CN104788092B - The method that a kind of heat treatment of ultraviolet auxiliary prepares Yt-Ba-Cu-O high-temperature superconductive film - Google Patents
The method that a kind of heat treatment of ultraviolet auxiliary prepares Yt-Ba-Cu-O high-temperature superconductive film Download PDFInfo
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Abstract
The invention discloses the method that a kind of heat treatment of ultraviolet auxiliary prepares Yt-Ba-Cu-O high-temperature superconductive film, using with the yttrium barium copper oxide solution to deep ultraviolet with photobehavior as precursor solution, prepare yttrium barium copper oxide forerunner's gel film, then in turn through drying, ultraviolet auxiliary photograph treatment, eventually treatment, Yt-Ba-Cu-O high-temperature superconductive film is obtained.The present invention using ultraviolet irradiation, under photo-thermal collective effect so that film cationic is evenly distributed, and film is finer and close, promotes the raising of performance in film thermal decomposition process；On the other hand, the ultraviolet of 185nm produces active oxygen in film thermal decomposition process in ultraviolet, it is suppressed that the segregation of Cu elements so that CuO distribution of particles is homogeneous, and the performance improvement for preparing multilayer thick film has positive effect.
Description
Technical field
The invention belongs to conductor of high-temperature superconductor coat preparing technical field, and in particular to prepared by a kind of ultraviolet auxiliary heat treatment
The method of Yt-Ba-Cu-O high-temperature superconductive film.
Background technology
Yttrium barium copper oxide (YBCO) has great applying value as second generation high temperature superconducting materia in forceful electric power light current field.
From each self-discovery T of scientist in 1987cYBa more than 90K2Cu3O7-x(YBCO) since superconductor, yttrium system high-temperature superconducting film is obtained
Extensive research is arrived.At present, in developed countries such as the U.S., Japan, high temperature superconducting materia has tentatively obtained small-scale metaplasia and has produced,
It plays irreplaceable effect in some key areas, generates huge economic worth.Its with excellent electromagnetic property,
Under high field conditions, with the critical current density higher than first generation bi tape, it is widely used in micro- electricity of high-end precision
The light current such as sub- device field, be made it is various precision electronic devices, such as superconducting quantum interference device (SQUID) (SQUID), Josephson junction,
Superconducting-coupled antenna, and super conductive filter etc.；Also found broad application in field of strong electricity simultaneously, be made power electronics device
Fault current limiter on part, cable etc., such as network system, energization cable etc..
The method for being presently used for preparing the films such as YBCO mainly has physical vacuum method and chemical solution method.Wherein, vacuum thing
Logos is both needed to be related to expensive vacuum equipment without follow-up annealing heat-treats；And chemical solution method belongs to chemical method
Masking technique, equipment is simple, with low cost compared to physical vacuum method, it is easy to control the stoichiometric proportion of metal ion, it is easy to
Production large area, long range superconducting tape or film.Chemical method prepares superconducting thin film and is most suitably adapted for superconducting tape industrialization
Approach, for the excellent superconducting thin film of processability, scientific worker expands in-depth study to this, from floride-free solution to three
Fluoroacetate-deposition of metal organic method (TFA-MOD) arrives few fluorine, low fluorine, ultralow fluorine solution again.Research finds, matches somebody with somebody in solution
Oil repellent is significant for improved thin film performance in reducing solution in side.However, in follow-up heat treatment process, no
It is evitable metal ion segregation occur, cause the drawback such as CuO particles and other granular size inequality, skewness.
The content of the invention
It is an object of the invention to provide the method that a kind of heat treatment of ultraviolet auxiliary prepares Yt-Ba-Cu-O high-temperature superconductive film, solution
There is metal ion segregation in existing preparation method heat treatment process of having determined, cause CuO particles and other granular sizes inequality, divide
The uneven problem of cloth.
The technical solution adopted in the present invention is that a kind of heat treatment of ultraviolet auxiliary prepares Yt-Ba-Cu-O high-temperature superconductive film
Method, specifically implements according to following steps：
Step 1, prepares yttrium barium copper oxide solution
Acetic acid yttrium is dissolved in mixed solution of the methyl alcohol with the methyl triethanol amine with light sensitive characteristic, solution A is obtained；
By trifluoroacetic acid barium be dissolved in methyl alcohol with have light sensitive characteristic acrylic acid mixed solution in, obtain solution B；Barium acetate is molten
Solution obtains solution C in methyl alcohol with acrylic acid mixed solution；Copper acetate is dissolved in methyl alcohol with acrylic acid mixed solution
In, obtain solution D；Solution A, solution B, solution C, solution D mixing after stirring, are obtained yttrium barium copper oxide solution, use methyl alcohol
Dilution controls the total concentration of the metal ion in solution to control in 0.5~1mol/L；
Step 2, prepares Yt-Ba-Cu-O high-temperature superconductive film
The yttrium barium copper oxide solution prepared using step 1 as precursor solution, using dip-coating method, in lanthanum aluminate list
Yttrium barium copper oxide forerunner's gel film is prepared on brilliant substrate, then in turn through drying, ultraviolet auxiliary photograph treatment, eventually treatment, yttrium is obtained
Barium copper oxygen high-temperature superconducting thin film.
The features of the present invention is also resided in,
Ruthenium ion and the mol ratio of methyl triethanol amine are 1.5~2 in step 1 solution A：1.
Acrylic acid and the mol ratio of barium ions are 8~10 in step 1 solution B：1.
Acrylic acid and the mol ratio of barium ions are 8~10 in step 1 solution C：1.
Acrylic acid and the mol ratio of copper ion are 3~6 in step 1 solution D：1.
Acetic acid yttrium, trifluoroacetic acid barium, barium acetate, the mol ratio of copper acetate are 3 in the yttrium barium copper oxide solution that step 1 is obtained：
x：6-x：9, the wherein value of x is 2≤x≤6.
Drying is that 5~20min is dried at 80~100 DEG C in step 2.
Ultraviolet auxiliary photograph treatment is that dried film is positioned under uviol lamp in step 2, in air or nitrogen atmosphere
10~30min, ultraviolet light wave a length of 185 and 254nm are irradiated at a temperature of 350 DEG C.
The specific operation process processed eventually in step 3 is：Film after ultraviolet irradiation is processed is placed in quartz tube type sintering
In stove, to being passed through nitrogen in quartz tube type sintering furnace, and in-furnace temperature is increased to 760 DEG C with the speed of 10~20 DEG C/min,
Atmosphere is switched to the mixed gas of the oxygen-nitrogen of moisture vapor when temperature is increased to 200 DEG C, the oxygen of mixed gas
Partial pressure is maintained at 200~500ppm, and steam partial pressure is maintained at 4~8kPa；1~3h is incubated after being warmed up to 760 DEG C, then by gas
Atmosphere switches to not moisture vapor and keeps the oxygen-nitrogen gaseous mixture of identical partial pressure of oxygen, and continues 10~30min of insulation, finally
With stove natural cooling, when temperature is cooled to 400~500 DEG C after atmosphere is switched into pure O again2, and it is incubated 1~3 hour；Insulation
After end, then after naturally cooling to room temperature with stove, atmosphere is closed, sintering obtains final product Yt-Ba-Cu-O high-temperature superconductive film；At above-mentioned end
During reason, sintering furnace is communicated with the external world, and the air pressure in stove maintains an atmospheric pressure all the time.
The beneficial effects of the invention are as follows the method that the present invention ultraviolet auxiliary heat treatment prepares Yt-Ba-Cu-O high-temperature superconductive film
Have the characteristics that：
1) methyl triethanol amine is used, with ruthenium ion complexing, form has photosensitization to 185 with 254nm ultraviolets
Functional group, meanwhile, with the addition of acrylic acid and Cu, Ba react the acrylic acid copper and acrylic acid barium to be formed, to the purple near 245nm
The energy that outside line has strong absorption, absorption promotes the thermal decomposition and crystallization of subsequent thin film, so as to obtain high-quality
Ybco film.
2) solution Oil repellent employs low fluorine content, lower than traditional TFA-MOD technology Oil repellents, F/Ba mol ratio controls
System is between 2~6 so that solution-stabilized, while avoiding BaCO3The generation of phase.
3) in film thermal decomposition process, aid in thermally decomposing using ultraviolet irradiation, under photo-thermal collective effect so that in film
Cation distribution is uniform, and film is finer and close, promotes the raising of performance；On the other hand, the ultraviolet of 185nm exists in ultraviolet
Active oxygen is produced in film thermal decomposition process, it is suppressed that the segregation of Cu elements so that CuO even particle distributions, it is many for preparing
The performance improvement of thickness film has positive effect.
4) compared to conventional pretreatment under the conditions of wet oxygen, ultraviolet irradiation auxiliary heat treatment is in air or condition of nitrogen gas
Under, the oxidation of Ni base band is slow down, prepared for large area film, the fabrication techniques are more convenient.
Brief description of the drawings
Fig. 1 is the XRD diffraction patterns that the ultraviolet irradiation of embodiment 1 is heat-treated rear film；
Fig. 2 is the XRD diffraction patterns of the Yt-Ba-Cu-O high-temperature superconductive film that embodiment 1 is prepared；
Fig. 3 is the SEM figures of the Yt-Ba-Cu-O high-temperature superconductive film that embodiment 1 is prepared；
Fig. 4 is the AFM figures of the Yt-Ba-Cu-O high-temperature superconductive film that embodiment 1 is prepared；
The phi scanning figures of (103) crystal face for the Yt-Ba-Cu-O high-temperature superconductive film that Fig. 5 embodiments 1 are prepared；
Fig. 6 is (103) crystal face Omega scanning figures of the Yt-Ba-Cu-O high-temperature superconductive film that embodiment 1 is prepared；
Fig. 7 is the J of the Yt-Ba-Cu-O high-temperature superconductive film that embodiment 1 is preparedc- H schemes；
Fig. 8 is the T of the Yt-Ba-Cu-O high-temperature superconductive film that embodiment 1 is preparedcFigure.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
The method that the present invention ultraviolet auxiliary heat treatment prepares Yt-Ba-Cu-O high-temperature superconductive film, specifically according to following steps reality
Apply：
Step 1, prepares yttrium barium copper oxide solution
1.1 are dissolved in mixed solution of the methyl alcohol with the methyl triethanol amine with light sensitive characteristic acetic acid yttrium, obtain molten
Liquid A；Ruthenium ion is 1.5~2 with the mol ratio of methyl triethanol amine：1；
1.2 by trifluoroacetic acid barium be dissolved in methyl alcohol with have light sensitive characteristic acrylic acid mixed solution in, obtain solution
B；Acrylic acid is 8~10 with the mol ratio of barium ions：1；
1.3 are dissolved in methyl alcohol and acrylic acid mixed solution barium acetate, obtain solution C；Acrylic acid and barium ions
Mol ratio is 8~10：1；
1.4 are dissolved in methyl alcohol and acrylic acid mixed solution copper acetate, obtain solution D；Acrylic acid and copper ion
Mol ratio is 3~6：1；
1.5 by solution A, solution B, solution C, and solution D mixing after stirring, obtains yttrium barium copper oxide solution, dilute with methyl alcohol
Release and control the total concentration of the metal ion in solution to control in 0.5~1mol/L；Acetic acid yttrium, trifluoroacetic acid in yttrium barium copper oxide solution
Barium, barium acetate, the mol ratio of copper acetate are 3：x：6-x：9, the wherein value of x is 2≤x≤6；
Step 2, ultraviolet irradiation treatment
The yttrium barium copper oxide solution prepared using step 1 as precursor solution, using dip-coating method, in lanthanum aluminate list
Yttrium barium copper oxide forerunner's gel film is prepared on brilliant substrate, 5~20min is then dried at 80~100 DEG C obtains cured film, will be solid
Change film to be positioned under uviol lamp, irradiate 10~30min, ultraviolet light wave a length of 185 in the air or nitrogen atmosphere at a temperature of 350 DEG C
And 254nm；
Step 3, eventually treatment
Film after ultraviolet irradiation is processed is placed in quartz tube type sintering furnace, to being passed through nitrogen in quartz tube type sintering furnace
Gas, and in-furnace temperature is increased to 760 DEG C with the speed of 10~20 DEG C/min, atmosphere is switched when temperature is increased to 200 DEG C
Into the mixed gas of the oxygen-nitrogen of moisture vapor, the partial pressure of the oxygen of mixed gas is maintained at 200~500ppm, water vapour
Partial pressure is maintained at 4~8kPa；1~3h is incubated after being warmed up to 760 DEG C, atmosphere is then switched into not moisture vapor and is kept identical
The oxygen-nitrogen gaseous mixture of partial pressure of oxygen, and continue 10~30min of insulation, finally with stove natural cooling, when temperature is cooled to 400
Atmosphere is switched into pure O again after at~500 DEG C2, and it is incubated 1~3 hour；After insulation terminates, then room temperature is naturally cooled to stove
Afterwards, atmosphere is closed, sintering obtains final product Yt-Ba-Cu-O high-temperature superconductive film；In above-mentioned whole processing procedure, sintering furnace is communicated with the external world, stove
Interior air pressure maintains an atmospheric pressure all the time.
Thickness to increase film, can be realized by the following method：
Repeat step 2) in gel film preparation and ultraviolet irradiation (UV) processing procedure several times：The wet film that will be lifted
Ultraviolet irradiation (UV) treatment is carried out after drying immediately.The like, the film after multilayer ultraviolet irradiation (UV) treatment is carried out most
Treatment eventually afterwards.
Embodiment 1
1) low fluorine yttrium barium copper oxide solution is prepared；
1.1 mixed solutions that 0.00167mol acetic acid yttriums are dissolved in methyl alcohol and the methyl triethanol amine with light sensitive characteristic
In, obtain solution A；Ruthenium ion is 2 with the mol ratio of methyl triethanol amine：1；
0.00111mol trifluoroacetic acid barium is dissolved in methyl alcohol with acrylic acid mixed solution with light sensitive characteristic by 1.2
In, solution B is obtained, acrylic acid is 10 with the mol ratio of barium ions：1；
1.3 are dissolved in methyl alcohol and acrylic acid mixed solution 0.00222mol barium acetates, obtain solution C, acrylic acid
It is 10 with the mol ratio of barium ions：1；
1.4 are dissolved in methyl alcohol and acrylic acid mixed solution 0.005mol copper acetates, obtain solution D, acrylic acid with
The mol ratio of copper ion is 6：1；
Solution A, solution B, solution C, solution D mixing after stirring, are obtained low fluorine yttrium barium copper oxide solution, use first by 1.5
Alcohol dilution controls the total concentration of the metal ion in solution to control in 1.0mol/L；Low fluorine yttrium barium copper oxide solution ruthenium ion, barium from
Son, the mol ratio of copper ion are 1：2：3, wherein trifluoroacetic acid barium and barium acetate mol ratio is 1：2, therefore F in solution：Ba=2：1；
2) preparation of film and ultraviolet irradiation are processed：
Using low fluorine yttrium barium copper oxide solution as precursor solution, using dip-coating method, with lanthanuma luminate single crystal substrate
Yttrium barium copper oxide forerunner's gel film is prepared, is then dried 20 minutes in 80 DEG C of temperature, obtain yttrium barium copper oxide cured film, solid
Change film to be positioned under uviol lamp, irradiated 30 minutes at a temperature of 350 DEG C in the air atmosphere, ultraviolet light wave a length of 185 and 254nm.
Plated film, and ultraviolet irradiation repeatedly totally 3 times, obtains cured film.
3) the whole treatment of film：
By step 2) film after treatment is placed in quartz tube type sintering furnace, to being passed through nitrogen in quartz tube type sintering furnace,
And in-furnace temperature is increased to 760 DEG C from room temperature with the speed of 20 DEG C/min, atmosphere is switched to and contained by temperature when being increased to 200 DEG C
The mixed gas of the oxygen-nitrogen of water vapour, the partial pressure of the oxygen of mixed gas is maintained at 200ppm, and steam partial pressure is maintained at
4kPa；After being warmed up to 760 DEG C, 3 hours are incubated, atmosphere is then switched into not moisture vapor and the oxygen of identical partial pressure of oxygen is kept
Gas-nitrogen mixture, and continue insulation 30 minutes, finally with stove natural cooling, atmosphere is cut again after temperature is cooled to 450 DEG C
Change pure O into2, and it is incubated 2 hours；After insulation terminates, then after naturally cooling to room temperature with stove, atmosphere is closed, sintered sample is
Yt-Ba-Cu-O high-temperature superconductive film；In above-mentioned whole processing procedure, sintering furnace is communicated with the external world, and the air pressure in stove maintains one all the time
Atmospheric pressure.
Fig. 1 is the XRD spectrum of the film after ultraviolet irradiation heat treatment.As can see from Figure 1 by thin after ultraviolet irradiation
BaF is formd in film2Phase, as shown in Fig. 2 it is converted into that there is the YBCO phases of stronger c-axis orientation in subsequent heat treatment process,
The crystal grain for not having obvious a axles orientation is generated, and this explanation film is by along c-axis epitaxial growth.From the result that XRD spectrum is obtained
With the SEM of Fig. 3 figure presented be it is consistent, it is along c that film surface does not have the crystal grain of random orientation, i.e. film as seen from Figure 3
Axle epitaxial growth.This good c-axis texture is the major premise for ensureing the good superconductivity of superconducting thin film.This outer film surface is caused
It is close without cavity, film thickness prepared by embodiment 1 is 269nm.
As shown in figure 4, atomic force 3D patterns are further illustrated in the area of 10 μm of 10 μ m, yttrium barium copper oxide high-temperature superconductor
Film average surface roughness Ra is only 31.5nm.
Phi scanning figures are observed that four high intensity diffraction maximums and are separated by 90 ° from Fig. 5, and barium copper oxygen high-temperature superconductor is thin
The average halfwidth (FWHM) of film is 1.84 °.Omega scanning figures very narrow, its average halfwidth that can see diffraction maximum in Fig. 6
(FWHM) it is only 0.74 °.Phi and Omega scanning results show that crystal grain arrangement more neat, the barium copper oxygen high-temperature superconductor of film is thin
Film has preferable biaxial orientation outside the inner face of face.
The J of barium copper oxygen high-temperature superconducting thin film prepared by embodiment 1cWith TcMeasurement result as shown in FIG. 7 and 8.Fig. 7 shows
The ybco film prepared with the low fluorine yttrium barium copper oxide solution prepared, under conditions of 0T and 77K, Jc5.97MA/ can be reached
cm2.Fig. 8 shows that the superconducting critical transition temperature of the film is 93K.
Embodiment 2
1) low fluorine yttrium barium copper oxide solution is prepared；
1.1 mixed solutions that 0.00083mol acetic acid yttriums are dissolved in methyl alcohol and the methyl triethanol amine with light sensitive characteristic
In, obtain solution A；Ruthenium ion is 1.8 with the mol ratio of methyl triethanol amine：1；
0.00111mol trifluoroacetic acid barium is dissolved in methyl alcohol with acrylic acid mixed solution with light sensitive characteristic by 1.2
In, solution B is obtained, acrylic acid is 9 with the mol ratio of barium ions：1；
1.3 are dissolved in methyl alcohol and acrylic acid mixed solution 0.00056mol barium acetates, obtain solution C, acrylic acid
It is 9 with the mol ratio of barium ions：1；
1.4 are dissolved in methyl alcohol and acrylic acid mixed solution 0.0025mol copper acetates, obtain solution D, acrylic acid with
The mol ratio of copper ion is 5：1；
Solution A, solution B, solution C, solution D mixing after stirring, are obtained low fluorine yttrium barium copper oxide solution, use first by 1.5
Alcohol dilution controls the total concentration of the metal ion in solution to control in 0.5mol/L.Low fluorine yttrium barium copper oxide solution ruthenium ion, barium from
Son, the mol ratio of copper ion are 1：2：3, wherein trifluoroacetic acid barium and the mol ratio of barium acetate is 2：1, therefore F in solution：Ba=4：
1。
2) preparation of film and ultraviolet irradiation (UV) are processed：
Using low fluorine yttrium barium copper oxide solution as precursor solution, using dip-coating method, made on lanthanuma luminate single crystal substrate
Standby yttrium barium copper oxide forerunner's gel film, then dries 15 minutes in 90 DEG C of temperature, obtains yttrium barium copper oxide cured film, solidification
Film is positioned under uviol lamp, is irradiated 20 minutes at a temperature of 350 DEG C in the nitrogen atmosphere, ultraviolet light wave a length of 185 and 254nm.
Plated film, and ultraviolet irradiation repeatedly totally 6 times, obtains cured film.
3) the whole treatment of film
Film after ultraviolet irradiation is processed is placed in quartz tube type sintering furnace, to being passed through nitrogen in quartz tube type sintering furnace
Gas, and in-furnace temperature is increased to 760 DEG C from room temperature with the speed of 15 DEG C/min, temperature switches atmosphere when being increased to 200 DEG C
Into the mixed gas of the oxygen-nitrogen of moisture vapor, the partial pressure of the oxygen of mixed gas is maintained at 250ppm, and steam partial pressure is protected
Hold in 6kPa；After being warmed up to 760 DEG C, 2 hours are incubated, atmosphere is then switched into not moisture vapor and identical partial pressure of oxygen is kept
Oxygen-nitrogen gaseous mixture, and continue insulation 20 minutes, finally with stove natural cooling, again by atmosphere after temperature is cooled to 400 DEG C
Switch to pure O2, and it is incubated 1 hour；After insulation terminates, then after naturally cooling to room temperature with stove, atmosphere is closed, sintered sample is
It is Yt-Ba-Cu-O high-temperature superconductive film；In above-mentioned whole processing procedure, sintering furnace is communicated with the external world, and the air pressure in stove maintains one all the time
Individual atmospheric pressure.
Embodiment 2 prepares yttrium barium copper oxide film, and critical transition temperature reaches more than 90K, JcReach 3.5MA/cm2With
On.
Embodiment 3
1) low fluorine yttrium barium copper oxide solution is prepared；
1.1 mixed solutions that 0.00083mol acetic acid yttriums are dissolved in methyl alcohol and the methyl triethanol amine with light sensitive characteristic
In, solution A is obtained, ruthenium ion is 1.8 with the mol ratio of methyl triethanol amine：1；
0.00167mol trifluoroacetic acid barium is dissolved in methyl alcohol with acrylic acid mixed solution with light sensitive characteristic by 1.2
In, solution B is obtained, acrylic acid is 8 with the mol ratio of barium ions：1；
1.3 are dissolved in methyl alcohol and acrylic acid mixed solution 0.0025mol copper acetates, obtain solution C, acrylic acid with
The mol ratio of copper ion is 5：1；
1.4 is last, and solution A, solution B, solution C liquid are mixed, and after stirring, obtains low fluorine yttrium barium copper oxide solution, uses
Methanol dilution controls the total concentration of the metal ion in solution to control in 0.5mol/L.Low fluorine yttrium barium copper oxide solution ruthenium ion, barium
Ion, the mol ratio of copper ion are 1：2：3, wherein barium acetate and trifluoroacetic acid barium mol ratio is 0：1, therefore F in solution：Ba=6：
1。
2) preparation of film and ultraviolet irradiation (UV) are processed：
Using low fluorine yttrium barium copper oxide solution as precursor solution, using dip-coating method, made on lanthanuma luminate single crystal substrate
Standby yttrium barium copper oxide forerunner's gel film, then dries 20 minutes in 80 DEG C of temperature, obtains yttrium barium copper oxide cured film, solidification
Film is positioned under uviol lamp, is irradiated 10 minutes at a temperature of 350 DEG C in the nitrogen atmosphere, ultraviolet light wave a length of 185 and 254nm.
Plated film, and ultraviolet irradiation repeatedly totally 6 times, obtains cured film.
3) the whole treatment of film：
Film after ultraviolet irradiation is processed is placed in quartz tube type sintering furnace, to being passed through nitrogen in quartz tube type sintering furnace
Gas, and in-furnace temperature is increased to 760 DEG C from room temperature with the speed of 10 DEG C/min, temperature switches atmosphere when being increased to 200 DEG C
Into the mixed gas of the oxygen-nitrogen of moisture vapor, the partial pressure of the oxygen of mixed gas is maintained at 500ppm, and steam partial pressure is protected
Hold in 8kPa, after being warmed up to 760 DEG C, be incubated 1 hour, atmosphere is then switched into not moisture vapor and identical partial pressure of oxygen is kept
Oxygen-nitrogen gaseous mixture, and continue insulation 10 minutes, finally with stove natural cooling, again by atmosphere after temperature is cooled to 500 DEG C
Switch to pure O2, and it is incubated 3 hours at this temperature；After insulation terminates, then after naturally cooling to room temperature with stove, atmosphere is closed,
Sintered sample is Yt-Ba-Cu-O high-temperature superconductive film；In above-mentioned whole processing procedure, sintering furnace is communicated with the external world, the air pressure in stove
All the time an atmospheric pressure is maintained.
The Yt-Ba-Cu-O high-temperature superconductive film that embodiment 3 is prepared, critical transition temperature reaches more than 90K, JcReach
2MA/cm2More than.
Claims (4)
1. a kind of ultraviolet auxiliary heat treatment method for preparing Yt-Ba-Cu-O high-temperature superconductive film, it is characterised in that specifically according to
Lower step is implemented：
Step 1, prepares yttrium barium copper oxide solution
Acetic acid yttrium is dissolved in mixed solution of the methyl alcohol with the methyl triethanol amine with light sensitive characteristic, solution A is obtained；By three
Fluoroacetic acid barium is dissolved in methyl alcohol and the acrylic acid mixed solution with light sensitive characteristic, obtains solution B；Barium acetate is dissolved in
In methyl alcohol and acrylic acid mixed solution, solution C is obtained；Copper acetate is dissolved in methyl alcohol and acrylic acid mixed solution, is obtained
To solution D；Solution A, solution B, solution C, solution D mixing after stirring, are obtained yttrium barium copper oxide solution, use methanol dilution
The total concentration of the metal ion in solution is controlled to control in 0.5~1mol/L；
Step 2, prepares Yt-Ba-Cu-O high-temperature superconductive film
The yttrium barium copper oxide solution prepared using step 1 as precursor solution, using dip-coating method, in lanthanuma luminate single crystal base
Yttrium barium copper oxide forerunner's gel film is prepared on piece, then in turn through drying, ultraviolet auxiliary photograph treatment, eventually treatment, yttrium barium copper is obtained
Oxygen high-temperature superconducting thin film；
Wherein ultraviolet auxiliary photograph treatment is that dried film is positioned under uviol lamp, 350 DEG C of temperature in air or nitrogen atmosphere
Degree 10~30min of lower irradiation, ultraviolet light wave a length of 185 and 254nm.
2. the method that ultraviolet auxiliary according to claim 1 heat treatment prepares Yt-Ba-Cu-O high-temperature superconductive film, its feature
It is that ruthenium ion and the mol ratio of methyl triethanol amine are 1.5~2 in step 1 solution A：1.
3. the method that ultraviolet auxiliary according to claim 1 heat treatment prepares Yt-Ba-Cu-O high-temperature superconductive film, its feature
It is that acrylic acid and the mol ratio of barium ions are 8~10 in step 1 solution B：1.
4. the method that ultraviolet auxiliary according to claim 1 heat treatment prepares Yt-Ba-Cu-O high-temperature superconductive film, its feature
It is that acetic acid yttrium in the yttrium barium copper oxide solution that step 1 is obtained, trifluoroacetic acid barium, barium acetate, the mol ratio of copper acetate are 3：x：6-
x：9, the wherein value of x is 2≤x<6.
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| Increase of achievable film thickness by UV-lamp irradiation in a fluorine-free metal-organic deposition process of YBa2Cu3O7;H. Matsui et al.;《Thin Solid Films》;20110708;第519卷;第8063页右栏第3段，第8064页左栏第1段，第8065页右栏第2段 * |
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