc. of human health's cause and the development of quiescent imaging association area and requirement, quiescent imaging scintillation material obtains extensive research.From early stage alkaline earth salt CaWO
4, BaFCl:Eu
2+, LaOBr:Tm
3+higher to density gradually, the LaOBr:Tm that 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), launch main peak position (610nm) and mate the advantages such as good with the spectrum sensitivity of ccd detector, and in x-ray imaging field by extensive concern and research (N.Kalyvas, P.Liaparinos, etal, ApplPhysA.106 (2012); XueLi, MinYu, etal, JournalofColloidandInterfaceScience349 (2010)).But due to Lu
2o
3: Eu
3+cost high, the features such as fall time is long greatly limit its application.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, fall time is 1.0ms, and the luminous intensity under excitation of X-rays is higher than Lu
2o
3: Eu
3+, be potential quiescent imaging flash luminous material (ZJZhang, HZhang, CJDuan.JAlloyCompd.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 scintillation material has three kinds of forms usually: monocrystalline, crystalline ceramics and film.But, research for such material is only confined to powder at present, and powder also exists dispersion inequality, easily occurs scattering center in application process, be difficult to be integrated in the shortcomings such as device and cause cannot using in concrete image device, monocrystalline is prepared so need badly, crystalline ceramics or film, just may meet this field to the demand of material with excellent imaging performance.
Summary of the invention
The present invention is intended to the deficiency overcoming existing quiescent imaging material and preparation method thereof, the invention provides a kind of Novel static imaging rare earth ion doped tungstate flash film and preparation method thereof.
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 containing soluble tungstate salt and/or tungsten aqueous acid or water and alcohol, add complexing agent and mix the first precursor liquid obtained containing W elements, control the pH value of the first precursor liquid between 7-10;
2) in the mixed solution of the aqueous solution containing soluble E u salt, solubility Ln salt or water and alcohol, add complexing agent and mix the second precursor liquid obtained 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) the first precursor liquid and the step 2 containing W elements prepared) after the second precursor liquid containing 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) in 400-700 DEG C, preheating is carried out to described precursor film;
6) in 700-1000 DEG C of anneal, described rare earth ion doped tungstate flash film is obtained to described precursor film;
Wherein, when a spin coating or lift, do not reach specific thickness through the precursor film of preheating time, repeat in the described precursor film not reaching 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 at least one in citric acid, ethylenediamine tetraacetic acid (EDTA), triethylenetetramine, dimercaprol dimercaptopropanol, 1,10-phenanthroline, oxine, thiocarbamide, urea.
Preferably, step 1) mol ratio of complexing agent and tungstate ion can be (2-6): 1.
Preferably, step 2) 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 and within 300-1000r/ minute, carry out first time coating, the Shi Jian≤5s of first time coating, then adopts 4000-6000r/ minute and carry out second time coating, the Shi Jian≤5s be coated with 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 1 μm-100 μm, and film grain colony is at 10-500nm.
Beneficial effect of the present invention:
Adopt Pechini legal system for thin film precursor colloidal sol, can ensure the mixing of the existing molecular level of metal ion core, make Elemental redistribution in the final film formed even, granular size is homogeneous and be Nano grade, avoids occurring light scattering phenomenon.Have preparation cost low, the features such as technique is simple, are conducive to industrialization scale operation;
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 Lu comparatively
2o
3: Eu
3+short, cost is lower;
This film meets the integrated requirement of quiescent imaging device, and solving powder cannot the difficult problem of integrated device;
There is strong red emission attribute under excitation of X-rays, launch main peak position (612nm) and be 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.
Accompanying drawing explanation
Fig. 1 shows the Lu prepared 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 prepared is Lu
2wO
6: Eu
3+pure phase;
Fig. 2 shows the Lu prepared 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 particle, and the length of rod-shpaed particle is about about 200nm, and film thickness is at about 1 μm;
Fig. 3 shows the Lu prepared in an embodiment of the invention
2wO
6: Eu
3+the stereoscan photograph of film surface, as seen from the figure, film is even compact comparatively;
Fig. 4 shows the Lu prepared 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 prepared with crystal pulling method is also at about 1 μm, and compactness is better;
Fig. 5 shows the Lu prepared 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 prepared 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 Lu comparatively
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 prepared in an embodiment of the invention
2wO
6: Eu
3+the burst of ultraviolel decay of luminescence curve of film, obtains the luminescence decay time t of sample according to two exponential attenuation matching 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 prepared 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 illustration of the present invention, 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 technical field of film preparation.Described flashing film is that trivalent rare earth is from (Eu
3+) tungstate material that activates, 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 transparent homogeneous Ln
2wO
6: Eu
3+precursor sol, and adopt spin coating or crystal pulling method to prepare the Ln with good flashing performance under specific program controls
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 comparatively Lu
2o
3: Eu
3+greatly reduce; Glow peak is positioned at 612nm, be in the spectrum sensitive district of typical ccd detector, to can be used in quiescent imaging system, as optical signal converter (X-ray being converted to 612nm ruddiness), therefore can be used on X ray computer tomoscan (CT) and many technical fields such as XRF intensifying screen or other energetic ray detections.
The present invention relates to a kind of Novel static imaging rare earth ion doped tungstate flash film and preparation method thereof, belong to wet chemistry method oxide compound flicker technical field of film preparation.This film is deposited on crystalline state (or non-crystalline state) substrate of non-conductive (or conduction) with crystal form form; Film grain colony is at 10-500nm; Film thickness scope in a few nanometer, between tens microns, and regulates and controls by spin coating or lift number of times.
The described rare earth ion doped tungstate flash film prepared, 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, and doping molar content x meets 0.01≤x≤0.30.
The tungstate flash film of described quiescent imaging doping with rare-earth ions, is characterized in that described flicker film dominant 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 preparation of Pechini method containing the solution of 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.Tungstate solution is made by the stoichiometric ratio of final rare earth ion doped tungstate system.Keep the molar ratio R of complexing agent and rare earth ion at (1-4): between 1, solution ph between 2-4, stirring at room temperature 1h (more than).
2) adopt the configuration of Pechini method containing the solution of 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, and complexing agent is citric acid, ethylenediamine tetraacetic acid (EDTA), triethylenetetramine, dimercaprol dimercaptopropanol, 1,10-phenanthroline, oxine, thiocarbamide, in urea one or more.Rare earth ion salts solution is made by the stoichiometric ratio of final rare earth ion doped tungstate system.Keep the molar ratio R of complexing agent and W ion at (2-6): between 1, solution 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 prepared adopts spin coating or crystal pulling method film forming, and spincoating procedures 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.The substrate that spin coating or lift adopt is crystalline state (or non-crystalline state) material of conduction (or non-conductive), such as silicon chip.
5) every spin coating or lift once all need preheating, and pre-burning atmosphere is air or oxygen, and during 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 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, during annealing, temperature rise rate is 4-10 DEG C/min, preferred temperature rise rate is 5-10 DEG C/min, holding temperature is 700-1000 DEG C, preferred 800-1000 DEG C, soaking time is 0.5-12h, preferred 1-6h.
The present invention relates to a kind of quiescent imaging rare earth ion (Eu
3+) doping tungstate flash film and preparation method thereof, the Ln prepared
(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 (about 2000 DEG C) that this kind of rear-earth-doped tungstate material of existing preparation has also belongs to oblique system, causes very difficult growing single-crystal or prepares crystalline ceramics.Cost prepared by combination film is low, and form such as easily to control at the feature, preparation evenly, fine and close, there is certain thickness and the film of luminescent properties excellence has great importance, this material will be made to be applied in order to reality in concrete image device.
The invention provides a kind of Novel static imaging flicker film and preparation method thereof.Successfully prepare evenly, thickness reaches micron order, have 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 the Pechini method of low cost has successfully been prepared containing rare earth ion Y
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, prepare by annealing the Ln with excellent luminance performance
2 (1-x)eu
2xwO
6(0.01≤x≤0.30) flicker film.
The Ln that 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 thin film precursor colloidal sol, can ensure the mixing of the existing molecular level of metal ion core, make Elemental redistribution in the final film formed even, granular size is homogeneous and be Nano grade, avoids occurring light scattering phenomenon.Have preparation cost low, the features such as technique is simple, are conducive to industrialization scale operation;
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 Lu comparatively
2o
3: Eu
3+short, cost is lower;
This film meets the integrated requirement of quiescent imaging device, and solving powder cannot the difficult problem of integrated device;
There is strong red emission attribute under excitation of X-rays, launch main peak position (612nm) and be 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 some exemplary embodiments are listed further better the present invention to be described.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in for illustration of the present invention and limit the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.In addition, concrete proportioning, time, temperature etc. in following processing parameter are also only 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 a certain amount of citric acid (CA) wherein, 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; Taking ammonium paratungstate (99.95%) 0.51 gram, with adding a certain amount of citric acid (CA) after appropriate hot water dissolving, keeping 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 formation C (Ln
3+the vitreosol of)=0.125mol/L.Above-mentioned colloidal sol is pressed I shelves 800r/min (5s), II shelves are that the program of 5000r/min (5s) is spin-coated on pretreated silicon chip, need be warming up to 600 DEG C, pre-burning 30min after each spin coating completes with 1 DEG C/min.After spin coating repeatedly, pre-burning 10 times, be warming up to 900 DEG C, insulation 1h, rear Temperature fall with 5 DEG C/min.Finally prepare the Lu with excellent luminance performance
2wO
6: Eu
3+(10%) film; The XRD figure spectrum of film is participated in Fig. 1 (a), illustrates that the sample prepared 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 particle, and the length of rod-shpaed particle is about about 200nm, and film thickness is at about 1 μm;
Fig. 3 is Lu prepared by embodiment 1
2wO
6: Eu
3+the stereoscan photograph of film surface.As seen from the figure, film comparatively 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 Lu comparatively
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 is obtained to the luminescence decay time t of sample according to two exponential attenuation matching
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 a certain amount of citric acid (CA) wherein, 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; Taking ammonium paratungstate (99.95%) 0.51 gram, with adding a certain amount of citric acid (CA) after appropriate hot water dissolving, keeping 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 formation C (Ln
3+the vitreosol of)=0.125mol/L.Pretreated silicon chip is immersed in above-mentioned colloidal sol and lifts with the speed of 0.2cm/s after 30s, be then warming up to 600 DEG C with 1 DEG C/min, pre-burning 30min; After repeatedly lifting pre-burning 10 times, be warming up to 900 DEG C with 5 DEG C/min, Temperature fall after insulation 1h.Finally prepare the Lu with excellent luminance performance
2wO
6: Eu
3+(10%) film.The XRD figure spectrum of film is participated in Fig. 1 (b), illustrates that the sample prepared 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 prepared with crystal pulling method is also at about 1 μm, 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
By the method repeating embodiment 1 with each component concentration of specifying in following table 1 and spincoating procedures, obtain 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
By the method repeating embodiment 2 with each component concentration of specifying in following table 1 and lift program, obtain Lu
2wO
6: Eu
3+(1%) light-emitting film.
Embodiment 5
By the method repeating embodiment 1 with each component concentration of specifying in following table 1 and spincoating procedures, obtain Lu
2wO
6: Eu
3+(30%) light-emitting film.
Embodiment 6
By the method repeating embodiment 2 with each component concentration of specifying in following table 1 and lift program, obtain Lu
2wO
6: Eu
3+(30%) light-emitting film.
Embodiment 7
By the method repeating embodiment 1 with each component concentration of specifying in following table 1 and spincoating procedures, obtain Y
2wO
6: Eu
3+(1%) light-emitting film.
Embodiment 8
By the method repeating embodiment 1 with each component concentration of specifying in following table 1 and spincoating procedures, obtain Y
2wO
6: Eu
3+(30%) light-emitting film.
Embodiment 9
By the method repeating embodiment 1 with each component concentration of specifying in following table 1 and spincoating procedures, obtain La
2wO
6: Eu
3+(1%) light-emitting film.
Embodiment 10
By the method repeating embodiment 1 with each component concentration of specifying in following table 1 and spincoating procedures, obtain La
2wO
6: Eu
3+(30%) light-emitting film.
Embodiment 11
By the method repeating enforcement 1 with each component concentration of specifying in following table 1 and spincoating procedures, obtain Gd
2wO
6: Eu
3+(1%) light-emitting film.
Embodiment 12
By the method repeating embodiment 1 with each component concentration of specifying in following table 1 and spincoating procedures, obtain Gd
2wO
6: Eu
3+(30%) light-emitting film.
Table 1Ln
2 (1-x)eu
2xwO
6(0.01≤x≤0.30) series thin film prepares embodiment
Claims (6)
1. a quiescent imaging preparation method for rare earth ion doped tungstate flash film, is characterized in that, 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 containing soluble tungstate salt and/or tungsten aqueous acid or water and alcohol, add complexing agent and mix the first precursor liquid obtained containing W elements, control the pH value of the first precursor liquid between 7-10, soluble tungstate salt is ammonium tungstate and/or ammonium paratungstate, and the mol ratio of complexing agent and tungstate ion is (2-6): 1;
2) in the mixed solution of the aqueous solution containing soluble E u salt, solubility Ln salt or water and alcohol, add complexing agent and mix the second precursor liquid obtained containing Eu, Ln, wherein Ln is at least one in Y, Lu, Gd, La, control the pH value of the second precursor liquid between 2-4, soluble E u salt is containing at least one in the nitrate of Eu, acetate, vitriol, chlorate, solubility Ln salt is that the mol ratio of complexing agent and Eu, Ln molar weight sum is (1-4): 1 containing at least one in the nitrate of Ln, acetate, vitriol, muriate;
3) the first precursor liquid and the step 2 containing W elements prepared by step 1)) after the second precursor liquid containing Eu, Ln of preparing mixes, stirring obtains presoma vitreosol, and in vitreosol, the concentration sum of Eu, Ln is 0.02-2.0mol/L;
4) the presoma vitreosol prepared in step 3) is adopted on substrate, to form precursor film by spin coating or crystal pulling method;
5) in 400 ~ 700 DEG C, preheating is carried out to described precursor film;
6) in 700-1000 DEG C of anneal, described rare earth ion doped tungstate flash film is obtained to described precursor film;
Wherein, when a spin coating or lift, do not reach specific thickness through the precursor film of preheating time, to repeat in the described precursor film not reaching specific thickness spin coating or crystal pulling method coating presoma vitreosol pre-burning under pre-sinter process in step 5) in by step 4), until the thickness of described precursor film is to specific thickness, then carry out step 6);
Step 1) and step 2) in, complexing agent is at least one in citric acid, ethylenediamine tetraacetic acid (EDTA), triethylenetetramine, dimercaprol dimercaptopropanol, 1,10-phenanthroline, oxine, thiocarbamide, urea.
2. preparation method according to claim 1, 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, and the time is 30-300 minute.
3. preparation method according to claim 1 and 2, it is characterized in that, in step 4), the processing parameter of spin coating is: first adopt and within 300-1000r/ minute, carry out first time coating, Shi Jian≤the 5s of first time coating, adopt 4000-6000r/ minute again and carry out second time coating, the Shi Jian≤5s of second time coating; The processing parameter of crystal pulling method is: the rate of pulling is 0.1-1cm/ second.
4. preparation method according to claim 1 and 2, 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.
5. preparation method according to claim 1 and 2, 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.
6. the rare earth ion doped tungstate flash film that in claim 1-5 prepared by arbitrary described method, is characterized in that, the thickness of described film is 1 μm-100 μm, and film grain colony is at 10-500nm.
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| CN1858150A (en) * | 2006-06-09 | 2006-11-08 | 中国科学院上海硅酸盐研究所 | X-ray excited rare-earth ion blended tungstate flash luminous material and its preparing method |
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