CN111087237A - Method for preparing yttrium barium copper oxide superconducting film by using zirconium-doped low-fluorine hybrid solution - Google Patents

Method for preparing yttrium barium copper oxide superconducting film by using zirconium-doped low-fluorine hybrid solution Download PDF

Info

Publication number
CN111087237A
CN111087237A CN201911389621.2A CN201911389621A CN111087237A CN 111087237 A CN111087237 A CN 111087237A CN 201911389621 A CN201911389621 A CN 201911389621A CN 111087237 A CN111087237 A CN 111087237A
Authority
CN
China
Prior art keywords
solution
film
zirconium
copper oxide
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201911389621.2A
Other languages
Chinese (zh)
Inventor
卞维柏
刘硕
潘诗韵
徐伟龙
蒋晓燕
郑敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou Institute of Technology
Original Assignee
Changzhou Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changzhou Institute of Technology filed Critical Changzhou Institute of Technology
Priority to CN201911389621.2A priority Critical patent/CN111087237A/en
Publication of CN111087237A publication Critical patent/CN111087237A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4504—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing rare earth oxides
    • C04B35/4508—Type 1-2-3
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624—Sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
    • C04B2235/6585—Oxygen containing atmosphere, e.g. with changing oxygen pressures at an oxygen percentage above that of air

Abstract

The invention discloses a method for preparing an yttrium barium copper oxide superconducting film by using a zirconium-doped low-fluorine hybrid solution, belonging to the technical field of preparation of high-temperature superconducting coated conductors. The preparation method of the invention obtains F/Ba with the concentration of 1-1 by controlling the proportion of fluorine-containing barium salt and fluorine-free barium salt<2, introducing Zr ions on the basis of the precursor solution to prepare a zirconium-doped low-fluorine hybrid solution; in order to avoid or relieve the defects of segregation of cations and nonuniform size of CuO particles, the method combines an ultraviolet radiation auxiliary heat treatment method to obtain the CuO particle containing a small amount of BaCO3And further comprises BaF2The mixed phases form a BZO phase after subsequent high-temperature crystallization heat treatment, namely Zr with excellent performance is prepared by conversion4+-a YBCO superconducting thin film.

Description

Method for preparing yttrium barium copper oxide superconducting film by using zirconium-doped low-fluorine hybrid solution
Technical Field
The invention relates to a method for preparing an yttrium barium copper oxide superconducting film by using a zirconium-doped low-fluorine hybrid solution, belonging to the technical field of preparation of high-temperature superconducting coated conductors.
Background
Yttrium Barium Copper Oxide (YBCO) is a second generation high temperature superconducting material that can be used in liquid nitrogen temperature region. Scientists discovered T since 1987cYBa greater than 90K2Cu3O7-xSince the past (YBCO) superconductors, yttrium-based high-temperature superconducting thin films have been widely studied and initially industrially used in japan, the united states, and the like. At present, the bismuth-based material has excellent electromagnetic properties, particularly has higher critical current density than that of a first-generation bismuth-based strip material under high field, and is widely applied to weak current fields such as high-end precise microelectronic devices and the like to manufacture various precise electronic devices, such as superconducting quantum interferometers (SQUIDs), Josephson junctions, superconducting coupling antennas, superconducting filters and the like, and strong current fields such as power electronics and the like, such as fault current limiters on power grid systems and the like.
At present, the methods for preparing the YBCO film mainly comprise a vacuum physical method and a chemical solution method. Wherein, the vacuum physical method does not need subsequent annealing heat treatment, but all need expensive vacuum equipment; the chemical solution method belongs to the chemical film preparation technology, has simple equipment, has low cost compared with a vacuum physical method, is easy to control the stoichiometric ratio of metal ions, and is easy to produce large-area long-distance superconducting tapes or films. In recent years, the chemical solution method has received great attention due to its many advantages, and in particular, the trifluoroacetate-metal organic deposition method (TFA-MOD) has been successfully used for preparing YBCO superconducting thin films. In the process, fluorine is introduced by introducing trifluoroacetate, and fluorine and barium are combined to form BaF in the heat treatment process2Intermediate phase and reacts with water vapor to form YBCO phase in the subsequent heat treatment process, thereby avoiding the easy formation of a large amount of BaCO by the method of fluorine-free solution3Defects of the hetero-phase. However, it is due to the introduction of fluorine that BaF is caused2The reaction with water vapor forms HF gas which is detrimental to the surface quality of the film, thereby seriously affecting the surface quality of the film. In addition, the cations of the film are unevenly distributed between the surface and the bottom layer during the curing process, and the organic metal salts have different decomposition temperatures, so that CuO particles and/or Cu particles are generated during the growth of YBCO,The distribution of Y and Ba metal salts is also uneven, thereby affecting the growth quality of the YBCO film.
Aiming at the defects of the traditional TFA-MOD in the process for preparing YBCO and other films, various improved methods are proposed, such as reducing the fluorine content in the solution by improving the formula of the solution, further reducing the F/Ba molar ratio, and providing a solution method with less fluorine and low fluorine. In combination with the current state of research, these processes produce considerable HF despite the reduced fluorine content. Over decades of development, almost all researchers in this field have had a consensus that F/Ba must be greater than 2 in the TFA-MOD process to adequately form BaF2Otherwise BaCO is introduced3And the high-performance YBCO film is not easy to obtain due to the impurity phase, so that the F/Ba in the precursor solution must be ensured to be more than 2. Based on the idea, in the literature or patent on the preparation of YBCO superconducting thin film by the fluorine-containing solution method reported at present, F/Ba is adopted>2. In addition, in order to obtain a high-performance superconducting thin film, in F/Ba>2, the pinning effect is often used to improve the superconducting property of the film. However, in this solution route, a large amount of HF gas which is unfavorable to the YBCO performance is also released during the heat treatment of the thin film, which is a great disadvantage for preparing a YBCO thick film. In addition, the non-uniform distribution of cations such as Y, Cu ions in the cured film still exists, and cannot be effectively relieved. Particularly, in the case of producing a multilayer film, the Cu element is segregated on the surface of the film in a large amount.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing an yttrium barium copper oxide superconducting film by doping zirconium, which obtains F/Ba with the concentration of 1-1 in a solution by controlling the proportion of fluorine-containing barium salt and fluorine-free barium salt<2, adding Zr ions into the low-fluorine precursor solution to prepare a zirconium-doped low-fluorine hybrid solution; then, by combining an ultraviolet irradiation auxiliary heat treatment method and performing high-temperature crystallization heat treatment, Zr with excellent performance is prepared under the condition of low fluorine4+-a YBCO superconducting thin film.
The first purpose of the invention is to provide a method for preparing an yttrium barium copper oxide superconducting film by doping zirconium, which comprises the following steps:
(1) preparing a zirconium-doped low-fluorine hybrid yttrium barium copper oxide solution:
dissolving barium trifluoroacetate in a methanol solution to obtain a solution A;
dissolving barium acetate in a mixed solution of methanol and acrylic acid to obtain a solution B;
dissolving copper acetate in a mixed solution of methanol and α -methacrylic acid to obtain a solution C;
dissolving yttrium acetate and zirconium acetylacetonate in a mixed solution of methanol and methyl triethanolamine to obtain a solution D;
mixing the solution A, the solution B, the solution C and the solution D to prepare yttrium acetate, barium trifluoroacetate, barium acetate, copper acetate and zirconium acetylacetonate with the molar ratio of 3: x: 6-x: 9: 0.24, wherein x is not less than 1<2, obtaining Zr after stirring evenly4+Diluting the doped low-fluorine hybrid yttrium barium copper oxide solution by using methanol to control the total concentration of metal ions in the solution to be 1-1.5 mol/L;
(2) preparation and Ultraviolet (UV) irradiation treatment of gel film: zr obtained in the step (1)4+Taking the doped low-fluorine hybrid yttrium barium copper oxide solution as a precursor solution, preparing an yttrium barium copper oxide precursor gel film on a substrate by using a dip-coating method, drying the gel film and carrying out ultraviolet irradiation treatment;
(3) preparing a zirconium-doped yttrium barium copper oxide high-temperature superconducting film: and (3) carrying out high-temperature crystallization heat treatment and oxygen permeation heat treatment on the film subjected to ultraviolet irradiation in the step (2) to obtain the zirconium-doped yttrium barium copper oxide high-temperature superconducting film.
In one embodiment of the invention, the molar ratio of acrylic acid in the solution B in the step (1) to barium ions in barium acetate is 8-10: 1.
in one embodiment of the invention, the molar ratio of α -methacrylic acid to copper acetate in the solution C in the step (1) is 3-6: 1.
In one embodiment of the invention, the molar ratio of methyl triethanolamine, yttrium acetate and zirconium acetylacetonate in the solution D in the step (1) is 1.5 to 2: 1: 0.08.
in one embodiment of the present invention, the pulling rate of the dip-pull method in the step (2) is 2.67 mm/s.
In one embodiment of the present invention, the substrate in the step (2) is one of a lanthanum aluminate single crystal substrate or a NiW base tape with a transition layer.
In one embodiment of the present invention, the drying treatment of the film in the step (2) is drying at 80 to 100 ℃ for 5 to 20min to obtain a cured film.
In one embodiment of the present invention, the conditions of the ultraviolet radiation treatment in the step (2) are: and (3) placing the dried film under an ultraviolet lamp, and irradiating for 10-20 min at 350 ℃ in air or nitrogen atmosphere, wherein the wavelength of the ultraviolet light is 185 and 254 nm.
In one embodiment of the present invention, the specific method for preparing the zirconium-doped yttrium barium copper oxide high temperature superconducting thin film in step (3) comprises: placing the film subjected to ultraviolet irradiation treatment in a quartz tube furnace with a nitrogen atmosphere with oxygen partial pressure of 500ppm, raising the temperature in the furnace to 775 ℃ at a speed of 10-20 ℃/min, and switching the atmosphere into oxygen-nitrogen mixed gas containing water vapor when the temperature is raised to 200 ℃, wherein the water vapor partial pressure is kept at 4-8 kPa; heating to 775 ℃, preserving heat for 1-3 h, then switching the atmosphere into oxygen-nitrogen mixed gas without water vapor, continuing preserving heat for 10-30 min, finally naturally cooling along with the furnace, and switching the atmosphere into pure O after the temperature is cooled to 400-500 DEG C2And (4) carrying out oxygen permeation, preserving the heat for 1-3 h, naturally cooling to room temperature along with the furnace, and closing the atmosphere to obtain the zirconium-doped yttrium barium copper oxide high-temperature superconducting film.
In one embodiment of the present invention, during the heat treatment in step (3), the tubular sintering furnace is kept in communication with the external environment, and the pressure in the furnace is always maintained at an atmospheric pressure.
In one embodiment of the present invention, if the thickness of the prepared YBCO superconducting film is to be increased, the method comprises the following steps:
1. repeating the preparation of the gel film and the ultraviolet irradiation (UV) treatment process in the step (2) for a plurality of times: and drying the wet film subjected to dip-coating and then carrying out film dip-coating once again. And by analogy, carrying out primary ultraviolet irradiation treatment on the multilayer cured film and then carrying out final heat treatment.
2. Repeating the preparation of the gel film and the ultraviolet irradiation (UV) treatment process in the step (2) for a plurality of times: and drying the wet film subjected to dip-draw, immediately performing ultraviolet irradiation (UV) treatment, performing dip-draw on the film subjected to ultraviolet irradiation (UV) treatment again, drying the wet film subjected to dip-draw, and immediately performing ultraviolet irradiation (UV) treatment. And performing final heat treatment on the film subjected to the multi-layer ultraviolet radiation (UV) treatment by analogy.
3. Repeating the step (2) and the step (3) for a plurality of times: and (3) preparing a layer of zirconium-doped yttrium barium copper oxide film by dip-coating, performing ultraviolet irradiation (UV) treatment, performing the heat treatment in the step (3), performing dip-coating, ultraviolet irradiation (UV) treatment and the heat treatment in the step (3) on the zirconium-doped yttrium barium copper oxide film after the heat treatment, and so on.
The second purpose of the invention is to provide the zirconium-doped yttrium barium copper oxide superconducting film prepared by the method.
The third purpose of the invention is to provide the application of the zirconium-doped yttrium barium copper oxide superconducting film in the field of microelectronic devices.
The fourth purpose of the invention is to provide the application of the zirconium-doped yttrium barium copper oxide superconducting film in the field of power electronics.
The invention has the beneficial effects that:
(1) the content of fluorine element in the solution is controlled by controlling the use amount of barium trifluoroacetate and barium acetate, namely F/Ba is more than or equal to 1 and less than 2, and the ultralow fluorine content enables the subsequent film heat treatment to release a very small amount of HF gas.
(2) The invention controls the F/Ba molar ratio to be 1-2, so that the pretreated film forms BaCO3And BaF2Mixing the phases. Wherein BaCO3The Zr and the Zr form a randomly oriented BZO phase at 500-600 ℃. The randomly oriented BZO has obvious effect on improving the pinning capability of YBCO, so that Jc is improved by 1.5 times, and high performance is obtained by doping zirconium ionsAnd YBCO film with high surface quality.
(3) The method combines an ultraviolet radiation auxiliary heat treatment method, under the irradiation of 185nm and 254nm ultraviolet light, excited oxygen atoms (O) are formed outside the film, and ozone gas (O) with strong oxidizing property is further generated3) Therefore, the amorphous oxide precursor film containing less impurities is easily obtained, and the defects of segregation of cations and nonuniform sizes of CuO particles are relieved.
Drawings
Fig. 1 is an XRD pattern of the film after uv irradiation in example 1.
FIG. 2 shows the results obtained in example 1 with F: ba ═ 1: 1 XRD pattern of the film prepared from the solution.
FIG. 3 shows a graph of the ratio of F: ba ═ 3: 1 XRD pattern of the film prepared from the solution.
FIG. 4 is the XRD pattern of the final zirconium doped yttrium barium copper oxide high temperature superconducting film obtained in example 1.
FIG. 5 shows the crystal plane of the YBCO high temperature superconducting thin film (103) prepared in example 1
Figure BDA0002344564650000041
And scanning the graph.
FIG. 6 is an SEM photograph of the YBCO high temperature superconducting thin film prepared in example 1.
FIG. 7 is J of an YBCO high temperature superconducting thin film prepared in example 1c-H diagram.
FIG. 8 is T of an YBCO high temperature superconducting thin film prepared in example 1cFigure (a).
FIG. 9 is J of an YBCO high temperature superconducting thin film prepared in example 2c-H diagram.
FIG. 10 is J of an YBCO high temperature superconducting thin film prepared in example 2c-H diagram.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
(1) Preparing a zirconium-doped low-fluorine hybrid yttrium barium copper oxide solution:
dissolving 0.00083mol of barium trifluoroacetate in a methanol solution to obtain a solution A;
0.00417mol of barium acetate is dissolved in a mixed solution of methanol and acrylic acid to obtain a solution B, and the molar ratio of acrylic acid to barium ions is 10: 1;
dissolving 0.0075mol of copper acetate in a mixed solution of methanol and α -methacrylic acid to obtain a solution C, wherein the molar ratio of α -methacrylic acid to copper acetate in the solution C is 6: 1;
dissolving 0.0025mol of yttrium acetate and 0.0002mol of zirconium acetylacetonate in a mixed solution of methanol and methyl triethanolamine to obtain a solution D, wherein the molar ratio of the methyl triethanolamine to the yttrium acetate to the zirconium acetylacetonate in the solution D is 2: 1: 0.08;
mixing the solution A, the solution B, the solution C and the solution D, and uniformly stirring to obtain Zr4+Doped low-fluorine hybrid yttrium barium copper oxide solution, diluting the solution with methanol to control the total concentration of metal ions in the solution to be 1.5mol/L, and mixing to obtain Zr4+The molar ratio of Y ions, Ba ions, Cu ions and Zr ions in the doped low-fluorine hybrid yttrium barium copper oxide solution is 1: 2: 3: 0.08, wherein the molar ratio of the barium trifluoroacetate to the barium acetate is 1: 5, so F in solution: ba ═ 1: 1.
(2) preparation and Ultraviolet (UV) irradiation treatment of gel film:
adding Zr4+The preparation method comprises the steps of taking a doped low-fluorine hybrid yttrium barium copper oxide solution as a precursor solution, preparing a zirconium-doped yttrium barium copper oxide precursor gel film on a lanthanum aluminate single crystal substrate at a pulling speed of 2.6mm/s by using a dip-coating method, drying for 10 minutes at the temperature of 100 ℃ to obtain a cured gel film, placing the cured gel film in a UV surface irradiation device, and irradiating for 20 minutes at the temperature of 350 ℃ in an air atmosphere, wherein the wavelength of ultraviolet light is 185 and 254 nm.
(3) Preparing a zirconium-doped yttrium barium copper oxide high-temperature superconducting film:
placing the film subjected to irradiation in the step (2) in a quartz tube furnace with a nitrogen atmosphere with oxygen partial pressure of 500ppm, increasing the temperature in the furnace from room temperature to 775 ℃ at a speed of 20 ℃/min, and increasing the atmosphere when the temperature is increased to 200 ℃ in the temperature increasing processSwitching to oxygen-nitrogen mixed gas containing water vapor, wherein the water vapor partial pressure is kept at 4 kPa; heating to 775 deg.C, keeping the temperature for 2 hr, switching the atmosphere to oxygen-nitrogen mixed gas containing no water vapor, keeping the temperature for 30min, naturally cooling with the furnace, and switching the atmosphere to pure O when the temperature is cooled to 500 deg.C2Carrying out oxygen permeation, preserving the heat for 2 hours at the temperature, then naturally cooling to room temperature along with the furnace, closing the atmosphere, and sintering to obtain the zirconium-doped yttrium barium copper oxide high-temperature superconducting film; in the heat treatment process, the quartz tube furnace is communicated with the outside, and the air pressure in the furnace is always maintained at one atmospheric pressure.
(4) Characterization test:
XRD (X-ray diffraction) test is carried out on the gel film after ultraviolet radiation in the step (2), figure 1 is the XRD pattern of the film after ultraviolet radiation in the example 1, and as shown in figure 1, BaCO is found to be present in the gel film after ultraviolet radiation3Phase, due to the presence of F: ba ═ 1: formation of BaF in a hypofluorite solution2Then the excess Ba atom must form BaCO3And (4) phase(s). XRD testing of the product of the film in step (3) during calcination, as shown in fig. 2, can find that the ratio of F: ba ═ 1: 1, and generating a BZO phase at 500-600 ℃. A set of control experiments was performed concurrently with F: ba ═ 3: 1, the preparation method is the same as the above preparation method, and only the F/Ba ratio is adjusted to 3: 1. XRD measurements were performed on the product of the film during calcination as shown in fig. 3. From fig. 3 it can be seen that with F: ba ═ 3: 1, the BZO phase begins to form at 600-700 ℃. In conjunction with previous reports of relevant studies, it is known that F: ba ═ 3: 1. the film produced from the solution of 1 is free of BaCO3Phase, i.e. description of BaF2The temperature of forming a BZO phase with Zr is between 600 and 700 ℃, thereby proving that the temperature of the Zr-: ba ═ 1: 1, the BZO phase generated in the film at 500-600 ℃ is BaCO3Coherent with the formation. Therefore, by doping the zirconium element, BaCO in the film prepared by the low-fluorine solution can be ensured3The BZO phase is generated, thereby solving the problem that the method of low fluorine solution is easy to form a large amount of BaCO3Defects of the heterogeneous phase.
FIG. 4 is the XRD pattern of the final zirconium doped yttrium barium copper oxide high temperature superconducting film obtained in example 1. As shown in FIG. 4, Zr prepared in example 14+The YBCO superconducting film has no obvious crystal grain growth with a-axis orientation, and shows stronger c-axis oriented diffraction peak from (002) to (009), namely the film is epitaxially grown along the c-axis. Meanwhile, BaCO does not exist on an X-ray diffraction pattern3、BaF2And other hetero-phase peaks appear, which shows that the film consists of YBCO phase with c-axis orientation, and the film is a conductive layer CuO in the superconducting coating2The premise of good communication of the surfaces. Further, the a-and b-axis biaxial orientation textures of the film were examined, and the film sample was subjected to
Figure BDA0002344564650000061
And (6) scanning. From FIG. 5, four high intensity diffraction peaks are observed at 90 ℃ intervals, and the average full width at half maximum (FWHM) of the film is 1.99 °, indicating that the arrangement of crystal grains in the a-b two-dimensional plane is relatively uniform and that the film has a relatively good biaxial orientation.
Zr prepared in example 14+The surface morphology of the-YBCO film is shown in figure 6, and as can be seen from figure 6, the surface of the film sample is relatively flat, the density is relatively high, the surface vacancies are relatively few, the crystal grains are in columnar arrangement morphology, and are relatively regular, the formation of a-axis crystal grains is not found on the surface, and only c-axis crystal grains are formed, which is consistent with the XRD analysis result. The atomic force morphology shows that Zr is in the area of 10 mu m multiplied by 10 mu m4+The average surface roughness Ra of YBCO is only 23.7 nm.
FIG. 7 is J of an YBCO high temperature superconducting thin film prepared in example 1cFIG. 7 shows Zr prepared with a low fluorine hybrid solution doped with Zr4+YBCO film, at 0T and 77K, JcCan reach 4.3MA/cm2. FIG. 8 is T of an YBCO high temperature superconducting thin film prepared in example 1cAs can be seen from FIG. 8, the superconducting critical transition temperature of the thin film is 92.8K.
Example 2
(1) Preparing a zirconium-doped low-fluorine hybrid yttrium barium copper oxide solution:
dissolving 0.00125mol of barium trifluoroacetate in a methanol solution to obtain a solution A;
0.00375mol of barium acetate is dissolved in a mixed solution of methanol and acrylic acid to obtain a solution B, and the molar ratio of propionic acid to barium ions is 8: 1;
dissolving 0.0075mol of copper acetate in a mixed solution of methanol and α -methacrylic acid to obtain a solution C, wherein the molar ratio of α -methacrylic acid to copper acetate in the solution C is 3: 1;
dissolving 0.0025mol of yttrium acetate and 0.0002mol of zirconium acetylacetonate in a mixed solution of methanol and methyl triethanolamine to obtain a solution D, wherein the molar ratio of the methyl triethanolamine to the yttrium acetate to the zirconium acetylacetonate in the solution D is 1.5: 1: 0.08;
mixing the solution A, the solution B, the solution C and the solution D. After stirring evenly, obtaining Zr4+And diluting the doped low-fluorine hybrid yttrium barium copper oxide solution by using methanol to control the total concentration of metal ions in the solution to be 1.5 mol/L. Zr obtained by mixing4+The molar ratio of Y ions, Ba ions, Cu ions and Zr ions in the doped low-fluorine hybrid yttrium barium copper oxide solution is 1: 2: 3: 0.08, wherein the molar ratio of the barium trifluoroacetate to the barium acetate is 1: 3, so F in solution: ba ═ 1.5: 1.
(2) preparation and Ultraviolet (UV) irradiation treatment of gel film:
adding Zr4+The preparation method comprises the steps of taking a doped low-fluorine hybrid yttrium barium copper oxide solution as a precursor solution, preparing a zirconium-doped yttrium barium copper oxide precursor gel film on a lanthanum aluminate single crystal substrate at a pulling speed of 2.6mm/s by using a dip-coating method, drying for 15 minutes at a temperature of 80 ℃ to obtain a cured film, placing the cured film in a UV surface irradiation device, and irradiating for 15 minutes at a temperature of 350 ℃ in an air atmosphere, wherein the wavelength of ultraviolet light is 185 and 254 nm.
(3) Preparing a zirconium-doped yttrium barium copper oxide high-temperature superconducting film:
placing the film subjected to irradiation in the step (2) in a quartz tube furnace with a nitrogen atmosphere with the oxygen partial pressure of 500ppm, raising the temperature in the furnace from room temperature to 775 ℃ at the speed of 15 ℃/min, and switching the atmosphere to 200 ℃ in the temperature raising processThe oxygen/nitrogen mixed gas containing water vapor, the water vapor partial pressure is kept at 6 kPa; heating to 775 deg.C, keeping the temperature for 1 hr, switching the atmosphere to oxygen/nitrogen gas mixture without water vapor, keeping the temperature for 20min, naturally cooling with the furnace, and switching the atmosphere to pure O when the temperature is cooled to 450 deg.C2Carrying out oxygen permeation, and keeping the temperature for 1 hour at the temperature; after the heat preservation is finished, naturally cooling to room temperature along with the furnace, closing the atmosphere, and sintering to obtain the yttrium barium copper oxide high-temperature superconducting film; in the heat treatment process, the quartz tube furnace is communicated with the outside, and the air pressure in the furnace is always maintained at one atmospheric pressure.
The YBCO high temperature superconducting thin film obtained in example 2 has a critical transition temperature of 90K or more, and FIG. 9 is a J-shape of the YBCO high temperature superconducting thin film prepared in this examplecH diagram, from which J of the YBCO high temperature superconducting thin film can be seencThe value reaches 3MA/cm2The above.
Example 3
(1) Preparing a zirconium-doped low-fluorine hybrid yttrium barium copper oxide solution:
dissolving 0.001mol of barium trifluoroacetate in a methanol solution to obtain a solution A;
dissolving 0.004mol of barium acetate in a mixed solution of methanol and acrylic acid to obtain a solution B, wherein the molar ratio of propionic acid to barium ions is 10: 1;
dissolving 0.0075mol of copper acetate in a mixed solution of methanol and α -methacrylic acid to obtain a solution C, wherein the molar ratio of α -methacrylic acid to copper acetate in the solution C is 3: 1;
dissolving 0.0025mol of yttrium acetate and 0.0002mol of zirconium acetylacetonate in a mixed solution of methanol and methyl triethanolamine to obtain a solution D, wherein the molar ratio of the methyl triethanolamine to the yttrium acetate to the zirconium acetylacetonate in the solution D is 1.5: 1: 0.08;
and uniformly mixing and stirring the solution A, the solution B, the solution C and the solution D to obtain a zirconium-doped low-fluorine hybrid yttrium barium copper oxide solution, and diluting with methanol to control the total concentration of metal ions in the solution to be 1.5 mol/L. Zr obtained by mixing4+Doped low-fluorine hybrid yttrium barium copper oxide solutionThe molar ratio of the Y ions, the Ba ions, the Cu ions and the Zr ions is 1: 2: 3: 0.08, wherein the molar ratio of the barium trifluoroacetate to the barium acetate is 1: 4, so F in solution: ba ═ 1.2: 1.
(2) preparation and Ultraviolet (UV) irradiation treatment of gel film:
adding Zr4+The doped low-fluorine hybrid yttrium barium copper oxide solution is used as a precursor solution, and a zirconium-doped yttrium barium copper oxide precursor gel film is prepared on a lanthanum aluminate single crystal substrate at a pulling speed of 2.6mm/s by using a dip-coating method. Then drying at 90 ℃ for 20 minutes to obtain a cured film, placing the cured film in a UV surface irradiation device, and irradiating at 350 ℃ for 10 minutes in a nitrogen atmosphere, wherein the wavelength of ultraviolet light is 185 and 254 nm;
(3) preparing a zirconium-doped yttrium barium copper oxide high-temperature superconducting film:
placing the film subjected to irradiation in the step (2) in a quartz tube furnace with a nitrogen atmosphere with the oxygen partial pressure of 500ppm, raising the temperature in the furnace from room temperature to 775 ℃ at the speed of 10 ℃/min, and in the temperature raising process, switching the atmosphere into a mixed gas of oxygen/nitrogen containing water vapor when the temperature is raised to 200 ℃, wherein the water vapor partial pressure is kept at 8 kPa; heating to 775 deg.C, keeping the temperature for 3 hr, switching the atmosphere to oxygen/nitrogen gas mixture without water vapor, keeping the temperature for 10 min, naturally cooling with the furnace, and switching the atmosphere to pure O when the temperature is cooled to 400 deg.C2Carrying out oxygen permeation, and keeping the temperature for 3 hours at the temperature; after the heat preservation is finished, naturally cooling to room temperature along with the furnace, closing the atmosphere, and obtaining a sintered sample, namely the yttrium barium copper oxide high-temperature superconducting film; in the heat treatment process, the quartz tube furnace is communicated with the outside, and the air pressure in the furnace is always maintained at one atmospheric pressure.
The critical transformation temperature of the YBCO high temperature superconducting thin film prepared in example 3 was 90K or more, and FIG. 10 is a J-shape diagram of the YBCO high temperature superconducting thin film prepared in this examplecH diagram, from which J of the YBCO high temperature superconducting thin film can be seencThe value reaches 3MA/cm2The above.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

1. A method for preparing an yttrium barium copper oxide superconducting film by doping zirconium is characterized by comprising the following steps:
(1) preparing zirconium-doped yttrium barium copper oxide solution:
dissolving barium trifluoroacetate in a methanol solution to obtain a solution A;
dissolving barium acetate in a mixed solution of methanol and acrylic acid to obtain a solution B;
dissolving copper acetate in a mixed solution of methanol and α -methacrylic acid to obtain a solution C;
dissolving yttrium acetate and zirconium acetylacetonate in a mixed solution of methanol and methyl triethanolamine to obtain a solution D;
mixing the solution A, the solution B, the solution C and the solution D to prepare yttrium acetate, barium trifluoroacetate, barium acetate, copper acetate and zirconium acetylacetonate with the molar ratio of 3: x: 6-x: 9: 0.24, wherein x is not less than 1<2, obtaining Zr after stirring evenly4+Diluting the doped yttrium barium copper oxide solution by using methanol to control the total concentration of metal ions in the solution to be 1-1.5 mol/L;
(2) preparation and Ultraviolet (UV) irradiation treatment of gel film: zr obtained in the step (1)4+Taking the doped yttrium barium copper oxide solution as a precursor solution, preparing an yttrium barium copper oxide precursor gel film on a substrate by using a dip-coating method, drying the gel film and carrying out ultraviolet irradiation treatment;
(3) preparing a zirconium-doped yttrium barium copper oxide high-temperature superconducting film: and (3) carrying out high-temperature crystallization heat treatment and oxygen permeation heat treatment on the film subjected to ultraviolet irradiation in the step (2) to obtain the zirconium-doped yttrium barium copper oxide high-temperature superconducting film.
2. The method according to claim 1, wherein the molar ratio of acrylic acid to barium ions in barium acetate in the solution B in the step (1) is 8-10: 1, the molar ratio of α -methacrylic acid to copper acetate in the solution C is 3-6: 1, and the molar ratio of methyl triethanolamine, yttrium acetate and zirconium acetylacetonate in the solution D is 1.5-2: 1: 0.08.
3. The method of claim 1, wherein the substrate in step (2) is one of a lanthanum aluminate single crystal substrate or a NiW tape with a transition layer.
4. The method according to claim 1, wherein the drying treatment of the film in the step (2) is drying at 80 to 100 ℃ for 5 to 20min to obtain a cured film.
5. The method according to claim 1, wherein the ultraviolet radiation treatment in step (2) is performed under the following conditions: and (3) placing the dried film under an ultraviolet lamp, and irradiating for 10-20 min at 350 ℃ in air or nitrogen atmosphere, wherein the wavelength of the ultraviolet light is 185 and 254 nm.
6. The method according to claim 1, wherein the specific method for preparing the zirconium-doped yttrium barium copper oxide high-temperature superconducting thin film in the step (3) is as follows: placing the film subjected to ultraviolet irradiation treatment in a quartz tube furnace with a nitrogen atmosphere with oxygen partial pressure of 500ppm, raising the temperature in the furnace to 775 ℃ at a speed of 10-20 ℃/min, and switching the atmosphere into oxygen-nitrogen mixed gas containing water vapor when the temperature is raised to 200 ℃, wherein the water vapor partial pressure is kept at 4-8 kPa; heating to 775 ℃, preserving heat for 1-3 h, then switching the atmosphere into oxygen-nitrogen mixed gas without water vapor, continuing preserving heat for 10-30 min, finally naturally cooling along with the furnace, and switching the atmosphere into pure O after the temperature is cooled to 400-500 DEG C2And (4) carrying out oxygen permeation, preserving the heat for 1-3 h, naturally cooling to room temperature along with the furnace, and closing the atmosphere to obtain the zirconium-doped yttrium barium copper oxide high-temperature superconducting film.
7. A zirconium-doped yttrium barium copper oxide superconducting film prepared according to any one of claims 1 to 6.
8. Use of the zirconium-doped yttrium barium copper oxide superconducting film of claim 7 in the field of microelectronic devices.
9. Use of the zirconium-doped yttrium barium copper oxide superconducting film of claim 7 in the power electronics field.
CN201911389621.2A 2019-12-30 2019-12-30 Method for preparing yttrium barium copper oxide superconducting film by using zirconium-doped low-fluorine hybrid solution Withdrawn CN111087237A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911389621.2A CN111087237A (en) 2019-12-30 2019-12-30 Method for preparing yttrium barium copper oxide superconducting film by using zirconium-doped low-fluorine hybrid solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911389621.2A CN111087237A (en) 2019-12-30 2019-12-30 Method for preparing yttrium barium copper oxide superconducting film by using zirconium-doped low-fluorine hybrid solution

Publications (1)

Publication Number Publication Date
CN111087237A true CN111087237A (en) 2020-05-01

Family

ID=70398456

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911389621.2A Withdrawn CN111087237A (en) 2019-12-30 2019-12-30 Method for preparing yttrium barium copper oxide superconducting film by using zirconium-doped low-fluorine hybrid solution

Country Status (1)

Country Link
CN (1) CN111087237A (en)

Similar Documents

Publication Publication Date Title
US7919434B2 (en) Oxide superconducting film and method of preparing the same
CN103184513A (en) Preparation method of high-temperature superconducting thin film
Nasui et al. Fluorine-free propionate route for the chemical solution deposition of YBa2Cu3O7− x superconducting films
US20110166026A1 (en) Method of fabricatiing oxide superconducting thin film
JP2013235766A (en) Oxide superconducting thin film and method for manufacturing the same
CN102603283B (en) Method for preparing high-temperature superconducting gadolinium-barium-copper-oxygen thin film by utilizing chemical solution method
Wong-Ng et al. Phase evolution of Ba2YCu3O6+ x films during the BaF2 process
CN102569636B (en) Method for preparing gadolinium-barium-copper-oxygen (GdBCO) high-temperature superconducting thin film by using chemical solution method
CN111087237A (en) Method for preparing yttrium barium copper oxide superconducting film by using zirconium-doped low-fluorine hybrid solution
CN101746807A (en) Method for increasing thickness of YBCO film prepared through TFA-MOD method
CN114164490A (en) Method for preparing high-temperature superconducting oxide ceramic epitaxial film by heating through induction method
Wang et al. High performance fluorine-free MOD YBa2Cu3O7-z film preparation by partial melting process
CN104788092B (en) The method that a kind of heat treatment of ultraviolet auxiliary prepares Yt-Ba-Cu-O high-temperature superconductive film
KR20110081112A (en) Coated conductor with improved grain orientation
Jin et al. Effect of fluorine on the intermediate phase evolution for GdBCO film growth
US8236733B2 (en) Method of forming a precursor solution for metal organic deposition and method of forming superconducting thick film using the same
CN112456538B (en) Preparation method of REBCO nano particle composite YBCO superconducting layer
AU2021102202A4 (en) Multilayer structure for high-temperature superconductor-coated conductors and method for preparing thick films
Siegal et al. Improving chemical solution deposited YBa2Cu3O7− δ film properties via high heating rates
Lee et al. Fabrication of high-quality epitaxial YBCO films prepared by fluorine-free MOD
JP2011253768A (en) Method of manufacturing oxide superconductor thin film
Boubeche et al. Thick REBaCuO superconducting films through single-coating of low-fluorine metallorganic solution
Mutlu et al. YBCO coated conductor development by continuous sol-gel process
Jin et al. Effect of relative humidity on morphology of YBCO films prepared by CSD method
CN103771852B (en) Preparation method of yttrium-group high-temperature superconducting thin film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20200501