CN104909722B - A kind of fluorine-free sol gel method synthesizes the preparation method of the superconducting thin films of Tl 2212 - Google Patents
A kind of fluorine-free sol gel method synthesizes the preparation method of the superconducting thin films of Tl 2212 Download PDFInfo
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Abstract
A kind of fluorine-free sol gel method synthesizes the preparation method of the superconducting thin films of T1 2212, thallium acetate using mol ratio as 2.8 3.5: 2: 1: 2.5 2.8, barium acetate, calcium acetate and copper acetate are that initiation material adds complexing agent respectively and solvent prepares solution A, B, C and D, TBCCO colloidal sols are made in the formamide that 20 45 times of amounts of barium acetate molal quantity are added after above-mentioned solution is mixed, then gel mould is made in TBCCO colloidal sols, pioneer's film is made in gel mould progress thermal decomposition process, by pioneer's film with accompanying burning target high temperature sintering containing thallium source, produce the superconducting thin films of T1 2212, wherein, preparing solution A, during B and D, propionic acid is with the addition of respectively.The colloidal sol composition of the present invention is well mixed, and chemical stability is good, has smooth surface and good superconductivity using superconducting thin film made from the colloidal sol.
Description
Technical field
The present invention relates to superconducting film material, and in particular to a kind of fluorine-free sol-gel method synthesis Tl-2212 superconducting thin films
Preparation method.
Background technology
Since oxide high temperature superconductor is found, high-temperature superconducting thin film is always the emphasis of various countries' computer MSR Information system research
One of problem.On the one hand, high-temperature superconducting thin film can be that the mechanism of high-temperature superconductor and physical property research provide strong material and supported.
On the other hand, high-quality epitaxial high temperature superconducting thin film is the basis of superconducting electronics application.In current practical high-temperature superconductor
Among film, Tl2Ba2CaCu2O8(Tl-2212) film has higher superconducting transition temperature (TcGenerally 105K), it is good
Structural stability, the advantages of particularly to the resistance of wet environment, relatively strong, performance is typically difficult to degenerate.Therefore, Tl-2212 is thin
Film is the important materials for developing high-performance high-frequency electronic device and Josephson junction devices.
It is more ripe using the technology of preparing of physical method in the various researchs for preparing Tl-2212 films, including magnetic control
Sputtering, electron beam evaporation, pulsed laser deposition (PLD) etc.；And use the Study on Preparation Technology of chemical method less, it is only few
Number computer MSR Information system once uses the method such as metallorganic chemical vapor deposition (MOCVD) and aerosol deposition (aerosol)
Studied, resulting sample is non-pure c-axis oriented film, still lacked to preparing Tl-2212 using remaining chemical method
The research of film.
Go deep into the application of superconductor, yttrium system superconducting thin film is prepared as one studied at present using chemical method
Focus.Wherein sol-gel (sol-gel) method has that materials are few, cost is low, is easily achieved large-scale production, compound is mixed
Close the advantages of uniform, component is easy to accurate control.Therefore, this method is used widely in development function film.This hair
Bright use fluorine-free sol-gel method quickly prepares thicker Tl-2212 superconducting thin films, and there is provided the preparation of TBCCO colloidal sols, pioneer's film
Three techniques such as preparation, the after annealing of pioneer's film, solve the problem of thicker Tl systems superconducting thin film preparation time is longer.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide one kind using fluorine-free sol-gel method synthesis Tl-2212 superconductions
The preparation method of film.
A further object of the invention be by adding propionic acid during colloidal sol is prepared, make to obtain when smearing every time compared with
Thick gel mould, reducing preparation pioneer's film needs to smear number of times.
A further object of the invention is by adding formamide during colloidal sol is prepared, suppressing BaCO3Formation,
And prevent gel mould from being cracked in heat treatment process.
A further object of the invention is by, using two sections of heating, improving heating rate in thermal decomposition process, reducing
Heating-up time.
The invention provides the preparation method that a kind of fluorine-free sol-gel method synthesizes Tl-2212 superconducting thin films, with mol ratio
For 2.8-3.5: 2: 1: 2.5-2.8 thallium acetate, barium acetate, calcium acetate and copper acetate be initiation material add respectively complexing agent and
Solvent prepares solution A, solution B, solution C and solution D, adds what 20-45 times of barium acetate molal quantity was measured after above-mentioned solution is mixed
TBCCO colloidal sols are made in formamide, and TBCCO colloidal sols then are made into gel mould, and gel mould progress thermal decomposition process is made into pioneer
Film, by pioneer's film with accompanying burning target high temperature sintering containing thallium source, produces Tl-2212 superconducting thin films, wherein, preparing solution A, molten
During liquid B and solution D, propionic acid is with the addition of respectively, addition is：The mol ratio of thallium acetate and propionic acid is 1: 3.8-5；Acetic acid
The mol ratio of barium and propionic acid is 1: 2.6-3.6；The mol ratio of copper acetate and propionic acid is 1: 2-2.6.
Preferably, during solution A is prepared, described complexing agent and solvent are diethylenetriamine and methanol, addition
Amount is that the mol ratio of thallium acetate, propionic acid, diethylenetriamine and methanol is 1: 3.8-5: 3-4: 100-140, is stirred at 70 DEG C
80min, obtains solution A；
During solution B is prepared, described complexing agent and solvent are lactic acid and methanol, and addition is barium acetate, third
The mol ratio of acid, lactic acid and methanol is 1: 2.6-3.6: 2-2.8: 30-50, stirs 80min at 70 DEG C, obtains solution B；
During solution C is prepared, described complexing agent and solvent are lactic acid and methanol, and addition is calcium acetate, breast
The mol ratio of acid and methanol is 1: 3.5-4.5: 100-150, is stirred at 50 DEG C, obtains solution C；
During solution D is prepared, described complexing agent and solvent are triethylene tetramine and methanol, and addition is acetic acid
Copper, propionic acid, triethylene tetramine, the mol ratio of methanol are 1: 2-2.6: 0.4-0.6: 50-100 mixing, are stirred at 70 DEG C
80min, obtains solution D；
The formamide of solution A, B, C, D and above-mentioned mol ratio is mixed, 80min is stirred at 70 DEG C, obtains TBCCO molten
Glue.
Preferably, concretely comprising the following steps for gel mould is made in TBCCO colloidal sols：
TBCCO colloidal sols are placed on lanthanuma luminate single crystal backing material, the gel mould of moistening is obtained using spin coating method, will
The gel mould, which is put into vacuum drying chamber at 80 DEG C, dries 1h, is then dried in air or other gases at 120 DEG C
1h, obtains gel mould.
Preferably, concretely comprising the following steps for pioneer's film is made in gel mould progress thermal decomposition process：
Gel mould is placed in quartz ampoule, then quartz ampoule is put into high temperature furnace thermally decomposed, wet argon gas is passed through, together
When, high temperature furnace rises to 370 DEG C with 3-5 DEG C/min speed, keeps 20min, is then shut off wet argon gas, is passed through wet oxygen, 370
10min is kept at DEG C, then is warming up to 450 DEG C with 5-10 DEG C/min speed and keeps 10min, room temperature is then naturally cooling to,
Obtain thin pioneer's film；It is repeated once, obtains pioneer's film of thickness.
Preferably, the specific preparation process for burning target of accompanying containing thallium source is：
Use BaO2, CaO and CuO coordinate grinding 30 minutes, the flowing oxygen at 890-940 DEG C according to mol ratio 2: 2: 3
Calcination 5-10 hours in atmosphere, ground again after cooling 30 minutes, calcination 5-10 hours in the flowing oxygen atmosphere at 890-940 DEG C,
BaCaCuO powder is made, by the BaCaCuO powder and Tl2O3Powder mixed grinding tabletting after 30 minutes, after sealed crucible
Calcination 2 hours in oxygen atmosphere are flowed at 850 DEG C, Tl is supplemented after cooling2O3Powder grinds 30 minutes and tabletting again, at 850 DEG C
Flowing oxygen atmosphere in calcination 2 hours, be made and accompany burning target containing thallium source.
Preferably, the high temperature sintering is concretely comprised the following steps：
Pioneer's film is placed on accompanying on burning target containing thallium source, and is enclosed within corundum crucible, then the corundum crucible is put
In quartz ampoule, high-temperature heat treatment is carried out under 101KPa oxygen atmosphere, thick pioneer's film is changed into Tl-2212 superconductions
Film, wherein, heating rate is 8 DEG C/min, and annealing temperature is 850 DEG C, and annealing time is 1h；After Temperature fall, you can obtain
Critical-temperature is 105.5K Tl-2212 superconducting thin films.
Preferably, the saturated vapor pressure of the wet argon gas is 17.54-49.65mmHg, and its flow velocity is 50-100mL/
min。
Preferably, the wet oxygen saturated vapor pressure is 17.54-49.65mmHg, and its flow velocity is 100-150mL/min.
The present invention has the following advantages that compared with the prior art：
1st, it is raw material in thallium acetate, barium acetate and copper acetate, using lactic acid, diethylenetriamine, triethylene tetramine, methanol as network
In the technique of mixture and solvent to prepare colloidal sol, propionic acid is additionally added, the thickness of TBCCO colloidal sols, Jin Er can be significantly improved
Thicker gel mould is obtained using spin coating method every time, reduces and smears number of times, show through overtesting, only needed by above technology
Smearing 2 times can make the thickness of gel mould reach 400nm, and 3 thickness are smeared in the case of without propionic acid and are also only reached
320nm, drastically increases the manufacturing speed of gel mould, secondly as the flatness of gel mould is with increasing for the number of plies of smearing
Reduction, therefore the present invention also correspondingly improves the flatness of gel mould, and then improve the quality of Tl-2212 superconducting thin films.
2nd, when configuring TBCCO colloidal sols, formamide is added, can effectively suppress BaCO3Formation, prevent gel mould in heat
Cracked in processing procedure, condition is provided for the preparation of gel mould.
3rd, in thermal decomposition process, 370 DEG C are warming up to using logical wet argon gas, then change logical wet oxygen is warming up to 450 DEG C two
Segmentation heating, overcomes the shortcoming that the maximum temperature being heat-treated in logical argon gas can only achieve 400 DEG C, makes pyrolysis more
Add entirely, while this technique can accelerate heating rate, 0.5-2 DEG C of script/min speed is brought up to 5-10 DEG C/min,
The time of whole thermal decomposition process is set to foreshorten to 100min by original about 400min, needed for can greatly reducing temperature-rise period
Time and process costs.
4th, prepare the source containing thallium accompany burning target during, Tl is supplemented before tabletting2O3Powder, is allowed for heat treated
The a small amount of Tl of Cheng Zhonghui volatilizations2O3, make Tl after supplement2O3It is maintained at the mixing ratio of BaCaCuO powder in rational scope, makes to accompany
Target better quality is burnt, and then the Tl-2212 superconducting thin film performances prepared are also more excellent.
5th, the present invention has the spies such as technique is simple, production cost is low, composition is easy to accurate control, suitable large-scale production
Point.Colloidal sol composition produced by the present invention is well mixed, and chemical stability is good, is had using superconducting thin film made from the colloidal sol smooth
Surface and good superconductivity.
Brief description of the drawings
Fig. 1 is the XRD of the Tl-2212 superconducting thin films made The present invention gives embodiment 3 on lanthanuma luminate single crystal substrate
Scanning figure.
Fig. 2 is the SEM of the Tl-2212 superconducting thin films made The present invention gives embodiment 3 on lanthanuma luminate single crystal substrate
Scanning figure.
Embodiment
With reference to embodiment, the present invention is described in further detail, to make those skilled in the art with reference to specification
Word can be implemented according to this.
Embodiment 1
A kind of fluorine-free sol-gel method synthesizes the preparation method of Tl-2212 superconducting thin films, using mol ratio as 2.8: 2: 1:
2.5 thallium acetate, barium acetate, calcium acetate and copper acetate is that initiation material adds complexing agent respectively and solvent prepares solution A, solution
B, solution C and solution D, it is molten that TBCCO is made in the formamide that 20-45 times of addition barium acetate molal quantity is measured after above-mentioned solution is mixed
Glue, is then made gel mould by TBCCO colloidal sols, gel mould progress thermal decomposition process is made into pioneer's film, by pioneer's film with containing
Target high temperature sintering is burnt in accompanying for thallium source, produces Tl-2212 superconducting thin films, wherein, preparing the process of solution A, solution B and solution D
In, propionic acid is with the addition of respectively, and addition is：The mol ratio of thallium acetate and propionic acid is 1: 3.8；The mol ratio of barium acetate and propionic acid is
1∶2.6；The mol ratio of copper acetate and propionic acid is 1: 2.
During solution A is prepared, described complexing agent and solvent are diethylenetriamine and methanol, and addition is acetic acid
Thallium, propionic acid, the mol ratio of diethylenetriamine and methanol are 1: 3.8: 3: 100, stir 80min at 70 DEG C, obtain solution A；
During solution B is prepared, described complexing agent and solvent are lactic acid and methanol, and addition is barium acetate, third
The mol ratio of acid, lactic acid and methanol is 1: 2.6: 2: 30, stirs 80min at 70 DEG C, obtains solution B；
During solution C is prepared, described complexing agent and solvent are lactic acid and methanol, and addition is calcium acetate, breast
The mol ratio of acid and methanol is 1: 3.5: 100, is stirred at 50 DEG C, obtains solution C；
During solution D is prepared, described complexing agent and solvent are triethylene tetramine and methanol, and addition is acetic acid
Copper, propionic acid, triethylene tetramine, the mol ratio of methanol are 1: 2: 0.4: 50 mixing, stir 80min at 70 DEG C, obtain solution D；
The formamide of solution A, B, C, D and above-mentioned mol ratio is mixed, 80min is stirred at 70 DEG C, obtains TBCCO molten
Glue.
Concretely comprising the following steps for gel mould is made in TBCCO colloidal sols：
TBCCO colloidal sols are placed on lanthanuma luminate single crystal backing material, the gel mould of moistening is obtained using spin coating method, will
The gel mould, which is put into vacuum drying chamber at 80 DEG C, dries 1h, is then dried in air or other gases at 120 DEG C
1h, obtains gel mould.
Concretely comprising the following steps for pioneer's film is made in gel mould progress thermal decomposition process：
Gel mould is placed in quartz ampoule, then quartz ampoule is put into high temperature furnace thermally decomposed, wet argon gas is passed through, together
When, high temperature furnace rises to 370 DEG C with 3 DEG C/min speed, keeps 20min, is then shut off wet argon gas, is passed through wet oxygen, at 370 DEG C
Lower holding 10min, then be warming up to 450 DEG C with 5 DEG C/min speed and keep 10min, room temperature is then naturally cooling to, obtains thin
Pioneer's film；It is repeated once, obtains pioneer's film of thickness.
It is described containing thallium source accompany burn target specific preparation process be：
Use BaO2, CaO and CuO coordinate in grinding 30 minutes, the flowing oxygen atmosphere at 890 DEG C according to mol ratio 2: 2: 3
Calcination 5 hours, grinds 30 minutes again after cooling, and calcination 5 hours, is made BaCaCuO powder in the flowing oxygen atmosphere at 890 DEG C
End, by the BaCaCuO powder and Tl2O3Powder mixed grinding tabletting after 30 minutes, with the flowing at 850 DEG C after sealed crucible
Calcination 2 hours, supplement Tl in oxygen atmosphere after cooling2O3Powder grinds 30 minutes and tabletting, the flowing oxygen atmosphere at 850 DEG C again
Middle calcination 2 hours, is made and accompanies burning target containing thallium source.
The high temperature sintering is concretely comprised the following steps：
Pioneer's film is placed on accompanying on burning target containing thallium source, and is enclosed within corundum crucible, then the corundum crucible is put
In quartz ampoule, high-temperature heat treatment is carried out under 101KPa oxygen atmosphere, thick pioneer's film is changed into Tl-2212 superconductions
Film, wherein, heating rate is 8C/min, and annealing temperature is 850 DEG C, and annealing time is 1h；After Temperature fall, you can faced
Boundary's temperature is 105.5K Tl-2212 superconducting thin films.
The saturated vapor pressure of the wet argon gas is 17.54mmHg, and its flow velocity is 50mL/min.
The wet oxygen saturated vapor pressure is 17.54mmHg, and its flow velocity is 100mL/min.
Embodiment 2
A kind of fluorine-free sol-gel method synthesizes the preparation method of Tl-2212 superconducting thin films, using mol ratio as 3.5: 2: 1:
2.8 thallium acetate, barium acetate, calcium acetate and copper acetate is that initiation material adds complexing agent respectively and solvent prepares solution A, solution
TBCCO colloidal sols are made in B, solution C and solution D, the formamide that 45 times of amounts of barium acetate molal quantity are added after above-mentioned solution is mixed, so
Gel mould is made in TBCCO colloidal sols afterwards, pioneer's film is made in gel mould progress thermal decomposition process, by pioneer's film with containing thallium source
Burning target high temperature sintering is accompanied, Tl-2212 superconducting thin films are produced, wherein, during solution A, solution B and solution D is prepared, respectively
Propionic acid is with the addition of, addition is：The mol ratio of thallium acetate and propionic acid is 1: 5；The mol ratio of barium acetate and propionic acid is 1: 3.6；Second
The mol ratio of sour copper and propionic acid is 1: 2.6.
Preferably, during solution A is prepared, described complexing agent and solvent are diethylenetriamine and methanol, addition
Amount is that the mol ratio of thallium acetate, propionic acid, diethylenetriamine and methanol is 1: 5: 4: 140, stirs 80min at 70 DEG C, obtains molten
Liquid A；
During solution B is prepared, described complexing agent and solvent are lactic acid and methanol, and addition is barium acetate, third
The mol ratio of acid, lactic acid and methanol is 1: 3.6: 2.8: 50, stirs 80min at 70 DEG C, obtains solution B；
During solution C is prepared, described complexing agent and solvent are lactic acid and methanol, and addition is calcium acetate, breast
The mol ratio of acid and methanol is 1: 4.5: 150, is stirred at 50 DEG C, obtains solution C；
During solution D is prepared, described complexing agent and solvent are triethylene tetramine and methanol, and addition is acetic acid
Copper, propionic acid, triethylene tetramine, the mol ratio of methanol are 1: 2.6: 0.6: 100 mixing, stir 80min at 70 DEG C, obtain solution
D；
The formamide of solution A, B, C, D and above-mentioned mol ratio is mixed, 80min is stirred at 70 DEG C, obtains TBCCO molten
Glue.
Concretely comprising the following steps for gel mould is made in TBCCO colloidal sols：
TBCCO colloidal sols are placed on lanthanuma luminate single crystal backing material, the gel mould of moistening is obtained using spin coating method, will
The gel mould, which is put into vacuum drying chamber at 80 DEG C, dries 1h, is then dried in air or other gases at 120 DEG C
1h, obtains gel mould.
Concretely comprising the following steps for pioneer's film is made in gel mould progress thermal decomposition process：
Gel mould is placed in quartz ampoule, then quartz ampoule is put into high temperature furnace thermally decomposed, wet argon gas is passed through, together
When, high temperature furnace rises to 370 DEG C with 5C/min speed, keeps 20min, is then shut off wet argon gas, is passed through wet oxygen, at 370 DEG C
Lower holding 10min, then be warming up to 450 DEG C with 10 DEG C/min speed and keep 10min, room temperature is then naturally cooling to, is obtained
Thin pioneer's film；It is repeated once, obtains pioneer's film of thickness.
It is described containing thallium source accompany burn target specific preparation process be：
Use BaO2, CaO and CuO coordinate in grinding 30 minutes, the flowing oxygen atmosphere at 940 DEG C according to mol ratio 2: 2: 3
Calcination 10 hours, grinds 30 minutes again after cooling, and calcination 10 hours, is made BaCaCuO powder in the flowing oxygen atmosphere at 940 DEG C
End, by the BaCaCuO powder and Tl2O3Powder mixed grinding tabletting after 30 minutes, with the flowing at 850 DEG C after sealed crucible
Calcination 2 hours, supplement Tl in oxygen atmosphere after cooling2O3Powder grinds 30 minutes and tabletting, the flowing oxygen atmosphere at 850 DEG C again
Middle calcination 2 hours, is made and accompanies burning target containing thallium source.
The high temperature sintering is concretely comprised the following steps：
Pioneer's film is placed on accompanying on burning target containing thallium source, and is enclosed within corundum crucible, then the corundum crucible is put
In quartz ampoule, high-temperature heat treatment is carried out under 101KPa oxygen atmosphere, thick pioneer's film is changed into Tl-2212 superconductions
Film, wherein, heating rate is 8 DEG C/min, and annealing temperature is 850 DEG C, and annealing time is 1h；After Temperature fall, you can obtain
Critical-temperature is 105.5K Tl-2212 superconducting thin films.
The saturated vapor pressure of the wet argon gas is 49.65mmHg, and its flow velocity is 100mL/min.
The wet oxygen saturated vapor pressure is 49.65mmHg, and its flow velocity is 150mL/min.
Embodiment 3
A kind of fluorine-free sol-gel method synthesizes the preparation method of Tl-2212 superconducting thin films, using mol ratio as 2.9：2∶1∶
2.7 thallium acetate, barium acetate, calcium acetate and copper acetate is that initiation material adds complexing agent respectively and solvent prepares solution A, solution
TBCCO colloidal sols are made in B, solution C and solution D, the formamide that 40 times of amounts of barium acetate molal quantity are added after above-mentioned solution is mixed, so
Gel mould is made in TBCCO colloidal sols afterwards, pioneer's film is made in gel mould progress thermal decomposition process, by pioneer's film with containing thallium source
Accompany burning target high temperature sintering, produce Tl-2212 superconducting thin films, its XRD scanning figure as shown in figure 1, its SEM scanning figure as shown in Fig. 2
Wherein, during solution A, solution B and solution D is prepared, propionic acid is with the addition of respectively, addition is：Thallium acetate and propionic acid
Mol ratio is 1: 4.2；The mol ratio of barium acetate and propionic acid is 1: 2.9；The mol ratio of copper acetate and propionic acid is 1: 2.3.
Preferably, during solution A is prepared, described complexing agent and solvent are diethylenetriamine and methanol, addition
Amount is that the mol ratio of thallium acetate, propionic acid, diethylenetriamine and methanol is 1: 4.2: 3.2: 120, stirs 80min at 70 DEG C, obtains
To solution A；
During solution B is prepared, described complexing agent and solvent are lactic acid and methanol, and addition is barium acetate, third
The mol ratio of acid, lactic acid and methanol is 1: 2.9: 2.4: 40, stirs 80min at 70 DEG C, obtains solution B；
During solution C is prepared, described complexing agent and solvent are lactic acid and methanol, and addition is calcium acetate, breast
The mol ratio of acid and methanol is 1: 4: 120, is stirred at 50 DEG C, obtains solution C；
During solution D is prepared, described complexing agent and solvent are triethylene tetramine and methanol, and addition is acetic acid
Copper, propionic acid, triethylene tetramine, the mol ratio of methanol are 1: 2.3: 0.5: 70 mixing, stir 80min at 70 DEG C, obtain solution
D；
The formamide of solution A, B, C, D and above-mentioned mol ratio is mixed, 80min is stirred at 70 DEG C, obtains TBCCO molten
Glue.
Concretely comprising the following steps for gel mould is made in TBCCO colloidal sols：
TBCCO colloidal sols are placed on lanthanuma luminate single crystal backing material, the gel mould of moistening is obtained using spin coating method, will
The gel mould, which is put into vacuum drying chamber at 80 DEG C, dries 1h, is then dried in air or other gases at 120 DEG C
1h, obtains gel mould.
Concretely comprising the following steps for pioneer's film is made in gel mould progress thermal decomposition process：
Gel mould is placed in quartz ampoule, then quartz ampoule is put into high temperature furnace thermally decomposed, wet argon gas is passed through, together
When, high temperature furnace rises to 370 DEG C with 4 DEG C/min speed, keeps 20min, is then shut off wet argon gas, is passed through wet oxygen, at 370 DEG C
Lower holding 10min, then be warming up to 450 DEG C with 6 DEG C/min speed and keep 10min, room temperature is then naturally cooling to, obtains thin
Pioneer's film；It is repeated once, obtains pioneer's film of thickness.
It is described containing thallium source accompany burn target specific preparation process be：
Use BaO2, CaO and CuO coordinate in grinding 30 minutes, the flowing oxygen atmosphere at 920 DEG C according to mol ratio 2: 2: 3
Calcination 8 hours, grinds 30 minutes again after cooling, and calcination 8 hours, is made BaCaCuO powder in the flowing oxygen atmosphere at 920 DEG C
End, by the BaCaCuO powder and Tl2O3Powder mixed grinding tabletting after 30 minutes, with the flowing at 850 DEG C after sealed crucible
Calcination 2 hours, supplement Tl in oxygen atmosphere after cooling2O3Powder grinds 30 minutes and tabletting, the flowing oxygen atmosphere at 850 DEG C again
Middle calcination 2 hours, is made and accompanies burning target containing thallium source.
The high temperature sintering is concretely comprised the following steps：
Pioneer's film is placed on accompanying on burning target containing thallium source, and is enclosed within corundum crucible, then the corundum crucible is put
In quartz ampoule, high-temperature heat treatment is carried out under 101KPa oxygen atmosphere, thick pioneer's film is changed into Tl-2212 superconductions
Film, wherein, heating rate is 8 DEG C/min, and annealing temperature is 850 DEG C, and annealing time is 1h；After Temperature fall, you can obtain
Critical-temperature is 105.5K Tl-2212 superconducting thin films.
The saturated vapor pressure of the wet argon gas is 25mmHg, and its flow velocity is 75mL/min.
The wet oxygen saturated vapor pressure is 28mmHg, and its flow velocity is 120mL/min.
As Fig. 1 shows, prepared Tl-2212 superconducting thin films are pure c-axis orientation, and crystal grain without other orientations occur.
SEM scanning figures such as Fig. 2 show that film surface is smooth, compact structure, without crackle.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited
In specific details and shown here as the legend with description.
Claims (8)
1. a kind of fluorine-free sol-gel method synthesizes the preparation methods of T1-2212 superconducting thin films, it is characterised in that using mol ratio as
2.8-3.5: 2: 1: 2.5-2.8 thallium acetate, barium acetate, calcium acetate and copper acetate is that initiation material adds complexing agent and molten respectively
Agent prepares solution A, solution B, solution C and solution D, and the first that 20-45 times of barium acetate molal quantity is measured is added after above-mentioned solution is mixed
TBCCO colloidal sols are made in acid amides, and TBCCO colloidal sols then are made into gel mould, and gel mould progress thermal decomposition process is made into pioneer's film,
By pioneer's film with accompanying burning target high temperature sintering containing thallium source, T1-2212 superconducting thin films are produced, wherein, preparing solution A, solution B
During solution D, propionic acid is with the addition of respectively, and addition is：The mol ratio of thallium acetate and propionic acid is 1: 3.8-5；Barium acetate
Mol ratio with propionic acid is 1: 2.6-3.6；The mol ratio of copper acetate and propionic acid is 1: 2-2.6.
2. fluorine-free sol as claimed in claim 1-gel method synthesizes the preparation method of T1-2212 superconducting thin films, its feature exists
In,
During solution A is prepared, described complexing agent and solvent are diethylenetriamine and methanol, addition be thallium acetate,
The mol ratio of propionic acid, diethylenetriamine and methanol is 1: 3.8-5: 3-4: 100-140, stirs 80min at 70 DEG C, obtains solution
A；
During solution B is prepared, described complexing agent and solvent are lactic acid and methanol, and addition is barium acetate, propionic acid, breast
The mol ratio of acid and methanol is 1: 2.6-3.6: 2-2.8: 30-50, stirs 80min at 70 DEG C, obtains solution B；
During solution C is prepared, described complexing agent and solvent are lactic acid and methanol, addition be calcium acetate, lactic acid and
The mol ratio of methanol is 1: 3.5-4.5: 100-150, is stirred at 50 DEG C, obtains solution C；
During solution D is prepared, described complexing agent and solvent are triethylene tetramine and methanol, addition be copper acetate,
Propionic acid, triethylene tetramine, the mol ratio of methanol are 1: 2-2.6: 0.4-0.6: 50-100 mixing, stir 80min at 70 DEG C, obtain
To solution D；
The formamide of solution A, B, C, D and above-mentioned mol ratio is mixed, 3h is stirred at 70 DEG C, obtains TBCCO colloidal sols.
3. fluorine-free sol as claimed in claim 2-gel method synthesizes the preparation method of T1-2212 superconducting thin films, its feature exists
In TBCCO colloidal sols are made into concretely comprising the following steps for gel mould：
TBCCO colloidal sols are placed on lanthanuma luminate single crystal backing material, the gel mould of moistening is obtained using spin coating method, will be described
Gel mould, which is put into vacuum drying chamber at 80 DEG C, dries 1h, then dries 1h at 120 DEG C in air or other gases, obtains
To gel mould.
4. fluorine-free sol as claimed in claim 3-gel method synthesizes the preparation method of T1-2212 superconducting thin films, its feature exists
In, by gel mould progress thermal decomposition process concretely comprising the following steps for pioneer's film is made：
Gel mould is placed in quartz ampoule, then quartz ampoule is put into high temperature furnace thermally decomposed, wet argon gas is passed through, meanwhile, it is high
Warm stove rises to 370 DEG C with 3-5 DEG C/min speed, keeps 20min, is then shut off wet argon gas, is passed through wet oxygen, at 370 DEG C
10min is kept, then is warming up to 450 DEG C with 5-10 DEG C/min speed and keeps 10min, room temperature is then naturally cooling to, obtains
Thin pioneer's film；It is repeated once, obtains pioneer's film of thickness.
5. fluorine-free sol as claimed in claim 4-gel method synthesizes the preparation method of T1-2212 superconducting thin films, its feature exists
In the specific preparation process for burning target of accompanying containing thallium source is：
Use BaO2, CaO and CuO coordinate in grinding 30 minutes, the flowing oxygen atmosphere at 890-940 DEG C according to mol ratio 2: 2: 3 and burn
Burn 5-10 hours, ground again after cooling 30 minutes, calcination 5-10 hours, is made in the flowing oxygen atmosphere at 890-940 DEG C
BaCaCuO powder, by the BaCaCuO powder and Tl2O3The tabletting after 30 minutes of powder mixed grinding, with after sealed crucible 850
Calcination 2 hours in oxygen atmosphere are flowed at DEG C, Tl is supplemented after cooling2O3Powder grinds 30 minutes and tabletting, the stream at 850 DEG C again
Calcination 2 hours, is made and accompanies burning target containing thallium source in dynamic oxygen atmosphere.
6. fluorine-free sol as claimed in claim 5-gel method synthesizes the preparation method of Tl-2212 superconducting thin films, its feature exists
In concretely comprising the following steps for, the high temperature sintering：
Pioneer's film is placed on accompanying on burning target containing thallium source, and is enclosed within corundum crucible, then the corundum crucible is placed in stone
Ying Guanzhong, carries out high-temperature heat treatment under 101KPa oxygen atmosphere, thick pioneer's film is changed into Tl-2212 superconducting thin films, its
In, heating rate is 8 DEG C/min, and annealing temperature is 850 DEG C, and annealing time is 1h；After Temperature fall, that is, obtaining critical-temperature is
105.5K Tl-2212 superconducting thin films.
7. fluorine-free sol as claimed in claim 6-gel method synthesizes the preparation method of Tl-2212 superconducting thin films, its feature exists
In the saturated vapor pressure of the wet argon gas is 17.54-49.65mmHg, and its flow velocity is 50-100mL/min.
8. fluorine-free sol as claimed in claim 7-gel method synthesizes the preparation method of Tl-2212 superconducting thin films, the wet oxygen
Gas saturated vapor pressure is 17.54-49.65mmHg, and its flow velocity is 100-150mL/min.
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