WO2010021159A1 - 酸化物超電導薄膜の製造方法 - Google Patents
酸化物超電導薄膜の製造方法 Download PDFInfo
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- WO2010021159A1 WO2010021159A1 PCT/JP2009/052769 JP2009052769W WO2010021159A1 WO 2010021159 A1 WO2010021159 A1 WO 2010021159A1 JP 2009052769 W JP2009052769 W JP 2009052769W WO 2010021159 A1 WO2010021159 A1 WO 2010021159A1
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- thin film
- intermediate heat
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- 239000010409 thin film Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 36
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 15
- 238000010304 firing Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 24
- 239000013078 crystal Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 21
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 11
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002887 superconductor Substances 0.000 description 6
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 5
- 125000005587 carbonate group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- -1 organic acid salt Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 1
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0324—Processes for depositing or forming copper oxide superconductor layers from a solution
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
- H01B12/02—Superconductive or hyperconductive conductors, cables, or transmission lines characterised by their form
- H01B12/06—Films or wires on bases or cores
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0548—Processes for depositing or forming copper oxide superconductor layers by deposition and subsequent treatment, e.g. oxidation of pre-deposited material
Definitions
- the present invention relates to a method for producing an oxide superconducting thin film, and more particularly to a method for producing an oxide superconducting thin film having a high critical current value used for producing a superconducting wire.
- One of the methods for producing an oxide superconductor is a method referred to as a coating organic decomposition method (Metal Organic Deposition, abbreviated as MOD method).
- a coating organic decomposition method Metal Organic Deposition, abbreviated as MOD method.
- the metal organic compound is calcined at, for example, around 500 ° C. and thermally decomposed, and the obtained thermal decomposition product (MOD calcined film) is further heated (for example, 800 ° C.).
- Jc critical current density
- Ic critical current value
- the coating pyrolysis method includes a TFA-MOD method (Metal Organic Deposition using TriFluoroAcates) using an organic acid salt containing fluorine as a raw material and a fluorine-free MOD method using a metal organic compound containing no fluorine.
- TFA-MOD method Metal Organic Deposition using TriFluoroAcates
- fluorine-free MOD method using a metal organic compound containing no fluorine.
- Patent Document 1 Japanese Unexamined Patent Publication No. 2007-165153 (hereinafter referred to as Patent Document 1) describes a thick film using the TFA-MOD method.
- Patent Document 1 describes a thick film using the TFA-MOD method.
- a method of manufacturing a superconductor has been proposed.
- a fluoride specifically, for example, BaF 2 is generated during calcination, and this BaF 2 decomposes during the main firing to generate dangerous hydrogen fluoride gas.
- Non-Patent Document 1 “ Manufacturing Superconducting Thin Film Using Laser Light Irradiation ”, AIST TODAY, National Institute of Advanced Industrial Science and Technology, 2006, Vol. .6-11, P12-15 ”(hereinafter, Non-Patent Document 2)).
- the fluorine-free MOD method does not generate a dangerous gas such as hydrogen fluoride, it has an advantage that it is environmentally friendly and does not require processing equipment.
- an alkaline earth metal carbonate specifically, for example, BaCO 3 is generated and included in the calcination film. If this BaCO 3 is not decomposed during the firing process, crystallization of the superconductor does not occur. In the conventional heat treatment method, BaCO 3 is thermally decomposed during the main baking process, but the crystal orientation may be disturbed.
- Non-Patent Document 1 describes an example of a method for producing an oxide superconducting thin film by a fluorine-free MOD method.
- Non-Patent Document 2 discloses a method for causing uniform crystal growth by uniformly decomposing a raw material contained in a coating film by excimer laser irradiation.
- Non-Patent Document 1 has a problem that high Jc cannot be obtained because it is not fluorine-free and high Jc cannot be formed because the CO 2 generated during the heat treatment process is insufficient. There is.
- Non-Patent Document 2 has a problem that an expensive laser device is required, leading to an increase in cost. Also, with this method, although 6 MA / cm 2 grade Jc is obtained, the film thickness is as thin as 0.1 ⁇ m, and high Ic cannot be obtained.
- the present invention provides an efficient method for producing BaCO 3 contained in a calcined film in a method for producing an oxide superconducting thin film used for producing a superconducting wire by a coating pyrolysis method using a metal organic compound not containing fluorine.
- Oxide superconductivity that enables decomposition and allows crystal growth from the substrate to proceed, resulting in a high Jc (eg, 1 MA / cm 2 or more) thick film and high reproducibility of high Ic values. It is an object to provide a method for manufacturing a thin film.
- heat treatment for heat treatment an intermediate heat treatment for decomposing carbonate in advance before a heat treatment for crystallization heat treatment (hereinafter referred to as “heat treatment for heat treatment”).
- the manufacturing method of an oxide superconducting thin film according to the present invention is a method of manufacturing an oxide superconducting thin film by using a metal organic compound containing no fluorine as a raw material and a coating pyrolysis method. It is. A step of performing an intermediate heat treatment for decomposing the carbonate contained in the thin film before the main heat treatment, and a step of performing a main heat treatment for the crystallization heat treatment on the thin film subjected to the intermediate heat treatment. It is a manufacturing method of an oxide superconducting thin film.
- an intermediate heat treatment for decomposing carbonate contained in the thin film subjected to the main annealing heat treatment is performed before the main annealing heat treatment, thereby inhibiting the crystal growth from the substrate. Therefore, in the main heat treatment, as a result of crystal growth from the substrate, an oxide superconducting thin film with improved orientation can be obtained. That is, a thick MOD main-fired film having a high Jc (for example, 1 MA / cm 2 or more) can be produced, and an oxide superconducting thin film having a high Ic value can be obtained with good reproducibility. And the obtained oxide superconducting thin film can be used suitably for manufacture of a superconducting wire.
- Jc for example, 1 MA / cm 2 or more
- the intermediate heat treatment is preferably performed in an atmosphere having a carbon dioxide concentration of 10 ppm or less.
- the present inventor has found that the carbon dioxide concentration in the atmosphere has a great influence in order to facilitate the decomposition of the carbonate in the intermediate heat treatment.
- the carbon dioxide concentration is 10 ppm or less, the decomposition of the carbonate easily proceeds, and a more stable high Ic oxide superconducting thin film is obtained.
- the metal organic compound is preferably a metal organic compound containing a ⁇ -diketone complex.
- the metal organic compound is a substance containing a ⁇ -diketone complex, the effect of the intermediate heat treatment is exhibited more.
- the intermediate heat treatment is preferably a heat treatment performed in a temperature range of 620 ° C. or higher and 750 ° C. or lower.
- the carbonate is more reliably decomposed.
- an oxide superconducting thin film with improved reproducibility and high Ic value can be obtained.
- the present invention uses an intermediate heat treatment for decomposing a carbonate contained in a thin film to be subjected to a main heat treatment before a main heat treatment for a crystallization heat treatment using a metal organic compound containing no fluorine as described above. It is characterized by doing.
- a step (S20) of performing a main heat treatment for the manufacturing method of an oxide superconducting thin film is performed by performing a main heat treatment for the manufacturing method of an oxide superconducting thin film.
- metal organic compounds that do not contain fluorine include metal salts having a carboxyl group (naphthenate, octylate, neodecanoate, isononanoate, etc.), amine metal salts having an amino group, amino groups, and carboxyl groups.
- Amino acid metal salts, nitrates, metal alkoxides, acetylacetonates, and the like are used. Of these, ⁇ -diketone complexes such as acetylacetonate are preferred.
- the step of performing the intermediate heat treatment is a step of decomposing the carbonate generated in the calcination process, and it is necessary to perform it at a temperature lower than the temperature in the calcination process in order to prevent crystallization.
- FIG. 6 is related to the present invention from “Dissociation curve of carbonate group of alkaline earth salt” shown on page 387 of “Takaki Tachiki and Toshizo Fujita” Science of High-Tc Superconductivity (Ikuwabo, 2001). to withdrawn the dissociation curves of BaCO 3 is a diagram created.
- FIG. 6 shows that, for example, at an atmospheric temperature of 700 ° C., BaCO 3 decomposes to BaO when the CO 2 concentration is 1.6 ppm or less.
- a test body a having a 1.65 ⁇ m-thick BaCO 3 film on the substrate and a test body b having a 0.30 ⁇ m-thick YBCO film on the substrate were prepared.
- each of the specimens a and b was heated to each temperature shown on the horizontal axis in FIGS. 7 and 8 and held for 10 minutes, and then cooled in the furnace to room temperature. Note that the CO 2 concentration at this time was 1 ppm or less.
- the peak intensity of XRD of YBCO (006) in the peak intensity, and the test body b by XRD of BaCO 3 (111) in the test body a The measurement results are shown in FIGS. 7 and 8, respectively.
- the peak intensity of BaCO 3 gradually decreases from about 620 ° C., and decreases with increasing temperature, and becomes 0 at 700 ° C.
- the decomposition of BaCO 3 starts gradually from about 620 ° C., the amount of decomposition increases as the temperature rises, and the decomposition of all BaCO 3 ends at 700 ° C.
- the peak intensity of YBCO (006) increases rapidly when it exceeds 750 ° C. This indicates that when the temperature exceeds 750 ° C., the YBCO crystal growth rate rapidly increases.
- the intermediate heat treatment is preferably performed in a temperature range not lower than a temperature at which decomposition of BaCO 3 starts and not higher than a temperature at which crystallization of the superconductor does not proceed, that is, a temperature range not lower than 620 ° C. and not higher than 750 ° C.
- the treatment time is preferably 10 minutes or more, but depends on the treatment temperature and film thickness. For example, when the film thickness is 0.3 ⁇ m and the temperature of the intermediate heat treatment is 680 ° C., it may be about 10 minutes, but is not limited to this condition.
- the oxygen concentration at that time is preferably about 100 ppm, and the CO 2 concentration is 10 ppm or less from FIG. preferable.
- disassembly of carbonate tends to advance.
- the maximum temperature in the step (S20) for performing the main annealing process is preferably 800 ° C. or lower, but is not particularly limited, and is determined to be an appropriate temperature depending on the type of metal or the like.
- Crystals constituting the uppermost layer are biaxially oriented.
- a superconducting layer is formed on a biaxially oriented substrate to grow a crystal with good orientation.
- the uppermost layer include a CeO 2 layer
- examples of the substrate include a substrate made of CeO 2 / YSZ / CeO 2 / Ni.
- Example 1 and Comparative Example 1 a YBCO thin film (Y-Ba-Cu-O oxide superconducting thin film made of Y123) on a substrate, and the molar ratio of Y: Ba: Cu is 1: 2: 3. This is an example of manufacturing an oxide superconducting thin film.
- a CeO 2 / YSZ / CeO 2 / Ni alloy substrate was used as the substrate, and Y, Ba, and Cu acetylacetonate complexes were formed on this substrate, and the molar ratio of Y: Ba: Cu was 1: 2: 3.
- a raw material solution dissolved in a solvent mixed solvent of methanol and 1-butanol
- the temperature was raised to 500 ° C. at a temperature rising rate of 20 ° C./min in an air atmosphere.
- the furnace was cooled and calcined. At this time, the film thickness increased by about 0.15 ⁇ m per treatment.
- a prescribed film thickness was obtained by repeating this coating / calcination step a plurality of times.
- a main heat treatment is performed at the heat treatment temperature and time shown in Table 1 in an argon / oxygen mixed gas (oxygen concentration: 100 ppm, CO 2 concentration: 1 ppm or less) atmosphere for crystallization, and then the oxygen concentration
- the furnace was cooled in a 100% atmosphere to obtain Y123 thin films having the film thicknesses shown in Examples 1-1, 1-2, and 1-3 in Table 1.
- a Y123 thin film of Comparative Example 1-1 was obtained under the same conditions as Example 1-1 except that no intermediate heat treatment was performed. Further, a Y123 thin film of Comparative Example 1-2 was obtained under the same conditions as Example 1-2 except that the intermediate heat treatment was not performed.
- Example 1-1 and Comparative Example 1-1 The following can be understood from Table 1, FIG. 2 and FIG. That is, when the film thickness is 0.3 ⁇ m (Example 1-1 and Comparative Example 1-1), Ic of Example 1-1 is 75 (A), whereas Ic of Comparative Example 1-1 is There is almost no difference from 72 (A), and when the film thickness is thin, the effect of the intermediate heat treatment is hardly exhibited. This is because, when the film thickness is thin, even if the main annealing heat treatment is performed without performing the intermediate heat treatment, BaCO 3 is sufficiently decomposed at an early stage of heating, and crystallization with less disorder of orientation proceeds. It is presumed that the difference due to the presence or absence has decreased.
- Example 1-2 In contrast, when the film thickness is 0.6 ⁇ m (Example 1-2 and Comparative Example 1-2), Ic of Example 1-2 is 114 (A), which is higher than that of Example 1-1. On the other hand, Ic of Comparative Example 1-2 is 27 (A), which is lower than that of Comparative Example 1-1. When the film thickness is 1.2 ⁇ m (Example 1-3), Ic is 132 (A), which is higher than that of Example 1-2.
- FIG. 3 illustrating the relationship between the Y123 (006) peak intensity and the film thickness in the examples and comparative examples of Table 1. That is, the peak intensity is an index indicating the c-axis orientation of crystals, and the increase in peak intensity is proportional to the amount of c-axis oriented crystals.
- the peak intensity of Example 1-2 is stronger than the peak intensity of Comparative Example 1-2. These have the same film thickness and a strong peak intensity indicates that the c-axis orientation has been improved.
- the peak intensity increases as the film thickness increases. That is, the peak intensity of Example 1-2 is higher than that of Example 1-1, and the peak intensity of Example 1-3 is higher than that of Example 1-2. It can be clearly seen that crystal growth has progressed and the amount of c-axis oriented crystals has increased.
- Example 2 and Comparative Example 2 In this example and comparative example, a HoBCO thin film (an oxide superconducting thin film made of Ho—Ba—Cu—O) represented by Ho123 on a substrate, and the molar ratio of Ho: Ba: Cu is 1: 2: 3. This is an example of manufacturing an oxide superconducting thin film.
- a HoBCO thin film an oxide superconducting thin film made of Ho—Ba—Cu—O
- Example 2 in Table 2 was performed in the same manner as in Example 1 and Comparative Example 1 except that Y in Example 1 and Comparative Example 1 was changed to Ho and the conditions for the intermediate heat treatment and the heat treatment for annealing were changed to the conditions shown in Table 2. -1 to 2-3 and Ho123 thin films having the thicknesses shown in Comparative Examples 2-1 and 2-2 were obtained, and the same measurements as in Example 1 were performed.
- FIG. 4 shows the relationship between Ic and film thickness
- FIG. 5 shows the relationship between Ho123 (006) peak intensity and film thickness.
- Example 2-1 when the film thickness is 0.3 ⁇ m (Example 2-1 and Comparative Example 2-1), Ic of Example 2-1 is 63 (A), whereas Ic of Comparative Example 2-1 is 60 (A) and Ic are almost the same as in Example 1, and when the thickness is small, the effect of the intermediate heat treatment is hardly exhibited.
- Ic of Example 2-2 when the film thickness is 0.6 ⁇ m (Example 2-2 and Comparative Example 2-2), Ic of Example 2-2 is 108 (A), which is higher than that of Example 2-1.
- Ic of Comparative Example 2-2 is 4 (A), which is lower than that of Comparative Example 2-1.
- the film thickness is 1.2 ⁇ m (Example 2-3)
- Ic 120 (A), which is higher than that of Example 2-2.
- the crystal growth from the substrate can be advanced by performing the intermediate heat treatment in advance before the main heat treatment, the crystal orientation is improved.
- a high Ic value can be obtained with good reproducibility.
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Abstract
Description
(原料について)
フッ素を含まない金属有機化合物としては、カルボキシル基を有する金属塩(ナフテン酸塩、オクチル酸塩、ネオデカン酸塩、イソノナン酸塩等)、アミノ基を有するアミン類金属塩、アミノ基およびカルボキシル基からなるアミノ酸金属塩、硝酸塩、金属アルコキシド、アセチルアセトナート等が用いられる。これらの内、アセチルアセトナート等のβジケトン錯体が好ましい。
(中間熱処理について)
中間熱処理を行なう工程(S10)は、仮焼過程において生成された炭酸塩を分解処理する工程であり、結晶化を防ぐために本焼過程における温度より低い温度で行う必要がある。
(本焼熱処理について)
本焼熱処理を行なう工程(S20)における最高温度としては、800℃以下であることが好ましいが、特に限定されるものではなく、金属の種類等により適切な温度に決定される。
(基板について)
本発明における基板としては、最上層を構成する結晶が2軸配向していることが好ましい。2軸配向している基板の上に超電導層が形成されて配向性のよい結晶が成長する。最上層としては、例えば、CeO2層を挙げることができ、基板として例えばCeO2/YSZ/CeO2/Ni合金の基板を挙げることができる。
(実施例1および比較例1)
本実施例および比較例は、基板上にY123で示されるYBCO薄膜(Y-Ba-Cu-Oよりなる酸化物超電導薄膜であって、Y:Ba:Cuのモル比が1:2:3である酸化物超電導薄膜)を製造した例である。
(実施例2および比較例2)
本実施例および比較例は、基板上にHo123で示されるHoBCO薄膜(Ho-Ba-Cu-Oよりなる酸化物超電導薄膜であって、Ho:Ba:Cuのモル比が1:2:3である酸化物超電導薄膜)を製造した例である。
Claims (4)
- 超電導線材の製造に用いる酸化物超電導薄膜を、フッ素を含まない金属有機化合物を原料とし、塗布熱分解法により製造する酸化物超電導薄膜の製造方法であって、
本焼熱処理を施す前の薄膜に含まれる炭酸塩を分解する中間熱処理を行なう工程(S10)と、
前記中間熱処理を行なった前記薄膜に対して、結晶化熱処理のための前記本焼熱処理を行なう工程(S20)とを備える、酸化物超電導薄膜の製造方法。 - 前記中間熱処理は、二酸化炭素濃度が10ppm以下の雰囲気中で行うことを特徴とする請求の範囲1に記載の酸化物超電導薄膜の製造方法。
- 前記金属有機化合物は、βジケトン錯体を含む金属有機化合物であることを特徴とする請求の範囲1に記載の酸化物超電導薄膜の製造方法。
- 前記中間熱処理は、620℃以上750℃以下の温度範囲で行う熱処理であることを特徴とする請求の範囲1に記載の酸化物超電導薄膜の製造方法。
Priority Applications (6)
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DE112009002003.8D DE112009002003B3 (de) | 2008-08-20 | 2009-02-18 | Verfahren zum Herstellen eines supraleitenden Oxid-Dünnfilms |
DE112009002003T DE112009002003T8 (de) | 2008-08-20 | 2009-02-18 | Verfahren zum Herstellen eines supraleitenden Oxid-Dünnfilms |
KR1020117006369A KR101482543B1 (ko) | 2008-08-20 | 2009-02-18 | 산화물 초전도 박막의 제조방법 |
CN2009801326161A CN102132359B (zh) | 2008-08-20 | 2009-02-18 | 制造氧化物超导薄膜的方法 |
RU2011110506/07A RU2476945C2 (ru) | 2008-08-20 | 2009-02-18 | Способ изготовления оксидной сверхпроводящей тонкой пленки |
US13/059,598 US20110166026A1 (en) | 2008-08-20 | 2009-02-18 | Method of fabricatiing oxide superconducting thin film |
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JP2008-212082 | 2008-08-20 | ||
JP2008212082A JP5421561B2 (ja) | 2008-08-20 | 2008-08-20 | 酸化物超電導薄膜の製造方法 |
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US (1) | US20110166026A1 (ja) |
JP (1) | JP5421561B2 (ja) |
KR (1) | KR101482543B1 (ja) |
CN (1) | CN102132359B (ja) |
DE (2) | DE112009002003B3 (ja) |
RU (1) | RU2476945C2 (ja) |
WO (1) | WO2010021159A1 (ja) |
Cited By (1)
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JP2012003975A (ja) * | 2010-06-17 | 2012-01-05 | Sumitomo Electric Ind Ltd | 酸化物超電導薄膜の製造方法 |
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JP2011253766A (ja) * | 2010-06-03 | 2011-12-15 | National Institute Of Advanced Industrial & Technology | 酸化物超電導薄膜の製造方法 |
JP2012234649A (ja) * | 2011-04-28 | 2012-11-29 | Sumitomo Electric Ind Ltd | 酸化物超電導膜とその製造方法 |
WO2013153651A1 (ja) * | 2012-04-12 | 2013-10-17 | 住友電気工業株式会社 | 酸化物超電導薄膜線材とその製造方法 |
RU2580213C1 (ru) * | 2015-02-02 | 2016-04-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Омский государственный университет им. Ф.М. Достоевского" | Способ формирования сверхпроводящей тонкой пленки с локальными областями переменной толщины |
JP5892480B2 (ja) * | 2015-04-20 | 2016-03-23 | 住友電気工業株式会社 | 酸化物超電導薄膜製造用の原料溶液 |
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DE112009002003T5 (de) | 2011-09-29 |
DE112009002003B3 (de) | 2020-12-03 |
RU2011110506A (ru) | 2012-09-27 |
RU2476945C2 (ru) | 2013-02-27 |
US20110166026A1 (en) | 2011-07-07 |
JP5421561B2 (ja) | 2014-02-19 |
CN102132359B (zh) | 2013-01-23 |
CN102132359A (zh) | 2011-07-20 |
DE112009002003T8 (de) | 2012-02-09 |
KR20110056389A (ko) | 2011-05-27 |
KR101482543B1 (ko) | 2015-01-16 |
JP2010049891A (ja) | 2010-03-04 |
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