CN105541317B - A kind of preparation method of yttrium barium copper oxide superconducting thick-film - Google Patents

A kind of preparation method of yttrium barium copper oxide superconducting thick-film Download PDF

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CN105541317B
CN105541317B CN201510882555.8A CN201510882555A CN105541317B CN 105541317 B CN105541317 B CN 105541317B CN 201510882555 A CN201510882555 A CN 201510882555A CN 105541317 B CN105541317 B CN 105541317B
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precursor liquid
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丁发柱
古宏伟
张慧亮
董泽斌
张贺
屈飞
尚红静
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Institute of Electrical Engineering of CAS
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Abstract

A kind of preparation method of yttrium barium copper oxide superconducting thick-film.Precursor liquid is prepared first, yttrium acetate, trifluoroacetic acid barium and copper acetate according to Y：Ba：Cu=1：2：3 mixed in molar ratio, it is dissolved in the mixed solution of acetic acid and propionic acid；Solvent evaporated in vacuo obtains gel after stirring；Add solvent evaporated after methanol stirs and obtain gel；Proper amount of methanol, polyethylene glycol and terpinol are then added, the precursor liquid that the metal ion species total concentration of Y, Ba and Cu tri- is 3.0 6.0mol/L is made；Then by precursor liquid coated on substrate；Coated film first undergoes 300 DEG C 500 DEG C of low temperature heat treatment, decomposing metal organic salt；Then 750 DEG C of 850 DEG C of high-temperature heat treatments are carried out and obtain yttrium barium copper oxide (YBCO) film with Tetragonal；Oxygen uptake is finally carried out at 500 DEG C 600 DEG C to handle to obtain the YBCO superconducting thick-films that thickness in monolayer is more than 6 microns.

Description

A kind of preparation method of yttrium barium copper oxide superconducting thick-film
Technical field
The present invention relates to a kind of preparation method of high temperature superconducting film, more particularly to a kind of preparation of yttrium barium copper oxide superconducting thick-film Method.
Background technology
High temperature superconducting materia promotes the practicality of high-temperature superconductor wire strip to become a useful person technology in the huge applications potentiality of field of strong electricity As the emphasis of various countries' research.Based on the first generation high-temperature superconductor band of BiSrCaCuO (BSCCO) superconduction system, in 20th century The latter stage nineties realizes commercialization.But due to Bi series superconducting materials irreversibility field for 0.5T (77K) left and right, application bar Part requires very strict, and the danger quenched is faced with once being applied under somewhat strong magnetic field environment, is more crucially existed Silver-colored sleeve pipe (PIT) technology is used during preparing band, raw material is costly, and significantly limit its scope should With.Second-generation high-temperature superconductor based on YBCO, compared with first generation superconducting tape, YBCO high temperature superconducting materias have higher Irreversibility field (7T) and higher current capacity (0.1~10MA/cm2).Meanwhile second-generation high-temperature superconductor is in preparation During be greatly lowered without using noble metal, cost：It is 50 dollars/kilo-ampere rice that bi tape, which is expected lowest price, and yttrium system The price of band can drop to 15-25 dollars/kilo-ampere rice, more Commercial Prospect.Therefore high temperature superconducting materia and its preparation skill Art quilt《National Program for Medium-to Long-term Scientific and Technological Development (2006-2010)》It is classified as cutting edge technology.
In recent years, the U.S., Japan, South Korea, China put into substantial amounts of human and material resources, financial resources YBCO bands preparation and In research work, a series of gratifying progress are obtained.2004, Japanese Fujikura company systems it is standby go out first hundred meter level in the world YBCO superconducting tapes, then by changing technique, step up the length and critical current of band, in 2008, prepare 504 meters, critical current 350A/cm superconducting tape；In 2010, it was 615 meters to prepare length, 609A/cm superconducting tape. On 2 12nd, 2011, the said firm prepared length up to 816.4 meters, and critical current reaches 572A/cm band.2014, the public affairs Department prepares length and is up to 1000 meters, and average current is higher than 600A/cm YBCO coating conductors.2010, American Superconductor Corp. The length of the YBCO superconducting tapes of production has reached 512 meters, and critical current density reaches 466A/cm.And Superpower is public Department just prepared two generation superconducting tapes of km level early in 2009, and critical current reaches 282A/cm.SuNAN companies of South Korea are near Significant achievement is also achieved within several years in the preparation of YBCO bands, the said firm in 2012 prepares the two generations height up to 1000 meters Temperature superconductive band, critical current reach 422A/cm.Domestic Shanghai Communications University combines Jiangxi quotient set group, Suzhou new material research Length is all each prepared within 2014 more than 1000 meters, I where the joint Chinese Academy of Sciences of Co., Ltd of institute electricianCClose to the second of 300A For high-temperature superconductor band.Critical electric current value multiplies length (IC× L) it is the high temperature superconductor technology development for weighing a country or company Horizontal mark.
But YBCO bands price is still sufficiently expensive at present, the best two generations manufacture businessman U.S. SuperPower in the world is public The price for taking charge of the YBCO superconducting tapes prepared is 400 dollars/kilo-ampere rice, is more than 50 times of copper cash, it is desirable to its application neck Domain more has competitiveness, it is necessary to which extensive demand could be met by further improving its performance and then improving cost performance.YBCO It can apply that have mainly due to it being capable of load current and the characteristic that is not lost in field of strong electricity as coating conductor.To super For conduction band material, constant its thickness of increase is kept also just to improve its current capacity in critical current density (Jc).Therefore, How to prepare the thick film with high critical current densities just turns into urgently to be resolved hurrily in current YBCO high-temperature superconducting coatings application process Key issue.It is domestic at present to only have the A of Chinese patent CN 101719399 (application publication date on June 2nd, 2010) to be referred to thickness The preparation of film.The patent replaces trifluoroacetic acid copper using chemical solution method with acrylic acid copper, and second two is added in precursor liquid Hydramine is prepared for the YBCO thick films that thickness is 1 micron.Although the patent is prepared for YBCO thick films, thickness is only 1 micron, right The current capacity for improving YBCO coatings is limited.More importantly for two most important critical electricity of index of evaluation superconductor Stream and critical current density are in that patent all without reference to can not evaluate its superconductivity.
The content of the invention
The purpose of the present invention is to overcome prior art to prepare YBCO thick films using cheap chemical solution method A kind of shortcoming, there is provided preparation method of the individual layer YBCO thick films with high current carrying capacity.
The present invention quickly prepares individual layer YBCO superconducting thick-films by using low fluorine full chemistry solwution method.Containing Y, Ba and Cu Terpinol and polyethylene glycol are added in the low fluorine solution of metal organic salt, precursor liquid is made into, this precursor liquid is passed through into low-temperature decomposition And high-temperature heat treatment, prepare the YBCO superconducting films that thickness is more than 6 microns.
The specific steps order of the present invention is as follows：
(1) according to Y：Ba：Cu=1：2：3 mol ratio mixes yttrium acetate, trifluoroacetic acid barium and copper acetate, at room temperature It is dissolved in the deionized water of the acetic acid containing 10-30mol% and propionic acid, is made into the low fluorine solution of metal organic salt, the solution The mol ratio of middle solute and solvent is 1：100；
(2) the low fluorine solution for the metal organic salt for preparing step (1) is through magnetic stirrer 1-3h, then uses rotation Evaporimeter is evaporated off solvent and obtains gel；
(3) gel made from the step (2) is added in methanol, the mol ratio of gel and methanol in this step is 1： 50, solvent is evaporated off after magnetic stirrer 0.5-1.5h, then using Rotary Evaporators, further to go moisture removal etc. miscellaneous Matter, obtain pure gel；
(4) gel made from the step (3) is added in methanol, terpinol and polyethylene glycol, methanol, terpinol and The volume ratio of polyethylene glycol is 2：1：1, the precursor liquid that tri- kinds of metal total ion concentrations of Y, Ba and Cu are 3.0-6.0mol/L is made；
(5) precursor liquid made of above-mentioned steps (4) is coated on substrate using spin coating or method of pulling up；
(6) substrate after step (5) coating is placed in high-temperature tubular quartz stove, entered at a temperature of 400 DEG C -600 DEG C Row 4h Low Temperature Heat Treatment, decomposing metal organic salt；The heating rate of the step is 100~150 DEG C/h；
(7) substrate by step (6) processing is placed at a high temperature of 750 DEG C -850 DEG C and is heat-treated 2-4h, generation four directions Phase YBCO films；The programming rate of this step is 400 DEG C/h；
(8) oxygen uptake processing is carried out at 450 DEG C -550 DEG C in the sample by step (7) processing, prepares thickness in monolayer YBCO superconducting thick-films more than 6 microns.
Substrate described in step (5) is alloy base band, lanthanum aluminate, strontium titanates or magnesium oxide single-crystal substrate.
Compared with prior art, the invention has the advantages that：
The present invention prepares YBCO thick films using the low fluorine precursor liquid of addition terpinol and polyethylene glycol.Due to containing in precursor liquid There is a small amount of fluorine, the effusion of only a small amount of hydrogen fluoride gas, quickly precursor liquid can be heat-treated.What is more important is gathered The addition of ethylene glycol and terpinol extends pyrolysis temperature range, and reduce easily makes film because pyrolysis temperature range is narrow The possibility cracked.In addition, polyethylene glycol and terpinol can also improve the solubility of solute, by increase solubility, Volatility is reduced to stablize trifluoroacetic acid copper precursor, so as to which the stress gradient in relaxation film is split to prevent thick film deformation generation Line.Therefore, it is still dense during using YBCO film thicknesses prepared by this method more than 6 microns, it is close in null field lower critical electric current Degree reaches 2.5MA/cm2, the current capacities of YBCO thick films is substantially increased, reduces the production cost of coating conductor.
Brief description of the drawings
Fig. 1 is the field emission scanning electron microscope picture of YBCO thick films prepared by embodiment 1；
Fig. 2 is the field emission scanning electron microscope picture of YBCO thick films prepared by embodiment 2；
Fig. 3 is the field emission scanning electron microscope picture of YBCO thick films prepared by embodiment 3；
Fig. 4 is the critical current density picture of YBCO thick films prepared by embodiment 4.
Embodiment
Embodiment 1
(1) it is respectively 0.015mol, 0.03mol and 0.045mol to weigh yttrium acetate, trifluoroacetic acid barium and copper acetate, by second Sour yttrium, trifluoroacetic acid barium and copper acetate mixing after being dissolved in the deionized water of the acetic acid containing 10mol% and propionic acid at room temperature Wiring solution-forming；
(2) by solution made from step (1) after magnetic stirrer 1h, then solvent is evaporated off using Rotary Evaporators and obtains To gel；
(3) 10mL methanol is added in gel made from the step (2), then after magnetic stirrer 0.5h again Use Rotary Evaporators that solvent is evaporated off further to remove the impurity such as moisture removal and obtains very pure gel；
(4) gel made from step (4) is added to the mixed of 15ml methanol, 7.5mL polyethylene glycol and 7.5ml terpinols Close in liquid, the solution that tri- kinds of metal total ion concentrations of Y, Ba and Cu are 3mol/L is made.Gained is contained into the molten of Y, Ba and Cu Liquid, which stirs, is prepared into precursor liquid；
(5) by precursor liquid made from step (4) with the speed dip-coating of 5 centimeters/minutes on strontium titanate monocrystal chip.
(6) coated step (5) coated substrate be placed in quartz boat be sent into high-temperature tubular quartz stove in carry out it is low Warm processing and high-temperature heat treatment, finally obtain YBCO high temperature superconducting films.
Low Temperature Heat Treatment is carried out under the Oxygen Condition of moistening, is that 500sccm oxygen is passed through into the glass equipped with distilled water Vapor is brought into reative cell by glass bottle, and it is 100hPa to make water vapour pressure in reative cell, from the average heating with 100 DEG C/h of room temperature Speed is warming up to 400 DEG C, and then stove is cooled to room temperature again.The purpose of Low Temperature Heat Treatment is decomposing metal organic salt, is formed without fixed The precursor film of type simultaneously discharges harmful residual substance.The whole resolving time is about 4h.
High-temperature heat treatment is carried out under the oxygen and argon gas mixed atmosphere of moistening, and 500sccm is contained 500ppm oxygen Argon gas mixed gas pass through vapor brought into reative cell equipped with the vial of distilled water, make the water vapour pressure in reative cell be 160hPa, 750 DEG C of the highest temperature was risen to 400 DEG C/h heating rate before this, 750 DEG C be incubated 2h after be passed directly into containing The argon gas mixed gas of 500ppm oxygen, is then cooled to 450 DEG C with 100 DEG C/h, is incubated in 450 DEG C of purity oxygen atmosphere 0.5h makes the YBCO oxygen uptakes of Tetragonal, is changed into the YBCO with superconductivity of orthorhombic phase, subsequent sample is under oxygen atmosphere It is furnace-cooled to room temperature.Morphology observation has been carried out to the section of sample with field emission scanning electron microscope, YBCO thick film surfaces are smooth, Densification, as shown in Figure 1.
Embodiment 2
(1) it is respectively 0.015mol, 0.03mol and 0.045mol to weigh yttrium acetate, trifluoroacetic acid barium and copper acetate, by second Sour yttrium, trifluoroacetic acid barium and copper acetate mixing after being dissolved in the deionized water of the acetic acid containing 20mol% and propionic acid at room temperature Wiring solution-forming；
(2) by solution made from step (1) after magnetic stirrer 2h, then solvent is evaporated off using Rotary Evaporators and obtains To gel；
(3) 10mL methanol is added in gel made from the step (2), then adopted again after magnetic stirrer 1h Solvent is evaporated off further to remove the impurity such as moisture removal with Rotary Evaporators and obtains very pure gel；
(4) gel made from step (4) is added to the mixed liquor of 10ml methanol, 5mL polyethylene glycol and 5ml terpinols In, the solution that tri- kinds of metal total ion concentrations of Y, Ba and Cu are 4.5mol/L is made.By the solution containing Y, Ba and Cu of gained Stir and be prepared into precursor liquid；
(5) precursor liquid made from step (4) is spin-coated on lanthanuma luminate single crystal substrate with 1000 revs/min of speed, spin coating Time is 90s.
(6) coated step (5) coated substrate be placed in quartz boat be sent into high-temperature tubular quartz stove in carry out it is low Warm processing and high-temperature heat treatment, finally obtain YBCO high temperature superconducting films.
Low Temperature Heat Treatment is carried out under the Oxygen Condition of moistening, is that 500sccm oxygen is passed through into the glass equipped with distilled water Vapor is brought into reative cell by glass bottle, and it is 130hPa to make water vapour pressure in reative cell, from the average heating with 125 DEG C/h of room temperature Speed is warming up to 500 DEG C, and then stove is cooled to room temperature again.The purpose of Low Temperature Heat Treatment is decomposing metal organic salt, is formed without fixed The precursor film of type simultaneously discharges harmful residual substance.The whole resolving time is about 4h.
High-temperature heat treatment is carried out under the oxygen and argon gas mixed atmosphere of moistening, and 500sccm is contained 500ppm oxygen Argon gas mixed gas pass through vapor brought into reative cell equipped with the vial of distilled water, make the water vapour pressure in reative cell be 200hPa, 800 DEG C of the highest temperature was risen to 400 DEG C/h heating rate before this, 800 DEG C be incubated 3h after be passed directly into containing The argon gas mixed gas of 500ppm oxygen, is then cooled to 500 DEG C with 100 DEG C/h, and 1h is incubated in 500 DEG C of purity oxygen atmosphere The YBCO oxygen uptakes of Tetragonal are made to be changed into the YBCO with superconductivity of orthorhombic phase, subsequent sample is furnace-cooled under oxygen atmosphere Room temperature.Morphology observation is carried out to the section of sample with field emission scanning electron microscope, the thickness of YBCO thick films is micro- more than 6 Rice, as shown in Figure 2.
Embodiment 3
(1) it is respectively 0.015mol, 0.03mol and 0.045mol to weigh yttrium acetate, trifluoroacetic acid barium and copper acetate, by second Sour yttrium, trifluoroacetic acid barium and copper acetate mixing after being dissolved in the deionized water of the acetic acid containing 30mol% and propionic acid at room temperature Wiring solution-forming；
(2) by solution made from step (1) after magnetic stirrer 3h, then solvent is evaporated off using Rotary Evaporators and obtains To gel；
(3) 10mL methanol is added in gel made from the step (2), then after magnetic stirrer 1.5h again Use Rotary Evaporators that solvent is evaporated off further to remove the impurity such as moisture removal and obtains very pure gel；
(4) gel made from step (4) is added to 7.5ml methanol, 3.75mL polyethylene glycol and 3.75ml terpinols In mixed liquor, the solution that tri- kinds of metal total ion concentrations of Y, Ba and Cu are 6mol/L is made.By gained containing Y, Ba and Cu Solution, which stirs, is prepared into precursor liquid；
(5) precursor liquid made from step (4) is spin-coated on metal base band with 1500 revs/min of speed, spin-coating time is 90s。
(6) coated step (5) coated substrate be placed in quartz boat be sent into high-temperature tubular quartz stove in carry out it is low Warm processing and high-temperature heat treatment, finally obtain YBCO high temperature superconducting films.
Low Temperature Heat Treatment is carried out under the Oxygen Condition of moistening, is that 500sccm oxygen is passed through into the glass equipped with distilled water Vapor is brought into reative cell by glass bottle, and it is 160hPa to make water vapour pressure in reative cell, from the average heating with 150 DEG C/h of room temperature Speed is warming up to 600 DEG C, and then stove is cooled to room temperature again.The purpose of Low Temperature Heat Treatment is decomposing metal organic salt, is formed without fixed The precursor film of type simultaneously discharges harmful residual substance.The whole resolving time is about 4h.
High-temperature heat treatment is carried out under the oxygen and argon gas mixed atmosphere of moistening, and 500sccm is contained 500ppm oxygen Argon gas mixed gas pass through vapor brought into reative cell equipped with the vial of distilled water, make water vapour pressure in reative cell For 240hPa, before this with 400 DEG C℃/ h heating rate rises to 850 DEG C of the highest temperature℃, at 850 DEG C℃It is passed directly into and contains after insulation 4h There is the argon gas mixed gas of 500ppm oxygen, be then cooled to 550 DEG C with 100 DEG C/h, be incubated in 550 DEG C of purity oxygen atmosphere 1h makes the YBCO oxygen uptakes of Tetragonal be changed into the YBCO with superconductivity of orthorhombic phase, and subsequent sample stove under oxygen atmosphere is cold To room temperature.Morphology observation is carried out to the surface of sample with field emission scanning electron microscope, YBCO thick film surfaces are smooth, cause It is close, as shown in Figure 3.
Embodiment 4
(1) it is respectively 0.015mol, 0.03mol and 0.045mol to weigh yttrium acetate, trifluoroacetic acid barium and copper acetate, by second Sour yttrium, trifluoroacetic acid barium and copper acetate mixing after being dissolved in the deionized water of the acetic acid containing 10mol% and propionic acid at room temperature Wiring solution-forming；
(2) by solution made from step (1) after magnetic stirrer 1h, then solvent is evaporated off using Rotary Evaporators and obtains To gel；
(3) 10mL methanol is added in gel made from the step (2), then after magnetic stirrer 0.5h again Use Rotary Evaporators that solvent is evaporated off further to remove the impurity such as moisture removal and obtains very pure gel；
(4) gel made from step (4) is added to the mixing of 15ml methanol, 7.5mL polyethylene glycol and 7.5ml terpinols In liquid, the solution that tri- kinds of metal total ion concentrations of Y, Ba and Cu are 3mol/L is made.By the solution containing Y, Ba and Cu of gained Stir and be prepared into precursor liquid；
(5) by precursor liquid made from step (4) with the speed dip-coating of 5 centimeters/minutes on magnesium oxide single-crystal substrate.
(6) coated step (5) coated substrate be placed in quartz boat be sent into high-temperature tubular quartz stove in carry out it is low Warm processing and high-temperature heat treatment, finally obtain YBCO high temperature superconducting films.
Low Temperature Heat Treatment is carried out under the Oxygen Condition of moistening, is that 500sccm oxygen is passed through into the glass equipped with distilled water Vapor is brought into reative cell by glass bottle, and it is 100hPa to make water vapour pressure in reative cell, from the average heating with 100 DEG C/h of room temperature Speed is warming up to 400 DEG C, and then stove is cooled to room temperature again.The purpose of Low Temperature Heat Treatment is decomposing metal organic salt, is formed without fixed The precursor film of type simultaneously discharges harmful residual substance.The whole resolving time is about 4h.
High-temperature heat treatment is carried out under the oxygen and argon gas mixed atmosphere of moistening, and 500sccm is contained 500ppm oxygen Argon gas mixed gas pass through vapor brought into reative cell equipped with the vial of distilled water, make the water vapour pressure in reative cell be 160hPa, 750 DEG C of the highest temperature was risen to 400 DEG C/h heating rate before this, 750 DEG C be incubated 2h after be passed directly into containing The argon gas mixed gas of 500ppm oxygen, is then cooled to 450 DEG C with 100 DEG C/h, is incubated in 450 DEG C of purity oxygen atmosphere 0.5h makes the YBCO oxygen uptakes of Tetragonal be changed into the YBCO with superconductivity of orthorhombic phase, subsequent sample stove under oxygen atmosphere It is cooled to room temperature.Performance test is carried out to sample with comprehensive physical property measuring system (PPMS), YBCO thick films are under 77K, null field Critical current density reaches 2.5MA/cm2, as shown in Figure 4.

Claims (2)

1. a kind of preparation method of yttrium barium copper oxide superconducting thick-film, it is characterised in that described preparation method uses low fluorine full chemistry Solwution method prepares individual layer YBCO superconducting thick-films；Terpinol is added in the low fluorine solution containing Y, Ba and Cu metal organic salt and is gathered Ethylene glycol, precursor liquid is made into, this precursor liquid is passed through into low-temperature decomposition and high-temperature heat treatment, prepare thickness in monolayer more than 6 microns YBCO thick films；
Described preparation method comprises the following steps：
(1) according to Y：Ba：Cu=1：2：3 mol ratio, yttrium acetate, trifluoroacetic acid barium and copper acetate are mixed, it is molten at room temperature In the deionized water of the acetic acid containing 10-30mol% and propionic acid, the low fluorine solution of metal organic salt is made into, in the solution The mol ratio of solute and solvent is 1：100；
(2) by the low fluorine solution of the metal organic salt of step (1) preparation through magnetic stirrer 1-3h, then using rotary evaporation Instrument is evaporated off solvent and obtains gel；
(3) gel made from the step (2) is added in methanol, the mol ratio of gel and methanol in this step is 1：50, Solvent is evaporated off after magnetic stirrer 0.5-1.5h, then using Rotary Evaporators, further to remove moisture impurity, obtains Pure gel；
(4) gel made from the step (3) is added in methanol, terpinol and polyethylene glycol, methanol, terpinol and poly- second The volume ratio of glycol is 2：1：1, the precursor liquid that tri- kinds of metal total ion concentrations of Y, Ba and Cu are 3.0-6.0mol/L is made；
(5) precursor liquid made of above-mentioned steps (4) is coated on substrate using spin coating or method of pulling up；
(6) substrate after step (5) coating is placed in high-temperature tubular quartz stove, 4h is carried out at a temperature of 400 DEG C -600 DEG C Low Temperature Heat Treatment, decomposing metal organic salt；The heating rate of the step is 100~150 DEG C/h；
(7) substrate by step (6) processing is placed at a high temperature of 750 DEG C -850 DEG C and is heat-treated 2-4h, generate Tetragonal YBCO films；The programming rate of this step is 400 DEG C/h；
(8) oxygen uptake processing is carried out at 450 DEG C -550 DEG C in the sample by step (7) processing, prepares described YBCO and surpass Lead thick film.
A kind of 2. preparation method of yttrium barium copper oxide superconducting thick-film as claimed in claim 1, it is characterised in that described step (5) in, the substrate is alloy base band, lanthanum aluminate, strontium titanates or magnesium oxide single-crystal substrate.
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