CN106242553B - A kind of preparation method of high-temperature superconductor REBCO film - Google Patents
A kind of preparation method of high-temperature superconductor REBCO film Download PDFInfo
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- CN106242553B CN106242553B CN201610623602.1A CN201610623602A CN106242553B CN 106242553 B CN106242553 B CN 106242553B CN 201610623602 A CN201610623602 A CN 201610623602A CN 106242553 B CN106242553 B CN 106242553B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000002887 superconductor Substances 0.000 title abstract description 34
- 239000010408 film Substances 0.000 claims abstract description 149
- 239000002243 precursor Substances 0.000 claims abstract description 135
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 85
- 239000011737 fluorine Substances 0.000 claims abstract description 85
- 239000007788 liquid Substances 0.000 claims abstract description 67
- 238000004528 spin coating Methods 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000002356 single layer Substances 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000010409 thin film Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 72
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 69
- 239000001301 oxygen Substances 0.000 claims description 69
- 229910052760 oxygen Inorganic materials 0.000 claims description 69
- 239000010453 quartz Substances 0.000 claims description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 239000012046 mixed solvent Substances 0.000 claims description 36
- 235000019260 propionic acid Nutrition 0.000 claims description 36
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 32
- 239000010410 layer Substances 0.000 claims description 25
- 229910052788 barium Inorganic materials 0.000 claims description 21
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 claims description 18
- OURWKHLDAVYMGO-UHFFFAOYSA-N 7-thiophen-2-ylpyrazolo[1,5-a]pyrimidine-3-carboxylic acid Chemical compound C=1C=NC2=C(C(=O)O)C=NN2C=1C1=CC=CS1 OURWKHLDAVYMGO-UHFFFAOYSA-N 0.000 claims description 16
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- BQJILRFOGPBJQJ-UHFFFAOYSA-L barium(2+);2,2,2-trifluoroacetate Chemical group [Ba+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F BQJILRFOGPBJQJ-UHFFFAOYSA-L 0.000 claims 3
- OYHFUCHGJKUPMK-UHFFFAOYSA-K [Gd+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O Chemical compound [Gd+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O OYHFUCHGJKUPMK-UHFFFAOYSA-K 0.000 claims 2
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 claims 2
- DKOUNIUITOMUNM-UHFFFAOYSA-K propanoate;yttrium(3+) Chemical group [Y+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O DKOUNIUITOMUNM-UHFFFAOYSA-K 0.000 claims 2
- 235000019441 ethanol Nutrition 0.000 description 32
- 238000010792 warming Methods 0.000 description 24
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 17
- QVLQKWQNKGVECJ-UHFFFAOYSA-N copper;propanoic acid Chemical compound [Cu].CCC(O)=O QVLQKWQNKGVECJ-UHFFFAOYSA-N 0.000 description 16
- 229910001882 dioxygen Inorganic materials 0.000 description 15
- KEGWJVHGHGSCSO-UHFFFAOYSA-N barium;2,2,2-trifluoroacetic acid Chemical compound [Ba].OC(=O)C(F)(F)F KEGWJVHGHGSCSO-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- JWHSHSIDBNVKTJ-UHFFFAOYSA-N propanoic acid;yttrium Chemical group [Y].CCC(O)=O JWHSHSIDBNVKTJ-UHFFFAOYSA-N 0.000 description 10
- 229910002244 LaAlO3 Inorganic materials 0.000 description 8
- WRYMWCYTOPBJJV-UHFFFAOYSA-N gadolinium;propanoic acid Chemical compound [Gd].CCC(O)=O WRYMWCYTOPBJJV-UHFFFAOYSA-N 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000007669 thermal treatment Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 239000004575 stone Substances 0.000 description 7
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 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
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- 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
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- 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
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- 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
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- Superconductor Devices And Manufacturing Methods Thereof (AREA)
Abstract
The present invention provides a kind of preparation method of high-temperature superconductor REBCO film, method includes the following steps: one, according to RE: Ba: Cu=1: 1.75: 3 atomic ratio prepare floride-free precursor liquid；Two, press RE: Ba: Cu=1: (1.5~2): 3 atomic ratio prepares fluorine-containing precursor liquid；Three, the floride-free precursor liquid is coated uniformly on by LaAlO using spin-coating method3On substrate, floride-free single layer precursor film is after heat treatment obtained；Four, fluorine-containing precursor liquid is coated uniformly on floride-free single layer precursor film using spin-coating method, after heat treatment obtains floride-free/fluorine-containing double-deck precursor film；Five, floride-free/fluorine-containing double-deck precursor film after heat treatment obtains REBCO superconducting thin film.Preparation method of the present invention is simple, and the high-temperature superconductor REBCO film of preparation has sharp keen cube orientation and excellent superconductivity, and improves current-carrying performance of the high-temperature superconductor REBCO film at 77K.
Description
Technical field
The invention belongs to high temperature superconducting materia technical fields, and in particular to a kind of preparation side of high-temperature superconductor REBCO film
Method.
Background technique
The multilayer materials that coating conductor is made of metal base band/buffer layer/superconducting layer/protective layer.Due to its
Excellent current-carrying capability under High-Field will be that high temperature superconducting materia is really realized in unique hope that liquid nitrogen temperature forceful electric power is applied, closely
Year over always developed country development core superconductor.At present using inexpensive chemical solution deposition technique preparation
REBa2Cu3Oy(REBCO) superconducting layer becomes one of research hotspot.
Chemical solution deposition prepares high-temperature superconductor REBCO film and generally comprises precursor liquid preparation, coating, pyrolysis, crystallization
With infiltration oxygen.Classified according to superconducting layer at phase mechanism, substantially includes two classes.The first is obtained floride-free using floride-free presoma
Precursor liquid is that presoma is decomposed to form BaCO at phase process3、CuO、RE2O3, the reaction generation REBCO superconduction of these three compounds
Phase.Second of fluorine-containing precursor preparation tradition perfluor precursor liquid of use, is made as " BaF at camera2Mechanism ".I.e. fluorine-containing presoma point
Solution is at BaF2、CuO、RE2O3, BaF2Be converted into BaO by reacting with water, further with CuO, RE2O3Reaction, ultimately forms
REBCO superconducting phase.Both methods has certain defect, and wherein first method contains during the preparation process is difficult to decompose
Barium carbonate, generally requiring can just completely remove compared with high crystallization temperature, and residual carbonate will lead to the performance drop of REBCO superconducting thin film
It is low.Second method fluorine content will lead into phase process liquid phase and be formed excessively, non-oriented forming core occurs, and slow growth can also be led
Cause reduced performance.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of high-temperature superconductor
The preparation method of REBCO film.This method is prepared for floride-free/fluorine-containing double-deck precursor film of REBCO, by the fluorine-containing precursor film in upper layer
Fluorine be diffused into lower layer's free-floride precursor film, it is suppressed that the carbon content in lower layer's free-floride precursor film can promote biaxial orientation
Forming core avoids residual barium carbonate from reducing the performance of superconducting thin film.Meanwhile in the fluorine-containing precursor film in upper layer fluorine gradually to lower layer
Floride-free forerunner's membrane diffusion, the fluorine content in the fluorine-containing precursor film in upper layer reduce, and advantageously reduce the fluorine-containing precursor film in upper layer into phase process
Liquid phase, reduce any bodily form core, form extension fast-growth.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of preparation of high-temperature superconductor REBCO film
Method, which is characterized in that method includes the following steps:
Step 1: preparing floride-free precursor liquid: by the propionate of RE, barium propionate, propionic acid copper according to RE: Ba: Cu=1: 1.75:
3 atomic ratio is dissolved in the in the mixed solvent of propionic acid and ethyl alcohol, stirs under conditions of 40 DEG C~100 DEG C to being completely dissolved, obtains
The floride-free precursor liquid for being 1.5mol/L to total cation molar concentration；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1:
(1~10)；The propionate of the RE is propionic acid yttrium or propionic acid gadolinium；
Step 2: preparing fluorine-containing precursor liquid: by the propionate of RE, the organic salt of barium, propionic acid copper by RE: Ba: Cu=1:
(1.5~2): 3 atomic ratio is dissolved in the in the mixed solvent of propionic acid and ethyl alcohol, stirs under conditions of 40 DEG C~100 DEG C to complete
Fully dissolved obtains the fluorine-containing precursor liquid that total cation molar concentration is 1.5mol/L~2mol/L；The in the mixed solvent propionic acid
Volume ratio with ethyl alcohol is 1: (1~10)；The propionate of the RE is propionic acid yttrium or propionic acid gadolinium；The organic salt of the barium is trifluoro
The mixture of barium acetate or trifluoroacetic acid barium and barium propionate；
The propionate of RE described in step 2 is identical with the propionate of RE described in step 1；
Step 3: preparing floride-free single layer precursor film: free-floride precursor liquid described in step 1 is uniformly coated using spin-coating method
In LaAlO3On substrate, it is subsequently placed in the quartz tube furnace that temperature is 120 DEG C~200 DEG C, and lead into the quartz tube furnace
Enter moist oxygen atmosphere, is warming up to 400 DEG C~500 DEG C with the rate of 5 DEG C/min, constant temperature 10min cools to room temperature with the furnace and obtains
To floride-free single layer precursor film；
Step 4: floride-free/fluorine-containing double-deck precursor film of preparation: fluorine-containing precursor liquid described in step 2 is uniform using spin-coating method
It is 120 DEG C~200 DEG C of quartz tube furnace coated in temperature on the precursor film of free-floride single layer described in step 3, is subsequently placed in, and
It is passed through moist oxygen atmosphere into the quartz tube furnace, is warming up to 400 DEG C~500 DEG C with the rate of 5 DEG C/min, constant temperature
10min cools to room temperature with the furnace and obtains floride-free/fluorine-containing double-deck precursor film；
Step 5: crystallization and thermal treatment: free-floride described in step 4/fluorine-containing double-deck precursor film is placed in quartz tube furnace,
It is passed through moist argon oxygen gas mixture to the quartz tube furnace, is then warming up to again with 10 DEG C/min~100 DEG C/min rate
770 DEG C~810 DEG C, 1h~2h is kept the temperature, 1h is kept the temperature when furnace temperature is down to 450 DEG C and carries out seeping oxygen processing, room temperature is cooled to the furnace, obtains
To high-temperature superconductor REBCO film of the critical-temperature more than liquid nitrogen temperature (77K).
The preparation method of above-mentioned high-temperature superconductor REBCO film, which is characterized in that stirred described in step 1 and step 2
Time be 1h~3h.
The preparation method of above-mentioned high-temperature superconductor REBCO film, which is characterized in that in the organic salt of barium described in step 2
The mole percent of trifluoroacetic acid barium is not less than 15%.
The preparation method of above-mentioned high-temperature superconductor REBCO film, which is characterized in that spin coating described in step 3 and step 4
Revolving speed be 500r/min~4500r/min, time of the spin coating is 30s~180s.
The preparation method of above-mentioned high-temperature superconductor REBCO film, which is characterized in that moist described in step 3 and step 4
The volumn concentration of oxygen is 97%~98% in oxygen atmosphere, and surplus is steam.
The preparation method of above-mentioned high-temperature superconductor REBCO film, which is characterized in that moist argon oxygen mixing described in step 5
The volumn concentration of argon gas is 95.73%~98.78% in gas, and the volumn concentration of oxygen is 0.02%~0.07%,
Surplus is steam.
Compared with the prior art, the present invention has the following advantages:
1, the present invention is prepared for free-floride/fluorine-containing double-deck precursor film of REBCO film, and the lower layer of the precursor film is floride-free forerunner
Film, upper layer are fluorine-containing precursor film, are diffused into lower layer's free-floride precursor film by the fluorine in the fluorine-containing precursor film in upper layer, it is suppressed that lower layer
Carbon content in floride-free precursor film can promote biaxial orientation forming core in lower layer's free-floride precursor film, avoid residual barium carbonate from reducing super
Lead the superconductivity of film, at the same in the fluorine-containing precursor film in upper layer fluorine gradually to lower layer's free-floride forerunner's membrane diffusion, upper layer forerunner
Fluorine content in film reduces, this is conducive to reduce the liquid phase at phase process, reduces any bodily form core, forms extension fast-growth, this
It invents high-temperature superconductor REBCO film obtained and solves traditional floride-free presoma or perfluor precursor preparation REBCO film superconduction
The bad problem of performance.
2, fluorine diffusion can be formed in the double-deck precursor film in the free-floride of REBCO film of the present invention/fluorine-containing double-deck precursor film
Fluorine gradient weakens the influence of superconduction bed boundary, avoids copper from being enriched in the interface of the fluorine-containing precursor film in upper layer, is conducive to epitaxial growth
Across interface, superconducting thin film is made to become an entirety.By reducing the cavity blemish in superconducting thin film, it is thin to improve high-temperature superconductor
The uniformity of film is integrally improved the superconductivity of high-temperature superconducting thin film.
3, preparation method of the present invention is simple, and the high-temperature superconductor REBCO film of preparation has sharp keen cube orientation, has good
Good superconductivity, and the structure by improving superconducting thin film improves current-carrying of the high-temperature superconductor REBCO film at 77K
Energy.
Technical solution of the present invention is described in further detail below by drawings and examples.
Detailed description of the invention
Fig. 1 is the X diffracting spectrum of HTS YBCO film prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope map of HTS YBCO film prepared by the embodiment of the present invention 1.
Fig. 3 is the X diffracting spectrum of high-temperature superconductor GdBCO film prepared by the embodiment of the present invention 2.
Fig. 4 is the scanning electron microscope map of high-temperature superconductor GdBCO film prepared by the embodiment of the present invention 2.
Specific embodiment
Embodiment 1
The present embodiment prepare HTS YBCO film method the following steps are included:
Step 1: preparing floride-free precursor liquid: by propionic acid yttrium, barium propionate, propionic acid copper according to Y: Ba: Cu=1: 1.75: 3 original
In the mixed solvent of the son than being dissolved in propionic acid and ethyl alcohol stirs 2h to being completely dissolved under conditions of 70 DEG C, obtains total cation
Molar concentration is the floride-free precursor liquid of 1.5mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 5.5；
Step 2: preparing fluorine-containing precursor liquid: by propionic acid yttrium, the organic salt of barium, propionic acid copper by Y: Ba: Cu=1: 1.75: 3
Atomic ratio is dissolved in the in the mixed solvent of propionic acid and ethyl alcohol, and 2h is stirred under conditions of 70 DEG C to being completely dissolved, obtain total sun from
Sub- molar concentration is the fluorine-containing precursor liquid of 1.8mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 5.5；It is described
The organic salt of barium is the mixture of trifluoroacetic acid barium and barium propionate, the mole percent of trifluoroacetic acid barium in the organic salt of the barium
It is 60%；
Step 3: preparing floride-free single layer precursor film: free-floride precursor liquid described in step 1 is uniformly coated using spin-coating method
In LaAlO3On substrate, it is subsequently placed in the quartz tube furnace that temperature is 160 DEG C, and humidity is passed through into the quartz tube furnace
Oxygen atmosphere is warming up to 450 DEG C, constant temperature 10min with the rate of 5 DEG C/min, cools to room temperature with the furnace and obtains floride-free single layer forerunner
Film；The revolving speed of the spin coating is 2500rpm, and the time of the spin coating is 105s；The body of oxygen in the oxygen atmosphere of the humidity
Product percentage composition is 97.5%, and surplus is steam；
Step 4: floride-free/fluorine-containing double-deck precursor film of preparation: fluorine-containing precursor liquid described in step 2 is uniform using spin-coating method
It is 160 DEG C of quartz tube furnace coated in temperature on the precursor film of free-floride single layer described in step 3, is subsequently placed in, and to the stone
It is passed through moist oxygen atmosphere in English tube furnace, is warming up to 450 DEG C with the rate of 5 DEG C/min, constant temperature 10min is cooled to the furnace
Room temperature obtains floride-free/fluorine-containing double-deck precursor film；The revolving speed of the spin coating is 2500rpm, and the time of the spin coating is 105s；It is described
The volumn concentration of oxygen is 97.5% in moist oxygen atmosphere, and surplus is steam；
Step 5: crystallization and thermal treatment: free-floride described in step 4/fluorine-containing double-deck precursor film is placed in quartz tube furnace,
It is passed through moist argon oxygen gas mixture to the quartz tube furnace, is then warming up to 790 DEG C again with the rate of 55 DEG C/min, heat preservation
1.5h keeps the temperature 1h when furnace temperature is down to 450 DEG C and carries out seeping oxygen processing, cools to room temperature with the furnace, obtain critical-temperature in liquid nitrogen temperature
Spend the HTS YBCO film of (77K) or more；The volumn concentration of argon gas is in the argon oxygen gas mixture of the humidity
97.23%, the volumn concentration of oxygen is 0.04%, and surplus is steam.
Fig. 1 is the X diffracting spectrum of HTS YBCO film prepared by the embodiment of the present invention 1, is as can be seen from Figure 1 made
Standby ybco film has the peak (00l), and substantially without other dephasign peaks, and display has good c-axis orientation, this illustrate it is floride-free/
Fluorine-containing bilayer precursor film promotes c-axis oriented nucleation and the growth of ybco film.Fig. 2 is high temperature prepared by the embodiment of the present invention 1
The scanning electron microscope map of superconduction ybco film, from figure 2 it can be seen that ybco film surface shows high-temperature superconductor without a axialite
Ybco film has good biaxial orientation, while tradition prepares high fluoro-gas volatilization in the method for ybco film will lead to film
Upper many holes occur, in comparison, the surface YBCO made from the present embodiment has minimal amount of hole, show it is floride-free/contain
Fluorine bilayer precursor film influences really and reduces the fluorine content of the HTS YBCO film, it is suppressed that due to foreign gas volatilization shape
At hole.
There is the HTS YBCO film of this example preparation sharp keen c-axis to be orientated, and surface hole defect is less, smooth, superconducting layer
77K reaches 3MA/cm from critical current density off field2。
Embodiment 2
The present embodiment prepare the method for high-temperature superconductor GdBCO film the following steps are included:
Step 1: preparing floride-free precursor liquid: by propionic acid gadolinium, barium propionate, propionic acid copper according to Gd: Ba: Cu=1: 1.75: 3
Atomic ratio is dissolved in the in the mixed solvent of propionic acid and ethyl alcohol, and 3h is stirred under conditions of 80 DEG C to being completely dissolved, obtain total sun from
Sub- molar concentration is the floride-free precursor liquid of 1.5mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 5；
Step 2: preparing fluorine-containing precursor liquid: by propionic acid gadolinium, the organic salt of barium, propionic acid copper by Gd: Ba: Cu=1: 1.8: 3
Atomic ratio is dissolved in the in the mixed solvent of propionic acid and ethyl alcohol, and 3h is stirred under conditions of 80 DEG C to being completely dissolved, obtain total sun from
Sub- molar concentration is the fluorine-containing precursor liquid of 1.8mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 5；The barium
Organic salt be trifluoroacetic acid barium and barium propionate mixture；The mole percent of trifluoroacetic acid barium is in the organic salt of the barium
50%；
Step 3: preparing floride-free single layer precursor film: free-floride precursor liquid described in step 1 is uniformly coated using spin-coating method
In LaAlO3On substrate, it is subsequently placed in the quartz tube furnace that temperature is 160 DEG C, and humidity is passed through into the quartz tube furnace
Oxygen atmosphere is warming up to 400 DEG C, constant temperature 10min with the rate of 5 DEG C/min, cools to room temperature with the furnace and obtains floride-free single layer forerunner
Film；The revolving speed of the spin coating is 3000rpm, and the time of the spin coating is 105s；The body of oxygen in the oxygen atmosphere of the humidity
Product percentage composition is 98%, and surplus is steam；
Step 4: floride-free/fluorine-containing double-deck precursor film of preparation: fluorine-containing precursor liquid described in step 2 is uniform using spin-coating method
It is 160 DEG C of quartz tube furnace coated in temperature on the precursor film of free-floride single layer described in step 3, is subsequently placed in, and to the stone
It is passed through moist oxygen atmosphere in English tube furnace, is warming up to 400 DEG C with the rate of 5 DEG C/min, constant temperature 10min is cooled to the furnace
Room temperature obtains floride-free/fluorine-containing double-deck precursor film；The revolving speed of the spin coating is 3000rpm, and the time of the spin coating is 105s；It is described
The volumn concentration of oxygen is 98% in moist oxygen atmosphere, and surplus is steam；
Step 5: crystallization and thermal treatment: free-floride described in step 4/fluorine-containing double-deck precursor film is placed in quartz tube furnace,
It is passed through moist argon oxygen gas mixture to the quartz tube furnace, is then warming up to 810 DEG C again with the rate of 60 DEG C/min, heat preservation
2h keeps the temperature 1h when furnace temperature is down to 450 DEG C and carries out seeping oxygen processing, cools to room temperature with the furnace, obtain critical-temperature in liquid nitrogen temperature
High-temperature superconductor GdBCO film more than (77K)；The volumn concentration of argon gas is 97% in the argon oxygen gas mixture of the humidity,
The volumn concentration of oxygen is 0.05%, and surplus is steam.
Fig. 3 is the X diffracting spectrum of high-temperature superconductor GdBCO film prepared by the embodiment of the present invention 2, from figure 3, it can be seen that
GdBCO film obtained has the peak (00l), and substantially without other dephasign peaks, display has good c-axis orientation, this illustrates nothing
Fluorine/fluorine-containing double-deck precursor film promotes c-axis oriented nucleation and the growth of GdBCO film.Fig. 4 is prepared by the embodiment of the present invention 2
The scanning electron microscope map of high-temperature superconductor GdBCO film, figure 4, it is seen that GdBCO film surface is without a axialite, and substantially without
Hole shows that film has good biaxial orientation and good microstructure.
There is the high-temperature superconductor GdBCO film of this example preparation sharp keen c-axis to be orientated, and surfacing, microscopic appearance are good,
77K reaches 2MA/cm from critical current density off field2。
Embodiment 3
The present embodiment prepare HTS YBCO film method the following steps are included:
Step 1: preparing floride-free precursor liquid: by propionic acid yttrium, barium propionate, propionic acid copper according to Y: Ba: Cu=1: 1.75: 3 original
Son stirs 1.5h to being completely dissolved than being dissolved in the in the mixed solvent of propionic acid and ethyl alcohol under conditions of 80 DEG C, obtain total sun from
Sub- molar concentration is the floride-free precursor liquid of 1.5mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 8；
Step 2: preparing fluorine-containing precursor liquid: by propionic acid yttrium, the organic salt of barium, propionic acid copper by Y: Ba: Cu=1: 1.75: 3
Atomic ratio is dissolved in the in the mixed solvent of propionic acid and ethyl alcohol, and 2h is stirred under conditions of 80 DEG C to being completely dissolved, obtain total sun from
Sub- molar concentration is the fluorine-containing precursor liquid of 1.8mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 8；The barium
Organic salt be trifluoroacetic acid barium and barium propionate mixture, the mole percent of trifluoroacetic acid barium is in the organic salt of the barium
75%；
Step 3: preparing floride-free single layer precursor film: free-floride precursor liquid described in step 1 is uniformly coated using spin-coating method
In LaAlO3On substrate, it is subsequently placed in the quartz tube furnace that temperature is 180 DEG C, and humidity is passed through into the quartz tube furnace
Oxygen atmosphere is warming up to 420 DEG C, constant temperature 10min with the rate of 5 DEG C/min, cools to room temperature with the furnace and obtains floride-free single layer forerunner
Film；The revolving speed of the spin coating is 3000rpm, and the time of the spin coating is 120s；The body of oxygen in the oxygen atmosphere of the humidity
Product percentage composition is 97%, and surplus is steam；
Step 4: floride-free/fluorine-containing double-deck precursor film of preparation: fluorine-containing precursor liquid described in step 2 is uniform using spin-coating method
It is 140 DEG C of quartz tube furnace coated in temperature on the precursor film of free-floride single layer described in step 3, is subsequently placed in, and to the stone
It is passed through moist oxygen atmosphere in English tube furnace, is warming up to 480 DEG C with the rate of 5 DEG C/min, constant temperature 10min is cooled to the furnace
Room temperature obtains floride-free/fluorine-containing double-deck precursor film；The revolving speed of the spin coating is 2500rpm, and the time of the spin coating is 150s；It is described
The volumn concentration of oxygen is 97% in moist oxygen atmosphere, and surplus is steam；
Step 5: crystallization and thermal treatment: free-floride described in step 4/fluorine-containing double-deck precursor film is placed in quartz tube furnace,
It is passed through moist argon oxygen gas mixture to the quartz tube furnace, is then warming up to 800 DEG C again with the rate of 80 DEG C/min, heat preservation
1.5h keeps the temperature 1h when furnace temperature is down to 450 DEG C and carries out seeping oxygen processing, cools to room temperature with the furnace, critical-temperature is in liquid nitrogen temperature
HTS YBCO film is obtained more than (77K)；The volumn concentration of argon gas is in the argon oxygen gas mixture of the humidity
97%, the volumn concentration of oxygen is 0.05%, and surplus is steam.
There is the HTS YBCO film of this example preparation sharp keen c-axis to be orientated, and surfacing, microscopic appearance are good,
77K reaches 2.6MA/cm from critical current density off field2。
Embodiment 4
The present embodiment prepare the method for high-temperature superconductor GdBCO film the following steps are included:
Step 1: preparing floride-free precursor liquid: by propionic acid gadolinium, barium propionate, propionic acid copper according to Gd: Ba: Cu=1: 1.75: 3
Atomic ratio is dissolved in the in the mixed solvent of propionic acid and ethyl alcohol, and 3h is stirred under conditions of 50 DEG C to being completely dissolved, obtain total sun from
Sub- molar concentration is the floride-free precursor liquid of 1.5mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 7；
Step 2: preparing fluorine-containing precursor liquid: by propionic acid gadolinium, trifluoroacetic acid barium, propionic acid copper by Gd: Ba: Cu=1: 2: 3 original
In the mixed solvent of the son than being dissolved in propionic acid and ethyl alcohol stirs 3h to being completely dissolved under conditions of 50 DEG C, obtains total cation
Molar concentration is the fluorine-containing precursor liquid of 1.5mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 7；
Step 3: preparing floride-free single layer precursor film: free-floride precursor liquid described in step 1 is uniformly coated using spin-coating method
In LaAlO3On substrate, it is subsequently placed in the quartz tube furnace that temperature is 200 DEG C, and humidity is passed through into the quartz tube furnace
Oxygen atmosphere is warming up to 400 DEG C, constant temperature 10min with the rate of 5 DEG C/min, cools to room temperature with the furnace and obtains floride-free single layer forerunner
Film；The revolving speed of the spin coating is 2500rpm, and the time of the spin coating is 180s；The body of oxygen in the oxygen atmosphere of the humidity
Product percentage composition is 97%, and surplus is steam；
Step 4: floride-free/fluorine-containing double-deck precursor film of preparation: fluorine-containing precursor liquid described in step 2 is uniform using spin-coating method
It is 200 DEG C of quartz tube furnace coated in temperature on the precursor film of free-floride single layer described in step 3, is subsequently placed in, and to the stone
It is passed through moist oxygen atmosphere in English tube furnace, is warming up to 400 DEG C with the rate of 5 DEG C/min, constant temperature 10min is cooled to the furnace
Room temperature obtains floride-free/fluorine-containing double-deck precursor film；The revolving speed of the spin coating is 2500rpm, and the time of the spin coating is 180s；It is described
The volumn concentration of oxygen is 97% in moist oxygen atmosphere, and surplus is steam；
Step 5: crystallization and thermal treatment: free-floride described in step 4/fluorine-containing double-deck precursor film is placed in quartz tube furnace,
It is passed through moist argon oxygen gas mixture to the quartz tube furnace, is then warming up to 810 DEG C again with the rate of 10 DEG C/min, heat preservation
1h keeps the temperature 1h when furnace temperature is down to 450 DEG C and carries out seeping oxygen processing, cools to room temperature with the furnace, obtain critical-temperature in liquid nitrogen temperature
High-temperature superconductor GdBCO film more than (77K)；The volumn concentration of argon gas is in the argon oxygen gas mixture of the humidity
98.78%, the volumn concentration of oxygen is 0.05%, and surplus is steam.
There is the high-temperature superconductor GdBCO film of this example preparation sharp keen c-axis to be orientated, and surfacing, microscopic appearance are good,
77K reaches 2.1MA/cm from critical current density off field2。
Embodiment 5
The present embodiment prepare HTS YBCO film method the following steps are included:
Step 1: preparing floride-free precursor liquid: by propionic acid yttrium, barium propionate, propionic acid copper according to Y: Ba: Cu=1: 1.75: 3 original
In the mixed solvent of the son than being dissolved in propionic acid and ethyl alcohol stirs 3h to being completely dissolved under conditions of 40 DEG C, obtains total cation
Molar concentration is the floride-free precursor liquid of 1.5mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 10；
Step 2: preparing fluorine-containing precursor liquid: by propionic acid yttrium, trifluoroacetic acid barium, propionic acid copper by Y: Ba: Cu=1: 2: 3 original
In the mixed solvent of the son than being dissolved in propionic acid and ethyl alcohol stirs 3h to being completely dissolved under conditions of 40 DEG C, obtains total cation
Molar concentration is the fluorine-containing precursor liquid of 2mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 10；
Step 3: preparing floride-free single layer precursor film: free-floride precursor liquid described in step 1 is uniformly coated using spin-coating method
In LaAlO3On substrate, it is subsequently placed in the quartz tube furnace that temperature is 200 DEG C, and humidity is passed through into the quartz tube furnace
Oxygen atmosphere is warming up to 500 DEG C, constant temperature 10min with the rate of 5 DEG C/min, cools to room temperature with the furnace and obtains floride-free single layer forerunner
Film；The revolving speed of the spin coating is 4500rpm, and the time of the spin coating is 30s；The volume of oxygen in the oxygen atmosphere of the humidity
Percentage composition is 98%, and surplus is steam；
Step 4: floride-free/fluorine-containing double-deck precursor film of preparation: fluorine-containing precursor liquid described in step 2 is uniform using spin-coating method
It is 200 DEG C of quartz tube furnace coated in temperature on the precursor film of free-floride single layer described in step 3, is subsequently placed in, and to the stone
It is passed through moist oxygen atmosphere in English tube furnace, is warming up to 500 DEG C with the rate of 5 DEG C/min, constant temperature 10min is cooled to the furnace
Room temperature obtains floride-free/fluorine-containing double-deck precursor film；The revolving speed of the spin coating is 4500rpm, and the time of the spin coating is 30s；It is described
The volumn concentration of oxygen is 98% in moist oxygen atmosphere, and surplus is steam；
Step 5: crystallization and thermal treatment: free-floride described in step 4/fluorine-containing double-deck precursor film is placed in quartz tube furnace,
It is passed through moist argon oxygen gas mixture to the quartz tube furnace, is then warming up to 810 DEG C again with the rate of 100 DEG C/min, heat preservation
1h keeps the temperature 1h when furnace temperature is down to 450 DEG C and carries out seeping oxygen processing, cools to room temperature with the furnace, obtain critical-temperature in liquid nitrogen temperature
HTS YBCO film more than (77K)；The volumn concentration of argon gas is in the argon oxygen gas mixture of the humidity
98.78%, the volumn concentration of oxygen is 0.07%, and surplus is steam.
HTS YBCO film manufactured in the present embodiment has good c-axis orientation and biaxial texture, and surfacing surpasses
It leads film 77K and reaches 2.7MA/cm from critical current density off field2。
Embodiment 6
The present embodiment prepare HTS YBCO film method the following steps are included:
Step 1: preparing floride-free precursor liquid: by propionic acid yttrium, barium propionate, propionic acid copper according to Y: Ba: Cu=1: 1.75: 3 original
In the mixed solvent of the son than being dissolved in propionic acid and ethyl alcohol stirs 1h to being completely dissolved under conditions of 100 DEG C, obtains total cation
Molar concentration is the floride-free precursor liquid of 1.5mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 1；
Step 2: preparing fluorine-containing precursor liquid: by propionic acid yttrium, the organic salt of barium, propionic acid copper by Y: Ba: Cu=1: 1.5: 3
Atomic ratio is dissolved in the in the mixed solvent of propionic acid and ethyl alcohol, and 1h is stirred under conditions of 100 DEG C to being completely dissolved, obtain total sun from
Sub- molar concentration is the fluorine-containing precursor liquid of 1.5mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 10；It is described
The organic salt of barium is the mixture of trifluoroacetic acid barium and barium propionate, the mole percent of trifluoroacetic acid barium in the organic salt of the barium
It is 15%；；
Step 3: preparing floride-free single layer precursor film: free-floride precursor liquid described in step 1 is uniformly coated using spin-coating method
In LaAlO3On substrate, it is subsequently placed in the quartz tube furnace that temperature is 120 DEG C, and humidity is passed through into the quartz tube furnace
Oxygen atmosphere is warming up to 400 DEG C, constant temperature 10min with the rate of 5 DEG C/min, cools to room temperature with the furnace and obtains floride-free single layer forerunner
Film；The revolving speed of the spin coating is 500rpm, and the time of the spin coating is 180s；The volume of oxygen in the oxygen atmosphere of the humidity
Percentage composition is 97%, and surplus is steam；
Step 4: floride-free/fluorine-containing double-deck precursor film of preparation: fluorine-containing precursor liquid described in step 2 is uniform using spin-coating method
It is 120 DEG C of quartz tube furnace coated in temperature on the precursor film of free-floride single layer described in step 3, is subsequently placed in, and to the stone
It is passed through moist oxygen atmosphere in English tube furnace, is warming up to 400 DEG C with the rate of 5 DEG C/min, constant temperature 10min is cooled to the furnace
Room temperature obtains floride-free/fluorine-containing double-deck precursor film；The revolving speed of the spin coating is 500rpm, and the time of the spin coating is 180s；It is described
The volumn concentration of oxygen is 97% in moist oxygen atmosphere, and surplus is steam；
Step 5: crystallization and thermal treatment: free-floride described in step 4/fluorine-containing double-deck precursor film is placed in quartz tube furnace,
It is passed through moist argon oxygen gas mixture to the quartz tube furnace, is then warming up to 770 DEG C again with the rate of 10 DEG C/min, heat preservation
2h keeps the temperature 1h when furnace temperature is down to 450 DEG C and carries out seeping oxygen processing, cools to room temperature with the furnace, obtain critical-temperature in liquid nitrogen temperature
HTS YBCO film more than (77K)；The volumn concentration of argon gas is in the argon oxygen gas mixture of the humidity
95.73%, the volumn concentration of oxygen is 0.02%, and surplus is steam.
HTS YBCO film manufactured in the present embodiment has good c-axis orientation and biaxial texture, and surfacing surpasses
It leads film 77K and reaches 2.5MA/cm from critical current density off field2。
Embodiment 7
The present embodiment prepare the method for high-temperature superconductor GdBCO film the following steps are included:
Step 1: preparing floride-free precursor liquid: by propionic acid gadolinium, barium propionate, propionic acid copper according to Gd: Ba: Cu=1: 1.75: 3
Atomic ratio is dissolved in the in the mixed solvent of propionic acid and ethyl alcohol, and 2h is stirred under conditions of 60 DEG C to being completely dissolved, obtain total sun from
Sub- molar concentration is the floride-free precursor liquid of 1.5mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 3；
Step 2: preparing fluorine-containing precursor liquid: by propionic acid gadolinium, the organic salt of barium, propionic acid copper by Gd: Ba: Cu=1: 2: 3 original
In the mixed solvent of the son than being dissolved in propionic acid and ethyl alcohol stirs 2h to being completely dissolved under conditions of 60 DEG C, obtains total cation
Molar concentration is the fluorine-containing precursor liquid of 2mol/L；The volume ratio of the in the mixed solvent propionic acid and ethyl alcohol is 1: 3；The barium has
Machine salt is the mixture of trifluoroacetic acid barium and barium propionate；The mole percent of trifluoroacetic acid barium is in the organic salt of the barium
35%；
Step 3: preparing floride-free single layer precursor film: free-floride precursor liquid described in step 1 is uniformly coated using spin-coating method
In LaAlO3On substrate, it is subsequently placed in the quartz tube furnace that temperature is 140 DEG C, and humidity is passed through into the quartz tube furnace
Oxygen atmosphere is warming up to 480 DEG C, constant temperature 10min with the rate of 5 DEG C/min, cools to room temperature with the furnace and obtains floride-free single layer forerunner
Film；The revolving speed of the spin coating is 4500rpm, and the time of the spin coating is 120s；The body of oxygen in the oxygen atmosphere of the humidity
Product percentage composition is 98%, and surplus is steam；
Step 4: floride-free/fluorine-containing double-deck precursor film of preparation: fluorine-containing precursor liquid described in step 2 is uniform using spin-coating method
It is 180 DEG C of quartz tube furnace coated in temperature on the precursor film of free-floride single layer described in step 3, is subsequently placed in, and to the stone
It is passed through moist oxygen atmosphere in English tube furnace, is warming up to 420 DEG C with the rate of 5 DEG C/min, constant temperature 10min is cooled to the furnace
Room temperature obtains floride-free/fluorine-containing double-deck precursor film；The revolving speed of the spin coating is 4500rpm, and the time of the spin coating is 120s；It is described
The volumn concentration of oxygen is 98% in moist oxygen atmosphere, and surplus is steam；
Step 5: crystallization and thermal treatment: free-floride described in step 4/fluorine-containing double-deck precursor film is placed in quartz tube furnace,
It is passed through moist argon oxygen gas mixture to the quartz tube furnace, is then warming up to 810 DEG C again with the rate of 30 DEG C/min, heat preservation
1h keeps the temperature 1h when furnace temperature is down to 450 DEG C and carries out seeping oxygen processing, cools to room temperature with the furnace, obtain critical-temperature in liquid nitrogen temperature
High-temperature superconductor GdBCO film more than (77K)；The volumn concentration of argon gas is 96% in the argon oxygen gas mixture of the humidity,
The volumn concentration of oxygen is 0.05%, and surplus is steam.
High-temperature superconductor GdBCO film manufactured in the present embodiment is orientated with good c-axis and biaxial texture, surfacing,
Superconducting thin film 77K reaches 1.9MA/cm from critical current density off field2。
The above is only presently preferred embodiments of the present invention, not does any restrictions to the present invention, all according to invention skill
Art any simple modification substantially to the above embodiments, change and equivalent structural changes, still fall within the technology of the present invention
In the protection scope of scheme.
Claims (4)
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| CN108752048B (en) * | 2018-06-29 | 2020-06-26 | 西北有色金属研究院 | A kind of preparation method of YBCO composite graphene coating |
| EP4562983A1 (en) | 2022-07-29 | 2025-06-04 | Consejo Superior de Investigaciones Científicas (CSIC) | Precursor solution suitable for the preparation of high performance epitaxial reba2cu3o7-x superconductors |
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| US5079221A (en) * | 1988-02-23 | 1992-01-07 | Fujitsu Limited | Superconductor passivated by an organic film and a method for forming the organic film |
| CN102807372A (en) * | 2012-08-28 | 2012-12-05 | 西北有色金属研究院 | Preparation method of gadolinium-barium-copper-oxygen compact film |
| CN103864461A (en) * | 2014-03-13 | 2014-06-18 | 西北有色金属研究院 | Method for preparing REBCO superconducting thin film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5079221A (en) * | 1988-02-23 | 1992-01-07 | Fujitsu Limited | Superconductor passivated by an organic film and a method for forming the organic film |
| CN102807372A (en) * | 2012-08-28 | 2012-12-05 | 西北有色金属研究院 | Preparation method of gadolinium-barium-copper-oxygen compact film |
| CN103864461A (en) * | 2014-03-13 | 2014-06-18 | 西北有色金属研究院 | Method for preparing REBCO superconducting thin film |
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