CN101587763A - Method for preparing buffer layers of high-temperature superconducting coating conductors - Google Patents
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Abstract
The invention discloses a method for preparing buffer layers of high-temperature superconducting coating conductors. The method comprises: introducing transition metal manganese elements as a stabilizer of cubic-phase zirconia; dissolving tetrahydrate manganese acetate and zirconium acetylacetonate as two organic salts in propionic acid or methanol as organic solvent according to the atomic ratio of Mn to Zr being x:1-x (x is more than or equal to 0.1, and less than or equal to 0.4); heating the obtained product to between 80 and 120 DEG C and keeping stirring to obtain precursor solution; spin-coating or dip-coating a SrTiO3(100) single chip or a Ni-5at.%W alloy/La2Zr2O7 substrate; and obtaining a uniform dense MnxZr1-xO2 buffer layer thin film through high-temperature crystallization, wherein the thin film has good cubic texture. As the method adopts a chemical solution method to replace yttrium with manganese as the stabilizer of a zirconia base, a prepared Mn-SZ film can epitaxially grow sharp cubic texture on single crystals and the other buffer layers thereof, and an epitaxial film has good surface crystallinity.
Description
Technical field
The invention belongs to the conductor of high-temperature superconductor coat technical field, particularly relate to a kind of preparation method of buffer layers of high-temperature superconducting coating conductors.
Background technology
Coating conductor is based on the intrinsic superconductivity of Y system high-temperature superconducting body excellence and very strong anisotropy and the superconducting tape with high critical current that grows up, its current capacity in high-intensity magnetic field has surpassed other practical superconductors, is the unique practical superconductor that can realize the high-intensity magnetic field application at liquid nitrogen temperature.Therefore, countries in the world, especially western developed country drops into huge man power and material aspect the coating conductor research, the U.S. and Japan have realized two hundred target (Ic>100A/cm of formulation before 5 years at present, L>100m), now to two thousand targets (Ic>1000A/cm, L>1000m) march.
The high temperature coating conductor mainly is made up of four parts: substrate, resilient coating, superconducting layer and protective layer.Wherein resilient coating is used to the chemical reaction diffusion between barrier metal substrate and the high-temperature oxide superconducting layer YBCO film, can overcome simultaneously exist between metallic substrates and the superconducting layer than Macrolattice mismatch, finish the texture transmission, realize the necessary biaxial texture of superconducting layer, to reach the high current carrying capacity of coating conductor excellence in high-intensity magnetic field.The coating conductor cost performance depends on the structure of resilient coating and the technology of preparing of resilient coating.The high-performance coating conductor adopts physical deposition techniques to prepare resilient coating usually in the world at present, as pulsed laser deposition, dc magnetron reactive sputtering method, electron beam evaporation etc., the high-vacuum apparatus of these Technology Need costlinesses, and need the factor complexity controlled on the technology, the coating conductor manufacturing cost is increased, be unfavorable for the large-scale application of coating conductor.Antivacuum chemical solution method technology of preparing for example deposition of metal organic method (MOD) or sol-gel process (sol-gel) method is to realize the effective ways of the low-cost coating conductor buffer layer of preparation fast.This technology can be mixed predecessor before film forming with molecular level, make stoichiometric proportion precisely controlled, and realize mass preparation easily.Existing in the world a lot of research institutions are developing the antivacuum chemical solution technology of preparing of resilient coating.
Pure zirconia has three kinds of crystal formations: cube phase (c-ZrO
2), cubic phase (t-ZrO
2), monocline phase (m-ZrO
2).Wherein monocline is the low-temperature stabilization phase mutually, cube is the high-temperature stable phase mutually.In the actual application, must consider to suppress the caused crackle of change in volume that zirconia causes owing to crystal transfer, therefore need make stabilization processes it.Through doping CaO, MgO, Y
2O
3Can at room temperature avoid the change in volume that produces owing to crystal transfer with cube mutually stable Deng behind the oxide, enlarge its application approach.For example YSZ (yttrium stable zirconium oxide) has obtained using widely as solid electrolyte material in Solid Oxide Fuel Cell, lambda sensor.Simultaneously YSZ also is a thermal stability and the reasonable cushioning layer material of chemical stability, and research units such as the U.S. and Japan adopt physical technique such as magnetron sputtering on the NiW alloy base band, extension CeO
2/ YSZ/Y
2O
3Resilient coating and CeO
2/ YSZ/CeO
2Resilient coating, wherein YSZ and inculating crystal layer and cap layer have good compatibility.When adopting wherein YSZ film of chemical solution method preparation, often need to surpass 1000 ℃ of ability and obtain the degree of crystallinity surface of good, but like this thermal stability of nickel-base alloy substrate texture is proposed higher requirement.
Summary of the invention
The objective of the invention is provides a kind of preparation method of buffer layers of high-temperature superconducting coating conductors in order to overcome the deficiencies in the prior art, can go out cube manganese-stabilized zirconia film good, surfacing in the epitaxial growth of different base interface to prepare.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of buffer layers of high-temperature superconducting coating conductors is characterized in that preparation process is:
(1) preparation of precursor solution: take by weighing acetylacetone,2,4-pentanedione zirconium powder end and four water acetic acid manganese powder ends, press Mn: Zr=x: the atomic ratio preparation of 1-x, 0.1≤x≤0.4 wherein, add organic solvent propionic acid or methyl alcohol again, low temperature 80-120 ℃ of dissolving obtains precursor aqueous solution, and the molar concentration of described precursor aqueous solution is 0.1M~0.5M;
(2) spin coating or dip-coating: choose the strontium titanate monocrystal sheet that acetone cleaned, or the Ni-5at.%W alloy is substrate and scribbles the La of cubic textureization
2Zr
2O
7The substrate of film, during spin coating, described single-chip or substrate level are placed on the spin coater suction inlet, and (1) described precursor aqueous solution is evenly dripped on single-chip or the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, behind the precursor aqueous solution 10s, extract out described in strontium titanate monocrystal sheet or the described substrate immersion step (1), put into 50~60 ℃ of baking ovens, obtain precursor film behind the 10min with 4cm/min;
(3) crystallization is handled: the precursor film in the step (2) is put into high temperature furnace, and the heating rate of stove is 3-4 ℃/min, rises to 900 ℃-1000 ℃, is incubated 0.5-5 hour, with the stove cooling, promptly obtains conductor of high-temperature superconductor coat Mn
xZr
1-xO
2Buffer layer thin film, wherein 0.1≤x≤0.4.
The prepared resilient coating technology of the present invention can obtain relevant checking: SrTiO by following two kinds of substrates
3(100); Ni-5at.%W/La
2Zr
2O
7After precursor aqueous solution was deposited in two kinds of substrates by spin coating or dip-coating, the crystallization and thermal treatment through above-mentioned technology obtained the Mn-SZ resilient coating, shows no random orientation through X-ray diffraction analysis, has good cubic texture.This technology also can deposit to precursor liquid the resilient coating that obtains good texture on the monocrystalline such as YSZ.
The present invention compared with prior art has the following advantages:
1. the Mn-SZ of growing cube-texture (manganese-stabilized zirconia) film fast.This process using chemical solution method (CSD) preparation precursor aqueous solution, mix by certain stoichiometric proportion, hot slightly i.e. dissolving rapidly in organic acid or organic solvent, manufacturing cycle is short, and can make predecessor evenly be blended in molecular level; Physicochemical properties can at room temperature not take place and change about one month of storage life in precursor aqueous solution.
2. adopt the prepared Mn-SZ of this technology (manganese-stabilized zirconia) film chemical composition even, crystal grain is tiny, greatly reduces the cubic texture formation temperature, and helps the biaxial texture growth of superconducting layer.
3.Mn the interpolation of element improves the barrier property of zirconium dioxide, effectively prevents the counterdiffusion mutually of metallic substrates and superconducting layer.
Below by drawings and Examples, the present invention is described in further detail.
Description of drawings
Fig. 1 is Mn: Zr=0.25: 7.25 o'clock, the present invention was at strontium titanates SrTiO
3The X-ray diffractogram of Mn-SZ film that can the epitaxial growth cubic texture (100).
Fig. 2 is Mn: Zr=0.25: 7.25 o'clock, the present invention was at Ni-5at.%W/La
2Zr
2O
7On can the epitaxial growth cubic texture the X-ray diffractogram of Mn-SZ film.
Among the figure: NiW is writing a Chinese character in simplified form of Ni-5at.%W, and LZO is La
2Zr
2O
7Write a Chinese character in simplified form, STO is SrTiO
3Writing a Chinese character in simplified form (100).
Embodiment
Embodiment 1
With acetylacetone,2,4-pentanedione zirconium and two kinds of organic reagents of four water acetic acid manganese by Mn: Zr=0.1: 0.90 atomic ratio is dissolved in the propionic acid, and heating obtains clear solution under low temperature 80-120 ℃ temperature.Be chosen in ultrasonic cleaning 10 * 10 * 0.5mmSrTiO in the acetone
3(100) monocrystal chip to remove surface and oil contaminant, washes out acetone solvent with deionized water afterwards, and nitrogen dries up.Adopt above-mentioned clear solution that substrate is carried out spin coating or dip-coating, substrate level is placed on the spin coater suction inlet during spin coating, and solution evenly drips on the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, after substrate immerses solution 10s, extract out, take out after all putting into 50-60 ℃ of baking oven 10min after spin coating or the dip-coating with 4cm/min.Substrate takes out and puts into high temperature furnace, is raised to 900 ℃ with 3-4 ℃/min heating rate, is incubated 5 hours, with the stove cooling, can obtain this preparation technology's Mn-SZ cubic texture buffer layer thin film.
Embodiment 2
With acetylacetone,2,4-pentanedione zirconium and two kinds of organic reagents of four water acetic acid manganese by Mn: Zr=0.1: 0.90 atomic ratio is dissolved in the propionic acid, and heating obtains clear solution under low temperature 80-120 ℃ temperature.Be chosen in that ultrasonic cleaning is substrate with Ni-5at.%W in the acetone, scribble textured MOD-La
2Zr
2O
7The substrate of film to remove surface and oil contaminant, washes out acetone solvent with deionized water afterwards, and nitrogen dries up.Adopt above-mentioned clear solution that substrate is carried out spin coating or dip-coating, substrate level is placed on the spin coater suction inlet during spin coating, and solution evenly drips on the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, after substrate immerses solution 10s, extract out, take out after all putting into 50-60 ℃ of baking oven 10min after spin coating or the dip-coating with 4cm/min.Substrate takes out and puts into high temperature furnace, is raised to 1000 ℃ with 3-4 ℃/min heating rate, is incubated 0.5 hour, with the stove cooling, can obtain this preparation technology's Mn-SZ cubic texture buffer layer thin film.
Embodiment 3
With acetylacetone,2,4-pentanedione zirconium and two kinds of organic reagents of four water acetic acid manganese by Mn: Zr=0.1: 0.90 atomic ratio is dissolved in the propionic acid, and heating obtains clear solution under low temperature 80-120 ℃ temperature.Be chosen in ultrasonic cleaning 10 * 10 * 0.5mmSrTiO in the acetone
3(100) monocrystal chip washes out acetone solvent with deionized water afterwards to remove surface and oil contaminant, and nitrogen dries up.Adopt above-mentioned solution that substrate is carried out spin coating or dip-coating, substrate level is placed on the spin coater suction inlet during spin coating, and solution evenly drips on the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, after substrate immerses solution 10s, extract out, take out after all putting into 50-60 ℃ of baking oven 10min after spin coating or the dip-coating with 4cm/min.Substrate takes out and puts into high temperature furnace, is raised to 1000 ℃ with 3-4 ℃/min heating rate, is incubated 0.5 hour, with the stove cooling, can obtain this preparation technology's Mn-SZ cubic texture buffer layer thin film.
Embodiment 4
With acetylacetone,2,4-pentanedione zirconium and two kinds of organic reagents of four water acetic acid manganese by Mn: Zr=0.25: 0.75 atomic ratio is dissolved in an amount of propionic acid, and heating obtains clear solution under low temperature 80-120 ℃ temperature.Be chosen in ultrasonic cleaning 10 * 10 * 0.5mmSrTiO in the acetone
3(100) monocrystal chip to remove surface and oil contaminant, washes out acetone solvent with deionized water afterwards, and nitrogen dries up.Adopt above-mentioned clear solution that substrate is carried out spin coating or dip-coating, substrate level is placed on the spin coater suction inlet during spin coating, and solution evenly drips on the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, after substrate immerses solution 10s, extract out, take out after all putting into 50-60 ℃ of baking oven 10min after spin coating or the dip-coating with 4cm/min.Substrate takes out and puts into high temperature furnace, is raised to 900 ℃ with 3-4 ℃/min heating rate, is incubated 5 hours, with the stove cooling, can obtain this preparation technology's Mn-SZ cubic texture buffer layer thin film.
Embodiment 5
With acetylacetone,2,4-pentanedione zirconium and two kinds of organic reagents of four water acetic acid manganese by Mn: Zr=0.25: 0.75 atomic ratio is dissolved in an amount of propionic acid, and heating obtains clear solution under low temperature 80-120 ℃ temperature.Be chosen in ultrasonic cleaning 10 * 10 * 0.5mmSrTiO in the acetone
3(100) monocrystal chip to remove surface and oil contaminant, washes out acetone solvent with deionized water afterwards, and nitrogen dries up.Adopt above-mentioned clear solution that substrate is carried out spin coating or dip-coating, substrate level is placed on the spin coater suction inlet during spin coating, and solution evenly drips on the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, after substrate immerses solution 10s, extract out, take out after all putting into 50-60 ℃ of baking oven 10min after spin coating or the dip-coating with 4cm/min.Substrate takes out and puts into high temperature furnace, is raised to 1000 ℃ with 3-4 ℃/min heating rate, is incubated 0.5 hour, with the stove cooling, can obtain this preparation technology's Mn-SZ cubic texture buffer layer thin film.
Mn-SZ film that can the epitaxial growth cubic texture on SrTiO3 (100) (being abbreviated as STO) when the resilient coating X ray result of Fig. 1 shows x=0.25;
Embodiment 6
With acetylacetone,2,4-pentanedione zirconium and two kinds of organic reagents of four water acetic acid manganese by Mn: Zr=0.25: 0.75 atomic ratio is dissolved in an amount of propionic acid, and heating obtains clear solution under low temperature 80-120 ℃ temperature.Be chosen in that ultrasonic cleaning is substrate with Ni-5at.%W in the acetone, scribble textured MOD-La
2Zr
2O
7The substrate of film to remove surface and oil contaminant, washes out acetone solvent with deionized water afterwards, and nitrogen dries up.Adopt above-mentioned clear solution that substrate is carried out spin coating or dip-coating, substrate level is placed on the spin coater suction inlet during spin coating, and solution evenly drips on the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, after substrate immerses solution 10s, extract out, take out after all putting into 50-60 ℃ of baking oven 10min after spin coating or the dip-coating with 4cm/min.Substrate takes out and puts into high temperature furnace, is raised to 900 ℃ with 3-4 ℃/min heating rate, is incubated 5 hours, with the stove cooling, can obtain this preparation technology's Mn-SZ cubic texture buffer layer thin film.
Embodiment 7
With acetylacetone,2,4-pentanedione zirconium and two kinds of organic reagents of four water acetic acid manganese by Mn: Zr=0.25: 0.75 atomic ratio is dissolved in an amount of propionic acid, and heating obtains clear solution under low temperature 80-120 ℃ temperature.Be chosen in that ultrasonic cleaning is substrate with Ni-5at.%W in the acetone, scribble textured MOD-La
2Zr
2O
7The substrate of film to remove surface and oil contaminant, washes out acetone solvent with deionized water afterwards, and nitrogen dries up.Adopt above-mentioned clear solution that substrate is carried out spin coating or dip-coating, substrate level is placed on the spin coater suction inlet during spin coating, and solution evenly drips on the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, after substrate immerses solution 10s, extract out, take out after all putting into 50-60 ℃ of baking oven 10min after spin coating or the dip-coating with 4cm/min.Substrate takes out puts into high temperature furnace,, be raised to 1000 ℃ with 3-4 ℃/min heating rate, be incubated 0.5 hour, with the stove cooling, can obtain this preparation technology's Mn-SZ cubic texture buffer layer thin film.
Embodiment 8
With acetylacetone,2,4-pentanedione zirconium and two kinds of organic reagents of four water acetic acid manganese by Mn: Zr=0.25: 0.75 atomic ratio is dissolved in an amount of propionic acid, and heating obtains clear solution under low temperature 80-120 ℃ temperature.Be chosen in that ultrasonic cleaning is substrate with Ni-5at.%W in the acetone, scribble textured MOD-La
2Zr
2O
7The substrate of film to remove surface and oil contaminant, washes out acetone solvent with deionized water afterwards, and nitrogen dries up.Adopt above-mentioned clear solution that substrate is carried out spin coating or dip-coating, substrate level is placed on the spin coater suction inlet during spin coating, and solution evenly drips on the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, after substrate immerses solution 10s, extract out, take out after all putting into 50-60 ℃ of baking oven 10min after spin coating or the dip-coating with 4cm/min.Substrate takes out and puts into high temperature furnace, is raised to 1000 ℃ with 3-4 ℃/min heating rate, is incubated 5 hours, with the stove cooling, can obtain this preparation technology's Mn-SZ cubic texture buffer layer thin film.
When the resilient coating X ray result of Fig. 2 shows x=0.25 at Ni-5at.%W/La
2Zr
2O
7On can the epitaxial growth cubic texture the Mn-SZ film;
Embodiment 9
With acetylacetone,2,4-pentanedione zirconium and two kinds of organic reagents of four water acetic acid manganese by Mn: Zr=0.4: 0.60 atomic ratio is dissolved in an amount of propionic acid, and heating obtains clear solution under low temperature 80-120 ℃ temperature.Be chosen in ultrasonic cleaning 10 * 10 * 0.5mmSrTiO in the acetone
3(100) monocrystal chip to remove surface and oil contaminant, washes out acetone solvent with deionized water afterwards, and nitrogen dries up.Adopt above-mentioned clear solution that substrate is carried out spin coating or dip-coating, substrate level is placed on the spin coater suction inlet during spin coating, and solution evenly drips on the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, after substrate immerses solution 10s, extract out, take out after all putting into 50-60 ℃ of baking oven 10min after spin coating or the dip-coating with 4cm/min.Substrate takes out and puts into high temperature furnace, is raised to 1000 ℃ with 3-4 ℃/min heating rate, is incubated 5 hours, with the stove cooling, can obtain this preparation technology's Mn-SZ cubic texture buffer layer thin film.
Embodiment 10
With acetylacetone,2,4-pentanedione zirconium and two kinds of organic reagents of four water acetic acid manganese by Mn: Zr=0.4: 0.60 atomic ratio is dissolved in an amount of propionic acid, and heating obtains clear solution under low temperature 80-120 ℃ temperature.Be chosen in that ultrasonic cleaning is substrate with Ni-5at.%W in the acetone, scribble textured MOD-La
2Zr
2O
7The substrate of film to remove surface and oil contaminant, washes out acetone solvent with deionized water afterwards, and nitrogen dries up.Adopt above-mentioned clear solution that substrate is carried out spin coating or dip-coating, substrate level is placed on the spin coater suction inlet during spin coating, and solution evenly drips on the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, after substrate immerses solution 10s, extract out, take out after all putting into 50-60 ℃ of baking oven 10min after spin coating or the dip-coating with 4cm/min.Substrate takes out and puts into high temperature furnace, is raised to 1000 ℃ with 3-4 ℃/min heating rate, is incubated 0.5 hour, with the stove cooling, can obtain this preparation technology's Mn-SZ cubic texture buffer layer thin film.
Embodiment 11
With acetylacetone,2,4-pentanedione zirconium and two kinds of organic reagents of four water acetic acid manganese by Mn: Zr=0.4: 0.60 atomic ratio is dissolved in an amount of propionic acid, and heating obtains clear solution under low temperature 80-120 ℃ temperature.Be chosen in that ultrasonic cleaning is substrate with Ni-5at.%W in the acetone, scribble textured MOD-La
2Zr
2O
7The substrate of film to remove surface and oil contaminant, washes out acetone solvent with deionized water afterwards, and nitrogen dries up.Adopt above-mentioned clear solution that substrate is carried out spin coating or dip-coating, substrate level is placed on the spin coater suction inlet during spin coating, and solution evenly drips on the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, after substrate immerses solution 10s, extract out, take out after all putting into 50-60 ℃ of baking oven 10min after spin coating or the dip-coating with 4cm/min.Substrate takes out and puts into high temperature furnace, is raised to 1000 ℃ with 3-4 ℃/min heating rate, is incubated 5 hours, with the stove cooling, can obtain this preparation technology's Mn-SZ cubic texture buffer layer thin film.
Result of study of the present invention shows, manganese mix compare that Y mixes can refinement zirconia crystal grain, indirect like this reduction the crystallization temperature of cube phase, thereby avoided because the caused nickel-base alloy base band of high-temperature process change of texture.Can enter ZrO by high-temperature process manganese
2Part replaces Zr in the lattice
4+Ion forms displaced type solid solution, thereby obtains the Mn-SZ (manganese-stabilized zirconia) of an eutectic point, makes cubic phase zircite remain into room temperature from high temperature.The present invention adopts chemical solution method to replace the stabilizer of yttrium as zirconia base with manganese, confirm by experiment, prepared Mn-SZ film can epitaxial growth go out sharp keen cubic texture on monocrystalline and other resilient coating, epitaxial film has surface of good degree of crystallinity, is the cushioning layer material that a kind of comparatively desirable chemical solution method prepares coating conductor.
Claims (1)
1. the preparation method of a buffer layers of high-temperature superconducting coating conductors is characterized in that, preparation process is:
(1) preparation of precursor solution: take by weighing acetylacetone,2,4-pentanedione zirconium powder end and four water acetic acid manganese powder ends, press Mn: Zr=x: the atomic ratio preparation of 1-x, 0.1≤x≤0.4 wherein, add organic solvent propionic acid or methyl alcohol again, low temperature 80-120 ℃ of dissolving obtains precursor aqueous solution, and the molar concentration of described precursor aqueous solution is 0.1M~0.5M;
(2) spin coating or dip-coating: choose the strontium titanate monocrystal sheet that acetone cleaned, or the Ni-5at.%W alloy is substrate and scribbles the La of cubic textureization
2Zr
2O
7The substrate of film, during spin coating, described single-chip or substrate level are placed on the spin coater suction inlet, and (1) described precursor aqueous solution is evenly dripped on single-chip or the substrate, and the speed of spin coater is 3000 commentaries on classics/min, and the spin coating time is 60s; During dip-coating, behind the precursor aqueous solution 10s, extract out described in strontium titanate monocrystal sheet or the described substrate immersion step (1), put into 50~60 ℃ of baking ovens, obtain precursor film behind the 10min with 4cm/min;
(3) crystallization is handled: the precursor film in the step (2) is put into high temperature furnace, and the heating rate of stove is 3-4 ℃/min, rises to 900 ℃-1000 ℃, is incubated 0.5-5 hour, with the stove cooling, promptly obtains conductor of high-temperature superconductor coat Mn
xZr
1-xO
2Buffer layer thin film, wherein 0.1≤x≤0.4.
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CN101916619A (en) * | 2010-07-09 | 2010-12-15 | 北京工业大学 | Nano particle doped REBCO film and preparation method thereof |
CN102222761A (en) * | 2011-04-12 | 2011-10-19 | 西南交通大学 | Preparation method of high temperature superconductive coating conductor La2Zr2O7 buffer layer film |
CN102299251A (en) * | 2011-08-13 | 2011-12-28 | 西北有色金属研究院 | Preparation method for perovskite buffer layer |
CN102299251B (en) * | 2011-08-13 | 2012-12-05 | 西北有色金属研究院 | Preparation method for perovskite buffer layer |
CN110785380A (en) * | 2017-07-14 | 2020-02-11 | 户田工业株式会社 | Positive electrode active material particle comprising lithium nickelate composite oxide and nonaqueous electrolyte secondary battery |
CN107785254A (en) * | 2017-09-28 | 2018-03-09 | 华南理工大学 | A kind of method that spin-coating method prepares alumina zirconia laminated dielectric |
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