WO2003091158A1 - Film mince supraconducteur, procede de production et limitateur de courant de defaut supraconducteur - Google Patents

Film mince supraconducteur, procede de production et limitateur de courant de defaut supraconducteur Download PDF

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Publication number
WO2003091158A1
WO2003091158A1 PCT/JP2003/004933 JP0304933W WO03091158A1 WO 2003091158 A1 WO2003091158 A1 WO 2003091158A1 JP 0304933 W JP0304933 W JP 0304933W WO 03091158 A1 WO03091158 A1 WO 03091158A1
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WO
WIPO (PCT)
Prior art keywords
thin film
superconducting thin
oxide superconducting
laser
film according
Prior art date
Application number
PCT/JP2003/004933
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English (en)
Japanese (ja)
Inventor
Shuji Hahakura
Kazuya Ohmatsu
Original Assignee
Sumitomo Electric Industries, Ltd.
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 Sumitomo Electric Industries, Ltd. filed Critical Sumitomo Electric Industries, Ltd.
Priority to AU2003235237A priority Critical patent/AU2003235237A1/en
Publication of WO2003091158A1 publication Critical patent/WO2003091158A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/087—Oxides of copper or solid solutions thereof
    • 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
    • H10N60/0521—Processes for depositing or forming copper oxide superconductor layers by pulsed laser deposition, e.g. laser sputtering
    • 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
    • H10N60/30—Devices switchable between superconducting and normal states

Definitions

  • Oxide superconducting thin film method for producing the same, and superconducting current limiter
  • the present invention relates to an oxide superconducting thin film, a method for producing the same, and a superconducting current limiter.
  • a method for forming an oxide superconducting thin film on a sapphire substrate, an oxide superconducting thin film produced by the method The present invention relates to a superconducting current limiter using the oxide superconducting thin film.
  • the superconducting thin film has the same critical current density, the thicker the film, the larger the current that can flow. Therefore, especially for power applications, a thick film is desired. For example, if a thick superconducting thin film capable of conducting a large current is used for the superconducting current limiting device, a compact superconducting current limiting device can be manufactured.
  • a superconducting thin film formed on a sapphire single-crystal substrate could only form a thin film having a thickness less than a conventional limit value.
  • the limit thickness of YBa2Cu3 ⁇ 7-X (YBCO) formed on a sapphire is typically 0.25 to 0.3 / zm.
  • 0.7 ⁇ is reported as the highest value.
  • one object of the present invention is to provide a thick oxide superconducting thin film having no cracks or excellent critical current density characteristics and a method for producing the same.
  • Another object of the present invention is to provide a high-thickness oxide superconducting thin film having no cracks or excellent critical current density characteristics, thereby exhibiting a high critical current value during normal operation, and in the case of a short circuit accident or the like. It is an object of the present invention to provide a superconducting current limiter exhibiting a high taench (normal conduction transition) resistance.
  • the oxide superconducting thin film is formed on a substrate containing sapphire by a laser vapor deposition method in which a raw material is irradiated with laser light and a substance scattered from the raw material is deposited on the substrate. It is characterized by being formed with a film thickness exceeding 7 ⁇ .
  • the inventors of the present invention have formed a superconducting oxide thin film on a sapphire substrate by using a laser vapor deposition method instead of the conventional thermal co-evaporation method and appropriately setting various conditions during laser vapor deposition.
  • a laser vapor deposition method instead of the conventional thermal co-evaporation method and appropriately setting various conditions during laser vapor deposition.
  • an oxide superconducting thin film having excellent critical current density characteristics can be formed with a thickness exceeding 0.7 ⁇ . This is because, in the case of the laser vapor deposition method, it is considered that a certain amount of particles are scattered as compared with the case of the thermal co-evaporation method. This is considered to be because distortion is easily alleviated.
  • the repetition frequency (hereinafter, referred to as a laser frequency) of pulse irradiation of a laser beam applied to a raw material is divided into at least two steps to thereby obtain an oxide superconducting film.
  • a thin film is formed.
  • the first-stage laser frequency is lower than the second-stage laser frequency.
  • the energy per pulse (hereinafter, referred to as laser power) is preferably at least 400 mJ.
  • the temperature of the substrate at the time of laser deposition is preferably at least 600 ° C. and less than 1200 ° C.
  • the gas pressure during laser deposition is from 1.33 Pa to 100 Pa, preferably from 1.33 Pa to 66.66. It is less than Pa.
  • an oxide superconducting thin film having a high critical current density can be obtained.
  • oxygen is contained in the atmosphere at the time of laser deposition.
  • an oxide superconducting thin film having a high critical current density can be obtained.
  • the oxide superconducting thin film of the present invention is formed by the above manufacturing method, and has a thickness exceeding 0.7 ⁇ .
  • the oxide superconducting thin film of the present invention it becomes possible to form a thick film exceeding 0.7 ⁇ having excellent critical current density characteristics and large critical current characteristics by a laser vapor deposition method. Since a thick oxide superconducting thin film can be realized as described above, a large current can be passed, and an oxide superconducting thin film particularly suitable for power use can be obtained.
  • the critical current density under a self-magnetic field in liquid nitrogen is 1 ⁇ 10 6 AZcm 2 or more, and the critical current characteristics are excellent.
  • the critical current density is as high as 1 ⁇ 10 6 A / cm 2 or more, and It is possible to increase the critical current value.
  • the critical current density under a self-magnetic field in liquid nitrogen is more than 7 OA / cm width per 1 cm width, and more than 280 A, cm width. This allows a large current to flow.
  • the above oxide superconducting thin film preferably, it has a RE123 structure, and the force RE is made of a material containing at least one of a rare earth element and a yttrium element.
  • oxide superconducting thin film having the RE123 structure capable of conducting a large current By using the oxide superconducting thin film having the RE123 structure capable of conducting a large current, an oxide superconducting thin film suitable for power use can be obtained.
  • RE in the “RE123 structure” means a material containing at least one of a rare earth element and a yttrium element.
  • the superconducting current limiter of the present invention is configured using the above-described oxide superconducting thin film.
  • the superconducting current limiting device exhibits a high critical current value during normal operation and a high quenching resistance value during a short-circuit accident or the like. You can get a bowl.
  • the current is limited by transitioning the oxide superconducting thin film from the superconducting state to the normal conducting state.
  • the present invention can be applied to a so-called superconducting / normal conducting (SN) transition type superconducting current limiter.
  • FIG. 1 is a diagram for explaining a method for manufacturing an oxide superconducting thin film according to one embodiment of the present invention.
  • FIG. 2 is a view showing a process of forming an oxide superconducting thin film by dividing a laser frequency of a laser beam into two stages in a laser vapor deposition method.
  • FIG. 3 is a cross-sectional view schematically showing a configuration of the oxide superconducting thin film according to one embodiment of the present invention.
  • FIG. 4 is a H o B a 2 C u 3 O x (H o BCO) measured result indicating a critical current density relationship of the superconducting layer under the self-magnetic field in the gas pressure and liquid nitrogen during the laser deposition method .
  • FIG. 5 is a diagram showing a configuration of a superconducting current limiter according to one embodiment of the present invention.
  • FIG. 6 is a plan view showing a coil made of a superconducting thin film used in the superconducting current limiter of FIG.
  • FIG. 7 is a cross-sectional view showing a coil formed of a superconducting thin film used in the superconducting current limiter of FIG. BEST MODE FOR CARRYING OUT THE INVENTION
  • FIG. 1 is a diagram illustrating a method for manufacturing an oxide superconducting thin film according to an embodiment of the present invention.
  • substrate 10 is placed on heater 2 in a state where substrate 10 is inclined at a predetermined angle with respect to target (raw material) 1.
  • a predetermined portion of the substrate 10 is covered with a mask (not shown), and a laser is applied to the target 1 by laser ablation.
  • One light 3 is irradiated.
  • the substance (plume) 4 scattered from the target 1 is deposited on the exposed surface of the substrate 10 to form an oxide superconducting thin film.
  • the laser frequency of the laser beam applied to the target 1 is preferably divided into two steps (steps S1 and S2) as shown in FIG.
  • the laser frequency in the first laser irradiation (step S1) is preferably lower than the laser frequency in the second laser irradiation (step S2).
  • the laser power is preferably 40 OmJ or more, more preferably 600 mJ or more, and further preferably 800 mJ to 1,000 mJ.
  • the temperature of the substrate 10 during the laser deposition is preferably 600 ° C. or more and less than 1200 ° C., and more preferably 800 ° C. or more and less than 1200 ° C.
  • the gas pressure during laser deposition is from 1.33 Pa to 100 Pa, and preferably from 1.33 Pa to 66.6 Pa. Preferably contains oxygen.
  • FIG. 3 is a cross-sectional view schematically showing a configuration of the oxide superconducting thin film according to one embodiment of the present invention.
  • oxide superconducting thin film 13 is formed on substrate 10.
  • This substrate 10 has a sapphire single crystal substrate 11 and an intermediate layer 12 made of, for example, cerium oxide.
  • the oxide superconducting thin film 13 preferably has a critical current density of 1 ⁇ 10 6 A / cm 2 or more under a self-magnetic field in liquid nitrogen, and has a critical current per 1 cm width. It is preferable that the width is 70 AZcm or more, and more than 28 OA / cm.
  • the material of the oxide superconductor thin film 1 3 is not limited Ho B a 2 C UsO, to, yo if a RE 1 2 3 Structure les.
  • RE in the RE123 structure is preferably at least one of a rare earth element and a yttrium element.
  • the oxide superconducting thin film 13 is formed directly on the sapphire single crystal substrate 11. May be.
  • FIG. 5 is a diagram showing a configuration of a superconducting current limiter according to an embodiment of the present invention.
  • FIGS. It is a figure and a sectional view.
  • the superconducting current limiter in the present embodiment has coils 28a and 28b that can be cooled by liquid nitrogen or the like.
  • the coils 28a and 28b for example, flat superconducting coils are used as shown in FIGS.
  • the superconducting coil 28 a is formed in a spiral shape on the surface of the insulating substrate 27, and the superconducting coil 28 b is formed in a spiral shape on the back surface of the insulating substrate 27.
  • One end of each of the superconducting coils 28a and 28b is electrically connected to each other by a front and back circuit connecting portion 29.
  • the other ends of the superconducting coils 28a and 28b are electrically connected to the terminals 26a and 26b, respectively.
  • Such a superconducting current limiter acts as a current limiter as follows.
  • a HoBa 2 Cu 3 O x superconducting layer was formed on a sapphire substrate with a cerium oxide intermediate layer (about 40 nm thick) deposited by laser deposition.
  • Ho B a 2 C u 3 ⁇ on a sintered target was irradiated with Xe C l excimer laser (wavelength 3 08 nm), the laser energy to 90 Om J, repetition rate of the first step The frequency was set to 5 Hz, the laser of the second step was repeated at a frequency of 4 OHz (each film was formed simultaneously), the film was formed under the conditions of a substrate temperature of 9 ° C and an oxygen atmosphere of 13.33 Pa. Was.
  • By varying the deposition time was deposited Ho B a 2 Cu 3 O x greater conductivity layer having various thickness.
  • cerium oxide intermediate layer on a sapphire substrate (thickness: about 40 nm) as a comparative example, it was formed H o B a 2 C u 3 O x superconducting layer by thermal co-evaporation. Ho, Ba, and Cu metals were scattered by resistance heating using raw materials, placed on the opposite surface, and vapor-deposited on a substrate heated to 700 ° C.
  • Critical current density and critical current value of HoBCO film produced by laser deposition method and thermal co-evaporation method * Relationship between * and film thickness (* Critical current value is value per film lcm width)
  • the critical current density becomes zero. It can be seen that the BCO film can maintain a high critical current value even at a thickness of 0.5 ⁇ or more, and can form a thick oxide superconducting thin film without causing cracks. Furthermore, in the case of a thick film exceeding 0.7 ⁇ , the oxide superconducting thin film has a higher critical current density and a larger critical current value per 1 cm width of the film than the conventional thin film, and is thus an excellent oxide superconducting thin film. Understand.
  • a superconducting thin film is formed on a sapphire substrate using laser evaporation. This indicates that an oxide superconducting thin film having a high critical current density and a large critical current can be formed with a thickness exceeding 0.7 / m.
  • a holmium-based superconducting thin film (HoBa 2 Cu 3 O x : HoBCO) was formed on a sapphire substrate with a cerium oxide intermediate layer (about 40 nm thick) deposited by laser deposition. At that time, the substrate temperature was changed as a parameter. During the film formation, in the first step, the film was formed at a repetition frequency of 5 Hz for 10 minutes, and then, in the second step, the film was formed at a repetition frequency of 40 Hz for 10 minutes. The film formation atmosphere was oxygen gas at 13.33 Pa and the laser power was 900 mJ, each of which was constant. In order to examine the characteristics of the superconducting layer, the critical current density of the HBCO superconducting layer in liquid nitrogen under a self-magnetic field was measured. The results are shown in Table 4.
  • an oxide superconducting thin film is formed on a sapphire substrate by a laser deposition method under appropriate conditions, so that 0.7 ⁇ It is possible to form an oxide superconducting thin film having a high critical current density and a large critical current characteristic with a thick film exceeding the above. For this reason, it becomes possible to manufacture an oxide superconducting thin film suitable for power applications requiring a large current.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Superconductor Devices And Manufacturing Methods Thereof (AREA)
  • Emergency Protection Circuit Devices (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Cette invention a trait à un procédé de production d'un film mince supraconducteur à base d'oxyde, d'une densité de courant critique élevé et dont l'épaisseur est supérieure à 0,7 νm déposé sur un substrat, notamment un substrat à base de monocristal de saphir. Ce procédé repose sur une technique de dépôt par laser. Dans le cadre de ce procédé, on soumet une cible aux effets de faisceaux laser, le matériau diffusé par la cible étant, de ce fait, déposé sur le substrat. L'invention concerne également le film mince supraconducteur à base d'oxyde obtenu grâce à ce procédé ainsi qu'un limitateur de courant de défaut pourvu de ce film.
PCT/JP2003/004933 2002-04-26 2003-04-17 Film mince supraconducteur, procede de production et limitateur de courant de defaut supraconducteur WO2003091158A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003235237A AU2003235237A1 (en) 2002-04-26 2003-04-17 Oxide superconductive thin-film, process for producing the same and superconducting fault current limiter

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-125719 2002-04-26
JP2002125719A JP2005344125A (ja) 2002-04-26 2002-04-26 酸化物超電導薄膜およびその製造方法ならびに超電導限流器

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WO2003091158A1 true WO2003091158A1 (fr) 2003-11-06

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JP5658891B2 (ja) * 2010-02-24 2015-01-28 株式会社フジクラ 酸化物超電導膜の製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04212214A (ja) * 1990-03-01 1992-08-03 Sumitomo Electric Ind Ltd 酸化物超電導薄膜の製造方法
JPH06132571A (ja) * 1992-10-21 1994-05-13 Sumitomo Electric Ind Ltd 限流素子および限流装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04212214A (ja) * 1990-03-01 1992-08-03 Sumitomo Electric Ind Ltd 酸化物超電導薄膜の製造方法
JPH06132571A (ja) * 1992-10-21 1994-05-13 Sumitomo Electric Ind Ltd 限流素子および限流装置

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JP2005344125A (ja) 2005-12-15

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