Ex-situ method for introducing columnar defect to high-temperature superconducting film and coated c

专利摘要:
The present disclosure relates to an eX-situ method for introducing a columnar defect to a high-temperature superconducting film and coated conductor. The method mainly solves the technical problem that When laser irradiation is used for manufacturing the columnar defect, an extremely high energy level is required. The present disclosure creatively provides a method for introducing a columnar defect through femtosecond laser irradiation in an intermediate process of phase formation of a YBazCu307.5 (YBCO) superconducting film tape. That is, in a preparation process, a surface of an intermediate product is subjected to various kinds of irradiation in a perpendicular direction, so as to generate a defect With a preferred orientation and further introduce the columnar defect into a final product. Thus, the practical application of the YBCO superconducting tape is expanded.
公开号:NL2028917A
申请号:NL2028917
申请日:2021-08-04
公开日:2021-12-01
发明作者:Huang Rongtie；Bai Chuanyi；Liu Zhiyong；Wang Tao；Cai Chuanbing；Chen Jing；Dou Wenzhi
申请人:Shanghai Shangchuang Superconducting Tech Co Ltd；Univ Shanghai；
IPC主号:

专利说明:

[01] [01] The present disclosure relates to an ex-situ method for introducing a columnar defect to a high-temperature superconducting film and coated conductor, that is, in a preparation process, a surface of an intermediate product is irradiated, in a perpendicular direction, by a femtosecond laser, so as to generate a defect with a preferred orientation and further introduce the columnar defect into a final product. The present disclosure belongs to the field of material design and processing.BACKGROUND ART
[02] [02] YBa:Cu;075 (YBCO) high-temperature superconducting film, with excellent properties and potential price advantages, has been a research hotspot in the field of practical superconducting materials. However, two major problems exist before the YBCO superconducting film will be practically applied. On the one hand, due to Josephson effect of grain boundaries of the YBCO superconducting film, current-carrying capabilities of the interiors of grains and grain boundaries of the superconductor are different, which limits critical current density; and on the other hand, in the case of an external magnetic field, widespread application of the YBCO superconducting film is limited on account of the low critical current density, and thus it is necessary to improve the properties of the YBCO superconducting film in magnetic fields.
[03] [03] Under the condition that the external magnetic field H is greater than a lower critical field, the YBCO superconductor, as the type II superconductor, is in a mixed state with magnetic flux vortex lines, and the vortex lines move under the action of Lorentz force to cause a dramatic decrease in the critical current density (Jc) of the superconductor. For the undoped YBCO superconductor, there are intrinsic pinning centers in the ab plane, and (8) has a strong peak when the external magnetic field H is parallel with the ab plane; but without corresponding intrinsic pinning center in the c-axis direction, Jc is much smaller when the external magnetic field H is parallel with the c axis; and accordingly, anisotropy of the critical current density of the undoped YBCO film is relatively strong.
[04] [04] In order to improve the electrical transport property of the YBCO 1 superconducting film in the external magnetic field, magnetic flux pinning centers are introduced into the YBCO superconducting film by researchers artificially, so as to pin the magnetic flux vortex lines. Artificial pinning centers (APCs) are classified as: (1) zero-dimensional APCs, such as oxygen vacancies, element substitutions and other point defects in the superconductor;(2) one-dimensional APCs, such as linear dislocations or artificial nanopillars in the superconductor;(3) two-dimensional APCs, stacking faults in the superconductor, and nanosheets, twin boundaries and other defects that can function as pinning centers, and(4) three-dimensional APCs, such as nano-scale outphase particles dispersed in the superconductor.
[05] [05] The artificial pinning centers can be introduced through the following three methods:(1) irradiating the high-temperature YBCO superconductor with high-energy heavy particle beams, so as to generate liner defects arranged in the c axis;(2) adding second phase nanoparticles comprising perovskite structure compounds of BaMO: (M=Zr, Hf, Sm, etc.); and (3) depositing a layer of nanoparticles on a metal substrate, and then epitaxially growing YBCO. For now, adding second phase nanoparticles is an effective method. However, no matter second phase nanoparticles are added through an in-situ method or an ex-situ method, the preparation and growth of the YBCO film will be directly affected at first, and hence the process parameters need to be adjusted in time; and then the size and distribution of the nanoparticles have a great impact on the properties of the YBCO superconducting film, and thus the YBCO film is sensitive to a preparation process. High-energy heavy particle beam irradiation is a pure and additive-free method, which directly bombards the completely-grown YBCO superconducting film with heavy particles, so as to produce columnar physical defects with small size and uniform distribution and parallel to the c-axis direction. Researches show that the defects formed by irradiation can effectively improve Jc when the external magnetic field H is parallel with the c axis, and improve the potential value of practical application of a YBCO coated conductor.
[06] [06] In the process of preparing a YBCO superconducting tape through a metal organic deposition method using trifluoroacetates (TFA-MOD), raw materials are subjected to precursor solution preparation, low-temperature coating and pyrolysis, intermediate-temperature pre-sintering, high-temperature phase formation sintering, oxygen absorption, silver protective layer plating, packaging and the like, to finally form the commercial YBCO high-temperature superconducting tape. In the whole process, a thickness of a low-temperature coating film shrinks by 100% from a colloid stage to a pyrolysis film stage; after intermediate-temperature pre-sintering, a thickness 2 of the film further shrinks by 10%; and finally, after high-temperature sintering, the thickness of the film shrinks by 50%. In the methods for introducing the artificial pinning centers, a surface of the substrate is modified before YBCO raw materials are coated; the second phase nanoparticles are added while a YBCO precursor solution is prepared; and nowadays, high-energy particle irradiation is directly carried out on a high-temperature crystallized film. In general, a YBCO dense ceramic film subjected to high-temperature phase formation sintering is irradiated and effectively bombarded with the high-energy heavy particles to form columnar defects, which requires the energy level to be GeV or above. By adjusting the energy level of the high-energy particle beams for irradiation, the size and density distribution of the defects in the film can be directly and effectively controlled, which is unattainable by other methods in the prior art. However, high-energy particle irradiation requires the energy level used to produce the columnar defects to be extremely high, which is restricting, and it requires overwhelmingly huge equipment cost and energy cost required to apply particle irradiation to the industrial mass production of YBCO superconducting tapes.SUMMARY
[07] [07] The present disclosure aims to provide an ex-situ method for introducing a columnar defect to a high-temperature superconducting film and coated conductor. The method mainly solves the technical problem that when laser irradiation is used for manufacturing the columnar defect, an extremely high energy level is required. The idea of the present disclosure is to creatively provide a method for introducing a columnar defect through femtosecond laser irradiation in an intermediate process of phase formation of a YBa2Cu307s (YBCO) superconducting film tape. That is, in a preparation process, a surface of an intermediate product is subjected to various kinds of irradiation in a perpendicular direction, so as to generate a defect with a preferred orientation and further introduce the columnar defect into a final product. The present disclosure belongs to the field of material design and processing.
[08] [08] According to the technical solution of the present disclosure, the ex-situ method for introducing a columnar defect to a high-temperature superconducting film and coated conductor includes:
[09] [09] (1) preparing a YBCO precursor solution: weighing raw materials of yttrium acetate, barium acetate and copper acetate, dissolving the yttrium acetate and barium acetate in deionized water and trifluoroacetic acid to obtain a mixed solution I and stirring the mixed solution I, dissolving the copper acetate in deionized water and 3 propionic acid to obtain a mixed solution II and stirring the mixed solution II, adding methanol into the mixed solution I and the mixed solution II to carry out reduced-pressure distillation three times, carrying out mixing, and adding methanol to a volume to prepare the YBCO precursor solution;
[10] [10] (2) spin-coating a Heusler alloy substrate with the trifluoroacetates-YBa:Cu3; 075 (TFA-YBCO) precursor solution on a spin coater to obtain a precursor film;
[11] [11] (3) carrying out low-temperature treatment: placing a film obtained by spin coating into a muffle furnace for low-temperature pyrolysis, introducing oxygen into deionized water at a room temperature and then into a hearth, and carrying out low-temperature treatment on the film in the hearth;
[12] [12] (4) carrying out intermediate-temperature treatment: carrying out intermediate-temperature treatment, in the presence of oxygen and water vapor, on a pyrolysis film subjected to the low-temperature treatment to obtain an intermediate-temperature treatment film;
[13] [13] (5) carrying out femtosecond laser irradiation drilling: placing the low-temperature pyrolysis film or the intermediate-temperature treatment film horizontally, placing a surface coated with the raw materials upwards, and carrying out, in a direction perpendicular to a plane of the film, irradiation drilling by a femtosecond laser;
[14] [14] (6) carrying out high-temperature treatment: carrying out, in a high-temperature hearth and in the presence of nitrogen, oxygen and water vapor, high-temperature heat treatment on an irradiated film; and then cooling, in the presence of nitrogen and oxygen, to obtain a high-temperature crystallized YBCO film with an irradiated columnar physical defect; and
[15] [15] (7) carrying out after-treatment: carrying out oxygen absorption treatment on the high-temperature crystallized film, and carrying out heat preservation in pure oxygen for a period of time to obtain the YBCO superconducting film tape.
[16] [16] In step (1), the yttrium acetate, barium acetate and copper acetate are weighed according to a stoichiometric ratio of 1:2:3.3; and the stirring lasts for 1-2 h to prepare the YBCO precursor solution with a total cation concentration of 2.5 mol/L.
[17] [17] In step (2), a rotating speed of the spin coater is 3000-6000 rpm, and spin coating duration is 1 min.
[18] [18] In the low-temperature treatment of step (3), a hearth temperature is reduced from 350°C to 150°C within 40 min.
[19] [19] In the intermediate-temperature treatment of step (4), heat treatment is carried out at 600°C for 10 min, total pressure of the water vapor and oxygen is about 20-23 Pa, preferable pressure of the oxygen is 13 Pa, and preferable pressure of the water vapor is 10 Pa.
[20] [20] In step (5), femtosecond laser energy is 4-10 uJ, preferably 5 u, and a spot diameter is 2 um.
[21] [21] In the high-temperature treatment of step (6), a room temperature rises to 780°C at a rate of 25°C, and heat preservation is carried out for 120 min, where in the first 60 min, nitrogen-oxygen mixed gas (with air pressure of 1 atm) with an oxygen content of 150 ppm is introduced into a water bath at 35°C and then into the hearth of the muffle furnace; and in the last 60 min, dry nitrogen-oxygen mixed gas introduced.
[22] [22] In the after-treatment of step (7), a temperature in a furnace is lowered to 450°C after the heat preservation in step (6) is completed, and preserved for 60 min, during which a reaction atmosphere is changed from nitrogen-oxygen mixed gas to pure oxygen; and the temperature in a furnace is lowered to a room temperature after heat preservation.
[23] [23] The pyrolysis film with a columnar defect is subjected to high-temperature sintering to obtain the high-temperature crystallized YBCO superconducting film with a columnar defect. Irradiation is carried out in a direction perpendicular to a surface of a sample by the femtosecond laser to form a columnar defect on the YBCO low-temperature pyrolysis film, and the film may also be broken down to form columnar defects perpendicular to the surface of the film.
[24] [24] The YBCO low-temperature pyrolysis film used for manufacturing the columnar defect has a thickness ranging from 100 nm to 3000 nm.
[25] [25] A size and density distribution of the columnar defect may be directly and effectively controlled by adjusting the energy and intensity of the femtosecond laser.
[26] [26] The present disclosure has the beneficial effects: the defect is introduced in an intermediate link of a process for preparing the YBCO superconducting film and coated conductor, and the low-temperature pyrolysis film and an intermediate-temperature pre-sintering film before high-temperature crystallization are relatively loose in structure such that the columnar defect may be manufactured on the film by adopting femtosecond laser irradiation with a lower energy level, and an effective artificial pinning center may be finally formed. The method is an innovative method, and has an extremely important significance for massively improving the properties of the YBCO superconducting tapes in magnetic fields during practical application.
[27] [27] FIG 1 is a process flow diagram of the present disclosure.
[28] [28] FIG 2 is a surface morphology image (under a scanning electron microscope (SEM)) of a low-temperature pyrolysis film drilled by a femtosecond laser according to Embodiment 1 of the present disclosure.
[29] [29] FIG 3 is a surface morphology image (under a SEM) of an intermediate-temperature treatment film drilled by a femtosecond laser according to Embodiment 1 of the present disclosure.
[30] [30] FIG 4 is a surface morphology image (under a SEM) of a drilled low-temperature pyrolysis film subjected to high-temperature crystallization according to Embodiment 1 of the present disclosure.
[31] [31] FIG 5 is a surface morphology image (under a SEM) of a drilled intermediate-temperature treatment film subjected to high-temperature crystallization according to Embodiment 1 of the present disclosure.DETAILED DESCRIPTION OF THE EMBODIMENTS
[32] [32] The present disclosure will be further illustrated with reference to the following embodiments, and it should be understood that the following embodiments are intended to illustrate the present disclosure, but not to limit the present disclosure. With reference to FIG 1,
[33] [33] A process for preparing a YBa2Cu30:.s (YBCO) superconducting film through a metal organic deposition method using trifluoroacetates (TFA-MOD)includes:
[34] [34] 1. weigh raw materials of yttrium acetate, barium acetate and copper acetate according to a stoichiometric ratio of (1:2:3.3), dissolve the yttrium acetate and barium acetate in a proper amount of deionized water and excessive trifluoroacetic acid to obtain a mixed solution I and stir the mixed solution I for 1-2 h; dissolve the copper acetate in a proper amount of deionized water and excessive propionic acid to obtain a mixed solution II and stir the mixed solution II for 1-2 h; add methanol into the mixed solution I and the mixed solution II to carry out reduced-pressure distillation three times; carry out mixing; and add methanol to a volume to prepare a YBCO precursor solution with a total cation concentration of 2.5 mol/L.
[35] [35] 2. Spin-coat, at a rotating speed of 3000-6000 rpm for 1 min, a Heusler alloy substrate with the YBCO precursor solution with a total cation concentration of 2.5 mol/L on a spin coater. 6
[36] [36] 3. Place a film obtained by spin coating into a muffle furnace for low-temperature pyrolysis, introduce oxygen with flow of 1.5 L/min into deionized water at a room temperature and then into a hearth, and carry out low-temperature treatment on the film in the hearth for 40 min, during which a temperature is reduced from 350°C to 150°C.
[37] [37] 4. Carry out, in the presence of oxygen with air pressure of 13 Pa and water vapor with air pressure of 10 Pa and at 600°C for 10 min, heat treatment on a pyrolysis film subjected to low-temperature treatment to obtain an intermediate-temperature treatment film.
[38] [38] 5. Place the low-temperature pyrolysis film or the intermediate-temperature treatment film horizontally under a femtosecond laser for perpendicular irradiation drilling, where a surface coated with the raw materials is placed upwards, femtosecond laser energy is 5 u, and a spot diameter is 2 um. A surface morphology image of the low-temperature pyrolysis film drilled by the femtosecond laser is shown in FIG 2, and a surface morphology image of the intermediate-temperature treatment film drilled by a femtosecond laser is shown in FIG 3
[39] [39] 6. Heat, in a high-temperature hearth, the irradiated film from a room temperature to 780°C at a rate of 25°C/min, and carry out heat preservation for 120 min, where in the first 60 min, nitrogen-oxygen mixed gas (with air pressure of 1 atm) with an oxygen content of 150 ppm is introduced into a water bath at 35°C and then introduced into a hearth of the muffle furnace, and in the last 60 min, dry nitrogen-oxygen mixed gas is introduced. A surface morphology image of a drilled low-temperature pyrolysis film subjected to high-temperature crystallization is shown in FIG 4, and a surface morphology image of a drilled intermediate-temperature treatment film subjected to high-temperature crystallization is shown in FIG 5.
[40] [40] 7. After the heat preservation, carry out oxygen absorption treatment, that is, carry out furnace cooling to 450°C, and carry out heat preservation for 60 min, during which the nitrogen-oxygen mixed gas is changed to pure oxygen (with air pressure of 1 atm); and carry out furnace cooling to a room temperature to obtain a YBCO superconducting film tape after oxygen absorption. 7

权利要求:
Claims (9)
[1]
An ex-situ method for introducing a columnar defect in a high-temperature superconducting film and clad conductor, comprising: (1) preparing a YBa2Cu307.s (YBCO) precursor solution: weighing raw materials from yttrium acetate, barium acetate and copper acetate, dissolving the yttrium acetate and barium acetate in deionized water and trifluoroacetic acid to obtain a mixed solution | and stirring the mixed solution |, dissolving the copper acetate in deionized water and propionic acid to obtain a mixed solution II, and stirring the mixed solution II, adding methanol into the mixed solution | and the mixed solution II for performing distillation under reduced pressure three times, performing mixing, and adding methanol to a volume to prepare the YBCO precursor solution; (2) spin coating a Heusler alloy substrate with the trifluoroacetate-YBa2Cu307.s (TFA-YBCO) precursor solution on a spin coater to obtain a precursor film; (3) performing a low temperature treatment: placing a film obtained by spin coating in a muffle furnace for low temperature pyrolysis, introducing oxygen into deionized water at a room temperature and then into a hearth, and performing a low temperature treatment on the film in the hearth; (4) performing an intermediate temperature treatment: performing an intermediate temperature treatment, in the presence of oxygen and water vapor, on a pyrolysis film subjected to the low temperature treatment to obtain an intermediate temperature treatment film; (5) performing irradiation drilling by a femtosecond laser: placing the low-temperature pyrolysis film or the intermediate temperature treatment film horizontally, raising a surface coated with the raw materials, and performing, in a direction perpendicular to a plane of the film, from irradiation bore through a femtosecond laser; (6) performing a high temperature treatment: performing, in a high temperature hearth and in the presence of nitrogen, oxygen and water vapor, a high temperature heat treatment on an irradiated film; and then cooling, in the presence of nitrogen and oxygen, to obtain a high temperature crystallized YBCO film having an irradiated columnar physical defect; and (7) performing a post-treatment: performing an oxygen absorption treatment on the high-temperature crystallized film, and performing heat preservation in pure oxygen for a period of time to obtain the YBCO superconductive film tape.
[2]
The ex-situ method for introducing a columnar defect in a high-temperature superconducting film and coated conductor according to claim 1, wherein in step (1) the yttrium acetate, barium acetate and copper acetate are weighed according to a stoichiometric ratio of 1:2 :3.3; and stirring takes 1-2 hours to prepare the YBCO precursor solution having a total cation concentration of 2.5 mol/L.
[3]
The ex-situ method for introducing a columnar defect in a high-temperature superconducting film and coated conductor according to claim 1, wherein in step (2), the spin coating is performed for 1 minute at a rotational speed of 3000-6000 revolutions per minute. minute.
[4]
The ex-situ method for introducing a columnar defect in a high-temperature superconducting film and clad conductor according to claim 1, wherein in the low-temperature treatment of step (3), a hearth temperature is reduced from 350 to 350 degrees within 40 minutes. °C to 150°C.
[5]
The ex-situ method for introducing a columnar defect in a high-temperature superconducting film and clad conductor according to claim 1, wherein in the intermediate temperature treatment of step (4), the heat treatment is carried out at 600°C for 10 minutes. .
[6]
The ex-situ method for introducing a columnar defect in a high-temperature superconducting film and coated conductor according to claim 1, wherein in step (5), the femtosecond laser energy is 4-10 HJ.
[7]
The ex-situ method for introducing a columnar defect in a high-temperature superconducting film and clad conductor according to claim 6, wherein the femtosecond laser energy is 5 HJ and a spot diameter is 2 µm.
[8]
The ex-situ method for introducing a columnar defect in a high-temperature superconducting film and clad conductor according to claim 1, wherein, in the high-temperature treatment of step (6), the high-temperature heat treatment is performed at 780°C for 120 minutes, and a heat preservation is performed for 120 minutes, wherein, in the first 60 minutes, first wet mixed nitrogen-oxygen gas having an oxygen content of 150 parts per million is introduced into a water bath at 35°C and, in the last 80 minutes, dry mixed nitrogen-oxygen gas is introduced.
[9]
The ex-situ method for introducing a columnar defect in a high-temperature superconducting film and coated conductor according to claim 1, wherein, in the post-treatment of step (7), an atmosphere of the pure oxygen is used, a air pressure is 1 atm, an oxygen absorption treatment temperature is 450°C and is maintained for 60 minutes, and finally a natural cooling is performed.

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