CN117079888A - Superconducting film containing double-doped phase REBCO and preparation method thereof - Google Patents
Superconducting film containing double-doped phase REBCO and preparation method thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
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- 238000001338 self-assembly Methods 0.000 claims abstract 2
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- 229910052802 copper Inorganic materials 0.000 claims description 5
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- FFWQPZCNBYQCBT-UHFFFAOYSA-N barium;oxocopper Chemical compound [Ba].[Cu]=O FFWQPZCNBYQCBT-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
- H01B12/02—Superconductive or hyperconductive conductors, cables, or transmission lines characterised by their form
- H01B12/06—Films or wires on bases or cores
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F6/00—Superconducting magnets; Superconducting coils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Abstract
The application discloses a REBCO superconducting film containing double doped phases and a preparation method thereof, wherein the REBCO superconducting film is prepared by uniformly dispersing nano particles of two non-superconducting doped phases in a REBCO superconducting parent phase, and the nano particles are BMO/REBa formed by two-phase self-assembly 2 Cu 3‑x Ca x O 7 A core-shell structure; wherein RE in REBCO is rare earth element, and is selected from one or more mixed rare earth of Y, gd, eu, sm. The diameter of the nano particles is 10-50 nm, and the volume percentage of the nano particles in the superconducting layer is 3-20%; the application aims to overcome the reduction of the current carrying capacity of the REBCO matrix caused by the second phase doping, and can also overcome the second phase agglomeration phenomenon under heavy doping, and the current carrying capacity of the REBCO superconducting film under low temperature Gao Cichang can be obviously improved.
Description
Technical Field
The application relates to the technical field of superconducting material preparation, in particular to a REBCO superconducting film containing a double-doped phase and a preparation method thereof, and especially relates to a process method suitable for producing the REBCO superconducting film containing the double-doped phase, wherein nano particles with a core-shell structure can be formed in a superconducting layer to serve as an artificial pinning phase, so that the carrying capacity of a superconducting tape under a low-temperature strong magnetic field is remarkably improved.
Background
The second-generation high-temperature superconducting Rare Earth Barium Copper Oxide (REBCO) film has the advantages of high superconducting transition temperature, high current carrying capacity, high irreversible field and the like, and has the irreplaceable advantage in a strong field magnet. In recent years, compact magnetic confinement nuclear fusion power generation of strong field magnets based on REBCO superconducting films is a strategic and emerging technology for solving the problem of ultimate energy of human beings, and the industry development is rapid. In order to improve the current carrying capacity of the REBCO film under an external magnetic field, the introduction of a doping phase as a pinning center is one of the most effective strategies. The BMO with the perovskite structure is taken as an important doped second phase, can be self-assembled into nano points, nano rods or nano columns in the REBCO superconducting film, and improves the field current carrying capacity of the superconducting film. However, due to the large lattice difference between BMO and REBCO, a large stress field exists between the doped BMO and REBCO substrates, which reduces the current carrying capacity of REBCO substrates. In addition, BMO with high doping amount can agglomerate in REBCO matrix to form large agglomerates, which cannot effectively improve the magnetic flux pinning capability under low-temperature strong magnetic field. REBCO is generally doped with Ca element to replace RE or Ba sites, forming a substance with super conductivity, which is generally used to improve grain boundary current. Studies show that the substitution position of Ca in REBCO is affected by stress, and Ca can more easily replace Cu element serving as a current carrier layer in REBCO under high stress to form a non-superconductivity solid solution phase. According to the application, ca element is doped in REBCO through a special process, so that the internal stress of the REBCO doped film can be released, and the current carrying capacity in the field is improved.
Disclosure of Invention
The application provides a REBCO superconducting film containing double doping phases, which is characterized in that,
the REBCO superconducting film is a core-shell structure formed by uniformly dispersing two non-superconducting doped phases in a REBCO superconducting parent phase, wherein the nano particles are two-phase self-assembled;
wherein RE in REBCO is rare earth element, and is selected from one or more mixed rare earth of Y, gd, eu, sm.
The diameter of the nano particles is 10-50 nm, and the volume percentage of the nano particles in the superconducting film is 3-20%;
preferably, the double doped phases are REBa respectively 2 Cu 3-x Ca x O 7 And BaMO 3 (BMO)。
Wherein the REBa 2 Cu 3-x Ca x O 7 Is partially occupied by Ca ion doped in REBCOThe CuO surface is provided with a substance which is formed by copper lattice sites and has no superconductivity, x is less than 1, and M is selected from one of Zr, hf and Sn.
Preferably, in the core-shell structure, BMO nano particles are cores with the diameter of 9-49 nm and REBa 2 Cu 3-x Ca x O 7 The thickness of the shell is 0.5 nm-3 nm.
The application also provides a preparation method of the REBCO superconducting film containing the double doping phases, which comprises the following steps:
s1, selecting a target material containing BMO and CaO double-doped REBCO;
s2, selecting a substrate with a texture;
and S3, adopting a pulse laser deposition technology to deposit the target material in the step S1 on the substrate in the step S2 in situ, and obtaining the REBCO superconducting film containing the double doping phases.
Preferably, in step S1, the REBCO target is a nanocrystalline target, and is made by mixing BMO, caO, and REBCO nanocrystalline powder.
Wherein the grain size of the REBCO nanocrystalline powder is between 200 and 500nm, and is determined by Shellac calculation through XRD measurement; the volume fraction of BMO is 2.9% -19%; the volume fraction of CaO is 0.1-1%.
Preferably, in step S3, the substrate with texture is LaAlO 3 A single crystal substrate, or a nickel-based or copper-based flexible metal base band.
Wherein the metal base band is rolled biaxial texture or coated with a single-layer or multi-layer oxide film, and the structure of the oxide film is CeO 2 /YSZ/Y 2 O 3 ，MgO，LaMnO 3 /MgO/Y 2 O 3 Al-O or CeO 2 /MgO/Y 2 O 3 One of/Al-O.
Preferably, in step S3, the excimer laser beam passes through a homogenizer, the energy is distributed in a flat top wave mode, and the energy of the laser spot on the target is 1-2J/cm 2 。
Preferably, in the step S3, the growth speed of the REBCO superconducting film prepared by in-situ deposition is less than or equal to 30nm/S; the liquidus temperature (T) of REBCO superconducting film 1 ) Is thatReference, coating temperature (T g ) Is lower than T when selected 1 50-100 ℃.
Preferably, in step S3, the REBCO superconducting film prepared by in-situ deposition has a thickness of 1-5 μm, and critical current density J under a 10T magnetic field perpendicular to the surface of the superconducting layer at 4.2K c Greater than or equal to 8MA/cm 2 。
Compared with the prior art, the application has the following beneficial effects:
1. the application ensures that the second phase self-assembles into BMO/REBa by doping BMO and Ca in REBCO 2 Cu 3-x Ca x O 7 Nanoparticles, REBa 2 Cu 3-x Ca x O 7 Can be well matched with REBCO matrix, reduces internal stress, and effectively reduces current carrying capacity attenuation of REBCO matrix caused by doping.
2. The method of the application ensures that the second phase particles form a core-shell structure and are uniformly distributed in the REBCO matrix, thereby effectively preventing the aggregation of the second phase particles and improving the second phase doping amount in REBCO.
3. The REBCO film containing the double doped phases prepared by the application has ultrahigh low-temperature high-field current carrying capacity and is beneficial to manufacturing high-field magnets.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a schematic cross-sectional structure of a dual-doped phase REBCO superconducting film of the present application; wherein 1 is a substrate, 2 is REBCO,3 is a nanoparticle, 4 is BMO, and 5 is REBa 2 Cu 3-x Ca x O 7 ；
FIG. 2 is a TEM image of a cross-sectional structure of a superconducting film containing double doped phase YBCO according to example 1;
fig. 3 is a TEM image of the cross-sectional structure of the doped YBCO superconducting film prepared in comparative example 1.
Detailed Description
The present application will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present application, but are not intended to limit the application in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present application.
Example 1
The embodiment relates to a YBCO superconducting film containing double doped phases, wherein the volume fraction of nano particles is 3%, the cross-section structure of the superconducting film is shown in figure 1, 1 is a substrate, 2 is YBCO,3 is nano particles, and 4 is BaZrO 3 (BZO), 5 is YBa 2 Cu 3-x Ca x O 7 The preparation method comprises the following steps:
(1) Selecting a BZO and CaO-containing double-doped YBCO nano crystal target, wherein the volume fraction of the BZO powder is 2.9%, the volume fraction of the CaO powder is 0.1%, the YBCO nano crystal is prepared by a spray pyrolysis method, the average grain size is 500nm, and the target is prepared by plasma sintering at 750 ℃;
(2) Selection of LaAlO 3 (001) Single crystals as a substrate;
(3) Depositing the target material in the step (1) on the substrate in the step (2) in situ by adopting a high-speed pulse laser deposition technology, wherein the energy of excimer laser beams passes through a homogenizer in the deposition process and is distributed in a flat top wave mode, and the energy of laser spots on the target material is 1J/cm 2 The growth speed is 20nm/s, the coating temperature is 800 ℃, and the YBCO superconducting film containing double doped phases is selected.
The thickness of the superconducting film prepared by the method described in example 1 was 1. Mu.m, and the YBCO superconducting film contained 10nm BZO as a core and 0.5nm YBa uniformly distributed 2 Cu 2.9 Ca 0.1 O 7 As a second phase nanoparticle of core-shell structure of shell, the transmission electron micrograph of its cross section is shown in FIG. 2, the superconducting film has a field current carrying capacity of 4.2K and 8MA/cm under a 10T magnetic field perpendicular to the surface of the superconducting layer 2 。
Example 2
The embodiment relates to a GdBCO superconducting film containing double doping phases, wherein the volume fraction of nano particles is 5%, and the preparation method comprises the following steps:
(1) Select to contain BaHfO 3 (BHO) and Ca double-doped GdBCO targets, wherein the volume fraction of the BHO is 4.7 percent, the volume fraction of the CaO is 0.3 percent, the GdBCO nanocrystals are prepared by a spray thermal decomposition method, the average grain size is 200nm, and the targets are prepared by plasma sintering at 750 ℃;
(2) Selecting a nickel-based alloy base band of the MgO biaxially-textured buffer layer as a substrate;
(3) Depositing the target material in the step (1) on the substrate in the step (2) in situ by adopting a high-speed pulse laser deposition technology, wherein the energy of excimer laser beams passes through a homogenizer in the deposition process and is distributed in a flat top wave mode, and the energy of laser spots on the target material is 1J/cm 2 The growth speed is 10nm/s, the coating temperature is 830 ℃, and the GdBCO superconducting film containing double doped phases is selected.
The thickness of the superconducting film prepared by the method described in example 2 was 3. Mu.m, and the GdBCO superconducting film contained 20nm BHO as a core and 0.8nm GdBA uniformly distributed 2 Cu 2.9 Ca 0.1 O 7 The second phase nano particle with core-shell structure as shell has superconductive film with field current carrying capacity of 4.2K and 10MA/cm under 10T magnetic field perpendicular to the surface of superconductive layer 2 。
Example 3
The embodiment relates to an EuBCO superconducting film containing double doping phases, wherein the volume fraction of nano particles is 10%, and the preparation method comprises the following steps:
(1) Selected to contain BaSnO 3 (BSO) and CaO double-doped EuBCO targets, wherein the volume fraction of the BSO is 9.5%, the volume fraction of the CaO is 0.5%, euBCO nanocrystals are prepared by a spray thermal decomposition method, the average grain size is 500nm, and the targets are prepared by plasma sintering at 750 ℃;
(2) Selecting LaMnO 3 /MgO/Y 2 O 3 The nickel-based alloy base band of the Al-O biaxial texture buffer layer is used as a substrate;
(3) Depositing the target material in the step (1) on the substrate in the step (2) in situ by adopting a high-speed pulse laser deposition technology, wherein the excimer laser beam passes through a homogenizer in the deposition process, and the energy is presentedDistributed in a flat top wave mode, and the energy of laser spots on the target is 1J/cm 2 The growth speed is 30nm/s, and the coating temperature is 780 ℃ for the EuBCO superconducting film containing double doped phases.
The thickness of the superconducting film prepared by the method described in example 3 was 2. Mu.m, and the EuBCO superconducting film contained 40nm BSO as a core and 2nm EuBa uniformly distributed 2 Cu 2.7 Ca 0.3 O 7 The second phase nano particle with core-shell structure as shell has superconductive film of 9MA/cm in the 10T magnetic field with current carrying capacity of 4.2K and perpendicular to the surface of the superconductive layer 2 。
Example 4
The embodiment relates to a SmBCO superconducting film containing double doped phases, wherein the volume fraction of nano particles is 15%, and the preparation method comprises the following steps:
(1) Selecting a target material containing BSO and CaO double-doped SmBCO, wherein the volume fraction of the BSO is 14%, the volume fraction of the CaO is 1%, smBCO nanocrystals are prepared by a spray pyrolysis method, the average grain size is 450nm, and the target material is prepared by plasma sintering at 750 ℃;
(2) CeO selection 2 /YSZ/Y 2 O 3 The nickel-based alloy of the biaxially-textured buffer layer is used as a substrate;
(3) Depositing the target material in the step (1) on the substrate in the step (2) in situ by adopting a high-speed pulse laser deposition technology, wherein the energy of excimer laser beams passes through a homogenizer in the deposition process and is distributed in a flat top wave mode, and the energy of laser spots on the target material is 2J/cm 2 The growth speed is 5nm/s, the coating temperature is selected to be 800 ℃, and the SmBCO superconducting film containing double doping phases.
The superconducting film prepared by the method described in example 4 has a thickness of 5 μm, and the SmBCO superconducting film has a uniform distribution. From 40nm BSO as core and 2nm SmBa 2 Cu 2.5 Ca 0.s O 7 The second phase nano particle with core-shell structure as shell has superconductive film of 8MA/cm in the 10T magnetic field with current carrying capacity of 4.2K and perpendicular to the surface of superconductive layer 2 。
Example 5
The embodiment relates to a double-doped semiconductor deviceGd of phase 0.5 Sm 0.5 BaCuO (GdSmBCO) superconducting film, the volume fraction of the nano particles is 20%, and the preparation method comprises the following steps:
(1) Selecting a target material containing BHO and Ca double-doped GdSmBCO, wherein the volume fraction of the BHO is 19%, the volume fraction of the CaO is 1%, the GdSmBCO nanocrystals are prepared by a spray thermal decomposition method, the average grain size is 300nm, and the target material is prepared by plasma sintering at 750 ℃;
(2) CeO selection 2 /MgO/Y 2 O 3 The copper-based metal baseband of the Al-O biaxially-textured buffer layer serves as a substrate;
(3) Depositing the target material in the step (1) on the substrate in the step (2) in situ by adopting a high-speed pulse laser deposition technology, wherein the energy of excimer laser beams passes through a homogenizer in the deposition process and is distributed in a flat top wave mode, and the energy of laser spots on the target material is 2J/cm 2 The growth speed is 10nm/s, the coating temperature is 750 ℃ and the GdSmBCO superconducting film containing double doping phases is selected.
The superconducting film prepared by the method described in example 5 has a thickness of 1. Mu.m, and the GdSmBCO superconducting film contains a uniform distribution of 50nm BHO as a core and 3nm GdSmBa 2 Cu 2 CaO 7 The second phase nano particle with core-shell structure as shell has superconductive film with field current carrying capacity of 4.2K and 10MA/cm under 10T magnetic field perpendicular to the surface of superconductive layer 2 。
Comparative example 1
This comparative example relates to a YBCO superconducting film containing a mixed artificial pinning phase, which is substantially identical to example 1, except that: the target is BZO and CaO double-doped YBCO, the grain size of YBCO is 5um, the volume fraction of powder BZO is 2.9%, the volume fraction of CaO is 0.1%, and the target is prepared by a hot pressing method at 880 ℃.
The BZO structure in the obtained YBCO superconducting film is columnar second phase structure, no Ca doped phase is observed, the transmission electron microscope photograph of the section is shown as figure 3, the superconducting film has a field current carrying capacity of 4.2K and 3MA/cm under a 10T magnetic field perpendicular to the surface of the superconducting layer 2 。
Comparative example 2
This comparative example relates to a YBCO superconducting film containing a mixed artificial pinning phase, which is substantially identical to example 1, except that: the growth rate was 50nm/s.
The BZO in the YBCO superconducting film is in a short rod shape, and YBa 2 Cu 2.9 Ca 0.1 O 7 The superconducting film is made into nano particles, the field current-carrying capacity of the superconducting film is 4.2K, and the 10T magnetic field perpendicular to the surface of the superconducting layer is 1.3MA/cm 2 。
Comparative example 3
This comparative example relates to a YBCO superconducting film containing a mixed artificial pinning phase, which is substantially identical to example 1, except that: the laser did not pass through the homogenizer.
BZO in the obtained YBCO superconducting film is in a columnar structure, no Ca doped phase is observed, and the superconducting film has a field current carrying capacity of 4.2K and a magnetic field of 2.1MA/em under 10T vertical to the surface of the superconducting layer 2 。
Comparative example 4
This comparative example relates to a EuBCO superconducting film containing an artificial pinning phase, which is substantially identical to example 3 except that: in this comparative example, the coating temperature was selected to be 900 ℃.
The BHO second phase in the obtained EuBCO superconducting film is agglomerated, the field current carrying capacity of the superconducting film is 0.5MA/cm under the 10T magnetic field perpendicular to the surface of the superconducting layer of 4.2K 2 。
Comparative example 5
This comparative example relates to a YBCO superconducting film containing a mixed artificial pinning phase, which is substantially identical to example 1, except that: BZO with the doping volume fraction of 3% is doped in the target material, and CaO doping is not added.
The BZO structure in the obtained YBCO superconducting film is a columnar second phase structure, the current carrying capacity of the superconducting film in the field is 4.2K, and the current carrying capacity of the superconducting film in the field is 2MA/cm under the 10T magnetic field perpendicular to the surface of the superconducting layer 2 。
Comparative example 6
This comparative example relates to a GdSmBCO superconducting film containing an artificial pinning phase, the method being substantially the same as in example 5 except that: in this comparative example, the target was doped with BHO at a volume fraction of 20% and no CaO dopant was added.
The second phase of BHO in the obtained GdSmBCO superconducting film is agglomerated, the field current carrying capacity of the superconducting film is 0.8MA/cm under the 10T magnetic field perpendicular to the surface of the superconducting layer of 4.2K 2 。
The foregoing describes specific embodiments of the present application. It is to be understood that the application is not limited to the particular embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the application. The embodiments of the application and the features of the embodiments may be combined with each other arbitrarily without conflict.
Claims (10)
1. A superconducting film containing double doped phase REBCO is characterized in that,
the REBCO superconducting film is a core-shell structure formed by uniformly dispersing nano particles of non-superconducting doping phases in REBCO superconducting parent phases, wherein the nano particles are formed by two-phase self-assembly;
wherein RE in REBCO is rare earth element, and is selected from one or more mixed rare earth of Y, gd, eu, sm.
2. The dual-doped-phase REBCO-containing superconducting film according to claim 1, wherein the nanoparticle diameter is 10-50 nm, and the volume percentage of the nanoparticle in the superconducting film is 3-20%.
3. The REBCO superconducting film according to claim 1, wherein the dual dopant phases are REBa respectively 2 Cu 3-x Ca x O 7 And BMO; wherein the REBa 2 Cu 3-x Ca x O 7 The material is a non-superconductivity material formed by partial occupation of Ca ions doped on copper lattice sites in a CuO surface in REBCO, wherein x is less than 1, and M is selected from one of Zr, hr and Sn.
4. The dual-doped-phase REBCO-containing superconducting film according to claim 1, wherein in the core-shell structure, BMO nanoparticles are cores and are straightThe diameter is 9-49 nm; REBa 2 Cu 3-x Ca x O 7 The thickness of the shell is 0.5 nm-3 nm.
5. A method for producing a double doped phase REBCO-containing superconducting film according to any one of claims 1 to 4, comprising the steps of:
s1, selecting a target material containing BMO and CaO double-doped REBCO;
s2, selecting a substrate with texture;
and S3, adopting a pulse laser deposition method to deposit the target material in the step S1 on the substrate in the step S2 in situ, and obtaining the REBCO superconducting film containing the double doping phases.
6. The method for preparing a superconducting film containing a double doped phase REBCO according to claim 5, wherein in step S1, the REBCO target is a nanocrystalline target, and is prepared by mixing BMO, caO and REBCO nanocrystalline powder; the average grain size of REBCO nanocrystals is between 200 and 500nm, which is determined by the Shelle public calculation through XRD measurement; the volume fraction of BMO in the double-doped REBCO target material is 2.9% -19%; the volume fraction of CaO is 0.1-1%.
7. The method of preparing a superconducting film containing a double doped phase REBCO according to claim 5, wherein in step S2, the textured substrate is LaAlO 3 A single crystal substrate, or a nickel-based or copper-based flexible metal base band; the metal base band is rolled biaxial texture or coated with a single-layer or multi-layer oxide film, and the structure of the oxide film is CeO 2 /YSZ/Y 2 O 3 ，MgO，LaMnO 3 /MgO/Y 2 O 3 A1-O or CeO 2 /MgO/Y 2 O 3 /A1-O。
8. The method of preparing a superconducting film containing a double doped phase REBCO according to claim 4, wherein in step S3, the excimer laser beam passes through a homogenizer with energy distributed in a flat top wave mode, and the laser spot energy on the target is 1 to the whole range2J/cm 2 。
9. The method for preparing a REBCO superconducting film containing double doped phases according to claim 4, wherein in step S3, the growth speed of the REBCO superconducting film prepared by in situ deposition is less than or equal to 30nm/S; the liquid phase temperature T of REBCO superconducting film 1 For reference, coating temperature T g Is selected to be lower than T 1 50-100 ℃.
10. The method of preparing a REBCO superconducting film containing double doped phases according to claim 4, wherein in step S3, the REBCO superconducting film prepared by in-situ deposition has a thickness of 1-5 μm, and a critical current density J under a 10T magnetic field perpendicular to the surface of the superconducting layer at 4.2K c Greater than or equal to 8MA/cm 2 。
Priority Applications (1)
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