CN105541317A - Preparation method of yttrium barium copper oxide superconducting thick film - Google Patents
Preparation method of yttrium barium copper oxide superconducting thick film Download PDFInfo
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Abstract
The invention relates to a preparation method of a yttrium barium copper oxide superconducting thick film. The method consists of: firstly preparing a precursor solution, mixing yttrium acetate, barium trifluoroacetate, and copper acetate according to a Y:Ba:Cu mole ratio of 1:2:3, dissolving the mixture in a mixed solution of acetic acid and propionic acid; stirring the substances evenly, then performing vacuum evaporation of the solvent to obtain a gel; then adding methanol and mixing the substances uniformly, then evaporating the solvent to obtain a gel; then adding a proper amount of methanol, polyethylene glycol and terpilenol to make the precursor solution with a 3.0-6.0mol/L total concentration of Y, Ba and Cu three metal ions; then coating a substrate with the precursor solution; subjecting the coated film firstly to a 300-500DEG C low temperature heat treatment process to decompose metal organic salt; then conducting 750DEG C-850DEG C high temperature heat treatment to obtain a yttrium barium copper oxide (YBCO) membrane with a tetragonal phase; and finally performing oxygen uptake treatment at 500-600DEG C so as to obtain a YBCO superconducting thick film with a monolayer thickness of greater than 6 micrometers.
Description
Technical field
The present invention relates to a kind of preparation method of high temperature superconducting film, particularly a kind of preparation method of yttrium barium copper oxide superconducting thick-film.
Background technology
High temperature superconducting materia impels the practicality technology of becoming a useful person of high-temperature superconductor wire strip to become the emphasis of various countries' research in the huge applications potentiality of field of strong electricity.Based on the first-generation belt material of high temperature superconduct of BiSrCaCuO (BSCCO) superconduction system, achieve commercialization in phase late 1990s.But, irreversibility field due to Bi series superconducting material is 0.5T (77K) left and right, application conditions requires very strict, once apply the danger being just faced with quench under magnetic field environment strong a little, more crucially in the process preparing band, adopt silver-colored sleeve pipe (PIT) technology, raw material cost intensive, significantly limit its range applications.Based on the second-generation high-temperature superconductor of YBCO, compared with first-generation superconducting tape, YBCO high temperature superconducting materia has higher irreversibility field (7T) and higher current capacity (0.1 ~ 10MA/cm
2).Meanwhile, second-generation high-temperature superconductor does not use precious metal in the process of preparation, and cost significantly reduces: it is 50 dollars/kilo-ampere rice that bi tape is expected minimum rate, and the price of yttrium frenulum material can drop to 15-25 dollar/kilo-ampere rice, has more Commercial Prospect.Therefore high temperature superconducting materia and technology of preparing thereof are classified as cutting edge technology by " National Program for Medium-to Long-term Scientific and Technological Development (2006-2010) ".
In recent years, the U.S., Japan, Korea S, China drop into a large amount of human and material resources, financial resources in the preparation and research work of YBCO band, obtain a series of gratifying progress.2004, the Fujikura Inc. of Japan, for the YBCO superconducting tape going out first hundred meter levels in the world, subsequently by changing technique, progressively improving length and the critical current of band, in 2008, preparing 504 meters, the superconducting tape of critical current 350A/cm; In 2010, preparing length was 615 meters, the superconducting tape of 609A/cm.On February 12nd, 2011, the said firm prepares length and reaches 816.4 meters, and critical current reaches the band of 572A/cm.2014, the said firm prepared length up to 1000 meters, and mean current is higher than the YBCO coating conductor of 600A/cm.2010, the length of the YBCO superconducting tape that American Superconductor Corp. produces reached 512 meters, and critical current density reaches 466A/cm.And Superpower company just prepared as far back as 2009 km level two generation superconducting tape, critical current reaches 282A/cm.SuNAN company of Korea S also achieved significant achievement in recent years in the preparation of YBCO band, the said firm in 2012 prepare reach 1000 meters two generation belt material of high temperature superconduct, critical current reaches 422A/cm.Associating Jiangxi quotient set group of domestic Shanghai Communications University, company limited of Suzhou new material research institute associating Chinese Academy of Sciences electrician place within 2014, prepare all separately length more than 1000 meters, I
cclose to the second-generation high-temperature superconductor of 300A.Critical electric current value takes advantage of length (I
c× L) be the mark of the high temperature superconductor technology developmental level of measurement country or company.
But YBCO band price is still very expensive at present, the price that the world manufactures the standby YBCO superconducting tape of SuperPower Inc. of businessman U.S. in best two generations is 400 dollars/kilo-ampere rice, it is more than 50 times of copper cash, want its Application Areas more to have competitive power, performance and then the raising cost performance that must improve it further could meet demand widely.YBCO as coating conductor can field of strong electricity application mainly due to it has can load current and the characteristic of not loss.Concerning superconducting tape, remain unchanged in critical current density (Jc) and increase the current capacity that its thickness also just improves it.Therefore, the key issue that the thick film with high critical current densities just becomes urgently to be resolved hurrily in current YBCO high-temperature superconducting coating application process how is prepared.The domestic preparation only having Chinese patent CN101719399A to be referred to thick film in (application publication date on June 2nd, 2010) at present.This patent adopts chemical solution method vinylformic acid copper to replace trifluoroacetic acid copper, and in precursor liquid, adds ethylene glycol amine prepared the YBCO thick film that thickness is 1 micron.Although this patent system is for YBCO thick film, thickness is only 1 micron, limited to the current capacity improving YBCO coating.The more important thing is that two most important index critical currents and critical current density for evaluating superconducting material all do not relate in that patent, its superconductivity cannot be evaluated.
Summary of the invention
The object of the invention is to overcome prior art can not adopt cheap chemical solution method to prepare the shortcoming of YBCO thick film, provides a kind of preparation method with the individual layer YBCO thick film of high current carrying capacity.
The present invention prepares individual layer YBCO superconducting thick-film fast by adopting the full chemical solution method of low fluorine.In containing the low fluorine solution of Y, Ba and Cu metal organic salt, add Terpineol 350 and polyoxyethylene glycol, be made into precursor liquid, by this precursor liquid through low-temperature decomposition and high-temperature heat treatment, prepare the YBCO superconducting film that thickness is greater than 6 microns.
Concrete steps order of the present invention is as follows:
(1) according to the mol ratio of Y:Ba:Cu=1:2:3, yttium acetate, trifluoroacetic acid barium and venus crystals are mixed, be dissolved in the deionized water of acetic acid containing 10-30mol% and propionic acid under room temperature, be made into the low fluorine solution of metal organic salt, in described solution, the mol ratio of solute and solvent is 1:100;
(2) the low fluorine solution of metal organic salt step (1) prepared through magnetic stirrer 1-3h, then adopts Rotary Evaporators to steam to desolventize and obtain gel;
(3) gel that described step (2) is obtained is added in methyl alcohol, gel in this step and the mol ratio of methyl alcohol are 1:50, after magnetic stirrer 0.5-1.5h, then adopt Rotary Evaporators steaming to desolventize, to remove the impurity such as moisture further, obtain pure gel;
(4) gel that described step (3) is obtained is joined in methyl alcohol, Terpineol 350 and polyoxyethylene glycol, the volume ratio of methyl alcohol, Terpineol 350 and polyoxyethylene glycol is 2:1:1, and making Y, Ba and Cu tri-kinds of metal total ion concentrations is the precursor liquid of 3.0-6.0mol/L;
(5) described precursor liquid above-mentioned steps (4) made adopts spin coating or method of pulling up to be coated on substrate;
(6) substrate after step (5) coating is placed in high-temperature tubular quartz stove, at 400 DEG C of-600 DEG C of temperature, carries out the low-temperature heat treatment of 4h, decomposing metal organic salt; The temperature rise rate of this step is 100 ~ 150 DEG C/h;
(7) substrate processed through step (6) is placed in thermal treatment 2-4h under the high temperature of 750 DEG C-850 DEG C, generates Tetragonal YBCO film; The heat-up rate of this step is 400 DEG C/h;
(8) at 450 DEG C-550 DEG C, carry out oxygen uptake process at the sample processed through step (7), prepare the YBCO superconducting thick-film that thickness in monolayer is greater than 6 microns.
Substrate described in step (5) is alloy base band, lanthanum aluminate, strontium titanate or magnesium oxide single-crystal substrate.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopts the low fluorine precursor liquid adding Terpineol 350 and polyoxyethylene glycol to prepare YBCO thick film.Owing to containing a small amount of fluorine in precursor liquid, only have a small amount of hydrogen fluoride gas effusion, can heat-treat precursor liquid fast.The interpolation of what is more important polyoxyethylene glycol and Terpineol 350 extends pyrolysis temperature range, reduces because pyrolysis temperature range is narrow and easily make the possibility that film cracks.In addition, polyoxyethylene glycol and Terpineol 350 can also improve the solubleness of solute, and by increasing solubleness, reduction volatility carrys out stable trifluoroacetic acid copper precursor, thus the stress gradient in lax film prevents thick film distortion to crack.Therefore, still dense when adopting the YBCO film thickness prepared of the method to be greater than 6 microns, reach 2.5MA/cm in null field lower critical current density
2, substantially increase the current capacity of YBCO thick film, reduce the production cost of coating conductor.
Accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope picture of YBCO thick film prepared by embodiment 1;
Fig. 2 is the field emission scanning electron microscope picture of YBCO thick film prepared by embodiment 2;
Fig. 3 is the field emission scanning electron microscope picture of YBCO thick film prepared by embodiment 3;
Fig. 4 is the critical current density picture of YBCO thick film prepared by embodiment 4.
Embodiment
Embodiment 1
(1) take yttium acetate, trifluoroacetic acid barium and venus crystals and be respectively 0.015mol, 0.03mol and 0.045mol, after yttium acetate, trifluoroacetic acid barium and venus crystals being mixed, under room temperature, be dissolved in wiring solution-forming in the deionized water of acetic acid containing 10mol% and propionic acid;
(2) by solution obtained for step (1) after magnetic stirrer 1h, then adopt Rotary Evaporators to steam to desolventize and obtain gel;
(3) methyl alcohol of 10mL is added in the obtained gel of described step (2), then after magnetic stirrer 0.5h, adopt Rotary Evaporators steaming to desolventize remove the impurity such as moisture further and obtain very pure gel again;
(4) joined in the mixed solution of 15ml methyl alcohol, 7.5mL polyoxyethylene glycol and 7.5ml Terpineol 350 by the gel that step (4) is obtained, making Y, Ba and Cu tri-kinds of metal total ion concentrations is the solution of 3mol/L.The solution stirring containing Y, Ba and Cu of gained is evenly prepared into precursor liquid;
(5) by precursor liquid obtained for step (4) with the speed dip-coating of 5 centimeters/minute on strontium titanate monocrystal chip.
(6) step (5) the coated substrate applied is placed on to send in quartz boat in high-temperature tubular quartz stove and carries out low-temperature heat treatment and high-temperature heat treatment, finally obtains YBCO high temperature superconducting film.
Low-temperature heat treatment is carried out under moistening Oxygen Condition, through the vial that distilled water is housed, water vapour is brought the oxygen of 500sccm into reaction chamber, water vapour pressure in reaction chamber is made to be 100hPa, on average be warming up to 400 DEG C with the temperature rise rate of 100 DEG C/h from room temperature, and then stove is cooled to room temperature.The object of low-temperature heat treatment is decomposing metal organic salt, forms unformed precursor film and discharges harmful residual substance.The whole resolving time is about 4h.
High-temperature heat treatment is carried out under moistening oxygen and argon gas mixed atmosphere, argon gas mixed gas 500sccm being contained 500ppm oxygen brings reaction chamber through the vial that distilled water is housed into water vapour, water vapour pressure in reaction chamber is made to be 160hPa, the highest temperature 750 DEG C was risen to before this with the temperature rise rate of 400 DEG C/h, the argon gas mixed gas containing 500ppm oxygen is directly passed into after 750 DEG C of insulation 2h, then 450 DEG C are cooled to 100 DEG C/h, the YBCO oxygen uptake that 0.5h makes Tetragonal is incubated in the purity oxygen atmosphere of 450 DEG C, change the YBCO with superconductivity of orthorhombic phase into, sample stove under oxygen atmosphere is chilled to room temperature subsequently.Carried out morphology observation with field emission scanning electron microscope to the section of sample, YBCO thick film surface is smooth, fine and close, as shown in Figure 1.
Embodiment 2
(1) take yttium acetate, trifluoroacetic acid barium and venus crystals and be respectively 0.015mol, 0.03mol and 0.045mol, after yttium acetate, trifluoroacetic acid barium and venus crystals being mixed, under room temperature, be dissolved in wiring solution-forming in the deionized water of acetic acid containing 20mol% and propionic acid;
(2) by solution obtained for step (1) after magnetic stirrer 2h, then adopt Rotary Evaporators to steam to desolventize and obtain gel;
(3) methyl alcohol of 10mL is added in the obtained gel of described step (2), then after magnetic stirrer 1h, adopt Rotary Evaporators steaming to desolventize remove the impurity such as moisture further and obtain very pure gel again;
(4) joined in the mixed solution of 10ml methyl alcohol, 5mL polyoxyethylene glycol and 5ml Terpineol 350 by the gel that step (4) is obtained, making Y, Ba and Cu tri-kinds of metal total ion concentrations is the solution of 4.5mol/L.The solution stirring containing Y, Ba and Cu of gained is evenly prepared into precursor liquid;
(5) be spin-coated on lanthanuma luminate single crystal substrate by the precursor liquid that step (4) is obtained with the speed of 1000 revs/min, spin-coating time is 90s.
(6) step (5) the coated substrate applied is placed on to send in quartz boat in high-temperature tubular quartz stove and carries out low-temperature heat treatment and high-temperature heat treatment, finally obtains YBCO high temperature superconducting film.
Low-temperature heat treatment is carried out under moistening Oxygen Condition, through the vial that distilled water is housed, water vapour is brought the oxygen of 500sccm into reaction chamber, water vapour pressure in reaction chamber is made to be 130hPa, on average be warming up to 500 DEG C with the temperature rise rate of 125 DEG C/h from room temperature, and then stove is cooled to room temperature.The object of low-temperature heat treatment is decomposing metal organic salt, forms unformed precursor film and discharges harmful residual substance.The whole resolving time is about 4h.
High-temperature heat treatment is carried out under moistening oxygen and argon gas mixed atmosphere, argon gas mixed gas 500sccm being contained 500ppm oxygen brings reaction chamber through the vial that distilled water is housed into water vapour, water vapour pressure in reaction chamber is made to be 200hPa, the highest temperature 800 DEG C was risen to before this with the temperature rise rate of 400 DEG C/h, the argon gas mixed gas containing 500ppm oxygen is directly passed into after 800 DEG C of insulation 3h, then 500 DEG C are cooled to 100 DEG C/h, in the purity oxygen atmosphere of 500 DEG C, be incubated 1h makes the YBCO oxygen uptake of Tetragonal change the YBCO with superconductivity of orthorhombic phase into, sample stove under oxygen atmosphere is chilled to room temperature subsequently.With field emission scanning electron microscope, morphology observation has been carried out to the section of sample, the thickness of YBCO thick film more than 6 microns, as shown in Figure 2.
Embodiment 3
(1) take yttium acetate, trifluoroacetic acid barium and venus crystals and be respectively 0.015mol, 0.03mol and 0.045mol, after yttium acetate, trifluoroacetic acid barium and venus crystals being mixed, under room temperature, be dissolved in wiring solution-forming in the deionized water of acetic acid containing 30mol% and propionic acid;
(2) by solution obtained for step (1) after magnetic stirrer 3h, then adopt Rotary Evaporators to steam to desolventize and obtain gel;
(3) methyl alcohol of 10mL is added in the obtained gel of described step (2), then after magnetic stirrer 1.5h, adopt Rotary Evaporators steaming to desolventize remove the impurity such as moisture further and obtain very pure gel again;
(4) joined in the mixed solution of 7.5ml methyl alcohol, 3.75mL polyoxyethylene glycol and 3.75ml Terpineol 350 by the gel that step (4) is obtained, making Y, Ba and Cu tri-kinds of metal total ion concentrations is the solution of 6mol/L.The solution stirring containing Y, Ba and Cu of gained is evenly prepared into precursor liquid;
(5) be spin-coated on metal base band by the precursor liquid that step (4) is obtained with the speed of 1500 revs/min, spin-coating time is 90s.
(6) step (5) the coated substrate applied is placed on to send in quartz boat in high-temperature tubular quartz stove and carries out low-temperature heat treatment and high-temperature heat treatment, finally obtains YBCO high temperature superconducting film.
Low-temperature heat treatment is carried out under moistening Oxygen Condition, through the vial that distilled water is housed, water vapour is brought the oxygen of 500sccm into reaction chamber, water vapour pressure in reaction chamber is made to be 160hPa, on average be warming up to 600 DEG C with the temperature rise rate of 150 DEG C/h from room temperature, and then stove is cooled to room temperature.The object of low-temperature heat treatment is decomposing metal organic salt, forms unformed precursor film and discharges harmful residual substance.The whole resolving time is about 4h.
High-temperature heat treatment is carried out under moistening oxygen and argon gas mixed atmosphere, argon gas mixed gas 500sccm being contained 500ppm oxygen brings reaction chamber through the vial that distilled water is housed into water vapour, water vapour pressure in reaction chamber is made to be 240hPa, before this with 400 DEG C
dEG Cthe temperature rise rate of/h rises to the highest temperature 850 DEG C
dEG C, at 850 DEG C
dEG Cthe argon gas mixed gas containing 500ppm oxygen is directly passed into after insulation 4h, then 550 DEG C are cooled to 100 DEG C/h, in the purity oxygen atmosphere of 550 DEG C, be incubated 1h makes the YBCO oxygen uptake of Tetragonal change the YBCO with superconductivity of orthorhombic phase into, and sample stove under oxygen atmosphere is chilled to room temperature subsequently.Carried out morphology observation with field emission scanning electron microscope to the surface of sample, YBCO thick film surface is smooth, fine and close, as shown in Figure 3.
Embodiment 4
(1) take yttium acetate, trifluoroacetic acid barium and venus crystals and be respectively 0.015mol, 0.03mol and 0.045mol, after yttium acetate, trifluoroacetic acid barium and venus crystals being mixed, under room temperature, be dissolved in wiring solution-forming in the deionized water of acetic acid containing 10mol% and propionic acid;
(2) by solution obtained for step (1) after magnetic stirrer 1h, then adopt Rotary Evaporators to steam to desolventize and obtain gel;
(3) methyl alcohol of 10mL is added in the obtained gel of described step (2), then after magnetic stirrer 0.5h, adopt Rotary Evaporators steaming to desolventize remove the impurity such as moisture further and obtain very pure gel again;
(4) joined in the mixed solution of 15ml methyl alcohol, 7.5mL polyoxyethylene glycol and 7.5ml Terpineol 350 by the gel that step (4) is obtained, making Y, Ba and Cu tri-kinds of metal total ion concentrations is the solution of 3mol/L.The solution stirring containing Y, Ba and Cu of gained is evenly prepared into precursor liquid;
(5) by precursor liquid obtained for step (4) with the speed dip-coating of 5 centimeters/minute on magnesium oxide single-crystal substrate.
(6) step (5) the coated substrate applied is placed on to send in quartz boat in high-temperature tubular quartz stove and carries out low-temperature heat treatment and high-temperature heat treatment, finally obtains YBCO high temperature superconducting film.
Low-temperature heat treatment is carried out under moistening Oxygen Condition, through the vial that distilled water is housed, water vapour is brought the oxygen of 500sccm into reaction chamber, water vapour pressure in reaction chamber is made to be 100hPa, on average be warming up to 400 DEG C with the temperature rise rate of 100 DEG C/h from room temperature, and then stove is cooled to room temperature.The object of low-temperature heat treatment is decomposing metal organic salt, forms unformed precursor film and discharges harmful residual substance.The whole resolving time is about 4h.
High-temperature heat treatment is carried out under moistening oxygen and argon gas mixed atmosphere, argon gas mixed gas 500sccm being contained 500ppm oxygen brings reaction chamber through the vial that distilled water is housed into water vapour, water vapour pressure in reaction chamber is made to be 160hPa, the highest temperature 750 DEG C was risen to before this with the temperature rise rate of 400 DEG C/h, the argon gas mixed gas containing 500ppm oxygen is directly passed into after 750 DEG C of insulation 2h, then 450 DEG C are cooled to 100 DEG C/h, in the purity oxygen atmosphere of 450 DEG C, be incubated 0.5h makes the YBCO oxygen uptake of Tetragonal change the YBCO with superconductivity of orthorhombic phase into, sample stove under oxygen atmosphere is chilled to room temperature subsequently.Carried out performance test with comprehensive physical property measuring system (PPMS) to sample, the critical current density of YBCO thick film under 77K, null field reaches 2.5MA/cm
2, as shown in Figure 4.
Claims (3)
1. a preparation method for yttrium barium copper oxide superconducting thick-film, is characterized in that, described preparation method adopts the full chemical solution method of low fluorine to prepare individual layer YBCO superconducting thick-film; In containing the low fluorine solution of Y, Ba and Cu metal organic salt, add Terpineol 350 and polyoxyethylene glycol, be made into precursor liquid, by this precursor liquid through low-temperature decomposition and high-temperature heat treatment, prepare the YBCO thick film that thickness in monolayer is greater than 6 microns.
2. according to the preparation method of yttrium barium copper oxide superconducting thick-film according to claim 1, it is characterized in that, described preparation method comprises the steps:
(1) according to the mol ratio of Y:Ba:Cu=1:2:3, yttium acetate, trifluoroacetic acid barium and venus crystals are mixed, be dissolved in the deionized water of acetic acid containing 10-30mol% and propionic acid under room temperature, be made into the low fluorine solution of metal organic salt, in described solution, the mol ratio of solute and solvent is 1:100;
(2) the low fluorine solution of metal organic salt step (1) prepared through magnetic stirrer 1-3h, then adopts Rotary Evaporators to steam to desolventize and obtain gel;
(3) gel that described step (2) is obtained is added in methyl alcohol, gel in this step and the mol ratio of methyl alcohol are 1:50, after magnetic stirrer 0.5-1.5h, then adopt Rotary Evaporators steaming to desolventize, to remove the impurity such as moisture further, obtain pure gel;
(4) gel that described step (3) is obtained is joined in methyl alcohol, Terpineol 350 and polyoxyethylene glycol, the volume ratio of methyl alcohol, Terpineol 350 and polyoxyethylene glycol is 2:1:1, and making Y, Ba and Cu tri-kinds of metal total ion concentrations is the precursor liquid of 3.0-6.0mol/L;
(5) described precursor liquid above-mentioned steps (4) made adopts spin coating or method of pulling up to be coated on substrate;
(6) substrate after step (5) coating is placed in high-temperature tubular quartz stove, at 400 DEG C of-600 DEG C of temperature, carries out the low-temperature heat treatment of 4h, decomposing metal organic salt; The temperature rise rate of this step is 100 ~ 150 DEG C/h;
(7) substrate processed through step (6) is placed in thermal treatment 2-4h under the high temperature of 750 DEG C-850 DEG C, generates Tetragonal YBCO film; The heat-up rate of this step is 400 DEG C/h;
(8) at 450 DEG C-550 DEG C, carry out oxygen uptake process at the sample processed through step (7), prepare the YBCO superconducting thick-film that thickness in monolayer is greater than 6 microns.
3. the preparation method of ybco film thick film as claimed in claim 1, it is characterized in that, in described step (5), described substrate is alloy base band, lanthanum aluminate, strontium titanate or magnesium oxide single-crystal substrate.
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| CN106653993A (en) * | 2016-11-10 | 2017-05-10 | 中国科学院电工研究所 | Preparation method of multilayer structurally yttrium barium copper oxide superconductor thick film |
| CN110600189A (en) * | 2019-09-23 | 2019-12-20 | 西北有色金属研究院 | Stripping and recycling method of coated conductor strip |
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| CN106653993A (en) * | 2016-11-10 | 2017-05-10 | 中国科学院电工研究所 | Preparation method of multilayer structurally yttrium barium copper oxide superconductor thick film |
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