CN106340584B - The fast preparation method of both precursor film used in Tl-2212 superconducting thin films - Google Patents
The fast preparation method of both precursor film used in Tl-2212 superconducting thin films Download PDFInfo
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 25
- 239000008139 complexing agent Substances 0.000 claims description 24
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000004310 lactic acid Substances 0.000 claims description 12
- 235000014655 lactic acid Nutrition 0.000 claims description 12
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 10
- 239000001639 calcium acetate Substances 0.000 claims description 10
- 235000011092 calcium acetate Nutrition 0.000 claims description 10
- 229960005147 calcium acetate Drugs 0.000 claims description 10
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 10
- HQOJMTATBXYHNR-UHFFFAOYSA-M thallium(I) acetate Chemical compound [Tl+].CC([O-])=O HQOJMTATBXYHNR-UHFFFAOYSA-M 0.000 claims description 10
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000003980 solgel method Methods 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- -1 lanthanum aluminate Chemical class 0.000 claims description 4
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- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
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- MYZAXBZLEILEBR-RVFOSREFSA-N (2S)-1-[(2S,3R)-2-[[(2R)-2-[[2-[[(2S)-2-[(2-aminoacetyl)amino]-5-(diaminomethylideneamino)pentanoyl]amino]acetyl]amino]-3-sulfopropanoyl]amino]-3-hydroxybutanoyl]pyrrolidine-2-carboxylic acid Chemical compound C[C@@H](O)[C@H](NC(=O)[C@H](CS(O)(=O)=O)NC(=O)CNC(=O)[C@H](CCCN=C(N)N)NC(=O)CN)C(=O)N1CCC[C@H]1C(O)=O MYZAXBZLEILEBR-RVFOSREFSA-N 0.000 description 2
- SFDZPIDEIFZWQV-UHFFFAOYSA-N acetic acid;barium Chemical group [Ba].CC(O)=O SFDZPIDEIFZWQV-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
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- MUJOIMFVNIBMKC-UHFFFAOYSA-N fludioxonil Chemical compound C=12OC(F)(F)OC2=CC=CC=1C1=CNC=C1C#N MUJOIMFVNIBMKC-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0772—Processes including the use of non-gaseous precursors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0548—Processes for depositing or forming copper oxide superconductor layers by deposition and subsequent treatment, e.g. oxidation of pre-deposited material
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0576—Processes for depositing or forming copper oxide superconductor layers characterised by the substrate
- H10N60/0604—Monocrystalline substrates, e.g. epitaxial growth
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
The invention discloses a kind of fast preparation methods of both precursor film used in 2212 superconducting thin films of Tl.This method is TBCCO colloidal sols to be obtained gel mould on the one or both sides of single crystalline substrate substrate using spin coating or leaching coating, then gel mould progress microwave drying is obtained TBCCO dry films, TBCCO dry films is carried out thermal decomposition process, specially：The TBCCO dry films are placed in microwave high-temperature stove, 10 30min of heated at constant temperature, set temperature is 350 370 DEG C, is cooled to room temperature, obtains both precursor film.The present invention substantially reduces 2212 superconducting thin film generated times of Tl, reduces production cost, while the binding force between 2212 superconducting thin films of Tl and substrate material made from both precursor film using the present invention is stronger.
Description
Technical field
The present invention relates to both precursor film materials.It is more particularly related to used in a kind of Tl-2212 superconducting thin films first
Drive the fast preparation method of film.
Background technology
Tl2Ba2CaCu2O8(Tl-2212) superconducting thin film has higher critical-temperature (Tc is up to 110K), higher faces
The advantages that boundary's current density and stronger moisture resistant ability is the important materials for developing high-performance high-temperature superconductor electronic device.
It prepares there are two types of thallium series film methods, one is physical method, technology of preparing is more mature.One is chemistry sides
Method, due to its preparation process complexity, people are less to this research.In numerous chemical preparation process, sol-gel process is
A kind of materials are few, it is at low cost, be easily achieved large-scale production, compound is uniformly mixed, component is easy to the preparation side accurately controlled
Method.Although this method has the advantages that more, also there is disadvantage, to prepare thicker film sample, need by repeatedly applying
It smears, dry, thermal decomposition process, causing the manufacturing cycle of single sample longer, considerably increase production cost.
Invention content
It is an object of the invention to solve at least the above, and provide the advantages of at least will be described later.
It is a still further object of the present invention to provide a kind of preparations for synthesizing both precursor film used in Tl-2212 superconducting thin films
Method substantially reduces synthesis Tl-2212 superconducting thin films generated time, reduces production cost, while using used in the present invention
Tl-2212 superconducting thin films binding force made from both precursor film is stronger.
In order to realize these purposes and other advantages according to the present invention, provide used in a kind of Tl-2212 superconducting thin films
The fast preparation method of both precursor film, by TBCCO colloidal sols on the one or both sides of single crystalline substrate substrate using spin coating or
It soaks coating and obtains gel mould, then the gel mould is dry that TBCCO dry films have TBCCO dry films progress thermal decomposition process
Body is：
The TBCCO dry films being placed in microwave high-temperature stove, heated at constant temperature 10-30min, set temperature is 350-370 DEG C,
It is cooled to room temperature, obtains both precursor film.
Preferably, gel mould it is dry TBCCO dry films, specially：
The gel mould is subjected to micro-wave drying using low-temperature zone and middle-temperature section in microwave high-temperature stove successively, is obtained
The TBCCO dry films；Wherein, the drying time of two sections of temperature is 5-15min, and low temperature drying temperature is 100 DEG C -160 DEG C, in
Warm drying temperature is 180 DEG C -250 DEG C, and the heating-up time controls in 2-5s.
Preferably, in thermal decomposition process, the time control of set temperature is warming up in 3-5s.
Preferably, the thickness control of the TBCCO dry films is at 20nm-2 μm.
Preferably, the preparation method of the TBCCO colloidal sols is：
With molar ratio for 2.8~3.5:2:1:Thallium acetate, barium acetate, calcium acetate and the copper acetate of 2.5-2.8 is that starting is former
Material adds complexing agent respectively and solvent prepares solution A, solution B, solution C and solution D, and decompression steaming is carried out after above-mentioned solution is mixed
Evaporate to remove acetic acid and water, be added methanol and be evaporated under reduced pressure later, until mixed solution liquid in the pasty state, and without acetic acid and
Polyvinyl butyral is added in water in liquid/paste, and 0.4-1h is stirred at 45~55 DEG C to get the TBCCO colloidal sols；Its
In, polyvinyl butyral accounts for the 3%~5% of liquid/paste quality.
Preferably,
During preparing solution A, the complexing agent and solvent are propionic acid, diethylenetriamine and distilled water, addition
Amount is that the molar ratio of thallium acetate, propionic acid, diethylenetriamine and distilled water is 1:3~5:0.5~1.5:100~200, at 50 DEG C
2h is stirred, solution A is obtained；
During preparing solution B, the complexing agent and solvent are propionic acid, lactic acid and distilled water, and additive amount is acetic acid
Barium, propionic acid, lactic acid and distilled water molar ratio be 1:1.5~2.5:1~1.5:50~100,1h is stirred at 50 DEG C, is obtained molten
Liquid B；
During preparing solution C, the complexing agent and solvent are propionic acid and distilled water, and additive amount is calcium acetate, third
The molar ratio of acid and distilled water is 1:1~1.5:50~100,30min is stirred at 50 DEG C, obtains solution C；
During preparing solution D, the complexing agent and solvent are propionic acid, distilled water, and additive amount is copper acetate, propionic acid
Molar ratio with distilled water is 1:2~2.6:100~150,1h is stirred at 50 DEG C, obtains solution D；
Preferably, the material of the single crystalline substrate substrate be lanthanum aluminate, sapphire, magnesia, yttrium stable zirconium oxide or
There is the metal substrate material of texture.
Preferably, the TBCCO colloidal sols are prepared using floride-free method, fluorine-containing method, sol-gel process or metal
Organic deposition method and these methods are combined prepared.
The present invention includes at least following advantageous effect：The present invention provides rapid draing and the TBCCO of a kind of TBCCO gel moulds
The thermal decomposition process of dry film uses micro-wave drying and thermal decomposition process.Micro-wave drying be different from it is traditional in it is low
Radiant drying method is warmed, traditional drying mode is external heat drying, and heat conducts to inside from sample surfaces, exists
Temperature gradient, drying time is longer.And microwave drying is a kind of inside and outside while heating method, sample is in microwave
In higher-order of oscillation electric field, polarization phenomena can occur for internal hydrone, polar molecule with direction of an electric field variation constantly
Make torsion alternation orientation movement, generate violent collision and friction, so that the temperature of water is increased and is left sample, to keep sample fast
Speed obtains drying.In addition, thermal decomposition time can also be shortened with this dry film, it is longer to solve thicker Tl systems superconducting thin film preparation time
The problem of, production cost is reduced, production technology is simplified, is more suitable for large-scale production.
It is dried using three sections of temperature of low, medium and high temperature and obtains pioneer's film with thermal decomposition process.The technology of preparing
Have the advantages that heating and cooling rate are fast, dry and thermal decomposition time is short, the Tl-2212 of pioneer's film preparation using the present invention
Superconducting thin film is the pure phase film that (00l) is orientated, and Tl-2212 superconducting thin films and substrate binding force are big, and has smooth table
Face, the structure of fine and close flawless and good superconductivity, Tc and Jc can respectively reach 105K and 1.2MA/cm2。
Part is illustrated to embody by further advantage, target and the feature of the present invention by following, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Description of the drawings
Fig. 1 is the SEM scanning figures for TBCCO pioneer's film that embodiment 1 makes on lanthanuma luminate single crystal substrate；
Fig. 2 is the SEM scanning figures for the Tl-2212 superconducting thin films that embodiment 1 makes on lanthanuma luminate single crystal substrate.
Specific implementation mode
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art with reference to specification text
Word can be implemented according to this.
It should be noted that experimental method described in following embodiments is unless otherwise specified conventional method, institute
Reagent and material are stated, unless otherwise specified, is commercially obtained.
Embodiment
The fast preparation method of both precursor film used in a kind of Tl-2212 superconducting thin films, by TBCCO colloidal sols in single crystalline substrate base
Gel mould is obtained using spin coating or leaching coating on the one or both sides of piece, then the gel mould is dry that TBCCO is done
TBCCO dry films are carried out thermal decomposition process, specially by film：
The TBCCO dry films being placed in microwave high-temperature stove, heated at constant temperature 10-30min, set temperature is 350-370 DEG C,
It is cooled to room temperature, obtains both precursor film.
The fast preparation method of both precursor film used in the Tl-2212 superconducting thin films, wherein gel mould it is dry TBCCO
Dry film, specially：
The gel mould is subjected to micro-wave drying using low-temperature zone and middle-temperature section in microwave high-temperature stove successively, is obtained
The TBCCO dry films；Wherein, the drying time of two sections of temperature is 5-15min, and low temperature drying temperature is 100 DEG C -160 DEG C, in
Warm drying temperature is 180 DEG C -250 DEG C, and the heating-up time controls in 2-5s.
The fast preparation method of both precursor film used in the Tl-2212 superconducting thin films, wherein in thermal decomposition process, rise
Temperature to set temperature time control in 3-5s, shorten the heating-up time, superconducting thin film made from thus both precursor film can be improved
Binding force, conductive effect are more preferable.
The fast preparation method of both precursor film used in the Tl-2212 superconducting thin films, wherein the thickness of the TBCCO dry films
At 20nm-2 μm, control is conducive to superconducting thin film densification flawless obtained in the range for degree control.
The fast preparation method of both precursor film used in the Tl-2212 superconducting thin films, wherein the system of the TBCCO colloidal sols
Preparation Method is：
With molar ratio for 2.8~3.5:2:1:Thallium acetate, barium acetate, calcium acetate and the copper acetate of 2.5-2.8 is that starting is former
Material adds complexing agent respectively and solvent prepares solution A, solution B, solution C and solution D, and decompression steaming is carried out after above-mentioned solution is mixed
Evaporate to remove acetic acid and water, be added methanol and be evaporated under reduced pressure later, until mixed solution liquid in the pasty state, and without acetic acid and
Polyvinyl butyral is added in water in liquid/paste, and 0.4-1h is stirred at 45~55 DEG C to get the TBCCO colloidal sols；Its
In, polyvinyl butyral accounts for the 3%~5% of liquid/paste quality, using polyvinyl butyral be conducive to improve film with
The binding force of substrate.
The fast preparation method of both precursor film used in the Tl-2212 superconducting thin films, wherein
During preparing solution A, the complexing agent and solvent are propionic acid, diethylenetriamine and distilled water, addition
Amount is that the molar ratio of thallium acetate, propionic acid, diethylenetriamine and distilled water is 1:3~5:0.5~1.5:100~200, at 50 DEG C
2h is stirred, solution A is obtained；
During preparing solution B, the complexing agent and solvent are propionic acid, lactic acid and distilled water, and additive amount is acetic acid
Barium, propionic acid, lactic acid and distilled water molar ratio be 1:1.5~2.5:1~1.5:50~100,1h is stirred at 50 DEG C, is obtained molten
Liquid B；
During preparing solution C, the complexing agent and solvent are propionic acid and distilled water, and additive amount is calcium acetate, third
The molar ratio of acid and distilled water is 1:1~1.5:50~100,30min is stirred at 50 DEG C, obtains solution C；
During preparing solution D, the complexing agent and solvent are propionic acid, distilled water, and additive amount is copper acetate, propionic acid
Molar ratio with distilled water is 1:2~2.6:100~150,1h is stirred at 50 DEG C, obtains solution D；
The fast preparation method of both precursor film used in the Tl-2212 superconducting thin films, wherein the single crystalline substrate substrate
Material is lanthanum aluminate, sapphire, magnesia, yttrium stable zirconium oxide or the metal substrate material for having texture.
The fast preparation method of both precursor film used in the Tl-2212 superconducting thin films, wherein prepared by the TBCCO colloidal sols
Institute is combined using floride-free method, fluorine-containing method, sol-gel process or deposition of metal organic method and these methods
It prepares.
Embodiment 1
1) TBCCO colloidal sols are using fluorine-free sol-gel method in the present embodiment, first with molar ratio for 3:2:1:
2.5 thallium acetate, barium acetate, calcium acetate and copper acetate is that starting material adds distilled water, propionic acid, lactic acid, divinyl three respectively
The complexing agents such as amine and solvent prepare solution A, solution B, solution C and solution D, wherein during preparing solution A, the network
Mixture and solvent are propionic acid, diethylenetriamine and distilled water, and additive amount is thallium acetate, propionic acid, diethylenetriamine and distilled water
Molar ratio be 1:3:0.5:100,2h is stirred at 50 DEG C, obtains solution A；During preparing solution B, the complexing agent
It is propionic acid, lactic acid and distilled water with solvent, additive amount is that the molar ratio of barium acetate, propionic acid, lactic acid and distilled water is 1:1.5:1:
50,1h is stirred at 50 DEG C, obtains solution B；During preparing solution C, the complexing agent and solvent are propionic acid and distillation
Water, additive amount are that the molar ratio of calcium acetate, propionic acid and distilled water is 1:1:50,30min is stirred at 50 DEG C, obtains solution C；
During preparing solution D, the complexing agent and solvent are propionic acid, distilled water, and additive amount is copper acetate, propionic acid and distilled water
Molar ratio is 1:2:100,1h is stirred at 50 DEG C, obtains solution D.
2) it is evaporated under reduced pressure after mixing above-mentioned A-D solution, removes acetic acid and water；Methanol is added, is depressurized again
Evaporation, is repeated twice, obtains the liquid/paste of no acetic acid and water.Then polyvinyl butyral is added, is stirred at 50 DEG C
The TBCCO colloidal sols can be made in 0.5h, and polyvinyl butyral accounts for the 3% of liquid/paste quality.
3) TBCCO colloidal sols are obtained on the lanthanum aluminate LAO monocrystalline substrate materials of single-sided polishing using spin coating methods
Gel mould.
4) gel mould is used into micro-wave drying technique, i.e., first in 140 DEG C of dry 10min of low temperature, then in high temperature
180 DEG C of dry 5min, so that it may obtain TBCCO dry films.
5) TBCCO dry films are put into microwave high-temperature stove, 350 DEG C are risen in 3-5s, constant temperature 10min.Thermally decompose program
After execution, it is naturally cooling to room temperature, obtains pioneer's film.
6) Tl-2212 superconducting thin films are prepared.Pioneer's film is accompanied to burn with thallium source and is enclosed in corundum crucible together with target, crucible
It is put into quartz ampoule, is passed through the oxygen of flowing, flow 10ml/min, then heating carries out thallation processing, makes amorphous
TBCCO both precursor films are changed into Tl-2212 superconducting phases.Wherein, heating rate is 8 DEG C/min, and annealing temperature is 830 DEG C, annealing
Time is 2h；After Temperature fall, you can obtain the Tl-2212 superconducting thin films that critical-temperature is 105.8K.Its conductive effect is good, faces
Boundary's current density can reach 1.2MA/cm2, critical-temperature 105K.
TBCCO both precursor films made from embodiment 1 are done into SEM scanning figures, see Fig. 1；TBCCO made from embodiment 1 is used in combination
Both precursor film makes Tl-2212 superconducting thin films, and obtained Tl-2212 superconducting thin films are done SEM scanning figures, sees Fig. 2.
TBCCO both precursor films obtained surface is smooth as seen from Figure 1, without any crackle, makes as seen from Figure 2
The Tl-2212 superconducting thin films surface of work is clean, no other impurities, compact crystallization.
Embodiment 2
1) TBCCO colloidal sols are using fluorine-free sol-gel method in the present embodiment, first with molar ratio for 3.5:2:
1:2.8 thallium acetate, barium acetate, calcium acetate and copper acetate is that starting material adds distilled water, propionic acid, lactic acid, divinyl respectively
The complexing agents such as triamine and solvent prepare solution A, solution B, solution C and solution D, wherein described during preparing solution A
Complexing agent and solvent are propionic acid, diethylenetriamine and distilled water, and additive amount is thallium acetate, propionic acid, diethylenetriamine and distillation
The molar ratio of water is 1:5:1:200,2h is stirred at 50 DEG C, obtains solution A；During preparing solution B, the complexing agent
It is propionic acid, lactic acid and distilled water with solvent, additive amount is that the molar ratio of barium acetate, propionic acid, lactic acid and distilled water is 1:2:1.5:
90,1h is stirred at 50 DEG C, obtains solution B；During preparing solution C, the complexing agent and solvent are propionic acid and distillation
Water, additive amount are that the molar ratio of calcium acetate, propionic acid and distilled water is 1:1.5:80,30min is stirred at 50 DEG C, obtains solution C；
During preparing solution D, the complexing agent and solvent are propionic acid, distilled water, and additive amount is copper acetate, propionic acid and distilled water
Molar ratio be 1:2.6:150,1h is stirred at 50 DEG C, obtains solution D.
2) it is evaporated under reduced pressure after mixing above-mentioned A-D solution, removes acetic acid and water；Methanol is added, is depressurized again
Evaporation, is repeated twice, obtains the liquid/paste of no acetic acid and water.Then polyvinyl butyral is added, 1h is stirred at 55 DEG C
The TBCCO colloidal sols can be made, polyvinyl butyral accounts for the 5% of liquid/paste quality.
3) it by TBCCO colloidal sols on the saphire substrate material with cerium oxide buffer layer, is obtained using dip-coating layer method
Gel mould.
4) gel mould is used into micro-wave drying technique, i.e., first in 100 DEG C of dry 5min of low temperature, then in high temperature
250 DEG C of dry 5min, so that it may obtain TBCCO dry films.
5) TBCCO dry films are put into microwave high-temperature stove, temperature is set as 370 DEG C, constant temperature 15min.Thermal decomposition program is held
After row, it is cooled to room temperature, obtains pioneer's film.
6) Tl-2212 superconducting thin films are prepared.Pioneer's film is accompanied to burn with thallium source and is enclosed in corundum crucible together with target, crucible
It is put into quartz ampoule, is passed through the oxygen of flowing, flow 10ml/min, then heating carries out thallation processing, makes amorphous
TBCCO both precursor films are changed into Tl-2212 superconducting phases.Wherein, heating rate is 8 DEG C/min, and annealing temperature is 830 DEG C, annealing
Time is 2h；After Temperature fall, you can obtain the Tl-2212 superconducting thin films that critical-temperature is 106K.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (7)
1. the fast preparation method of both precursor film used in a kind of Tl-2212 superconducting thin films, which is characterized in that TBCCO colloidal sols exist
Gel mould is obtained using spin coating or leaching coating on the one or both sides of single crystalline substrate substrate, then the gel mould is dried
TBCCO dry films are obtained, TBCCO dry films are subjected to thermal decomposition process, specially：
The TBCCO dry films are placed in microwave high-temperature stove, heated at constant temperature 10-30min, set temperature is 350-370 DEG C, cooling
To room temperature, both precursor film is obtained；
Gel mould it is dry TBCCO dry films, specially：
The gel mould is subjected to micro-wave drying using low-temperature zone and middle-temperature section in microwave high-temperature stove successively, is obtained described
TBCCO dry films；Wherein, the drying time of two sections of temperature is 5-15min, and low temperature drying temperature is 100 DEG C -160 DEG C, and medium temperature is dry
Dry temperature is 180 DEG C -250 DEG C, and the heating-up time controls in 2-5s.
2. the fast preparation method of both precursor film used in Tl-2212 superconducting thin films as described in claim 1, which is characterized in that
In thermal decomposition process, the time control of set temperature is warming up in 3-5s.
3. the fast preparation method of both precursor film used in Tl-2212 superconducting thin films as described in claim 1, which is characterized in that
The thickness control of the TBCCO dry films is at 20nm-2 μm.
4. the fast preparation method of both precursor film used in Tl-2212 superconducting thin films as described in claim 1, which is characterized in that
The preparation method of the TBCCO colloidal sols is：
With molar ratio for 2.8~3.5:2:1:Thallium acetate, barium acetate, calcium acetate and the copper acetate of 2.5-2.8 is starting material point
Not Tian Jia complexing agent and solvent prepare solution A, solution B, solution C and solution D, will above-mentioned solution mix after be evaporated under reduced pressure with
Acetic acid and water are removed, methanol is added later and is evaporated under reduced pressure, until mixed solution liquid in the pasty state, and without acetic acid and water,
Polyvinyl butyral is added in liquid/paste, 0.4-1h is stirred at 45~55 DEG C to get the TBCCO colloidal sols；Wherein,
Polyvinyl butyral accounts for the 3%~5% of liquid/paste quality.
5. the fast preparation method of both precursor film used in Tl-2212 superconducting thin films as claimed in claim 4, which is characterized in that
During preparing solution A, the complexing agent and solvent are propionic acid, diethylenetriamine and distilled water, and additive amount is
Thallium acetate, propionic acid, diethylenetriamine and distilled water molar ratio be 1:3~5:0.5~1.5:100~200, it is stirred at 50 DEG C
2h obtains solution A；
During preparing solution B, the complexing agent and solvent are propionic acid, lactic acid and distilled water, and additive amount is barium acetate, third
The molar ratio of acid, lactic acid and distilled water is 1:1.5~2.5:1~1.5:50~100,1h is stirred at 50 DEG C, obtains solution B；
During preparing solution C, the complexing agent and solvent are propionic acid and distilled water, additive amount be calcium acetate, propionic acid and
The molar ratio of distilled water is 1:1~1.5:50~100,30min is stirred at 50 DEG C, obtains solution C；
During preparing solution D, the complexing agent and solvent are propionic acid, distilled water, and additive amount is copper acetate, propionic acid and steaming
The molar ratio of distilled water is 1:2~2.6:100~150,1h is stirred at 50 DEG C, obtains solution D.
6. the fast preparation method of both precursor film used in Tl-2212 superconducting thin films as described in claim 1, which is characterized in that
The material of the single crystalline substrate substrate is lanthanum aluminate, sapphire, magnesia, yttrium stable zirconium oxide or the metal liner ground for having texture
Material.
7. the fast preparation method of both precursor film used in Tl-2212 superconducting thin films as described in claim 1, which is characterized in that
The TBCCO colloidal sols prepare using floride-free method, fluorine-containing method, sol-gel process or deposition of metal organic method and
These methods are combined prepared.
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| WO2012079747A1 (en) * | 2010-12-16 | 2012-06-21 | Stichting Dutch Polymer Institute | Method for preparing microstructured patterns of superconductive materials |
| CN103304232A (en) * | 2013-07-05 | 2013-09-18 | 广西师范学院 | Preparation method for synthesizing T1-2212 superconducting thin film by employing sol-gel method |
| CN104445382A (en) * | 2014-12-03 | 2015-03-25 | 北方民族大学 | Method for preparing Bi12TiO20 nano-powder by virtue of microwave-assisted sol-gel method |
| CN104909722A (en) * | 2015-05-27 | 2015-09-16 | 广西师范学院 | Preparation method for synthesizing T1-2212 superconducting thin film through fluorine-free sol-gel method |
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| WO2012079747A1 (en) * | 2010-12-16 | 2012-06-21 | Stichting Dutch Polymer Institute | Method for preparing microstructured patterns of superconductive materials |
| CN103304232A (en) * | 2013-07-05 | 2013-09-18 | 广西师范学院 | Preparation method for synthesizing T1-2212 superconducting thin film by employing sol-gel method |
| CN104445382A (en) * | 2014-12-03 | 2015-03-25 | 北方民族大学 | Method for preparing Bi12TiO20 nano-powder by virtue of microwave-assisted sol-gel method |
| CN104909722A (en) * | 2015-05-27 | 2015-09-16 | 广西师范学院 | Preparation method for synthesizing T1-2212 superconducting thin film through fluorine-free sol-gel method |
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