CN101723659B - Method for preparing superconductive layer of coated conductor by organic deposition of low-fluorine metal - Google Patents

Method for preparing superconductive layer of coated conductor by organic deposition of low-fluorine metal Download PDF

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CN101723659B
CN101723659B CN2009100239774A CN200910023977A CN101723659B CN 101723659 B CN101723659 B CN 101723659B CN 2009100239774 A CN2009100239774 A CN 2009100239774A CN 200910023977 A CN200910023977 A CN 200910023977A CN 101723659 B CN101723659 B CN 101723659B
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金利华
张云
卢亚锋
李成山
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Northwest Institute for Non Ferrous Metal Research
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Abstract

The invention discloses a method for preparing a superconductive layer of a coated conductor by the organic deposition of low-fluorine metal, which comprises the following steps of: dissolving precursor yttrium benzoate or yttrium 1,3,5-benzenetricarboxylic acid, barium trifluoroacetate and copper benzoate or copper 1,3,5-benzenetricarboxylic acid in a mixed solvent of methanol and propanoic acid, introducing the methanol, performing repeated distillation under reduced pressure by using a rotary evaporator to obtain a colloid, and dissolving the colloid in the mixed solvent of the methanol and the propanoic acid to obtain precursor solution; coating the precursor solution on a substrate with a buffer layer by a spin-coating method or a dip-coating method to obtain a precursor film; performing low-temperature decomposition on the dried precursor film in a tubular furnace; and performing high-temperature crystallization on the precursor film after the low-temperature decomposition in high-temperature flowing argon/oxygen atmosphere. The method overcomes the defects of a slow low-temperature heat treatment process in the conventional process, shortens the time, improves the preparation efficiency, and meets the requirement of industrialized production; and the surface of the prepared superconductive layer is intact and has no defects such as cracks and the like, and the prepared superconductive layer has high biaxial texture and good superconducting property.

Description

A kind of method of preparing superconductive layer of coated conductor by organic deposition of low-fluorine metal
Technical field
The invention belongs to the high temperature superconducting materia preparing technical field, particularly relate to a kind of method of preparing superconductive layer of coated conductor by organic deposition of low-fluorine metal.
Background technology
Coating conductor is by metal base band/impact plies/REBa 2Cu 3O yThe practical high temperature superconducting materia of the multilayered structure type that superconducting layer/resist constitutes.In order to obtain high current-carrying coating conductor, people propose and have developed two type coating conductors technology: the physical vapor deposition (PVD) of vacuum and antivacuum chemical solution deposition (CSD) technology.The former is representative with ion beam assisted depositing/pulsed laser deposition (IBAD/PLD) technical combinations, and the latter is representative with rolling auxiliary biaxial texture/metal organic deposit (RABiTS/MOD) technical combinations.The IBAD/PLD technology is the main means of preparation high-performance coating conductor, and the RABiTS/MOD technology is considered to the striving direction of low-cost coating conductor.Antivacuum technical characterstic is that equipment cost is low, can accurately control the stoichiometric ratio of metal constituent element, but the homogeneity of the heterogeneous microstructure of long band and superconductivity needs to optimize.Wherein trifluoroacetate-metal organic deposit (TFA-MOD) technology is the main flow technology of CSD technology, has been used in (M.W.Rupich et al, MRS Bulletin/Augest, 2004,572 in the low-cost mass production; T.Araki et al, Supercond.Sci.Technol., 2003,16, R71).At present, American Superconductor Corp. (AMSC) and Japan are clear adopts the TFA-MOD technology all can successfully prepare critical current greater than the long band of hundred meter levels of 300A/cm-w (77K, self-fields) with cable company (SWCC).
The principal feature that the TFA-MOD technology is different from other CSD technology is: adopting full trifluoroacetate is presoma, can avoid the precursor of barium to form stable barium carbonate in the high-temperature heat treatment stage.Trifluoroacetic acid barium resolves into barium fluoride earlier in the low-temperature decomposition stage, high temperature become the phase stage through with the water reaction conversion be barium oxide, finally can form the high quality superconducting thin film hanging down into the phase thermal treatment temp.
But trifluoroacetic acid copper has the distillation of being prone to, the violent characteristic of decomposition reaction in the full trifluoroacetate presoma of tradition, and whole presoma fluorine too high levels simultaneously influences the continuous preparation efficiency of superconducting layer.Precursor liquid is improved or the development of new precursor liquid is the focus of coating conductor research current focus.A plurality of research units all are under the constant situation of the trifluoroacetate that keeps barium, replace to trifluoroacetic acid copper, and exploitation is with " BaF 2Mechanism " be the modified version precursor liquid on basis, reduce the susceptibility of precursor liquid to preparation technology.U.S. Sandia National Laboratory carries out study on the modification to precursor liquid, and trifluoroacetic acid barium, trifluoroacetic acid barium in the presoma are remained unchanged, and mantoquita replaces with the venus crystals that contains diethylolamine; Realize preparation (J.T.Dawley et al, Physica C, 2004 fast; 402,103).Japan SRL-ISTEC proposes and has developed Advanced TFA-MOD technology, mainly adopts copper naphthenate replacement trifluoroacetic acid copper, reduces the total content of fluorine in the presoma; Shorten the low-temperature heat treatment time; Low-temperature decomposition speed has improved 10 times of (Y.Tokunaga et al, Cryogenics, 2004 than traditional technology; 44,817).U.S.'s Oak Ridge National Laboratory (ORNL) adopts copper sulfate replacement trifluoroacetic acid copper to reduce the content of fluorine; The low-temperature decomposition time shortens to 1/4 (M.S.Bhuiyan et al, IEEETranscations on Applied Superconductivity, 2007 of traditional technology; 17,3557).These research units select free-floride and the more stable mantoquita of character to replace trifluoroacetic acid copper usually, thereby realize preparation fast.
Summary of the invention
The objective of the invention is provides a kind of method of preparing superconductive layer of coated conductor by organic deposition of low-fluorine metal in order to overcome the deficiency of prior art.This method technology is simple, low cost, and it is long effectively to overcome the low-temperature decomposition time that exists among traditional TFA-MOD, to defectives such as processing parameter sensitivities, can simplify technology simultaneously, realizes efficient production, satisfies industrial demand; Perfect the falling in superconducting layer surface of preparation has strong biaxial texture, and superconductivity is good.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of method of preparing superconductive layer of coated conductor by organic deposition of low-fluorine metal is characterized in that this method may further comprise the steps:
(1) preparation of precursor liquid: according to atomicity than Y: Ba: Cu=1: 2: 3 with presoma phenylformic acid yttrium or 1; 3,5-benzene tricarboxylic acid yttrium and trifluoroacetic acid barium and cupric benzoate or 1,3; 5-benzene tricarboxylic acid copper dissolution obtains preparatory precursor liquid in the mixed solvent of methyl alcohol and propionic acid; With Rotary Evaporators and introduce methyl alcohol and said preparatory precursor liquid is carried out repeatedly underpressure distillation obtain colloid, colloid is dissolved in the mixed solvent of methyl alcohol and propionic acid and obtains precursor liquid, controlling said precursor liquid metals ion total mol concentration is 1.5M; Wherein, the volume ratio of methyl alcohol in the said mixed solvent and propionic acid is 1: 1;
(2) coating and dry: the precursor liquid in the step (1) is coated on the substrate with impact plies with spin-coating method or dip coating, and under temperature 100-150 ℃ condition, carries out the dry precursor film that gets, said substrate is Ni-5W/La 2Zr 2O 7/ CeO 2Or YSZ/La 2Zr 2O 7/ CeO 2, wherein, YSZ is the stable zirconium white of yttrium;
(3) low-temperature decomposition: dried precursor film is carried out low-temperature decomposition in tube furnace, top temperature is 400 ℃, and atmosphere is controlled to be the mobile oxygen atmosphere; Whole low-temperature decomposition thermal treatment route is divided into two stages: from the room temperature to 150-200 ℃, temperature rise rate is controlled to be 5 ℃/minute, and atmosphere is the exsiccant oxygen atmosphere; Be 1-5 ℃/minute with the temperature rise rate and continue to be warmed up to 400 ℃, introduce moist oxygen in this stage, steam dividing potential drop content is controlled to be 0.6%-3.1%, after reaction finishes, stops logical oxygen, lowers the temperature with stove;
(4) high temperature becomes phase: the precursor film after the low-temperature decomposition at high temperature 780-800 ℃, is carried out the high temperature crystallization in tube furnace under mobile argon/oxygen atmosphere; Whole high temperature crystallization and thermal treatment route is: with the temperature rise rate be 10-25 ℃/minute furnace temperature risen to 780-800 ℃ from room temperature, constant temperature 1-3 hour, oxygen partial pressure content was controlled at 200-1000ppm, and steam dividing potential drop content is controlled to be 0.6%-3.1%; When in exsiccant argon/oxygen atmosphere, being cooled to 525 ℃ then, atmosphere is replaced by the exsiccant oxygen atmosphere, at 450 ℃ of constant temperature 1-3h precursor film is oozed the oxygen processing at last and obtain coating conductor superconducting layer;
Said low fluorine is meant that presoma fluorine content is the 30wt% of presoma fluorine content in the full trifluoroacetic acid metal organic deposit of tradition in the low-fluorine metal organic deposit.
The exsiccant time described in the above-mentioned steps (2) is 10 minutes.
The present invention compared with prior art has the following advantages:
1, the novel precursor liquid that adopts new type of copper salt and yttrium salt to prepare has overcome the shortcoming that traditional precursor liquid is prone to suction; Make the precursor liquid of preparation more stable; Can preserve for a long time, reduce novel precursor liquid susceptibility to atmospheric moisture in coating procedure, help continuously long band preparation.
2, adopt novel precursor liquid, can effectively overcome the shortcoming that the reaction of trifluoroacetic acid copper in traditional precursor liquid is violent, be prone to distillation, novel precursor thermal decomposition behavior and trifluoroacetic acid barium are approaching simultaneously, make precursor liquid pyrolysis character homogeneous.Help simplifying thermal treatment process; The whole low-temperature decomposition stage was reduced to for 3 steps by the 6 traditional steps; Heat treatment time shortens to the 1/3-1/5 of traditional technology; Help realizing control, be applicable to the interior in a big way wet conversion temp of doing, satisfy the demand of big batch production heat treatment process parameter.
Below in conjunction with accompanying drawing and concrete embodiment the present invention is described further, embodiment is just to explanation of the present invention and non-limiting.
Description of drawings
Fig. 1 is the YSZ/La of the embodiment of the invention 1 2Zr 2O 7/ CeO 2The x diffraction θ-2 θ scintigram of/YBCO coating conductor.
Fig. 2 is the YSZ/La of the embodiment of the invention 1 2Zr 2O 7/ CeO 2ESEM (SEM) figure of/YBCO coating conductor surface topography.
Fig. 3 is the YSZ/La of the embodiment of the invention 1 2Zr 2O 7/ CeO 2/ YBCO coating conductor supraconductivity transition curve.
Fig. 4 is the Ni5W/La of the embodiment of the invention 2 2Zr 2O 7/ CeO 2The x diffraction θ-2 θ scintigram of/YBCO coating conductor.
Fig. 5 is the Ni5W/La of the embodiment of the invention 2 2Zr 2O 7/ CeO 2ESEM (SEM) figure of/YBCO coating conductor surface topography.
Fig. 6 is the Ni5W/La of the embodiment of the invention 2 2Zr 2O 7/ CeO 2/ YBCO coating conductor supraconductivity transition curve.
Embodiment
Embodiment 1
With presoma phenylformic acid yttrium, trifluoroacetic acid barium and cupric benzoate by atomicity than Y: Ba: Cu=1: be dissolved at 2: 3 in the mixed solvent of methyl alcohol and propionic acid; Obtain preparatory precursor liquid; With Rotary Evaporators and introduce methyl alcohol and said preparatory precursor liquid is carried out repeatedly underpressure distillation remove water impurity and obtain colloid, colloid is dissolved in the mixed solvent of methyl alcohol and propionic acid and obtains precursor liquid, controlling precursor liquid metals ion total concn is 1.5M; Wherein, the volume ratio of methyl alcohol and propionic acid is 1: 1.Adopt spin-coating method precursor liquid to be coated on the substrate YSZ/La that has impact plies 2Zr 2O 7/ CeO 2On, and be 100 ℃ in temperature and carry out drying, 10 minutes time, impel solvent evaporates.Dried film is carried out low-temperature decomposition in tube furnace, atmosphere is controlled to be the mobile oxygen atmosphere.From room temperature to 150 ℃, temperature rise rate is controlled to be 5 ℃/minute, and atmosphere is the exsiccant oxygen atmosphere; Continue to heat up from 150 ℃ to 400 ℃ with 1 ℃/minute, introduce moist oxygen in this stage, steam dividing potential drop content is controlled to be 0.6%.Complete precursor film after the low-temperature decomposition is 25 ℃/minute with temperature rise rate furnace temperature is risen to 800 ℃ from room temperature; Constant temperature 1 hour; Under mobile argon/oxygen atmosphere; Oxygen partial pressure content is controlled at 1000ppm, and steam dividing potential drop content is controlled to be 0.6%, in tube furnace, the precursor film after the low-temperature decomposition is carried out the high temperature crystallization.When under dry argon/oxygen atmosphere, being cooled to 525 ℃ after constant temperature finishes, atmosphere is replaced by the exsiccant oxygen atmosphere, at 450 ℃ of constant temperature 1h precursor film is oozed the oxygen processing at last and obtain coating conductor superconducting layer.
Fig. 1 is the superconducting layer (YSZ/La of present embodiment preparation 2Zr 2O 7/ CeO 2(ordinate zou is a diffraction intensity to/YBCO) x diffractogram among the figure, A.U.; X-coordinate is the 2Theta diffraction angle, and unit is degree), explain that the YBCO coating has good extension texture.Fig. 2 is the sem photograph of present embodiment superconducting layer, and magnification is 5000 times, and surfacing is fine and close and do not have an a axialite; (ordinate zou is a resistance to Fig. 3, unit ohm for the resistance temperature curve of present embodiment superconducting layer; X-coordinate is a temperature, and unit is Kelvin), the result shows that superconducting transition temperature is 90K, superconducting layer film superconductivity is good.Wherein, YBCO is the yttrium barium copper oxide superconducting layer, and LZO is La 2Zr 2O 7Abbreviation.
Embodiment 2
With presoma 1,3,5-benzene tricarboxylic acid yttrium, trifluoroacetic acid barium and 1; 3; 5-benzene tricarboxylic acid copper by atomicity than Y: Ba: Cu=1: be dissolved at 2: 3 in the mixed solvent of methyl alcohol and propionic acid, obtain preparatory precursor liquid, with Rotary Evaporators and introduce methyl alcohol and said preparatory precursor liquid is carried out repeatedly underpressure distillation remove water impurity and obtain colloid; Colloid is dissolved in the mixed solvent of methyl alcohol and propionic acid and obtains precursor liquid; Control precursor liquid metals ion total concn is 1.5M, and wherein, the volume ratio of methyl alcohol and propionic acid is 1: 1.Adopt dip coating precursor liquid to be coated on the substrate Ni5W/La that has impact plies 2Zr 2O 7/ CeO 2On, and be 110 ℃ in temperature and carry out drying, 10 minutes time, impel solvent evaporates.Dried film is carried out low-temperature decomposition in tube furnace, atmosphere is controlled to be the mobile oxygen atmosphere.From room temperature to 180 ℃, temperature rise rate is controlled to be 5 ℃/minute, and atmosphere is the exsiccant oxygen atmosphere; Continue to heat up from 180 ℃ to 400 ℃ with 1 ℃/minute, introduce moist oxygen in this stage, steam dividing potential drop content is controlled to be 1.2%.Complete precursor film after the low-temperature decomposition is 10 ℃/minute with temperature rise rate furnace temperature is risen to 780 ℃ from room temperature; Constant temperature 2 hours; Under mobile argon/oxygen atmosphere; Oxygen partial pressure content is controlled at 200ppm, and steam dividing potential drop content is controlled to be 0.6%, in tube furnace, the precursor film after the low-temperature decomposition is carried out the high temperature crystallization.When under dry argon/oxygen atmosphere, being cooled to 525 ℃ after constant temperature finishes, atmosphere is replaced by the exsiccant oxygen atmosphere, at 450 ℃ of constant temperature 3h precursor film is oozed the oxygen processing at last and obtain coating conductor superconducting layer.
Fig. 4 is the superconducting layer (Ni5W/La of present embodiment preparation 2Zr 2O 7/ CeO 2(ordinate zou is a diffraction intensity to/YBCO) x diffractogram among the figure, A.U.; X-coordinate is the 2Theta diffraction angle, and unit is degree), explain that the YBCO coating has good extension texture, wherein, YBCO is the yttrium barium copper oxide superconducting layer, LZO is La 2Zr 2O 7Abbreviation.Fig. 5 is the sem photograph of present embodiment superconducting layer, and magnification is 5000 times, surface compact and do not have a axialite; (ordinate zou is a resistance to Fig. 6, unit ohm for the resistance temperature curve of present embodiment superconducting layer; X-coordinate is a temperature, and unit is Kelvin), the result shows that superconducting transition temperature is 90K, superconducting layer film superconductivity is good.
Embodiment 3
With presoma 1,3,5-benzene tricarboxylic acid yttrium, trifluoroacetic acid barium, cupric benzoate by atomicity than Y: Ba: Cu=1: be dissolved at 2: 3 in the mixed solvent of methyl alcohol and propionic acid; Obtain preparatory precursor liquid; With Rotary Evaporators and introduce methyl alcohol and said preparatory precursor liquid is carried out repeatedly underpressure distillation remove water impurity and obtain colloid, colloid is dissolved in the mixed solvent of methyl alcohol and propionic acid and obtains precursor liquid, controlling precursor liquid metals ion total concn is 1.5M; Wherein, the volume ratio of methyl alcohol and propionic acid is 1: 1.Adopt dip coating precursor liquid to be coated on (Ni5W/La on the substrate that has impact plies 2Zr 2O 7/ CeO 2), and be 120 ℃ in temperature and carry out drying, 10 minutes time, impel solvent evaporates.Dried film is carried out low-temperature decomposition in tube furnace, atmosphere is controlled to be the mobile oxygen atmosphere.From room temperature to 190 ℃, temperature rise rate is controlled to be 5 ℃/minute, and atmosphere is the exsiccant oxygen atmosphere; Continue to heat up from 190 ℃ to 400 ℃ with 3 ℃/minute, introduce moist oxygen in this stage, steam dividing potential drop content is controlled to be 1.8%.Complete precursor film after the low-temperature decomposition is 20 ℃/minute with temperature rise rate furnace temperature is risen to 790 ℃ from room temperature; Constant temperature 2 hours; Under mobile argon/oxygen atmosphere; Oxygen partial pressure content is controlled at 500ppm, and steam dividing potential drop content is controlled to be 1.8%, in tube furnace, the precursor film after the low-temperature decomposition is carried out the high temperature crystallization.When under dry argon/oxygen atmosphere, being cooled to 525 ℃ after constant temperature finishes, atmosphere is replaced by the exsiccant oxygen atmosphere, at 450 ℃ of constant temperature 2h precursor film is oozed the oxygen processing at last and obtain coating conductor superconducting layer.
Embodiment 4
With presoma phenylformic acid yttrium, trifluoroacetic acid barium, 1,3,5-benzene tricarboxylic acid copper by atomicity than Y: Ba: Cu=1: be dissolved at 2: 3 in the mixed solvent of methyl alcohol and propionic acid; Obtain preparatory precursor liquid; With Rotary Evaporators and introduce methyl alcohol and said preparatory precursor liquid is carried out repeatedly underpressure distillation remove water impurity and obtain colloid, colloid is dissolved in the mixed solvent of methyl alcohol and propionic acid and obtains precursor liquid, controlling precursor liquid metals ion total concn is 1.5M; Wherein, the volume ratio of methyl alcohol and propionic acid is 1: 1.Adopt dip coating precursor liquid to be coated on the substrate Ni5W/La that has impact plies 2Zr 2O 7/ CeO 2On, and be 150 ℃ in temperature and carry out drying, 10 minutes time, impel solvent evaporates.Dried film is carried out low-temperature decomposition in tube furnace, atmosphere is controlled to be the mobile oxygen atmosphere.From room temperature to 200 ℃, temperature rise rate is controlled to be 5 ℃/minute, and atmosphere is the exsiccant oxygen atmosphere; Continue to heat up from 200 ℃ to 400 ℃ with 5 ℃/minute, introduce moist oxygen in this stage, steam dividing potential drop content is controlled to be 3.1%.Complete precursor film after the low-temperature decomposition is 10 ℃/minute with temperature rise rate furnace temperature is risen to 800 ℃ from room temperature; Constant temperature 3h; Under mobile argon/oxygen atmosphere; Oxygen partial pressure content is controlled at 700ppm, and steam dividing potential drop content is controlled to be 3.1%, in tube furnace, the precursor film after the low-temperature decomposition is carried out the high temperature crystallization.When under dry argon/oxygen atmosphere, being cooled to 525 ℃ after constant temperature finishes, atmosphere is replaced by the exsiccant oxygen atmosphere, at 450 ℃ of constant temperature 3h precursor film is oozed the oxygen processing at last and obtain coating conductor superconducting layer.

Claims (2)

1. the method for a preparing superconductive layer of coated conductor by organic deposition of low-fluorine metal is characterized in that, this method may further comprise the steps:
(1) preparation of precursor liquid: according to atomicity than Y: Ba: Cu=1: 2: 3 with presoma phenylformic acid yttrium or 1; 3,5-benzene tricarboxylic acid yttrium and trifluoroacetic acid barium and cupric benzoate or 1,3; 5-benzene tricarboxylic acid copper dissolution obtains preparatory precursor liquid in the mixed solvent of methyl alcohol and propionic acid; With Rotary Evaporators and introduce methyl alcohol and said preparatory precursor liquid is carried out repeatedly underpressure distillation obtain colloid, colloid is dissolved in the mixed solvent of methyl alcohol and propionic acid and obtains precursor liquid, controlling said precursor liquid metals ion total mol concentration is 1.5M; Wherein, the volume ratio of methyl alcohol in the said mixed solvent and propionic acid is 1: 1;
(2) coating and dry: the precursor liquid in the step (1) is coated on the substrate with impact plies with spin-coating method or dip coating, and under temperature 100-150 ℃ condition, carries out the dry precursor film that gets, said substrate is Ni-5W/La 2Zr 2O 7/ CeO 2Or YSZ/La 2Zr 2O 7/ CeO 2, wherein, YSZ is the stable zirconium white of yttrium;
(3) low-temperature decomposition: dried precursor film is carried out low-temperature decomposition in tube furnace, top temperature is 400 ℃, and atmosphere is controlled to be the mobile oxygen atmosphere; Whole low-temperature decomposition thermal treatment route is divided into two stages: from the room temperature to 150-200 ℃, temperature rise rate is controlled to be 5 ℃/minute, and atmosphere is the exsiccant oxygen atmosphere; Be 1-5 ℃/minute with the temperature rise rate and continue to be warmed up to 400 ℃, introduce moist oxygen in this stage, steam dividing potential drop content is controlled to be 0.6%-3.1%, after reaction finishes, stops logical oxygen, lowers the temperature with stove;
(4) high temperature becomes phase: the precursor film after the low-temperature decomposition at high temperature 780-800 ℃, is carried out the high temperature crystallization in tube furnace under mobile argon/oxygen atmosphere; Whole high temperature crystallization and thermal treatment route is: with the temperature rise rate be 10-25 ℃/minute furnace temperature risen to 780-800 ℃ from room temperature, constant temperature 1-3 hour, oxygen partial pressure content was controlled at 200-1000ppm, and steam dividing potential drop content is controlled to be 0.6%-3.1%; When in exsiccant argon/oxygen atmosphere, being cooled to 525 ℃ then, atmosphere is replaced by the exsiccant oxygen atmosphere, at 450 ℃ of constant temperature 1-3h precursor film is oozed the oxygen processing at last and obtain coating conductor superconducting layer;
Said low fluorine is meant that presoma fluorine content is the 30wt% of presoma fluorine content in the full trifluoroacetic acid metal organic deposit of tradition in the low-fluorine metal organic deposit.
2. the method for a kind of preparing superconductive layer of coated conductor by organic deposition of low-fluorine metal according to claim 1 is characterized in that, the exsiccant time described in the step (2) is 10 minutes.
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CN102807372A (en) * 2012-08-28 2012-12-05 西北有色金属研究院 Preparation method of gadolinium-barium-copper-oxygen compact film
CN103265280A (en) * 2013-05-14 2013-08-28 上海大学 Method for preparing YBCO (yttrium barium copper oxide) film by use of low-fluorine MOD (metal organic deposition) process
CN103352212B (en) * 2013-07-09 2015-06-17 东北大学 Method for preparing YBCO (yttrium barium copper oxide) film by taking ethanol as solvent through low-fluorine MOD (metal organic deposition) method
CN114164490A (en) * 2021-11-05 2022-03-11 上海大学 Method for preparing high-temperature superconducting oxide ceramic epitaxial film by heating through induction method

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