CN103755382B - A kind of conductor of high-temperature superconductor coat RESbO 3buffer layer and preparation method thereof - Google Patents
A kind of conductor of high-temperature superconductor coat RESbO 3buffer layer and preparation method thereof Download PDFInfo
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- CN103755382B CN103755382B CN201410016180.2A CN201410016180A CN103755382B CN 103755382 B CN103755382 B CN 103755382B CN 201410016180 A CN201410016180 A CN 201410016180A CN 103755382 B CN103755382 B CN 103755382B
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Abstract
One prepares conductor of high-temperature superconductor coat RESbO
3buffer layer and preparation method thereof, belongs to high temperature superconducting materia preparing technical field.Described buffer layers of high-temperature superconducting coating conductors is by RE
2o
3and Sb
2o
3the RESbO that extension becomes phase thermal treatment to generate
3oxide solid solution, RE is Y(yttrium), Sm(samarium), Dy(dysprosium) or Ho(holmium) in one.It can more than 900 DEG C hydrogen argon reducing gas environment in extension generate, and compact structure, surfacing, can in the preparation process of coating conductor superconducting layer subsequently holding structure stable.The preparation method of described buffer layers of high-temperature superconducting coating conductors adopts the chemical solution deposition using acetate as precursor to be prepared in hydrogen argon reducing atmosphere, possesses simple to operate, with low cost, is applicable to the advantages such as extensive deposition.Mainly for the preparation of the RESbO of conductor of high-temperature superconductor coat
3buffer layer.
Description
Technical field
The invention belongs to high temperature superconducting materia preparing technical field, particularly relate to a kind of buffer layers of high-temperature superconducting coating conductors and technology of preparing thereof.
Background technology
As second-generation high-temperature superconductor, RE, Ba and Cu oxide (REBCO) coating conductor, due to its current capacity excellent under upfield, is gathered around and is had broad application prospects in power system.Such as in multiple superconducting device, there is a lot of application, such as cable, transformer, generator and electric motor.Each developed country is from the technical renovation of national electric power energy and long-term interest, and carry forward vigorously the research of s-generation high-temperature superconductor and practicalization, international competition is more and more fierce.
The feature possessed due to REBCO superconducting layer material self on the one hand will cause conductor of high-temperature superconductor coat all to have substrate, buffer layer (at least one deck) and REBCO superconducting coating three-decker, each developed country input huge fund Developing through two more than ten years has gone out a series of cushioning layer material with practical level.Such as SrTiO
3, La
2zr
2o
7, CeO
2, YSZ, RE
2o
3deng.The consequent will be the monopolization of intellecture property and the restriction of high price.On the other hand, along with biaxial texture method is assisted in employing RABiTS(rolling) prepare reaching its maturity of the Ni base alloy baseband of biaxial texture, become at the buffer layer of the Ni base alloy baseband epitaxy high-quality of RABiTS and follow-up superconducting layer the major technique trend preparing second-generation high-temperature superconductor gradually.But in Ni base alloy substrates during depositing oxide buffer layers, due to the spontaneous non-directional oxidation of Ni base alloy substrates, be easy to cause generating the mixed and disorderly NiO of orientation, and then have a strong impact on the texture growing of follow-up superconducting layer.In order to address this problem, be mostly prepared in reducing atmosphere.
In addition, the technology of the preparation of current conductor of high-temperature superconductor coat, mainly based on the physical method of vacuum technique, comprises pulsed laser deposition (PLD), magnetron sputtering method (MSP), electron-beam evaporation (EBE) etc.The use of traditional physical method based on vacuum technique will cause its preparation cost to remain high, and be difficult to by large-scale application and commercialization.And have with low cost based on the technology of preparing (CSD) of chemical solution method, simple to operate, the unique advantage such as accurate and applicable extensive deposition of Composition Control, will be with a wide range of applications.
Summary of the invention
The object of the present invention is to provide a kind of conductor of high-temperature superconductor coat RESbO
3buffer layer and preparation method thereof.This buffer layer can epitaxy in hydrogen argon reducing gas below 980 DEG C, its compact structure and surfacing.And in the preparation process of the superconducting layer of conductor of high-temperature superconductor coat subsequently holding structure stable.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of conductor of high-temperature superconductor coat RESbO
3buffer layer, it is by RE
2o
3and Sb
2o
3the RESbO that extension becomes phase thermal treatment to generate
3oxide solid solution, RE is Y(yttrium), Sm(samarium), Dy(dysprosium), Ho(holmium) in one.
RESbO
3(RE=Y, Sm, Dy, Ho) buffer layer all possesses cubic structure, and its counterfeit lattice parameter and REBCO superconducting layer and Ni base alloy substrates all have good matching, by RE
2o
3and Sb
2o
3the RESbO that solid solution generates
3(RE=Y, Sm, Dy, Ho) extension will become phase more than 900 DEG C, the extension far above REBCO superconducting layer be become phase temperature (about 800 DEG C), make RESbO
3(RE=Y, Sm, Dy, Ho) buffer layer stablizing by holding structure in the preparation process of the superconducting layer of conductor of high-temperature superconductor coat subsequently.
RESbO of the present invention
3the performance of (RE=Y, Sm, Dy, Ho) buffer layer will have experiment provided by the present invention to be verified.
Another object of the present invention is to provide one to prepare conductor of high-temperature superconductor coat RESbO
3the method of buffer layer thin film.It adopts the chemical solution deposition using acetate as precursor to be prepared in hydrogen argon reducing atmosphere, has simple to operate, with low cost, is applicable to the advantages such as extensive deposition.The steps include:
Prepared by a, anhydrous solution: be dissolved in propionic acid by the acetate of precursor RE and antimony acetate in the ratio of metal cation ratio RE:Sb=1:1, forms anhydrous solution;
Prepared by b, colloid: in the anhydrous solution of a step, add the colloid that polyvinyl butyral acetal forms good film-forming property;
The coating of c, colloid is with dry: b walk obtained colloid and be coated on substrate, oven dry, for subsequent use;
D, thermal decomposition process: the substrate being coated with colloid is placed in sintering oven, and in sintering oven, pass into the H of 5% volume content
2-Ar mixed gas, then makes furnace temperature rise to 440 DEG C ~ 500 DEG C from room temperature with 0.6 DEG C/min, then rises to 570 DEG C ~ 620 DEG C with the speed of 1.4 ~ 2 DEG C/min, and be incubated 0.5 ~ 1 hour;
E, sinter phase into: the substrate after thermal decomposition process is put into sintering oven, in sintering oven, first pass into the H of 5% volume content
2-Ar mixed gas, then rises to 900 DEG C ~ 980 DEG C by furnace temperature with the speed of 25 ~ 100 DEG C/min and is incubated 40 ~ 60 minutes, then allowing furnace temperature Temperature fall to room temperature, obtain conductor of high-temperature superconductor coat RESbO
3buffer layer.
Above-mentioned polyvinyl butyral acetal (PVB) add-on is 2% ~ 4% of colloid total mass.Such ratio can ensure the colloid good film-forming property made.
Above-mentioned substrate is the LaAlO of biaxial texture
3monocrystal chip.
The on-chip concrete practice in above-mentioned c step, colloid being coated in coating conductor is: by colloid drops on substrate, then use sol evenning machine spin coated on substrate.
Temperature time dry in above-mentioned c step is 100 DEG C ~ 200 DEG C, under such temperature conditions, can make the propionic acid in colloid can more, vapor away quickly.
Compared with prior art, the invention has the beneficial effects as follows:
Before sintering, by the temperature-gradient method predecomposition process of selected heat-up rate, can make to sinter the coating formed more smooth, finer and close.Sinter phase time into, in sintering oven, first pass into the H of 5% volume content
2-Ar mixed gas.RESbO can be ensured like this
3good biaxial texture can be formed.The starting raw material that preparation process uses is the comparatively cheap metal acetate of price, reduces cost of manufacture; The film-forming high molecular compound added is cheap, uses extensive, nontoxic polyvinyl butyral acetal (PVB), and its add-on is also few, reduce further cost of manufacture; Only by gained colloid, need be coated on substrate and sinter, manufacture craft is simple, and operation controls easily.
Accompanying drawing explanation
Fig. 1 is the YSbO of embodiment one
3the X ray diffracting spectrum of buffer layer.
Fig. 2 is the YSbO of embodiment one
35000 times of scanning electronic microscope (SEM) photos of buffer layer.
Fig. 3 is the SmSbO of embodiment two
3the X ray diffracting spectrum of buffer layer.
Fig. 4 is the SmSbO of embodiment two
35000 times of scanning electronic microscope (SEM) photos of buffer layer.
Fig. 5 is the DySbO of embodiment three
3the X ray diffracting spectrum of buffer layer.
Fig. 6 is the DySbO of embodiment three
35000 times of scanning electronic microscope (SEM) photos of buffer layer.
Fig. 7 is the HoSbO of embodiment four
3the X ray diffracting spectrum of buffer layer.
Fig. 8 is the HoSbO of embodiment four
35000 times of scanning electronic microscope (SEM) photos of buffer layer.
Fig. 1, the ordinate zou of 3,5,7 is diffracted intensity (Intensity), arbitrary unit (a.u.); X-coordinate is diffraction angle 2Theta, and unit is degree (deg).
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment one
The invention provides a kind of conductor of high-temperature superconductor coat RESbO
3buffer layer, it is by Y
2o
3and Sb
2o
3the oxide solid solution that extension becomes phase thermal treatment to generate; And one prepares conductor of high-temperature superconductor coat YSbO
3the method of buffer layer thin film, the steps include:
Prepared by a, anhydrous solution: be dissolved in propionic acid by the acetate of precursor Y and Sb in the ratio of metal cation ratio Y:Sb=1:1, forms anhydrous solution.
Prepared by b, colloid: in the anhydrous solution of a step, add polyvinyl butyral acetal (PVB) ultrasonic dissolution, be formed with the colloid of viscosity.The add-on of polyvinyl butyral acetal (PVB) accounts for 2% of colloid total mass.
The coating of c, colloid is with dry: b is walked obtained colloid and be coated on substrate, then dry at 100 DEG C.
D, thermal decomposition process: the substrate being coated with colloid is placed in sintering oven, and in sintering oven, pass into the H of 5% volume content
2-Ar mixed gas, makes furnace temperature rise to 440 DEG C from room temperature with the speed of 0.6 DEG C/min, then rises to 570 DEG C with the speed of 1.4 DEG C/min, and be incubated 0.5 hour.
E, sinter phase into: the substrate after thermal decomposition process is put into sintering oven, in sintering oven, first pass into the H of 5% volume content
2-Ar mixed gas, then furnace temperature is risen to 900 DEG C fast with the speed of 25 DEG C/min and is incubated 40 minutes, then allow stove Temperature fall to room temperature, obtain YSbO
3buffer layers of high-temperature superconducting coating conductors.
According to the YSbO of embodiment one
3the X ray diffracting spectrum of buffer layer, can find out except YSbO
3buffer layer (200) diffraction peak and substrate LaAlO
3diffraction peak outside, without YSbO
3other assorted peaks, suggest YSbO
3there is texture outside very strong face in buffer layer thin film.
According to embodiment one YSbO
35000 times of scanning electronic microscope (SEM) photos of buffer layer, known film sample surfacing, densification, seamless without hole.It can thus be appreciated that this embodiment one has prepared texture well, the YSbO that surface compact is smooth
3buffer layer thin film.
Embodiment two
The invention provides a kind of conductor of high-temperature superconductor coat RESbO
3buffer layer, it is by Sm
2o
3and Sb
2o
3the RESbO that extension becomes phase thermal treatment to generate
3oxide solid solution; And one prepares conductor of high-temperature superconductor coat SmSbO
3the method of buffer layer thin film, the steps include:
Prepared by a, anhydrous solution: be dissolved in propionic acid by the acetate of precursor Sm and Sb in the ratio of metal cation ratio Sm:Sb=1:1, forms anhydrous solution.
Prepared by b, colloid: in the anhydrous solution of a step, add polyvinyl butyral acetal (PVB) ultrasonic dissolution, be formed with the colloid of viscosity.The add-on of polyvinyl butyral acetal (PVB) accounts for 3% of colloid total mass.
The coating of c, colloid is with dry: b is walked obtained colloid and be coated on substrate, then dry at 140 DEG C.
D, thermal decomposition process: the substrate being coated with colloid is placed in sintering oven, and in sintering oven, pass into the H of 5% volume content
2-Ar mixed gas, makes furnace temperature rise to 460 DEG C from room temperature with the speed of 0.6 DEG C/min, then rises to 580 DEG C with the speed of 1.6 DEG C/min, and be incubated 40 minutes.
E, sinter phase into: the substrate after thermal decomposition process is put into sintering oven, in sintering oven, first pass into the H of 5% volume content
2-Ar mixed gas, then furnace temperature is risen to 960 DEG C fast with the speed of 35 DEG C/min and is incubated 50 minutes, then allow stove Temperature fall to room temperature, obtain SmSbO
3buffer layers of high-temperature superconducting coating conductors.
According to the SmSbO of embodiment two
3the X ray diffracting spectrum of buffer layer, can find out except SmSbO
3buffer layer (200) diffraction peak and substrate LaAlO
3diffraction peak outside, without SmSbO
3other assorted peaks, suggest SmSbO
3there is texture outside very strong face in buffer layer thin film.
According to embodiment two SmSbO
35000 times of scanning electronic microscope (SEM) photos of buffer layer.As shown in Figure 2: film sample surfacing, densification, seamless without hole.It can thus be appreciated that this embodiment two has prepared texture well, the SmSbO that surface compact is smooth
3buffer layer thin film.
Embodiment three
The invention provides a kind of conductor of high-temperature superconductor coat RESbO
3buffer layer, it is by Dy
2o
3and Sb
2o
3the DySbO that extension becomes phase thermal treatment to generate
3oxide solid solution; And one prepares conductor of high-temperature superconductor coat DySbO
3the method of buffer layer thin film, the steps include:
Prepared by a, anhydrous solution: be dissolved in propionic acid by the acetate of precursor Dy and Sb in the ratio of metal cation ratio Dy:Sb=1:1, forms anhydrous solution.
Prepared by b, colloid: in the anhydrous solution of a step, add polyvinyl butyral acetal (PVB) ultrasonic dissolution, be formed with the colloid of viscosity.The add-on of polyvinyl butyral acetal (PVB) accounts for 3.2% of colloid total mass.
The coating of c, colloid is with dry: b is walked obtained colloid and be coated on substrate, then dry at 170 DEG C.
D, thermal decomposition process: the substrate being coated with colloid is placed in sintering oven, and in sintering oven, pass into the H of 5% volume content
2-Ar mixed gas, makes furnace temperature rise to 480 DEG C from room temperature with the speed of 0.6 DEG C/min, then rises to 590 DEG C with the speed of 1.8 DEG C/min, and be incubated 50 minutes.
E, sinter phase into: the substrate after thermal decomposition process is put into sintering oven, in sintering oven, first pass into the H of 5% volume content
2-Ar mixed gas, then furnace temperature is risen to 970 DEG C fast with the speed of 50 DEG C/min and is incubated 55 minutes, then allow stove Temperature fall to room temperature, obtain DySbO
3buffer layers of high-temperature superconducting coating conductors.
According to the DySbO of embodiment three
3the X ray diffracting spectrum of buffer layer, can find out except DySbO
3buffer layer (200) diffraction peak and substrate LaAlO
3diffraction peak outside, without DySbO
3other assorted peaks, suggest DySbO
3there is texture outside very strong face in buffer layer thin film.
According to embodiment three DySbO
35000 times of scanning electronic microscope (SEM) photos of buffer layer, known film sample surfacing, densification, seamless without hole.It can thus be appreciated that this embodiment three has prepared texture well, the DySbO that surface compact is smooth
3buffer layer thin film.
Embodiment four
The invention provides a kind of conductor of high-temperature superconductor coat RESbO
3buffer layer, it is by Ho
2o
3and Sb
2o
3the HoSbO that extension becomes phase thermal treatment to generate
3oxide solid solution; And one prepares conductor of high-temperature superconductor coat HoSbO
3the method of buffer layer thin film, the steps include:
Prepared by a, anhydrous solution: be dissolved in propionic acid by the acetate of precursor Ho and Sb in the ratio of metal cation ratio Y:Ho=1:1, forms anhydrous solution.
Prepared by b, colloid: in the anhydrous solution of a step, add polyvinyl butyral acetal (PVB) ultrasonic dissolution, be formed with the colloid of viscosity.The add-on of polyvinyl butyral acetal (PVB) accounts for 4% of colloid total mass.
The coating of c, colloid is with dry: b is walked obtained colloid and be coated on substrate, then dry at 200 DEG C.
D, thermal decomposition process: the substrate being coated with colloid is placed in sintering oven, and in sintering oven, pass into the H of 5% volume content
2-Ar mixed gas, makes furnace temperature rise to 500 DEG C from room temperature with the speed of 0.6 DEG C/min, then rises to 620 DEG C with the speed of 2 DEG C/min, and be incubated 1 hour.
E, sinter phase into: the substrate after thermal decomposition process is put into sintering oven, in sintering oven, first pass into the H of 5% volume content
2-Ar mixed gas, then furnace temperature is risen to 980 DEG C with the speed of 100 DEG C/min and is incubated 60 minutes, then allow stove Temperature fall to room temperature, obtain HoSbO
3buffer layers of high-temperature superconducting coating conductors.
According to the HoSbO of embodiment four
3the X ray diffracting spectrum of buffer layer, can find out except HoSbO
3buffer layer (200) diffraction peak and substrate LaAlO
3diffraction peak outside, without HoSbO
3other assorted peaks, suggest HoSbO
3there is texture outside very strong face in buffer layer thin film.
According to embodiment four HoSbO
35000 times of scanning electronic microscope (SEM) photos of buffer layer, known film sample surfacing, densification, seamless without hole.It can thus be appreciated that this embodiment four has prepared texture well, the HoSbO that surface compact is smooth
3buffer layer thin film.
RESbO of the present invention
3its purity of propionic acid used in the preparation process of (RE=Y, Sm, Dy, Ho) coating conductor buffer layer reaches more than 99.5%, also namely uses chemical pure propionic acid.The acetate of the RE used in its preparation process, Sb is also analytical pure.When adding propionic acid toward all precursors, precursor can fully dissolve, and can be formed with the colloid of viscosity; When usual precursor total amount is 1 mole, the volume of organic solvent is 0.5-3 liter.Mixed gas is high-purity argon gas and high-purity hydrogen mixing, and namely purity is preferably 99.99%, and the performance of finished product can be guaranteed; Otherwise the performance of finished product will reduce.
Claims (5)
1. a conductor of high-temperature superconductor coat RESbO
3buffer layer, is characterized in that: it is by RE
2o
3and Sb
2o
3the RESbO that extension becomes phase thermal treatment to generate
3oxide solid solution; Wherein RE is the one in Y, Sm, Dy or Ho.
2. a conductor of high-temperature superconductor coat RESbO as claimed in claim 1
3the preparation method of buffer layer, is made up of following steps:
Prepared by a, anhydrous solution: be dissolved in propionic acid by the acetate of precursor RE and antimony acetate in the ratio of metal cation ratio RE:Sb=1:1, forms anhydrous solution;
Prepared by b, colloid: in the anhydrous solution of a step, add the colloid that polyvinyl butyral acetal forms good film-forming property;
The coating of c, colloid is with dry: b walk obtained colloid and be coated on substrate, oven dry, for subsequent use;
D, thermal decomposition process: the substrate being coated with colloid is placed in sintering oven, and in sintering oven, pass into the H of 5% volume content
2-Ar mixed gas, then makes furnace temperature rise to 440 DEG C ~ 500 DEG C from room temperature with 0.6 DEG C/min, then rises to 570 DEG C ~ 620 DEG C with the speed of 1.4 ~ 2 DEG C/min, and be incubated 0.5 ~ 1 hour;
E, sinter phase into: the substrate after thermal decomposition process is put into sintering oven, in sintering oven, first pass into the H of 5% volume content
2-Ar mixed gas, then rises to 900 DEG C ~ 980 DEG C by furnace temperature with the speed of 25 ~ 100 DEG C/min and is incubated 40 ~ 60 minutes, then allowing furnace temperature Temperature fall to room temperature, obtain conductor of high-temperature superconductor coat RESbO
3buffer layer.
3. conductor of high-temperature superconductor coat RESbO according to claim 2
3the preparation method of buffer layer, is characterized in that: described polyvinyl butyral acetal add-on is 2% ~ 4% of colloid total mass.
4. conductor of high-temperature superconductor coat RESbO according to claim 2
3the preparation method of buffer layer, is characterized in that: in described c step, colloid being coated in the on-chip concrete practice is: by colloid drops on substrate, rotate, colloid is evenly coated on substrate with sol evenning machine.
5. conductor of high-temperature superconductor coat RESbO according to claim 2
3the preparation method of buffer layer, is characterized in that: temperature when drying in described c step is 100 DEG C ~ 200 DEG C.
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Citations (1)
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CN1862712A (en) * | 2006-04-27 | 2006-11-15 | 西南交通大学 | Buffer layer of high temp superconductive coated conductor |
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CN1862712A (en) * | 2006-04-27 | 2006-11-15 | 西南交通大学 | Buffer layer of high temp superconductive coated conductor |
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Title |
---|
涂层导体 DyBiO3(DBO)缓冲层的低温制备;孙瑞萍等;《稀有金属材料与工程》;20090531;第38卷(第5期);第901-904页 * |
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