CN102690114A - Method for preparing YBCO superconducting composite film - Google Patents
Method for preparing YBCO superconducting composite film Download PDFInfo
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- CN102690114A CN102690114A CN2012101148030A CN201210114803A CN102690114A CN 102690114 A CN102690114 A CN 102690114A CN 2012101148030 A CN2012101148030 A CN 2012101148030A CN 201210114803 A CN201210114803 A CN 201210114803A CN 102690114 A CN102690114 A CN 102690114A
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Abstract
Disclosed is a method for preparing a YBa2Cu3O7-x (YBCO) superconducting composite film, comprising mixing and dissolving ytterbium acetate <Y(CH3COO)3>, barium acetate <Ba(CH3COO)2>, and cupric acetate <Cu(CH3COO)2> into a water solution of trifluoroacetic acid according to a molar ratio of Y:Ba:Cu of 1.5:2:3; uniformly stirring, and evaporating the above solvent to dryness in vacuum to acquire a gel; adding methanol, uniformly stirring, and evaporating the resulting solvent to dryness to acquire a gel; adding methanol to prepare a precursor liquid in which the total concentration of the three types of metal ions of Y, Ba, and Cu is 1.5-3.0mol/L; coating the precursor liquid on a substrate; allowing the coated film to undergo a process of low-temperature heat treatment to decompose trifluoroacetate; allowing the coated film to undergo a process of high-temperature heat treatment to acquire a YBCO film having a tetragonal phase; coating a precursor liquid of cerium acetylacetonate on the YBCO film and carrying out a high-temperature heat treatment at a temperature ranged from 1000 DEG C to 1100 DEG C; and coating the precursor of Y, Ba, and Cu and the precursor of cerium acetylacetonate in turn repeatedly and carrying out corresponding heat treatment to acquire the YBCO superconducting film having a five-layer structure of YBCO/CeO2/YBCO/CeO2/YBCO with a thickness of 1.5 microns.
Description
Technical field
The present invention relates to a kind of preparation method of conductor of high-temperature superconductor coat, particularly a kind of preparation method of YBCO superconduction composite package.
Background technology
With YBa
2Cu
3O
7-x(YBCO) superconducting coating be the s-generation belt material of high temperature superconduct of conductor because its excellent intrinsic performance (under the 77K irreversible reach 7T, critical current density reaches 10
6A/cm
2), attracting continuous exploration of people and research in fact with the technology of becoming a useful person.S-generation belt material of high temperature superconduct is the important development direction of present superconducting material, has broad application prospects and huge market potential, can be widely used in aspects such as the energy, war industry, medical treatment, traffic and scientific research.Therefore, high temperature superconducting materia and technology of preparing are classified as the cutting edge technology of National Program for Medium-to Long-term Scientific and Technological Development (2006-2020).
Have at least five tame units to prepare length at present in the world and surpass the YBCO superconducting tape that 500m, critical current (Ic) surpass 250A.Also obtained breakthrough domestic recent years, reported at the beginning of the Shanghai Communications University 2011 that succeeding in developing current capacity reaches 194 amperes, the s-generation belt material of high temperature superconduct of hundred meter levels.Yet the cost for preparing the YBCO band at present is high.The price of being made the YBCO superconducting tape of businessman U.S. SuperPower company preparation by the world two best generations is 400 a dollars/kilo-ampere rice; Be more than 50 times of copper cash; The Application Areas that wants it has competitive power more, must further improve its performance and then raising cost performance and could satisfy demand widely.YBCO as coating conductor can use in the forceful electric power field mainly be since it have can load current and the characteristic of not loss.Concerning superconducting tape, remaining unchanged in critical current density (Jc) increases its thickness and has also just improved its current capacity.Therefore, how to prepare thick film and just become the key issue that needs to be resolved hurrily in the current YBCO high-temperature superconducting coating application process with high critical current densities.United States Air Force laboratory T.Haugan research group has reported pulsed laser deposition (PLD) method on Nature, this method adopts two different target alternating deposit ybco films and non-superconducting Y mutually
2BaCuO
5(211).Sedimentary " 211 " nanoparticle size is 0.5～1.5nm, and density is 5～6 * 10
11/ cm
2These highdensity point defects have played the effect of flux pinning, make the 2-3MA/cm of critical current density by pure ybco film
2Bring up to 4MA/cm
2More than.They finally through having prepared high performance YBCO coating with the synergetic mode of multilayer film, have improved its current capacity.Although the United States Air Force laboratory adopts the PLD method to prepare the YBCO thick film through the synergetic mode of multilayer, the pulsed laser deposition that this method adopts needs expensive vacuum system, and sedimentation rate is lower, and technology more complicated, cost are very high.The domestic preparation of having only Chinese patent CN 101719399A to mention thick film at present.This patent adopts chemical solution method to replace trifluoroacetic acid copper with vinylformic acid copper, and in precursor liquid interpolation terepthaloyl moietie amine to have prepared thickness be 1 micron YBCO thick film.Although this patent has prepared the YBCO thick film, thickness is merely 1 micron, and is limited to the current capacity that improves the YBCO coating.The more important thing is for two most important index critical currents estimating superconducting material and critical current density in this patent, all not relate to, can't estimate its superconductivity.
Summary of the invention
The objective of the invention is to overcome the more weak shortcoming of YBCO superconducting thin film current capacity of prior art for preparing, a kind of preparation method with multilayer YBCO film of high current carrying capacity is provided.
The present invention adopts full chemical solution method on matrix, alternately to deposit YBCO film and CeO
2Film, promptly preparing structure is multiwalled YBCO/CeO
2Film, thickness reach 1.5 microns YBCO superconducting film.The multilayer film that the present invention is prepared, particularly YBCO/CeO
2/ YBCO/CeO
2/ YBCO five tunics, its structure is: at first sedimentary on matrix is the YBCO film, and promptly first tunic is the YBCO film, sedimentary CeO on the first layer YBCO film
2Film is second tunic, and the like, at second layer CeO
2Sedimentary the 3rd layer is the YBCO film on the film, and the 4th layer is CeO
2Film, layer 5 are the YBCO film.
Concrete steps of the present invention order is as follows:
(1) according to Y: Ba: Cu=1.5: 2: 3 mol ratio is Y (CH
3COO)
3, Ba (CH
3COO)
2And Cu (CH
3COO)
2Three kinds of powder are dissolved under room temperature in the deionized water of the trifluoroacetic acid that contains 10-30mol%, wiring solution-forming, and the mol ratio of solute and solvent is 1: 100 in the described solution;
(2) with the described solution of step (1) preparation through magnetic stirrer 1-3h, adopt Rotary Evaporators to steam to desolventize again and obtain gel;
(3) gel that said step (2) is made adds in the methyl alcohol, and the mol ratio of gel described in this step and methyl alcohol is 1: 50.Behind magnetic stirrer 0.5-1.5h, adopt Rotary Evaporators to steam again and desolventize, with impurity such as further removal moisture, obtain purified gel;
(4) gel that said step (3) is made joins in the methyl alcohol, the precursor liquid that to process Y, Ba and three kinds of metal total ion concentrations of Cu be 1.5-3.0mol/L;
(5) precursor liquid of said step (4) being processed adopts spin coating or method of pulling up to be coated on the substrate;
(6) will place the quartzy stove of high-temperature tubular through the substrate after step (5) applies, under 300 ℃ of-500 ℃ of temperature, carry out the low-temperature heat treatment of 10h, decompose trifluoroacetate; The temperature rise rate of this step is 40 ℃/h;
(7) will pass through thermal treatment 2-4h under the high temperature that substrate that step (6) handles places 750 ℃-850 ℃, generate cubic phase YBCO film; The heat-up rate of this step is 400 ℃/h;
(8) the methyl ethyl diketone cerium is dissolved in the methyl alcohol under room temperature, preparation obtains the precursor liquid that the metallic cerium ionic concn is 0.1～0.5mol/L; This precursor liquid is spin-coated on through on step (7) the agglomerating ybco film;
(9) will pass through thermal treatment 1-2h under the high temperature that sample that step (8) handles places 1000 ℃-1100 ℃, generate CeO
2Film; The heat-up rate of this step is 400 ℃/h;
(10) on the sample of handling through step (9) successively according to step (5)-(7) and step (8)-(9) alternating deposit YBCO film and CeO
2Film is heat-treated in the oxygen atmosphere at last, and preparing structure is YBCO/CeO
2/ YBCO/CeO
2Five layers of/YBCO, thickness are 1.5 microns YBCO superconducting thick-film.
Substrate described in the step (5) is lanthanum aluminate, strontium titanate or magnesium oxide single-crystal substrate.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopts chemical solution method to prepare ultrafine CeO with epitaxial structure on the basis of trifluoroacetate-metal organic deposit YBCO film
2Film.This layer CeO
2Film can not only play the effect of transmitting biaxial texture, can also be as the effective pinning center of YBCO film, and the stress in the YBCO thick film that can also relax, avoid cracking.Adopt the not decay rapidly of YBCO thick film critical current density of this method preparation, reach 3.8MA/cm in null field lower critical current density
2, improved the current capacity of YBCO thick film greatly, reduced the production cost of coating conductor, widened the range of application of YBCO coating conductor.
Description of drawings
Fig. 1 is the field emission scanning electron microscope picture of the YBCO thick film of embodiment 1 preparation;
Fig. 2 is the X-ray diffraction halfwidth collection of illustrative plates of YBCO thick film (005) face of embodiment 2 preparations;
Fig. 3 is the X-ray diffraction halfwidth collection of illustrative plates of YBCO thick film (005) face of embodiment 3 preparations;
Fig. 4 is the field emission scanning electron microscope picture of the YBCO thick film of embodiment 4 preparations;
Fig. 5 is the X-ray diffraction halfwidth collection of illustrative plates of YBCO thick film (005) face of embodiment 4 preparations;
Fig. 6 be the YBCO thick film of embodiment 4 preparation critical current density (77K, 0T).
The specific embodiment mode
(1) takes by weighing yttium acetate, NSC 75794 and venus crystals and be respectively 0.005mol, 0.01mol and 0.015mol, wiring solution-forming in the 100ml deionized water that is dissolved in the trifluoroacetic acid that contains 10mol% after yttium acetate, NSC 75794 and the venus crystals mixing;
(2) solution that step (1) is made adopts Rotary Evaporators to steam to desolventize again and obtains gel behind magnetic stirrer 1h;
(3) methyl alcohol of 30mL is added in the gel that said step (2) makes, behind magnetic stirrer 0.5h, adopt Rotary Evaporators to steam again again to desolventize with impurity such as further removal moisture to obtain very purified gel;
(4) gel that step (3) is made joins in the 20ml methyl alcohol, the precursor liquid that to process Y, Ba and three kinds of metal total ion concentrations of Cu be 1.5mol/L;
(5) precursor liquid that step (4) is made is spin-coated on the strontium titanate monocrystal chip with 1500 rev/mins speed, and the spin coating time is 90s;
(6) the coated substrate of step (5) that coating is good is placed on to send in the quartz boat in the quartzy stove of high-temperature tubular and carries out low-temperature heat treatment and high-temperature heat treatment, obtains the YBCO film of cubic phase at last;
Described low-temperature heat treatment is to carry out under the moistening oxygen condition; Be to bring the oxygen of 500sccm into reaction chamber to water vapour through the vial that zero(ppm) water is housed; Make that water vapour pressure is 100hPa in the reaction chamber; On average be warming up to 300 ℃ from room temperature, and then stove is cooled to room temperature with the temperature rise rate of 40 ℃/h.The purpose of low-temperature heat treatment is to decompose trifluoroacetate, forms unformed precursor film and discharges deleterious residual substance.The whole resolving time is about 10h.
Described high-temperature heat treatment is under moistening oxygen and argon gas mixed atmosphere, to carry out; The argon gas mixed gas that contains 500sccm 500ppm oxygen is brought water vapour into reaction chamber through the vial that zero(ppm) water is housed; Make that water vapour pressure is 160hPa in the reaction chamber, the temperature rise rate with 400 ℃/h rose to 750 ℃ of the highest temperatures before this, behind 750 ℃ of insulation 2h, directly fed the argon gas mixed gas that contains 500ppm oxygen; Be cooled to room temperature with 100 ℃/h then, obtain the YBCO film of cubic phase;
(7) the methyl ethyl diketone cerium with 0.0001mol is dissolved in the methyl alcohol of 10mL in room temperature, and preparation obtains the precursor liquid that the metallic cerium ionic concn is 0.1mol/L; The speed of this precursor liquid with 1500 rev/mins is spin-coated on through on step (6) the agglomerating ybco film;
(8) will pass through thermal treatment 1h under the high temperature that sample that step (7) handles places 1000 ℃, generate CeO
2Film; The heat-up rate of this step is 400 ℃/h;
(9) on the sample of handling through step (8) successively according to step (5)-(6) and step (7)-(8) alternating deposit YBCO film and CeO
2Film carries out 500 ℃ of thermal treatment 1h at last in 500sccm oxygen atmosphere, prepare YBCO/CeO
2/ YBCO/CeO
2/ YBCO five layer thicknesses are 1.5 microns YBCO superconducting thick-film.With field emission scanning electron microscope this sample has been carried out the surface topography observation, the YBCO thick film surface is smooth, fine and close, does not have crackle, like Fig. 1 institute not.
Embodiment 2
(1) takes by weighing yttium acetate, NSC 75794 and venus crystals and be respectively 0.01mol, 0.02mol and 0.03mol, wiring solution-forming in the 200ml deionized water that is dissolved in the trifluoroacetic acid that contains 20mol% after yttium acetate, NSC 75794 and the venus crystals mixing;
(2) solution that step (1) is made adopts Rotary Evaporators to steam to desolventize again and obtains gel behind magnetic stirrer 2h;
(3) methyl alcohol of 60mL is added in the gel that said step (2) makes, behind magnetic stirrer 1h, adopt Rotary Evaporators to steam again again to desolventize with impurity such as further removal moisture to obtain very purified gel;
(4) gel that step (3) is made joins in the 30ml methyl alcohol, the precursor liquid that to process Y, Ba and three kinds of metal total ion concentrations of Cu be 2mol/L;
(5) precursor liquid that step (4) is made is spin-coated on the lanthanuma luminate single crystal substrate with 3000 rev/mins speed, and the spin coating time is 90s.
(6) the coated substrate of step (5) that coating is good is placed on to send in the quartz boat in the quartzy stove of high-temperature tubular and carries out low-temperature heat treatment and high-temperature heat treatment, obtains the YBCO film of cubic phase at last;
Low-temperature heat treatment is to carry out under the moistening oxygen condition; Be to bring the oxygen of 500sccm into reaction chamber to water vapour through the vial that zero(ppm) water is housed; Make that water vapour pressure is 130hPa in the reaction chamber; On average be warming up to 400 ℃ from room temperature, and then stove is cooled to room temperature with the temperature rise rate of 40 ℃/h.The purpose of low-temperature heat treatment is to decompose trifluoroacetate, forms unformed precursor film and discharges deleterious residual substance.The whole resolving time is about 10h;
High-temperature heat treatment is under moistening oxygen and argon gas mixed atmosphere, to carry out; The argon gas mixed gas that contains 500sccm 500ppm oxygen is brought water vapour into reaction chamber through the vial that zero(ppm) water is housed; Make that water vapour pressure is 200hPa in the reaction chamber, the temperature rise rate with 400 ℃/h rose to 800 ℃ of the highest temperatures before this, behind 800 ℃ of insulation 3h, directly fed the argon gas mixed gas that contains 500ppm oxygen; Be cooled to room temperature with 100 ℃/h then, obtain the YBCO film of cubic phase;
(7) the methyl ethyl diketone cerium with 0.00025mol is dissolved in the methyl alcohol of 10mL in room temperature, and preparation obtains the precursor liquid that the metallic cerium ionic concn is 0.25mol/L; The speed of this precursor liquid with 3000 rev/mins is spin-coated on through on step (6) the agglomerating ybco film;
(8) will pass through thermal treatment 1.5h under the high temperature that sample that step (7) handles places 1050 ℃, generate CeO
2Film; The heat-up rate of this step is 400 ℃/h;
(9) on the sample of handling through step (8) successively according to step (5)-(6) and step (7)-(8) alternating deposit YBCO film and CeO
2Film carries out 500 ℃ of thermal treatment 1h at last in 500sccm oxygen atmosphere, prepare YBCO/CeO
2/ YBCO/CeO
2/ YBCO five layer thicknesses are 1.5 microns YBCO superconducting thick-film.Be used in PhilipsX ' Pert type X-ray diffractometer sample has been done the ω scanning of (005) face, as shown in Figure 2.The halfwidth at YBCO (005) peak is merely 0.83 °, explains that ybco film has orientation in the good face, does not exist high-angle boundary.
Embodiment 3
(1) takes by weighing yttium acetate, NSC 75794 and venus crystals and be respectively 0.015mol, 0.03mol and 0.045mol, wiring solution-forming in the 300ml deionized water that is dissolved in the trifluoroacetic acid that contains 30mol% after yttium acetate, NSC 75794 and the venus crystals mixing;
(2) solution that step (1) is made adopts Rotary Evaporators to steam to desolventize again and obtains gel behind magnetic stirrer 3h;
(3) methyl alcohol of 90mL is added in the gel that said step (2) makes, behind magnetic stirrer 1.5h, adopt Rotary Evaporators to steam again again to desolventize with impurity such as further removal moisture to obtain very purified gel;
(4) gel that step (3) is made joins in the 30ml methyl alcohol, the precursor liquid that to process Y, Ba and three kinds of metal total ion concentrations of Cu be 3.0mol/L;
(5) precursor liquid that step (4) is made is spin-coated on the magnesium oxide single-crystal substrate with 4500 rev/mins speed, and the spin coating time is 90s;
(6) the coated substrate of step (5) that coating is good is placed on to send in the quartz boat in the quartzy stove of high-temperature tubular and carries out low-temperature heat treatment and high-temperature heat treatment, obtains the YBCO film of cubic phase at last;
Low-temperature heat treatment is to carry out under the moistening oxygen condition; Be to bring the oxygen of 500sccm into reaction chamber to water vapour through the vial that zero(ppm) water is housed; Make that water vapour pressure is 160hPa in the reaction chamber; On average be warming up to 500 ℃ from room temperature, and then stove is cooled to room temperature with the temperature rise rate of 40 ℃/h.The purpose of low-temperature heat treatment is to decompose trifluoroacetate, forms unformed precursor film and discharges deleterious residual substance.The whole resolving time is about 10h;
High-temperature heat treatment is under moistening oxygen and argon gas mixed atmosphere, to carry out; The argon gas mixed gas that contains 500sccm 500ppm oxygen is brought water vapour into reaction chamber through the vial that zero(ppm) water is housed; Make that water vapour pressure is 240hPa in the reaction chamber, the temperature rise rate with 400 ℃/h rose to 850 ℃ of the highest temperatures before this, behind 850 ℃ of insulation 4h, directly fed the argon gas mixed gas that contains 500ppm oxygen; Be cooled to room temperature with 100 ℃/h then, obtain the YBCO film of cubic phase;
(7) the methyl ethyl diketone cerium with 0.0005mol is dissolved in the methyl alcohol of 10mL in room temperature, and preparation obtains the precursor liquid that the metallic cerium ionic concn is 0.5mol/L; The speed of this precursor liquid with 4500 rev/mins is spin-coated on through on step (6) the agglomerating ybco film;
(8) will pass through thermal treatment 2h under the high temperature that sample that step (7) handles places 1100 ℃, generate CeO
2Film; The heat-up rate of this step is 400 ℃/h;
(9) on the sample of handling through step (8) successively according to step (5)-(6) and step (7)-(8) alternating deposit YBCO film and CeO
2Film carries out 500 ℃ of thermal treatment 1h at last in 500sccm oxygen atmosphere, prepare YBCO/CeO
2/ YBCO/CeO
2/ YBCO five layer thicknesses are 1.5 microns YBCO superconducting thick-film.Be used in PhilipsX ' Pert type X-ray diffractometer sample has been done the ω scanning of (005) face, as shown in Figure 3.The halfwidth at YBCO (005) peak is merely 0.85 °, explains that ybco film has orientation in the good face, does not exist high-angle boundary.
Embodiment 4
(1) takes by weighing yttium acetate, NSC 75794 and venus crystals and be respectively 0.01mol, 0.02mol and 0.03mol, wiring solution-forming in the 200ml deionized water that is dissolved in the trifluoroacetic acid that contains 20mol% after yttium acetate, NSC 75794 and the venus crystals mixing;
(2) solution that step (1) is made adopts Rotary Evaporators to steam to desolventize again and obtains gel behind magnetic stirrer 2h;
(3) methyl alcohol of 60mL is added in the gel that said step (2) makes, behind magnetic stirrer 1h, adopt Rotary Evaporators to steam again again to desolventize with impurity such as further removal moisture to obtain very purified gel;
(4) gel that step (3) is made joins in the 30ml methyl alcohol, the precursor liquid that to process Y, Ba and three kinds of metal total ion concentrations of Cu be 2mol/L;
(5) precursor liquid that step (4) is made is coated on the lanthanuma luminate single crystal substrate with the pull rate of 10cm/min;
(6) the coated substrate of step (5) that coating is good is placed on to send in the quartz boat in the quartzy stove of high-temperature tubular and carries out low-temperature heat treatment and high-temperature heat treatment, obtains the YBCO film of cubic phase at last;
Low-temperature heat treatment is to carry out under the moistening oxygen condition; Be to bring the oxygen of 500sccm into reaction chamber to water vapour through the vial that zero(ppm) water is housed; Make that water vapour pressure is 130hPa in the reaction chamber; On average be warming up to 400 ℃ from room temperature, and then stove is cooled to room temperature with the temperature rise rate of 40 ℃/h.The purpose of low-temperature heat treatment is to decompose trifluoroacetate, forms unformed precursor film and discharges deleterious residual substance.The whole resolving time is about 10h;
High-temperature heat treatment is under moistening oxygen and argon gas mixed atmosphere, to carry out; The argon gas mixed gas that contains 500sccm 500ppm oxygen is brought water vapour into reaction chamber through the vial that zero(ppm) water is housed; Make that water vapour pressure is 200hPa in the reaction chamber, the temperature rise rate with 400 ℃/h rose to 800 ℃ of the highest temperatures before this, behind 800 ℃ of insulation 3h, directly fed the argon gas mixed gas that contains 500ppm oxygen; Be cooled to room temperature with 100 ℃/h then, obtain the YBCO film of cubic phase;
(7) the methyl ethyl diketone cerium with 0.00025mol is dissolved in the methyl alcohol of 10mL in room temperature, and preparation obtains the precursor liquid that the metallic cerium ionic concn is 0.25mol/L; The speed of this precursor liquid with 3000 rev/mins is spin-coated on through on step (6) the agglomerating ybco film;
(8) will pass through thermal treatment 1.5h under the high temperature that sample that step (7) handles places 1050 ℃, generate CeO
2Film; The heat-up rate of this step is 400 ℃/h;
(9) on the sample of handling through step (8) successively according to step (5)-(6) and step (7)-(8) alternating deposit YBCO film and CeO
2Film carries out 500 ℃ of thermal treatment 1h at last in 500sccm oxygen atmosphere, prepare YBCO/CeO
2/ YBCO/CeO
2/ YBCO five layer thicknesses are 1.5 microns YBCO superconducting thick-film.With field emission scanning electron microscope this sample has been carried out the surface topography observation, the YBCO thick film surface is smooth, fine and close, does not have crackle, and is as shown in Figure 4.The ω that adopts Philips X ' Pert type X-ray diffractometer that sample has been made (005) face scans, and is as shown in Figure 5.The halfwidth at YBCO (005) peak is merely 0.72 °, explains that ybco film has orientation in the good face, does not exist high-angle boundary.With Lepi-system the YBCO thick film that prepared one-tenth contains nano-titanium oxide has been carried out the test of critical current density, critical current Ic/cm maximum reaches 570A/cm, and is as shown in Figure 6.
Claims (2)
1. the preparation method of a YBCO superconduction composite package is characterized in that, described preparation YBCO superconducting thick-film method comprises the steps:
(1) according to Y: Ba: Cu=1.5: 2: 3 mol ratio is with Y (CH
3COO)
3, Ba (CH
3COO)
2And Cu (CH
3COO)
2Mix, under room temperature, be dissolved in the deionized water of the trifluoroacetic acid that contains 10-30mol%, be made into the solution of trifluoroacetate, the mol ratio of solute and solvent is 1: 100 in the said trifluoroacetic acid salts solution;
(2) with the trifluoroacetic acid salts solution of step (1) preparation through magnetic stirrer 1-3h, adopt Rotary Evaporators to steam to desolventize again and obtain gel;
(3) gel that said step (2) is made adds in the methyl alcohol; The gel in this step and the mol ratio of methyl alcohol are 1: 50, behind magnetic stirrer 0.5-1.5h, adopt Rotary Evaporators to steam again and desolventize; With impurity such as further removal moisture, obtain purified gel;
(4) gel that said step (3) is made joins in the methyl alcohol, the precursor liquid that to process Y, Ba and three kinds of metal total ion concentrations of Cu be 1.5-3.0mol/L;
(5) the said precursor liquid of above-mentioned steps (4) being processed adopts spin coating or method of pulling up to be coated on the substrate;
(6) will place the quartzy stove of high-temperature tubular through the substrate after step (5) applies, under 300 ℃ of-500 ℃ of temperature, carry out the low-temperature heat treatment of 10h, decompose trifluoroacetate; The temperature rise rate of this step is 40 ℃/h;
(7) will pass through thermal treatment 2-4h under the high temperature that substrate that step (6) handles places 750 ℃-850 ℃, generate cubic phase YBCO film; The heat-up rate of this step is 400 ℃/h;
(8) the methyl ethyl diketone cerium is dissolved in the methyl alcohol in room temperature, preparation obtains the precursor liquid that the metallic cerium ionic concn is 0.1～0.5mol/L; This precursor liquid is spin-coated on through on step (7) the agglomerating ybco film;
(9) will pass through thermal treatment 1-2h under the high temperature that sample that step (8) handles places 1000 ℃-1100 ℃, generate CeO
2Film; The heat-up rate of this step is 400 ℃/h;
(10) on the sample of handling through step (9) successively according to step (5)-(7) and step (8)-(9) alternating deposit YBCO film and CeO
2Film is heat-treated in the oxygen atmosphere at last and is prepared YBCO/CeO
2/ YBCO/CeO
2/ YBCO five layer thicknesses are 1.5 microns YBCO superconducting thick-film.
2. the preparation method of YBCO superconduction composite package as claimed in claim 1 is characterized in that, substrate described in the said step (5) is lanthanum aluminate, strontium titanate or magnesium oxide single-crystal substrate.
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| US20010056041A1 (en) * | 2000-06-21 | 2001-12-27 | Quanxi Jia | Architecture for high critical current superconducting tapes |
| CN102255041A (en) * | 2011-07-13 | 2011-11-23 | 中国科学院电工研究所 | Preparation method of YBCO (Yttrium Barium Copper Oxide) superconducting thin film |
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| US20010056041A1 (en) * | 2000-06-21 | 2001-12-27 | Quanxi Jia | Architecture for high critical current superconducting tapes |
| CN102255041A (en) * | 2011-07-13 | 2011-11-23 | 中国科学院电工研究所 | Preparation method of YBCO (Yttrium Barium Copper Oxide) superconducting thin film |
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| CN103086722A (en) * | 2013-01-31 | 2013-05-08 | 清华大学 | Preparation method of high temperature superconducting film |
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