EP1027737A1 - Structure supraconductrice comportant un substrat de verre sur lequel est depose un supraconducteur haute temperature, et procede de production de cette structure - Google Patents
Structure supraconductrice comportant un substrat de verre sur lequel est depose un supraconducteur haute temperature, et procede de production de cette structureInfo
- Publication number
- EP1027737A1 EP1027737A1 EP98961034A EP98961034A EP1027737A1 EP 1027737 A1 EP1027737 A1 EP 1027737A1 EP 98961034 A EP98961034 A EP 98961034A EP 98961034 A EP98961034 A EP 98961034A EP 1027737 A1 EP1027737 A1 EP 1027737A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- superconductor
- structure according
- glass
- substrate
- superconductor structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000011521 glass Substances 0.000 title claims abstract description 50
- 239000000758 substrate Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000463 material Substances 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000009466 transformation Effects 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 239000002887 superconductor Substances 0.000 claims description 45
- 230000008021 deposition Effects 0.000 claims description 8
- 239000005357 flat glass Substances 0.000 claims description 7
- 238000005137 deposition process Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 239000005354 aluminosilicate glass Substances 0.000 claims description 4
- 238000007735 ion beam assisted deposition Methods 0.000 claims description 4
- 238000000608 laser ablation Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 125000002524 organometallic group Chemical group 0.000 claims 1
- 238000007650 screen-printing Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000002207 thermal evaporation Methods 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 32
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910004247 CaCu Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010549 co-Evaporation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 metal oxide compounds Chemical class 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000005336 safety glass Substances 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- ZYPGADGCNXOUJP-CXVPHVKISA-N Variotin Chemical compound CCCC[C@@H](O)\C=C(/C)\C=C\C=C\C(=O)N1CCCC1=O ZYPGADGCNXOUJP-CXVPHVKISA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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
- H10N60/30—Devices switchable between superconducting and normal states
-
- 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
- H10N60/0576—Processes for depositing or forming copper oxide superconductor layers characterised by the substrate
Definitions
- the invention relates to a superconductor structure with a substrate, at least one buffer layer deposited on the substrate and a layer deposited on the buffer layer made of a metal-oxide superconductor material with a high transition temperature, the substrate consisting of a glass material which has a maximum temperature during manufacture the buffer layer and the superconductor layer are sufficiently temperature-resistant.
- the invention further relates to a method for producing a corresponding superconductor structure.
- Such a structure and a corresponding manufacturing process can be found in "Physica C", Vol. 261, 1996, pages 355 to 360.
- Jump temperatures T of over 77 K are known, which are therefore also referred to as high-T r superconductor materials or HTS materials and in particular allow an LN 2 cooling technology.
- Such metal oxide compounds include, in particular, cuprates of special material systems such as, for example, the types Y-Ba-Cu-0 or Bi-Sr-Ca-Cu-O, where the Bi component can be partially substituted by Pb.
- Several superconducting high-T c phases can occur within individual material systems, which differ in the number of copper-oxygen network planes or layers within the crystalline unit cell and which have different transition temperatures.
- HTS materials are attempted to be deposited on different substrates for different applications. the, whereby in general the phase-pure superconductor material is sought.
- metallic substrates are particularly provided for conductor applications.
- DE 195 20 205 ⁇ generally shows the use of substrates made of glass material as carriers for conductor tracks made of HTS material with current limiting devices.
- a buffer layer suitable for this purpose on the surface of the substrate to be coated with the HTS material.
- the object of the present invention is therefore to design the superconductor structure with the features mentioned at the outset and the method for its production in such a way that comparatively higher critical current densities can be obtained.
- the glass material of the superconductor structure according to the invention should have a coefficient of thermal expansion which is greater than 6 10 ⁇ 6 K "1 , and a transformation temperature of over 550 ° C.
- the invention is based on the knowledge that the (linear) thermal expansion coefficient of the glass material to be regarded as "soft glass” together with the transformation temperature, which is important with regard to the maximum temperature required for the deposition or formation of the superconducting material, the decisive factor with regard to a high critical current density is J. C. If the glass material is selected with the claimed values of the expansion coefficient and the transformation temperature, then crack formation in the HTS material, as is known in the known superconductor structure, can advantageously be carried out observed according to the cited reference "Physica C", at least largely avoided. Because the claimed value of the expansion coefficient is that of the HTS material, which is of the order of magnitude
- 10 10 "6 K " 1 lies, at least largely adapted.
- a glass material with an expansion coefficient of over 7 10 ⁇ 6 K _1 can therefore be regarded as particularly advantageous.
- the measuring range for the mentioned values of the expansion coefficients usually extends from 20 ° C to 300 ° C.
- Glazers suitable as substrate material are relatively inexpensive, so that they can be used in particular for large-area substrates with a coatable area of at least 10 cm 2 , preferably over 100 cm 2 , as are to be provided in particular for current limiting devices. In such facilities, a total area of HTS material of more than 2 m 2 is required for a power to be limited of, for example, about 10 MVA.
- Special aluminosilicate glasses can advantageously be selected as the glass material, since they can best meet the required combination of glass properties.
- a glass material preferably has about 50 to 70% by weight of SiO 2 and about 10 to 30% by weight of Al? 0 3 , the values mentioned being able to deviate by ⁇ 5%.
- the glass material used advantageously has cerium, in particular in the form of a cerium oxide additive. With such an addition, the transformation temperature of the glass material can be increased to a certain extent.
- At least one deposition process for the material of the buffer layer and / or the superconductor layer is advantageously chosen for the production of a corresponding structure, in which the maximum temperature at the substrate is at most 100 K higher, preferably at most 50 K higher than the transformation temperature of the glass material. In this way, dimensional stability, in particular of large-area substrates, can advantageously be ensured.
- the superconductor structure according to the invention can be provided particularly advantageously for devices in which large-area substrate surfaces of preferably at least 10 cm 2 , in particular over 100 cm 2, serve as the substrate for the HTS material.
- a corresponding device is, for example, a short-circuit current limiter device with a planar conductor configuration, the basic embodiment of which is generally known (cf., for example, the aforementioned DE 195 20 205 A or EP 0 523 374 A).
- Current limiter devices of this type in particular require substrate surfaces of up to over 2000 cm 2 .
- the use of special glasses as large-area substrates enables then light a relatively inexpensive manufacture of the corresponding superconductor structure.
- a section of a cross section through a conductor structure of such a short-circuit current limiter device is shown in the figure.
- the structure generally designated 2
- a layer 5 made of an HTS material is deposited on the buffer layer, which can be structured if necessary.
- the HTS layer 5 can be combined with at least one further layer such as e.g. a protective layer or a layer 6 serving as a shunt resistor.
- a shunt resistance layer is particularly advantageous for current limiter applications.
- a plate with a thickness di of a few millimeters and with the required area made of a special flat glass is used, which is preferably drawn from the melt and, if appropriate, is then thermally leveled. In thermal leveling, small waves and other unevenness are smoothed out by heating the surface. The fused surface then has a sufficiently low micro-roughness for the subsequent coating processes.
- the roughness determined by the maximum roughness depth R t should advantageously be less than 50 nm, preferably less than 20 nm, based on a measuring path of 500 ⁇ .
- a glass material should be selected for the substrate which, on the one hand, has a sufficiently high transformation temperature of at least 550 ° C., preferably of at least 580 ° C., with reference to the maximum temperature (at the substrate) that occurs in the subsequent deposition processes.
- the transformation temperature should only be at most 100 ° C below this maximum temperature of the process.
- the temperature of the deposition process lies between the transformation temperature and the softening temperature of the glass material.
- the glass material should have a linear coefficient of thermal expansion in a usual temperature range between 20 ° and 300 ° C, which is greater than 6 10 ⁇ 6 K "1 and in particular is above 7 10 " 6 K _1 .
- aluminum silicate glasses which in particular contain about 50 to 70% by weight SiO 2 and 10 to 30% by weight A1 2 0 3 in addition to other components.
- a suitable aluminum silicate glass is a glass from the company "Deutsche Spezialglas AG",
- This glass which belongs to the category of safety glass and which, for example, and space travel, which is used in the lighting and window industry as well as for glasses and watch glasses as well as for substrates for photomasks, has a thermal expansion coefficient of 8.9 10 "6 K _1 at a softening temperature of 870 ° C and a transformation temperature of 607 ° C on. It was recognized that this glass material can serve particularly advantageously as a large-area substrate material for HTS layers, in particular for current limiting devices.
- glass materials known as flat glass which are known per se, are also suitable as starting materials which, although they have the required coefficient of thermal expansion, but whose transformation temperature is too low, by adding cerium in the form of CeO 2 between 0.5 to 40% by weight , in particular between 1 and 30% by weight of the known material such as, for example, an aluminum silicate, the transformation temperature can then be raised to the required value.
- the at least one buffer layer must consist of a material that ensures such growth.
- a layer 4 with a texture adapted to the crystalline dimensions of the HTS material is therefore particularly suitable.
- Biaxially textured, yttrium-stabilized zirconium oxide (abbreviation: "YSZ”) is advantageous.
- buffer layer materials such as Ce0 2 , YSZ + Ce0 2 (as a double layer), Pr 6 0n, MgO, YSZ + tin-doped ln 2 0 3 (as a double layer), SrT ⁇ 0 3 or La ⁇ - x Ca x Mn0 3.
- IBAD process .Ion Beam-assisted deposition methods
- the layer thickness d 2 of the textured buffer layer 4 thus produced generally being between 0.05 and 2 ⁇ m.
- the HTS material is then generally coated on the buffer layer 4 with the aid of known deposition processes while heating the substrate to a thickness d 3 Applied micrometers.
- the minimum thickness of d 3 is expediently at least 0.2 ⁇ m, in particular at least 0.5 ⁇ m.
- maximum thicknesses of d 3 of 5 ⁇ m, preferably of at most 3 ⁇ m, are sufficient for this application.
- a method is advantageously selected for the deposition of the HTS material which requires a maximum temperature for the deposition and for the formation of the HTS material which is at most 100 ° higher, preferably at most 50 ° C higher than the required transformation temperature of the selected one Glass material.
- the deposition or formation temperature should be at least 100 ° C lower than the softening temperature of the glass material.
- the latter method can advantageously be carried out at relatively low substrate temperatures of about 650 ° C.
- CVD (Chemical Vapor Deposition) processes, in particular using metal-organic starting materials, are also suitable.
- TlBa 2 Ca 2 Cu 3 0 come as HTS materials 9 + x , HgBa 2 CaCu 2 0 6 + x , Bi 2 Sr 2 CaCu 2 0 8 - x or (Bi, Pb) 2 Cr 2 Ca 2 Cu 3 0 ⁇ 1 _ x in question.
- a glass substrate 3 made of the known aluminosilicate glass with the product designation “SG-11” with a thickness di of approximately 2 mm and an extension of its surface of 10 10 cm 2 selected.
- thermal co-evaporation of the components of the material with the supply of oxygen at a substrate temperature of 620 ° to 650 ° C. was provided by means of a known coating apparatus.
- the HTS layer 5 was then covered with a 0.5 mm thick Au shunt resistance layer 6.
- the HTS layer of structure 2 then had a critical current density J c (in the zero field, at 77 K, with 0.1 ⁇ V / cm as a characteristic of the critical current I c ) of over 5 10 5 A / cm 2 .
- the superconductor material should only be on one side of the substrate.
- coating on both sides is also possible (see e.g.
- EP 0 731 986 B1 Such an embodiment is particularly advantageous from the point of view of minimizing mechanical stresses in the substrate.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Surface Treatment Of Glass (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Containers, Films, And Cooling For Superconductive Devices (AREA)
Abstract
L'invention concerne une structure supraconductrice (2) qui comporte un substrat (3) consitué d'un verre résistant aux températures élevées, une couche tampon (4) déposée sur le substrat, ainsi qu'une couche (5) déposée sur celle-ci est constituée d'un matériau supraconducteur à température de transition élevée, à oxyde de métal. Il faut utiliser un verre présentant un coefficient de dilatation thermique supérieur à 6 . 10 <-6> K<-1> et une température de transformation supérieure à 550 DEG C. Pour produire la structure selon l'invention, on sélectionne au moins un procédé de dépôt, selon lequel la température maximale dépasse, au maximum, de 100 K, la température de transformation du verre.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19747767 | 1997-10-29 | ||
DE19747767 | 1997-10-29 | ||
PCT/DE1998/003116 WO1999022412A1 (fr) | 1997-10-29 | 1998-10-23 | Structure supraconductrice comportant un substrat de verre sur lequel est depose un supraconducteur haute temperature, et procede de production de cette structure |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1027737A1 true EP1027737A1 (fr) | 2000-08-16 |
Family
ID=7846988
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98961034A Withdrawn EP1027737A1 (fr) | 1997-10-29 | 1998-10-23 | Structure supraconductrice comportant un substrat de verre sur lequel est depose un supraconducteur haute temperature, et procede de production de cette structure |
Country Status (5)
Country | Link |
---|---|
US (1) | US6309767B1 (fr) |
EP (1) | EP1027737A1 (fr) |
JP (1) | JP2001521298A (fr) |
CA (1) | CA2309086A1 (fr) |
WO (1) | WO1999022412A1 (fr) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6765151B2 (en) * | 1999-07-23 | 2004-07-20 | American Superconductor Corporation | Enhanced high temperature coated superconductors |
US6828507B1 (en) * | 1999-07-23 | 2004-12-07 | American Superconductor Corporation | Enhanced high temperature coated superconductors joined at a cap layer |
DE10159646C1 (de) * | 2001-12-05 | 2003-04-17 | Siemens Ag | Verfahren zur nur einseitigen Beschichtung eines planaren Substrats mit einer Schicht aus Hochtemperatur-Supraleiter-Material |
US6764770B2 (en) * | 2002-12-19 | 2004-07-20 | Ut-Battelle, Llc | Buffer layers and articles for electronic devices |
US7774035B2 (en) * | 2003-06-27 | 2010-08-10 | Superpower, Inc. | Superconducting articles having dual sided structures |
US20040266628A1 (en) * | 2003-06-27 | 2004-12-30 | Superpower, Inc. | Novel superconducting articles, and methods for forming and using same |
US7025826B2 (en) * | 2003-08-19 | 2006-04-11 | Superpower, Inc. | Methods for surface-biaxially-texturing amorphous films |
KR100586570B1 (ko) | 2004-11-25 | 2006-06-07 | 엘에스전선 주식회사 | 크랙 방지 구조를 갖는 초전도 선재 |
US20080257517A1 (en) * | 2005-12-16 | 2008-10-23 | General Electric Company | Mold assembly for use in a liquid metal cooled directional solidification furnace |
US7627356B2 (en) * | 2006-07-14 | 2009-12-01 | Superpower, Inc. | Multifilament AC tolerant conductor with striated stabilizer and devices incorporating the same |
US8716188B2 (en) | 2010-09-15 | 2014-05-06 | Superpower, Inc. | Structure to reduce electroplated stabilizer content |
US9564258B2 (en) | 2012-02-08 | 2017-02-07 | Superconductor Technologies, Inc. | Coated conductor high temperature superconductor carrying high critical current under magnetic field by intrinsic pinning centers, and methods of manufacture of same |
US9362025B1 (en) | 2012-02-08 | 2016-06-07 | Superconductor Technologies, Inc. | Coated conductor high temperature superconductor carrying high critical current under magnetic field by intrinsic pinning centers, and methods of manufacture of same |
WO2019224830A1 (fr) * | 2018-05-24 | 2019-11-28 | Guy Deutscher | Limiteur de courant de défaut |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4994435A (en) * | 1987-10-16 | 1991-02-19 | The Furukawa Electric Co., Ltd. | Laminated layers of a substrate, noble metal, and interlayer underneath an oxide superconductor |
JP2639961B2 (ja) * | 1988-03-25 | 1997-08-13 | 三洋電機株式会社 | 超電導素子の製造方法 |
JPH0227614A (ja) | 1988-07-15 | 1990-01-30 | Nippon Sheet Glass Co Ltd | 酸化物超伝導薄膜の積層構造 |
JPH033277A (ja) * | 1989-05-30 | 1991-01-09 | Murata Mfg Co Ltd | 軸配向した超伝導薄膜 |
DE4119984A1 (de) | 1991-06-18 | 1992-12-24 | Hoechst Ag | Resistiver strombegrenzer |
US5204289A (en) * | 1991-10-18 | 1993-04-20 | Minnesota Mining And Manufacturing Company | Glass-based and glass-ceramic-based composites |
DE19520205A1 (de) | 1995-06-01 | 1996-12-05 | Siemens Ag | Resistive Strombegrenzungseinrichtung unter Verwendung von Hoch-T¶c¶Supraleitermaterial |
-
1998
- 1998-10-23 JP JP2000518417A patent/JP2001521298A/ja not_active Withdrawn
- 1998-10-23 WO PCT/DE1998/003116 patent/WO1999022412A1/fr not_active Application Discontinuation
- 1998-10-23 EP EP98961034A patent/EP1027737A1/fr not_active Withdrawn
- 1998-10-23 CA CA002309086A patent/CA2309086A1/fr not_active Abandoned
-
2000
- 2000-05-01 US US09/563,393 patent/US6309767B1/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO9922412A1 * |
Also Published As
Publication number | Publication date |
---|---|
US6309767B1 (en) | 2001-10-30 |
JP2001521298A (ja) | 2001-11-06 |
CA2309086A1 (fr) | 1999-05-06 |
WO1999022412A1 (fr) | 1999-05-06 |
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