CA2378833A1 - Enhanced high temperature coated superconductors - Google Patents

Enhanced high temperature coated superconductors Download PDF

Info

Publication number
CA2378833A1
CA2378833A1 CA002378833A CA2378833A CA2378833A1 CA 2378833 A1 CA2378833 A1 CA 2378833A1 CA 002378833 A CA002378833 A CA 002378833A CA 2378833 A CA2378833 A CA 2378833A CA 2378833 A1 CA2378833 A1 CA 2378833A1
Authority
CA
Canada
Prior art keywords
superconductor
layer
high temperature
substrate
layers
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.)
Abandoned
Application number
CA002378833A
Other languages
French (fr)
Inventor
Leslie G. Fritzemeier
Cornelis Leo Hans Thieme
Steven Fleshler
John D. Scudiere
Gregory L. Snitchler
Bruce B. Gamble
Robert E. Schwall
Dingan Yu
Gilbert N. Riley, Jr.
Alexander Otto
Elliott D. Thompson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
American Superconductor Corp
Original Assignee
Individual
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
Priority claimed from US09/500,717 external-priority patent/US6562761B1/en
Application filed by Individual filed Critical Individual
Publication of CA2378833A1 publication Critical patent/CA2378833A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00Superconducting devices
    • H10N60/01Manufacture or treatment
    • H10N60/0268Manufacture or treatment of devices comprising copper oxide
    • H10N60/0801Processes peculiar to the manufacture or treatment of filaments or composite wires
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/002Controlling or regulating
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02Epitaxial-layer growth
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/16Oxides
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00Superconducting devices
    • H10N60/01Manufacture or treatment
    • H10N60/0268Manufacture or treatment of devices comprising copper oxide
    • H10N60/0296Processes for depositing or forming superconductor layers
    • H10N60/0324Processes for depositing or forming superconductor layers from a solution
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00Superconducting devices
    • H10N60/01Manufacture or treatment
    • H10N60/0268Manufacture or treatment of devices comprising copper oxide
    • H10N60/0296Processes for depositing or forming superconductor layers
    • H10N60/0548Processes for depositing or forming superconductor layers by precursor deposition followed by after-treatment, e.g. oxidation
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00Superconducting devices
    • H10N60/01Manufacture or treatment
    • H10N60/0268Manufacture or treatment of devices comprising copper oxide
    • H10N60/0296Processes for depositing or forming superconductor layers
    • H10N60/0576Processes for depositing or forming superconductor layers characterised by the substrate
    • H10N60/0632Intermediate layers, e.g. for growth control
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00Superconducting devices
    • H10N60/20Permanent superconducting devices
    • H10N60/203Permanent superconducting devices comprising high-Tc ceramic materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12014All metal or with adjacent metals having metal particles
    • Y10T428/12028Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]

Abstract

This invention relates to a practical superconducting conductor based upon biaxially textured high temperature superconducting coatings. In particular, methods for producing flexible and bend strain-resistant articles and articles produced in accordance therewith are described which provide improved current sharing, lower hysteretic losses under alternating current conditions, enhanced electrical and thermal stability and improved mechanical properties between otherwise isolated films in a coated high temperature superconducting (HTS) wire. Multilayered materials including operational material which is sensitive to bend strain can be constructed, in which the bend strain in the region in which such operational material is located is minimized. The invention also provides a means for splicing coated tape segments and for termination of coated tape stack ups or conductor elements. In one embodiment, a multi-layer high temperature superconductor is provided and includes first and second high temperature superconductor coated tape elements (11a, 11b).
Each element includes s substrate (12a, 12b), at least one buffer (14a, 14b) deposited on the substrate, a high temperature superconductor layer (16a, 16b) and a metallic cap layer (18a, 18b). The first and second high temperature superconductor coated elements are joined at the first and second cap layers using soldering, diffusion bounding or the like.

Description

Enhanced High Temperature Coated Superconductors This application claims priority under 35 U.S.C. ~ 119(e)(1) to United States Provisional Patent Application No. 60/145,468, filed July 23, 1999, entitled "Enhanced High Temperature Coated Superconductors," which is incorporated herein by reference.
TECHNICAL FIELD
The present invention generally relates to methods for manufacturing enhmced current sharing for coated conductor high temperature superconducting tapes and articles formed in accordance therewith.
BACKGROUND
Development efforts in the area of coated high temperature superconductors ("HTS") thus far have been directed at production of single tapes, that is, tapes typically including a substrate that can be textured or untextured, one or more biaxially textured buffer layers, an epitaxial HTS layer, and cap layers. In particular, attempts have been directed toward the production of high current carrying tapes from single substrate layers. In an effort to improve the overall current carrying capability of those proposed single tapes, high temperature superconductor (HTS) films will need to be very thick or will have to be deposited on both sides of a single substrate.
Additionally, the articles created utilizing such construction present an unfavorable architecture regarding several critical performance parameters, including critical stress or strain parameters.
The use of a single tape with a very thick superconducting layer will not be practical for commercial applications. This may in part be due to the likelihood of the HTS layer to fracture as the thickness of the HTS layer increases (i.e. a known reduction in fracture strength). It is also likely that thickness will be limited by difficulty in controlling texture, and hence performance, as the HTS layer grows.
While current carrying capability may be improved by depositing a superconducting layer on each side of the substrate, this approach suffers other potential drawbacks. For example, the handling and processing of such a tape will be difficult relative to a single sided tape. In addition, the HTS films for two sided tapes will be in the least favorable position for several critical performance parameters.
Moreover, the possible use of conductive buffer layers to provide for a current path between the HTS filament and the substrate has been discussed extensively.
While this solution appears to be possible it is severely limiting. The choices of conductive materials are limited because they should provide chemical compatibility with the superconductor and the substrate, exhibit a lattice match that enables epitaxial growth from the substrate, provide a template for epitaxial superconductor growth and possess good mechanical and physical properties. This is especially true since the resistance at the interface between the buffer and any other layer will govern the current transfer. It is likely that this interfacial resistance will still be high relative to the bulk resistance of the conductive buffer layer. The growth of a native oxide layer from the substrate material, which further increases the resistivity between the substrate and the buffer layer, is also likely to occur.
In the context of HTS coated conductors, it would therefore be desirable to provide methods and articles that overcome the shortcomings associated with the prior art.
SUMMARY OF THE INVENTION
This invention relates to a practical superconducting conductor based upon biaxially textured high temperature superconducting coatings. In particular, methods for producing articles, and articles produced in accordance therewith, are described which provide improved current sharing, lower hysteretic losses under alternating current conditions, enhanced electrical and thermal stability and improved mechanical properties between otherwise isolated films in a coated high temperature supercond~:cting (HTS) wire. The invention also provides a means for splicing coated tape segments and for termination of coated tape stack ups or conductor elements.
The invention further relates to multilayered materials which include sensitive HTS
operational layers that can have laminate materials layered onto the multilayered materials so as to achieve desirable electrical, magnetic, thermal and mechanical properties of the composite tape.
In one embodiment, a mufti-layer high temperature superconductor is provided and includes first and second high temperature superconductor coated elements.
Each element includes a substrate, at least one buffer deposited on the substrate, a high temperature superconductor layer, and a cap layer. The first and second high temperature superconductor coated elements are joined at the first and second cap layers. Alternatively, if cap layers are not present, the first and second HTS
coated elements are joined with an intervening, typically metallic, layer between the two HTS layers.
In one aspect, the invention provides a mufti-layer high temperature superconductor, including a first high temperature superconductor coated element, which includes a first substrate (which can be biaxially textured, for example, be deformation); at least one first buffer deposited on the first substrate (which can be metal oxides, for example cerium oxide and/or gadolinium oxide, and can fiuther optionally include yttria stabilized zirconia, all of which can be epitaxially deposited);
at least one first high temperature superconductor layer (which can include metal oxide, such as rare earth oxide, including (RE)Ba2Cu30~_s, wherein RE is selected from the group consisting of rare earth elements and yttrium, and 8 is a number greater than zero and less than one); and a first cap layer. The mufti-layer high temperature superconductor also includes a second high temperature superconductor coated element, which includes a second substrate; at least one second buffer deposited on the second substrate; at least one second high temperature superconductor layer; and a second cap layer, where the first and second high temperature superconductor coated elements are joined at the first and second cap layers. The first or second substrates can include nickel, such as for example, nickel-chromium, nickel-copper, or nickel-vanadium alloys. At least two buffers, for example three buffers, can be sequentially deposited on the first substrate.
The first cap layer can be deposited on the first high temperature superconducting layer. The first and second substrates, the first and second buffers, the first and second high temperature superconducting layers, and the first and second cap layers can independently be of substantially identical composition. Thus, the first and second high temperature superconductor coated elements can be of substantially identical composition. The the first and second cap layers can be continuously joined at their uppermost surfaces. Alternately, the first and second cap layers can be a single continuous layer. The superconductor can be in the form of a tape. The substrates can optionally be substantially untextured, and the buffers and high temperature superconductor layers can be biaxiahly textured. The first and second high temperature superconductor coated elements can be registered at their respective edges. The first and second high temperature superconductor coated elements can be offset along their lengths. At least one of the first and second cap layers can extend along the edge of at least the first and second high temperature superconductor coated element. The superconductor can include a multifilamentary structure, such as when the first and second high temperature superconducting layers are divided into a plurality of filaments. The superconductor can further include a stabilizer, where the first and second cap layers can be joined to opposing surfaces of the stabilizer.
In a further aspect, the invention provides another multi-layer high temperature superconductor, including a first high temperature superconductor coated element, which includes a first substrate; at least one first buffer deposited on the first substrate; at least one first high temperature superconductor layer; and a first cap layer. The superconductor also includes a second high temperature superconductor coated element, which includes a second substrate; at least one second buffer deposited on the second substrate; at least one second high temperature superconductor layer; and a second cap layer, where the first and second high temperature superconductor coated elements are joined with an intervening metallic layer.
In yet a further aspect, the invention provides a mufti-layer high temperature superconductor, as described immediately above but without cap layers, where the first and second high temperature superconductor coated elements are joined with an intervening metallic layer.
Unless otherwise defined, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials simihar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control: In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
For a fuller understanding of the present invention, reference is had to the following description taken in conjunction with the accompanying drawings, in which:
Fig. 1 A is an illustration of an HTS coated conductor in accordance with the present invention;
Fig. 1 B is an illustration of an expanded view of Fig. 1A;
Fig. 2A is an illustration of an alternative embodiment of HTS coated conductor in accordance with the present invention;
Fig. 2B is an illustration of an expanded view of Fig. 2A;
Fig. 2C is an illustration of another alternative embodiment of an HTS coated conductor in accordance with the present invention;
Fig. 3A is an illustration of yet another alternative embodiment of an HTS
coated conductor in accordance with the present invention;
Fig. 3B is an illustration of an expanded view of Fig. 3A;
Fig. 4A is an illustration of yet another alternative embodiment of an HTS
coated conductor in accordance with the present invention; and Fig. 4B is an illustration of an expanded view of Fig. 4A.
Similar reference characters refer to similar parts throughout the several views of the drawing s DETAILED DESCRIPTION
This invention relates to a practical superconducting wire based upon biaxially textured high temperature superconducting coatings. In particular, methods for producing articles, and articles produced in accordance therewith, are described which provide improved current sharing, lower hysteretic losses under alternating current conditions, eWanced electrical and thermal stability and improved mechanical properties between otherwise isolated films in a coated high temperature superconducting (HTS) wire. Specific configurations of such articles are designed in such a way as to substantially avoid mechanical degradation of the operational HTS
layer during bending. The material can be used in a variety of applications which employ operational HTS layers. For example, the flexible material can be used in high temperature superconducting tapes with additional electrical, magnetic, electro-optic, dielectric, thermal, mechanical or environmental (protective) properties. The invention also provides a means for splicing coated tape segments and for termination of coated tape stack ups or conductor elements.
A number of important issues must be addressed in order to develop a commercially viable conductor that can advantageously use the performance benefits of the biaxially textured HTS films. For example, well-textured, high critical current density HTS films can only be produced by epitaxial growth on a flat, open surface.
In addition, HTS oxide films cannot sustain high levels of strain without fracture and loss of electrical continuity. A means to mitigate this strain is desirable.
Moreover, unlike first generation HTS wire, which contains a multitude of filaments that can share electrical current transport, the biaxially textured films consist of a single, wide filament. Damage in a single filament could result in local heating and increase the risk of thermal runaway and quenching of the superconducting state, rendering the conductor useless. Further, transfer of current into and out of an isolated HTS layer is also a necessary consideration for practical conductors. Recall that the layers for a conductor made of stacked single tapes would be separated by the substrate, an oxide buffer layer and a capping layer. Current transfer is required to provide for splicing of lengths of conductor and to provide current transfer at conductor terminations.

It is therefore desirable to provide for a useful conductor having multiple tapes stacked relative to one another and/or laminated to provide sufficient ampacity, dimensional stability and mechanical strength. Many, if not all of the above practical issues can be addressed by appropriate engineering of the conductor architecture to take advantage of two or more superconducting layers in close proximity to each other. As described herein, two superconducting layers are bonded "face-to-face"
with an intervening layer, preferably metallic, which may or may not include cap layers. Additional layers may be laminated, particularly in ways which keep the neutral mechanical axis under bending at or near the two superconducting layers.
The commercial production of practical superconducting wires based upon coated HTS (e.g. YBCO) tapes now appears feasible following disclosure of high critical current densities in films produced on flexible metallic substrates.
Y, Ba and Cu can be present in a stoichiometry of 1:2:3, respectively.
The substrate can be formed of alloys having one or more surfaces that are biaxially textured (e.g., (113)[211]) or cube textured (e.g., (100)[001] or (100)[011]).
The alloys can have a relatively low Curie temperature (e.g., at most about 80K, at most about 40K, or at most about 20K).
Ir~ cer taro embodiments, the substrate is a binary alloy that contains two of the following metals: copper, nickel, chromium, vanadium, aluminum, silver, iron, palladium, molybdenum, gold and zinc. For example, a binary alloy can be formed of nickel and chromium (e.g., nickel and at most 20 atomic percent chromium, nickel and from about five to about 18 atomic percent chromium, or nickel and from about 10 to about 1 S atomic percent chromium). As another example, a binary alloy can be formed of nickel and copper (e.g., copper and from about five to about 45 atomic percent nickel, copper and from about 10 to about 40 atomic percent nickel, or copper and from about 25 to about 35 atomic percent nickel). A binary alloy can further include relatively small amounts of impurities (e.g., less than about 0.1 atomic percent of impurities, less than about 0.01 atomic percent of impurities, or less than about 0.005 atomic percent of impurities).

In some embodiments, the substrate contains more than two metals (e.g., a ternary alloy or a quarternary alloy). In these embodiments the alloy can contain one or more oxide formers (e.g., Mg, Al, Ti, Cr, Ga, Ge, Zr, Hf, Y, Si, Pr, Eu, Gd, Tb, Dy, Ho, Lu, Th, Er, Tm, Be, Ce, Nd, Sm, Yb and/or La, with A1 being the preferred oxide former), as well as two of the following metals: copper, nickel, chromium, vanadium, aluminum, silver, iron, palladium, molybdenum, gold and zinc. The alloys can contain at least about 0.5 atomic percent oxide former (e.g., at least about one atomic percent oxide former, or at least about two atomic percent oxide former) and at most about 25 atomic percent oxide former (e.g., at most about 10 atomic percent oxide former, or at most about four atomic percent oxide former). For example, the alloy can include an oxide former (e.g., at least about 0.5 aluminum), from about 25 atomic percent to about 55 atomic percent nickel (e.g., from about 35 atomic percent to about 55 atomic percent nickel, or from about 40 atomic percent to about 55 atomic percent nickel) with the balance being copper. As another example, the alloy can include an oxide former (e.g., at least about 0.5 atomic aluminum), from about five atomic percent to about 20 atomic percent chromium (e.g., from about 10 atomic percent to about 18 atomic percent chromium, or from about 10 atomic percent to about 15 atomic percent chromium) with the balance being nickel. The alloys can include relatively small amounts of impurities (e.g., less than about 0.1 atomic percent of impurities, less than about 0.01 atomic percent of impurities, or less than about 0.005 atomic percent of impurities).
An alloy can be produced by, for example, combining the constituents in powder form, melting and cooling or, for example, by diffusing the powder constituents together in solid state. The alloy can then be formed by deformation texturing (e.g, annealing and rolling, swaging, extrusion and/or drawing) to form a textured surface (e.g., biaxially textured or cube textured). Alternatively, the alloy constituents can be stacked in a jelly roll configuration, and then deformation textured. In some embodiments, a material with a relatively low coefficient of thermal expansion (e.g, Nb, Mo, Ta, V, Cr, Zr, Pd, Sb, NbTi, an intermetallic such as NiAI or Ni,AI, or mixtures thereof) can be formed into a rod and embedded into the alloy prior to deformation texturing.

These methods are described in commonly owned U.S. Patent Application No.
09/283,775, filed March 31, 1999, and entitled "Alloy Materials;" commonly owned U.S. Patent Application No. 09/283,777, filed March 31, 1999, and entitled "Alloy Materials;" PCT Publication No. WO 99/17307, published on April 8, 1999, and entitled "Substrates with Improved Oxidation Resistance;" and PCT Publication No.
WO 99/16941, published on April 8, 1999, and entitled "Substrates for Superconductors," all of which are hereby incorporated by reference. Non-textured substrates can be used when a texturing process is used (see below).
In some embodiments, stable oxide formation can be mitigated until a first epitaxial (for example, buffer) layer is formed on the biaxially textured alloy surface, using an intermediate layer disposed on the surface of the substrate.
Intermediate layers suitable for use in the present invention include those epitaxial metal or alloy layers that do not form surface oxides when exposed to conditions as established by Po2 and temperature required for the initial growth of epitaxial buffer layer films. In addition, the buffer layer acts as a barrier to prevent substrate elements) from migrating to the surface of the intermediate layer and forming oxides during the initial growth of the epitaxial layer. Absent such an intermediate layer, one or more elements in the substrate would be expected to form thermodynamically stable oxides) at the substrate surface which could significantly impede the deposition of epitaxial layers due to, for example, lack of texture in this oxide layer.
In some embodiments, the intermediate layer is transient in nature.
"Transient," as used herein, refers to an intermediate layer that is wholly or partly incorporated into or with the biaxially textured substrate following the initial nucleation and growth of the epitaxial film. Even under these circumstances, the intermediate layer and biaxially textured substrate remain distinct until the epitaxial nature of tl~e deposited film has been established. The use of transient intermediate layers may be preferred when the intermediate layer possesses some undesirable property, for example, the intermediate layer is magnetic, such as nickel.
Exemplary intermediate metal layers include nickel, gold, silver, palladium, and alloys thereof. Impurities or alloys may include alloys of nickel and/or copper.
Epitaxial films or layers deposited on an intermediate layer can include metal oxides, chalcogenides, halides, and nitrides. In preferred embodiments, the intermediate metal layer does not oxidize under epitaxial film deposition conditions.
Care should be taken that the deposited intermediate layer is not completely incorporated into or does not completely diffuse into the substrate before nucleation and growth of the initial buffer layer structure causes the epitaxial layer to be established. This means that after selecting the metal (or alloy) for proper attributes such as diffusion constant in the substrate alloy, thermodynamic stability against oxidation under practical epitaxial buffer layer growth conditions and lattice matching with the epitaxial layer, the thickness of the deposited metal layer has to be adapted to the epitaxial layer deposition conditions, in particular to temperature.
Deposition of the intermediate metal layer can be done in a vacuum process such as evaporation or sputtering, or by electro-chemical means such as electroplating (with or without electrodes). These deposited intermediate metal layers may or may not be epitaxial after deposition (depending on substrate temperature during deposition), but epitaxial orientation can subsequently be obtained during a post-deposition heat treatment.
In certain embodiments, the formation of oxide buffer layers can be carried out so as to promote wetting of an underlying substrate layer. Additionally, in particular embodiments, the formation of metal oxide layers can be carried out using metal alkoxide precursors (for example, "sol gel" precursors), in which the level of carbon contamination can be greatly reduced over other known processes using metal alkoxide precursors.
In certain embodiments, solution coating processes can be used for deposition of one or a combination of any of the oxide layers on textured substrates;
however, they can be particularly applicable for deposition of the initial (seed) layer on a textured metal substrate. The role of the seed layer is to provide 1) protection of the substrate from oxidation during deposition of the next oxide layer when carried out in an oxidizing atmosphere relative to the substrate (for example, magnetron sputter deposition of yttria-stabilized zirconia from an oxide target); and 2) an epitaxial template for growth of subsequent oxide layers. In order to meet these requirements, to the seed layer should grow epitaxially aver the entire surface of the metal substrate and be free of any contaminants that may interfere with the deposition of subsequent epitaxial oxide layers.
The formation of oxide buffer layers can be carried out so as to promote wetting of an underlying substrate layer. Additionally, in particular embodiments, the formation of metal oxide layers can be carried out using metal alkoxide precursors (for example, "sol gel" precursors), in which the level of carbon contamination can be greatly reduced over other known processes using metal alkoxide precursors.
This heating step can be carried out after, or concurrently with, the drying of excess solvent from the sol gel precursor film. It must be carried out prior to decomposition of the precursor film, however.
The carbon contamination accompanying conventional oxide film preparation in a reducing environment (e.g., 4%HZ-Ar) is believed to be the result of an incomplete removal of the organic components of the precursor film. The presence of carbon-containing contaminants CXHy and CaHbO~ in or near the oxide layer can be detrimental, since they can alter the epitaxial deposition of subsequent oxide layers.
Additionally, it is likely that the trapped carbon-containing contaminants buried in the film can be oxidized during the processing steps for subsequent oxide layers, which can utilize oxidizing atmospheres. The oxidation of the carbon-containing contaminants can result in COz formation, and the subsequent blistering of the film, and possible delamination of the film, or other defects in the composite structure.
Thus, it is undesirable to allow carbon-containing contaminants arising from metal alkoxide decomposition to become oxidized only after the oxide layer is formed.
Preferably, the carbon-containing contaminants are oxidized (and hence removed from the film structure as COZ) as the decomposition occurs. Also the presence of carbon-containing species on or near film surfaces can inhibit the epitaxial growth of subsequent oxide layers.
According to particular embodiments, after coating a metal substrate or buffer layer, the precursor solution can be air dried, and then heated in an initial decomposition step. Alternatively, the precursor solution can be directly heated in an initial decomposition step, under an atmosphere that is reducing relative to the metal substrate. Once the oxide layer initially nucleates on the metal substrate in the desired epitaxial orientation, the oxygen level of the process gas is increased, for example, by adding water vapor or oxygen. The nucleation step requires from about 5 minutes to about 30 minutes to take place under typical conditions.
These methods are described in U.S. Patent Application Serial No.
filed on even date herewith, and entitled "Enhanced Purity Oxide Layer Formation," which is hereby incorporated by reference.
In certain embodiments, an epitaxial buffer layer can be formed using a low vacuum vapor deposition process (e.g., a process performed at a pressure of at least about 1x10-3 Torr). The process can include forming the epitaxial layer using a relatively high velocity and/or focused gas beam of buffer layer material.
The buffer layer material in the gas beam can have a velocity of greater than about one meter per second (e.g., greater than about 10 meters per second or greater than about 100 meters per second). At least about 50% of the buffer layer material in the beam can be incident on the target surface (e.g., at least about 75% of the buffer layer material in the beam can be incident on the target surface, or at least about 90%
of the buffer layer material in the beam can be incident on the target surface).
The method can include placing a target surface (e.g., a substrate surface or a buffer layer surface) in a low vacuum environment, and heating the target surface to a temperature which is greater than the threshold temperature for forming an epitaxial layer of the desired material on the target surface in a high vacuum environment (e.g., less than about 1x10-3 Torr, such as less than about 1x10 Ton) under otherwise identical conditions. A gas beam containing the buffer layer material and optionally an inert carrier gas is directed at the target surface at a velocity of at least about one meter per second. A conditioning gas is provided in the low vacuum environment.
The conditioning gas can be contained in the gas beam, or the conditioning gas can be introduced into the low vacuum environment in a different manner (e.g., leaked into the environment). The conditioning gas can react with species (e.g., contaminants) present at the target surface to remove the species, which can promote the nucleation of the epitaxial buffer layer.
The epitaxial buffer layer can be grown on a target surface using a low vacuum (e.g., at least about 1x10-3 Torr, at least about 0.1 Ton, or at least about 1 Torr) at a surface temperature below the temperature used to grow the epitaxial layer using physical vapor deposition at a high vacuum (e.g., at most about 1x10' Torr).
The temperature of the target surface can be, for example, from about 25°C to about 800°C (e.g., from about 500°C to about 800°C, or from about 500°C to about 650°C).
The epitaxial layer can be grown at a relatively fast rate, such as, for example, at least about 50 Angstroms per second.
These methods are described in U.S. Patent No. 6,027,564, issued February 22, 2000, and entitled "Low Vacuum Process for Producing Epitaxial Layers;"
U.S.
Patent No. 6,022, 832, issued February 8, 2000, and entitled "Low Vacuum Process for Producing Superconductor Articles with Epitaxial Layers;" and/or commonly owned U.S. Patent Application No. 09/007,372, filed January 15, 1998, and entitled "Low Vacuum Process for Producing Epitaxial Layers of Semiconductor Material,"
all of which are hereby incorporated by reference.
In some embodiments, a buffer layer can be formed using ion beam assisted deposition (IBAD). In this technique, a buffer layer material is evaporated using, for example, electron beam evaporation, sputtering deposition, or pulsed laser deposition while an ion beam (e.g., an argon ion beam) is directed at a smooth amorphous surface of a substrate onto which the evaporated buffer layer material is deposited.
For example, the buffer layer can be formed by ion beam assisted deposition by evaporating a buffer layer material having a rock-salt like structure (e.g., a material having a rock salt structure, such as an oxide, including MgO, or a nitride) onto a smooth, amorphous surface (e.g., a surface having a root mean square roughness of less than about 100 Angstroms) of a substrate so that the buffer layer material has a surface with substantial alignment (e.g., about 13° or less), both in-plane and out-of plane.

WO 01/08233 PCT/tJS00/19345 The conditions used during deposition of the buffer layer material can include, for example, a substrate temperature of from about 0°C to about 400°C (e.g., from about room temperature to about 400°C), a deposition rate of from about 1.0 Angstrom per second to about 4.4 Angstroms per second, an ion energy of from about 200 eV to about 1200 eV, and/or an ion flux of from about 110 microamperes per square centimeter to about 120 microamperes per square centimeter.
In some embodiments, the substrate is formed of a material having a polycrystal line, non-amorphous base structure (e.g., a metal alloy, such as a nickel alloy) with a smooth amorphous surface formed of a different material (e.g., Si3N4).
In certain embodiments, a plurality of buffer layers can be deposited by epitaxial growth on an original IBAD surface. Each buffer layer can have substantial alignment (e.g., about 13° or less), both in-plane and out-of plane.
These methods are described in PCT Publication No. WO 99/25908, published on May 27, 1999, and entitled "Thin Films Having A Rock-Salt-Like Structure Deposited on Amorphous Surfaces," which is hereby incorporated by reference.
In some embodiments, an epitaxial buffer layer can be deposited by sputtering from a metal or metal oxide target at a high throughput. Heating of the substrate can be accomplished by resistive heating or bias and electric potential to obtain an epitaxial morphology. A deposition dwell may be used to form an oxide epitaxial film from a metal or metal oxide target.
The oxide layer typically present on substrates can be removed by exposure of the substrate surface to energetic ions within a reducing environment, also known as Ion Beam etching. Ion Beam etching can be used to clean the substrate prior to film deposition, by removing residual oxide or impurities from the substrate, and producing an essentially oxide-free preferably biaxially textured substrate surface.
This improves the contact between the substrate and subsequently deposited material.
Energetic ions can be produced by various ion guns, for example, which accelerate ions such as Ar+ toward a substrate surface. Preferably, gridded ion sources with beam voltages greater than 150 ev are utilized. Alternatively, a plasma can be established in a region near the substrate surface. Within this region, ions chemically interact with a substrate surface to remove material from that surface, including metal oxides, to produce substantially oxide-free metal surface.
Another method to remove oxide layers from a substrate is to electrically bias the substrate. If the substrate tape or wire is made negative with respect to the anode potential, it will be subjected to a steady bombardment by ions from the gas prior to the deposition (if the target is shuttered) or during the entire film deposition. This ion bombardment can clean the wire or tape surface of absorbed gases that might otherwise he incorporated in the film and also heat the substrate to elevated deposition temperatures. Such ion bombardment can be further advantageous by improving the density or smoothness of the epitaxial film.
Upon formation of an appropriately textured, substantially oxide-free substrate surface, deposition of a buffer layer can begin. One or more buffer layers, each including a single metal or oxide layer, can be used. In some preferred embodiments, the substrate is allowed to pass through an apparatus adapted to carry out steps of the deposition method of these embodiments. For example, if the substrate is in the form of a wire or tape, the substrate can be passed linearly from a payout reel to a take-up reel, and steps can be performed on the substrate as it passes between the reels.
According to some embodiments, substrate materials are heated to elevated temperatures which are less than about 90% of the melting point of the substrate material but greater than the threshold temperature for forming an epitaxial layer of the desired material on the substrate material in a vacuum environment at the predetermined deposition rate. In order to form the appropriate buffer layer crystal structure and buffer layer smoothness, high substrate temperatures are generally preferred. Typical lower limit temperatures for the growth of oxide layers on metal are approximately 200°C to 800°C, preferably 500°C to 800°C, and more preferably, 650°C to 8U0°C. Various well-known methods such as radiative heating, convection heating, and conduction heating are suitable for short (2 cm to 10 cm) lengths of substrate, but for longer (lm to 100 m) lengths, these techniques may not be well suited. Also to obtain desired high throughput rates in a manufacturing process, the substrate wire or tape must be moving or transferring between deposition stations during the process. According to particular embodiments, the substrates are heated by resistive heating, that is, by passing a current through the metal substrate, which is easily scaleable to long length manufacturing processes. This approach works well while instantaneously allowing for rapid travel between these zones.
Temperature control can be accomplished by using optical pyrometers and closed loop feedback systems to control the power supplied to the substrate being heated. Current can be supplied to the substrate by electrodes which contact the substrate in at least two different segments of the substrate. For example, if the substrate, in the form of a tape or wire, is passed between reels, the reels themselves could act as electrodes.
Alternatively, if guides are employed to transfer the substrate between reels, the guides could act as electrodes. The electrodes could also be completely independent of any guides or reels as well. In some preferred embodiments, current is applied to the tape beaween current wheels.
In order that the deposition is carried out on tape that is at the appropriate temperature, the metal or oxide material that is deposited onto the tape is desirably deposited in a region between the current wheels. Because the current wheels can be efficient heat sinks and can thus cool the tape in regions proximate to the wheels, material is desirably not deposited in regions proximate to the wheels. In the case of sputtering, the charged material deposited onto the tape is desirably not influenced by other charged surfaces or materials proximate to the sputter flux path. For this reason, the sputter chamber is preferably configured to place components and surfaces which could influence or deflect the sputter flux, including chamber walls, and other deposition elements, in locations distant from the deposition zone so that they do not alter the desired deposition of metal or metal oxide in regions of the tape at the proper deposition temperature.
More details are provided in commonly owned United States Patent Application Serial No. 09/500,701, filed on February 9, 2000, and entitled "Oxide Layer Method," and commonly owned United States Patent Application Serial No.
filed on even date herewith, and entitled "Oxide Layer Method," both of which are hereby incorporated by reference in their entirety.
In p referred embodiments, three buffer layers are used. A layer of Y203 or Ce02 (e.g.. from about 20 nanometers to about SO nanometers thick) is deposited (e.g., using electron beam evaporation) onto the substrate surface. A layer of YSZ
(e.g., from about 0.2 micron to about 1 micron thick, such as about 0.5 micron thick) is deposited onto the surface of the Y203 or CeOz layer using sputtering (e.g, using magnetron sputtering). A Ce02 layer (e.g., about 20 manometers thick) is deposited (e.g, using ,magnetron sputttering) onto the YSZ surface. The surface of one or more of these layers can be chemically andlor thermally conditioned as described herein.
In certain embodiments, the underlying layer (e.g., a buffer layer or a different superconductor layer) can be conditioned (e.g., thermally conditioned and/or chemically conditioned) so that the superconductor layer is formed on a conditioned surface. The conditioned surface of the underlying layer can be biaxially textured (e.g., (113)[211]) or cube textured (e.g., (100)[011] or (100)[011]), have peaks in an X-ray diffraction pole figure that have a full width at half maximum of less than about 20° (e.g., less than about 15°, less than about 10°, or from about 5° to about 10°), be smoother than before conditioning as determined by high resolution scanning electron microscopy or atomic force microscopy, have a relatively high density, have a relatively low density of impurities, exhibit enhanced adhesion to other material layers (e.g., a superconductor layer or a buffer layer) and/or exhibit a relatively small rocking curve width as measured by x-ray diffraction.
"Chemical conditioning" as used herein refers to a process which uses one or more chemical species (e.g., gas phase chemical species and/or solution phase chemical species) to affect changes in the surface of a material layer, such as a buffer layer or a superconductor material layer, so that the resulting surface exhibits one or more of the above noted properties.
"Thermal conditioning" as used herein refers to a process which uses elevated temperature with or without chemical conditioning to affect changes in the surface of a material layer, such as a buffer layer or a superconductor material layer, so that the resulting surface exhibits one or more of the above noted properties.
Preferably, thermal conditioning occurs in a controlled environment (e.g., controlled gas pressure, controlled alas environment and/or controlled temperature).

Thermal conditioning can include heating the surface of the underlying layer to a temperature at least about 5°C above the deposition temperature or the crystallization temperature of the underlying layer (e.g., from about 15°C to about 500°C above the deposition temperature or the crystallization temperature of the underlying layer, from about 75°C to about 300°C above the deposition temperature or the crystallization temperature of the underlying layer, or from about 150°C to about 300°C above the deposition temperature or the crystallization temperature of the underlying layer). Examples of such temperatures are from about 500°C to about 1200°C (e.~., From about 800°C to about 1050°C). Thermal conditioning can be performed under a variety of pressure conditions, such as above atmospheric pressure, below atmospheric pressure, or at atmospheric pressure. Thermal conditioning can also be pert ormed using a variety of gas environments (e.g., an oxidizing gas environment, a reducing gas environment, or an inert gas environment).
"Deposition temperature" as used herein refers to the temperature at which the layer being conditioned was deposited.
"Crystallization temperature" as used herein refers to the temperature at which a layer of material (e.g., the underlying layer) takes on a crystalline form.
Chemical conditioning can include vacuum techniques (e.g., reactive ion etching, plasma etching and/or etching with fluorine compounds, such as BF3 and/or CF4). Chemical conditioning techniques are disclosed, for example, in Silicon Processing for the VLSI Era, Vol. 1, eds. S. Wolf and R.N. Tanber, pp. 539-574, Lattice Press, Sunset Park, CA, 1986.
Alternatively or additionally, chemical conditioning can involve solution phase techniques, such as disclosed in Metallurgy and Metallurgical Engineering Series, 3d ed., George L. Kehl, McGraw-Hill, 1949. Such techniques can include contacting the surface of the underlying layer with a relatively mild acid solution (e.g., an acid solution containing less about 10 percent acid, less than about two percent acid, or less than about one percent acid). Examples of mild acid solutions include perchloric acid, nitric acid, hydrofluoric acid, hydrochloric acid, acetic acid and buffered acid solutions. In one embodiment, the mild acid solution is about one percent aqueous nitric acid. In certain embodiments, bromide-containing and/or bromine-containing compositions (e.g., a liquid bromine solution) can be used to condition the surface of a buffer layer or a superconductor layer.
This method can be used to form multiple buffer layers (e.g., two, three, four, or more buffer layers), with one or more of the buffer layers having a conditioned surface.
The method can also be used to form multiple superconductor layers, with one or more of the superconductor layers having a conditioned surface. For example, a superconductor layer can be formed and then thermally and/or chemically conditioned as described above. An additional superconductor layer can then be formed on the conditioned surface of the first superconductor layer. This process can be repeated as many times as desired.
These methods are described in commonly owned U.S. Provisional Patent Application No. 60/166, 140, filed November 18, 1999, and entitled "Mufti-Layer Articles and Methods of Making Same," and commonly owned U.S. Patent Application Serial No. , filed on even date herewith, and entitled "Mufti-layer Articles anct Methods of Making Same," both of which are hereby incorporated by reference.
In certain embodiments, the superconductor layer can be formed from a precursor composition that has a relatively small amount of free acid. In aqueous solutions, this can correspond to a precursor composition with a relatively neutral pH
(e.g., neither strongly acidic nor strongly basic). The precursor composition can be used to prepare mufti-layer superconductors using a wide variety of materials which can be uscc: as the underlying layer on which the superconductor layer is formed.
The total free acid concentration of the precursor composition can be less than about 1x10-- molar (e.g., less than about 1x10-5 molar or about 1x10-7 molar).
Examples of free acids that can be contained in a precursor composition include trifluoroacctic acid, acetic acid, nitric acid, sulfuric acid, acids of iodides, acids of bromides and acids of sulfates.

When the precursor composition contains water, the precursor composition can have a pH of at least about 3 (e.g., at least about 5 or about 7).
In some embodiments, the precursor composition can have a relatively low water content (e.g., less than about 50 volume percent water, less than about volume percent water, less than about 25 volume percent water).
In embodiments in which the precursor composition contains trifluoroacetic acid and an alkaline earth metal (e.g., barium), the total amount of trifluoroacetic acid can be selected so that the mole ratio of fluorine contained in the precursor composition (e.g., in the form of trifluoroacetate) to the alkaline earth metal (e.g., barium ions) contained in the precursor composition is at least about 2:1 (e.g., from about 2:1 to about 18.5:1, or from about 2:1 to about 10:1).
Superconducting articles formed from such precursor compositions can include more than one superconductor layer (e.g., two superconductor layers disposed on each other). The combined thickness of the superconductor layers can be at least about one ~;ncron (e.g., at least about two microns, at least about three microns, at least about lour microns, at least about five microns, or at least about six microns).
The combined critical current density of the superconductor layers can be at least about SxlO, .Amperes per square centimeter (e.g., at least about 1x106 Amperes per square centimeter, or at least about 2x106 Amperes per square centimeter).
In general, the precursor compositions can be prepared by combining soluble compounds of a first metal (e.g., copper), a second metal (e.g., an alkaline earth metal), and a rare earth metal with one or more desired solvents and optionally water.
As used herein, "soluble compounds" of the first, second and rare earth metals refer to compounds of these metals that are capable of dissolving in the solvents) contained in the precursor compositions. Such compounds include, for example, salts (e.g., nitrates, acetates, alkoxides, iodides, sulfates and trifluoroacetates), oxides and hydroxides of these metals.
These methods and composition s are described in commonly owned U.S.
Provisional Patent Application Serial No. 60/166, 297, filed on November 18, 1999, and entitled "Superconductor Articles and Compositions and Methods for Making Same," and commonly owned U.S. Patent Application No. , filed on even date herewith, and entitled "Superconductor Articles and Compositions and Methods for Making Same," both of which are hereby incorporated by reference.
In certain embodiments, a precursor solution is formed of an organic solution containing metal trifluoroacetates prepared from powders of BaC03, YC03~3H20 and Cu(OH)2CU; combined and reacted using methods known to those skilled in the art.
For example, the powders can be combined in a 2:1:3 ratio with between 20-30%
(5.5-6.0 M 1 excess trifluoroacetic acid in methyl alcohol and then refluxed (e.g., for approximau~lv four to ten hours) to produce a solution substantially 0.94 M
based on copper content.
The precursor solution is then applied to a surface (e.g., a buffer layer surface), such as by spin coating or other techniques known to those skilled in the art.
After application to the surface (e.g, the buffer layer surface), the precursor solution is heat treated. Generally, the solution is heated at a rate of from about 0.5°C
per minute to about 10°C per minute in moist oxygen (e.g., having a dew point in the range of from about 20°C to about 75°C) to a temperature in the range of from about 300°C to about S00°C. The coating is then heated for about one hour to a temperature of less than about 860°C (e.g., less than about 810°C) in a moist reducing nitrogen-oxygen gas mixture (e.g., having a composition including from about 0.5% to about 5% oxygen ~. Optionally, the coating can be further heated to a temperature of from about 860°C to about 950°C for from about five to about 25 minutes. The coating is subsequently heated to a temperature of from about 400°C to about 500°C for at least about eight hours at in dry oxygen. The coating can then be cooled to room temperature in static dry oxygen.
These methods are described in U.S. Patent No. 5,231,074, issued on July 27, 1993, and entitled "Preparation of Highly Textured Oxide Superconducting Films from MOD Precursor Solutions," which is hereby incorporated by reference.
In ~,::~me embodiments, a metal oxyfluoride is deposited using one or more standard te~:hniques, such as metalorganic solution deposition, metalorganic chemical vapor deposition, reactive evaporation, plasma spray, molecular beam epitaxy, laser ablation, ion beam sputtering, electron beam evaporation, depositing a metal trifluoroacetate coating and decomposing the coating as described herein.
Multiple layers of metal oxyfluoride may be deposited.
Other constituent metallic elements of the desired oxide superconductor are also deposited in substantially stoichiometric proportions.
The metal oxyfluoride is converted into an oxide superconductor at a rate of conversion selected by adjusting temperature, vapor pressure of gaseous water or both. For example, the metal oxyfluoride can be converted in a processing gas having a moisture content of less than 100% relative humidity (e.g., less than about 95%
relative humidity, less than about 50% relative humidity, or less than about 3%
relative hum idity) at 25°C to form some oxide superconductor, then completing the conversion using a processing gas having a higher moisture content (e.g., from about 95% relative humidity to about 100% relative humidity at 25°C). The temperature for converting the metal oxyfluoride can be in the range of from about 700°C to about 900°C (e.g., from about 700°C to about 835°C). The processing gas preferably contains from about 1 volume percent oxygen gas to about 10 volume percent oxygen gas.
These methods are described in PCT Publication No. WO 98/58415, published on December 23, 1998, and entitled "Controlled Conversion of Metal Oxyfluorides into Superconducting Oxides," which is hereby incorporated by reference.
In certain embodiments, the preparation of the superconductor layer includes using a precursor composition containing a trifluoroacetate salt of one or more metals and a controlled total water content (e.g., controlled content of liquid water in the precursor composition and controlled content of water vapor in the surrounding environment) present when treating the precursor composition to form an intermediate of the superconductor layer (e.g., a metal oxyfluoride intermediate of the superconductor layer). For example, the precursor composition can have a relatively low water content (e.g., less than about 50 volume percent water, less than about 35 volume percent water, or less than about 25 volume percent water) and/or a relatively high solids content, whereas the surrounding gas environment can have a relatively high vapor pressure of water (e.g., from about 5 Torr to about SO Torr water, from about 5 Torn to about 30 Torr water, or from about 10 Torr to about 25 Torr water).
The superc~:~nductor layer intermediate (e.g., metal oxyfluoride intermediate) can be formed in a relatively short period of time (e.g., less than about five hours, less than about three Fours, or less than about one hour).
Trecning the precursor composition can include heating the precursor composition from an initial temperature (e.g., room temperature) to a temperature of from about 190°C to about 215°C (e.g., about 210°C) at a rate of at least about 5°C
per minute ~ ~.~., at least about 8°C per minute, or at least about 10°C per minute) in a water vapor pressure of from about 5 Torr to about 50 Torr water vapor (e.g., from about 5 To.-r to about 30 Torr water vapor, or from about 10 Torr to about 25 Torr water vapor; . The nominal partial pressure of oxygen can be, for example, from about 0.1 7-orr to about 760 Torr.
Herring is then continued to a temperature of from about 220°C to about 290°C (e.y.. about 220°C) at a rate of from about 0.05°C
per minute to about 0.4°C
per minute ~ e.g., from about 0.1 °C per minute to about 0.4°C
per minute) in a water vapor pressure of from about 5 Torr to about SO Torr water vapor (e.g., from about 5 Ton to about 30 Torr water vapor, or from about 10 Torr to about 25 Torr water vapor). The nominal partial pressure of oxygen can be, for example, from about 0.1 Torr to about 760 Torr.
This is followed by heating to about 400°C at a rate of at least about 2°C per minute (e.~~.. at least about 3°C per minute, or at least about 5°C per minute) in a water vapor pressure of from about 5 Torr to about 50 Torr water vapor (e.g., from about S Torr to about 30 Torr water vapor, or from about 10 Torr to about 25 Torr water vapor) to form an intermediate of the superconductor material (e.g., a metal oxyfi~aoriW~ intermediate). The nominal partial pressure of oxygen can be, for example, from about 0.1 Torr to about 760 Torr.
The intermediate can be heated to form the desired superconductor layer. For example, tl~c intermediate can be heated to a temperature of from about 700°C to about 825 '~:_' i n an environment containing from about 0.1 Torr to about 50 Torr oxygen anti i-rom about 0.1 Torr to about 150 Torr water vapor (e.g., about 12 Torr water vapor i with the balance being, for example, nitrogen and/or argon.
The ;nethod can result in a well-ordered superconductor layer (e.g., biaxially textured or cube textured) having a relatively high critical current density (e.g., at least about W 1 OS Amperes per square centimeter).
These methods are described in commonly owned U.S. Provisional Patent Application Serial No. 60/166,145, filed on November 18, 1999, and entitled "Methods <<; .c1 Compositions for Making a Multi-Layer Article," and commonly owned U.S. Patent Application No. , filed on even date herewith, and entitled "M cthods and Compositions for Making a Multi-layer Article," both of which are hereby ;ncoiporated by reference.
In certain embodiments, a metal oxyfluoride intermediate of a superconductor material can be prepared using a process that involves relatively few temperature ramps (e.g.. less than three ramps, such as two ramps).
Alternatively or additionally, forming the metal oxyfluoride can include one or more steps i n which the temperature is held substantially constant (e.g., constant within abou; 10°C, within about 5°C, within about 2°C, within about 1°C) for a relatively lcmy~ period of time (e.g., more than about one minute, more than about five minutes, more than about 30 minutes, more than about an hour, more than about two hours, more than about four hours) after a first temperature ramp to a temperature greater than about room temperature (e.g., at least about 50°C, at least about 100°C, at least about ?00°C, at least about 215°C, from about 215°C
to about 225°C, about 220°C).
Formation of the metal oxyfluoride intermediate can involve using more than one gas environment (e.g., a gas environment having a relatively high water vapor pressure an;i a gas environment having a relatively low water vapor pressure) while maintaining the temperature substantially constant (e.g., constant within about 10°C, within abou: ~°C, within about 2°C, within about 1°C) for a relatively long period of time (e.g., more than about one minute, more than about five minutes, more than about 30 m;~wntes, more than about an hour, more than about two hours, more than about four hours). As an example, in a high water vapor pressure environment, the water vapor pressure can be from about 17 Ton to about 40 Torr (e.g., from about 25 Torr to about 38 Torr, such as about 32 Torr). A low water vapor pressure environmem can have a water vapor pressure of less than about 1 Ton (e.g., less than S about 0.1 T~~rr, less than about 10 milliTorr, about five milliTorr).
Generally, the metal oxyfluoride is formed by disposing a composition (e.g., a precursor solution) on a surface (e.g., a substrate surface, a buffer layer surface or a supercunciu; for layer surface) and heating the composition. The methods of disposing the composiion on the surface include spin coating, dip coating, web coating and other techn::ues known in the art.
Tyl~cally, in an initial decomposition step, the initial temperature in this step is about roo m temperature, and the final temperature is from about 215 ~ C to about 225°C usin~~ a temperature ramp of 100C per minute or less. During this step, the partial pressure of water vapor in the nominal gas environment is preferably maintained at from about 17 Torr to about 40 Ton. The partial pressure of oxygen in the nominal Jas environment can be maintained at from about 0.1 Ton to about Torr. The mmperature and nominal gas environment are then held substantially constant for a relatively long period of time.
After this time period, the gas environment is changed to a relatively dry gas environment (e.g., less than about one Torr water vapor, less than about 0.1 Torr water vapor. less than about 10 milliTorr water vapor, five milliTorr water vapor) while maintaining the temperature substantially constant. The temperature and nominal gay: environment are then held substantially constant for a relatively long period oftimc.
Afmr this time period, the nominal gas environment is maintained substantial ) v- constant and heating is continued to a temperature sufficient to form the metal oxyfluoride intermediate (e.g., about 4000C). This step is preferably performed using a temperature ramp of 100C per minute or less.
The metal oxyfluoride intermediate can then be heated to form the desired supercondumor layer. Typically, this step is performed by heating to a temperature of from about ; 00 ~ C to about 825 ~ C. During this step, the nominal gas environment typically c~,v contain from about 0.1 Torr to about 50 Ton oxygen and from about 0.1 Ton to abo ~u 150 Torr (e.g., about 12 Torr) of water vapor with the balance being nitrogen an~i~or argon. Preferably, the metal oxyfluoride intermediate has a relatively low defect ~ic,nsity.
Thc::c methods are described in commonly owned U.S. Patent Application Serial No. , filed on even date herewith, and entitled "Methods of Making A
Superconductor," which is hereby incorporated by reference.
In c.wuain embodiments, the superconducting layer can be formed from solid-state, or sci-:i solid state, precursor materials deposited in the form of a dispersion.
These prec~,:rsor compositions allow for example the substantial elimination of BaC03 formation i., final YBCO superconducting layers, while also allowing control of film nucleation and growth.
Two g eneral approaches are presented for the formulation of precursor compositions. In one approach, the cationic constituents of the precursor composition are provided in components taking on a solid form, either as elements, or preferably, compounded with other elements. The precursor composition is provided in the form of ultrafine particles which are dispersed so that they can be coated onto and adhere onto the surnace of a suitable substrate, intermediate-coated substrate, or buffer-coated substrate. ~I'hcse ultrafine particles can be created by aerosol spray, by evaporation or by similar icchniques which can be controlled to provide the chemical compositions and sizes drsired. The ultrafine particles are less than about 500 nm, preferably less than about ~ ~0 nm, more preferably less than about 100 nm and even more preferably less than about 50 nm. In general, the particles are less than about SO% the thickness of the desi r~~ ~: final film thickness, preferably less than about 30% most preferably less than about O~'~a of the thickness of the desired final film thickness. For example, the precursor c;~.oposition can comprise ultrafine particles of one or more of the constituent: of the superconducting layer in a substantially stoichiometric mixture, present in ~, carrier. This earner comprises a solvent, a plasticizer, a binder, a dispersant. ~.~r a similar system known in the art, to form a dispersion of such particles.
Each ultraiinc particle can contain a substantially compositionally uniform, homogeneous mixture of such constituents. For example, each particle can contain BaF2, and r;;l-c-earth oxide, and copper oxide or rare earth/barium/copper oxyfluoride in a substal II Tally stoichiometric mixture. Analysis of such particles would desirably reveal a rare-earth:barium:copper ratio as substantially 1:2:3 in stoichiometry, with a fluorine:bari um ratio of substantially 2:1 in stoichiometry. These particles can be either cryst., T I ire, or amorphous in form.
In a second approach, the precursor components can be prepared from elemental s~_~urces, or from a substantially stoichiometric compound comprising the desired cousiituents. For example, evaporation of a solid comprising a substantially StO1Ch10111c'LI-IC compound of desired REBCO constituents (for example, YBa2Cu30~_X) or a number of solids, each containing a particular constituent of the desired final supercondu~aing layer (for example, Y203, BaF2, Cu0) could be used to produce the ultrafine p~luicles for production of the precursor compositions.
Alternatively, spray drying or ae rosolization of a metalorganic solution comprising a substantially stoichiomclric mixture of desired REBCO constituents could be used to produce the ultrafine p~;wicles used in the precursor compositions. Alternatively, one or more of the cationic ~~onstituents can be provided in the precursor composition as a metalorgaoc salt or metalorganic compound, and can be present in solution. The metalorganic solution can act as a solvent, or earner, for the other solid-state elements or compoul ~~is. According to this embodiment, dispersants and/or binders can be substantiali~, eliminated from the precursor composition. For example, the precursor composition can comprise ultrafine particles of rare-earth oxide and copper oxide in substantial l ~, a 1:3 stoichiometric ratio, along with a solublized barium-containing salt, for ex~nnple, barium-trifluoroacetate dissolved in an organic solvent, such as methanol.
If t1 ~.~ superconducting layer is of the REBCO type, the precursor composition can contain a rare earth element, barium, and copper in the form of their oxides;
halides suci, as fluorides, chlorides, bromides and iodides; carboxylates and alcoholatcs. for example, acetates, including trihaloacetates such as trifluroracetates, formates, c, .elates, lactates, oxyfluorides, propylates, citrates, and acetylacetonates, and, chlor~ll~~ and nitrates. The precursor composition can include any combination of such ele~oents (rare earth element, barium, and copper) in their various forms, which can ~ onvert to an intermediate containing a barium halide, plus rare earth oxyfluorid~ and copper(oxyfluoride) without a separate decomposition step or with a decomposition step that is substantially shorter than that which may be required for precursors . n which all constituents are solubilized, and without substantial formation of BaCO;> :,pct which can subsequently be treated using high temperature reaction processes to yield an epitaxial REBCO f lm with T~ of no less than about 89K, and J
greater than about 500,000 A/cmz at a film thickness of 1 micron or greater.
For example, tcv ~~ YBa2Cu30~_x superconducting layer, the precursor composition could contain bar ~;m halide (for example, barium fluoride), yttrium oxide (for example, Y203), and popper oxide; or yttrium oxide, barium trifluoroacetate in a trifluoroacc:ateimethanol solution, and a mixture of copper oxide and copper trifluoroacctate in trifluoroacetate/methanol. Alternatively, the precursor composition could COlltalll Ba-trifluoroacetate, Y203, and CuO. Alternatively, the precursor composition could contain barium trifluoroacetate and yttrium trifluoroaeetate in methanol. and CuO. Alternatively, the precursor composition could contain BaF2 and yttrium ace;ate and CuO. In some preferred embodiments, barium-containing particles are present as BaF2 particles, or barium fluoroacetate. In some embodiments the precurs~;r could be substantially a solublized metalorganic salt containing some or all of the ca ~ i on constituents, provided at least a portion of one of the compounds containinyl ~~ltion constituents present in solid form. In certain embodiments, the precursor in a dispersion includes a binder and/or a dispersant and/or solvent(s).
The precursor compositions can be applied to substrate or buffer-treated substrates by a number of methods, which are designed to produce coatings of substantially homogeneous thickness. For example, the precursor compositions can be applied wing spin coating, slot coating, gravure coating, dip coating, tape casting, or sprayin'. The substrate is desirably uniformly coated to yield a superconducting film of from about 1 to 10 microns, preferably from about 1 to 5 microns, more preferably i rom about 2 to 4 microns.
More details are provided in commonly owned United States Patent Application serial No. 09/500,717, filed on February 9, 2000, and entitled "Coated Conductor ~'hiclc Film Precursor," which is hereby incorporated by reference in its entirety.
In particular embodiments, methods can be employed to minimize the formation o f undesirable a-axis oriented oxide layer grains, by inhibiting the formation o t~ the oxide layer until the required reaction conditions are attained.
Com. cntional processes developed for decomposition and reaction of fluoride-containing precursors use a constant, and low, non-turbulent flow of process gas that is introducca! into the decomposition furnace in an orientation that is parallel to the film surface. resulting in a stable boundary layer at the film/gas interface.
In the apparatus tv;~cs typically used for oxide layer precursor decomposition and reaction, the diffusio;a of gaseous reactants and products through this gas/film boundary layer appears to ~:~ntrol the overall reaction rates. In thin, small area films (for example, less than ah.~ut 0.4 microns thick and less than about a square centimeter), the diffusion o~~ HBO into the film and the diffusion of HF out of the film occur at rates such that tl~~;; formation of the YBaZCu307_X phase does not begin at any significant rate until the sample reaches the processing temperature. However, as the film thickness or area increases, the rates of gaseous diffusion into and out of the film decrease, al i other parameters being equal. This results in longer reaction times and/or incomplete formation of the YBa2Cu30~_X phase, resulting in reduced crystallo~~rapl~ic texture, lower density, and reduced critical current density. Thus, the overall rate of YBa2Cu30~_x phase formation is determined, to a significant extent, by the diffusion of gases tlu-ough the boundary layer at the film surface.
0m approach to eliminating these boundary layers is to produce a turbulent flow at the ! i Im surface. Under such conditions, the local gas composition at the interface is ;oaintained essentially the same as in the bulk gas (that is, the pH20 is constant, ar:,i the pHF is approximately zero). Thus, the concentration ofthe gaseous products/r cactants in the film is not controlled by the diffusion through the gas/film surface boundary layer condition, but rather by diffusion through the film. In order to minimize the nucleation of a-axis YBaZCu307_X oriented grains on a substrate surface, the formatia~n of the YBa~Cu307_X phase is inhibited until desired process conditions are reached. For example, the formation of the YBazCu30~_X phase can be inhibited until desire;i process temperature is reached.
In o; ~e embodiment, a combination of: 1) low (non-turbulent) process gas flow, so than a stable boundary layer is established at the film/gas interface, during the ramp to tenv ~;crature, and 2) high (turbulent) process gas flow, so that the boundary layer is disrupted at the film/gas interface, is employed. For example, in a three inch tube furnace. the flow can be from about 0.5 to about 2.0 L/min during the temperature ramp from ambient temperature to the desired process temperature.
Thereafter. ;he f7ow can be increased to a value of from about 4 to about 15 L/min during the i:me at which the film is being processed. Thus, the rate of formation of YBa2Cu30- .. and epitaxial texture formation can be increased at high temperature, while mini;-:;izing the amount ofunwanted a-axis nucleation and growth at low temperature during ramp up. According to these processes, a-axis nucleated grains are desirab i v present in an amount of less than about 1 %, as determined by scanning electronmi~aoscopy.
Mor:~ details are provided in commonly owned U.S. Patent Application Serial No. f i 1 ed on even date herewith, and entitled "Control of Oxide Layer Reaction Rates," which is hereby incorporated by reference.
Rel~urring now to Figs. 1A and 1B, a conductor 10 formed in accordance with the present . nvention is shown. Figure 1 shows this in the simplest configuration, where two ropes are bonded face to face. As described hereinbefore, each tape includes a suUstrate which can be a metal or alloy, and is preferably a nonmagnetic alloy; a bui~, cr layer which can include single or multiple layers formed of oxides, nitrides an~i or metals; and, the superconducting layer which is typically YBCO or alternativcl ~, with a rare earth substituted for the Y. An additional cap layer may be deposited. ~, i,ich is most preferably silver and could incorporate as an option an additional r;~rmal metal layer to provide thermal and electrical mass. This conductor can be bomi~d to the cap layer of another tape at mirror image using soldering, diffusion b~-riding or other similar processes.

Mop ~ specifically, conductor 10 is formed of two coated conductor tapes l la and l 1b ir; :. sandwich configuration. As shown in Figs. 1A and 1B, conductor l la includes su;strate 12a, buffer layer 14a, HTS layer 16a, and cap layer 18a.
Likewise, conductor ~ I b includes substrate 12b, buffer layer 14b, HTS layer 16b and cap layer 18b.
Co~:.uctors 11a and 11b can be formed using known processes, such as for example the IBAD, DeTex, epitaxial deposition processes as described above.
Preferably. ,ubstrates 12a and 12b are nonmagnetic and are formed using one of the above-desc;-ibed DeTex processes.
B a i ; ~ r layers 14a and 14b are preferably deposited epitaxially using one of the above-desc;~i bcd methods. Buffer layers 14a and 14b each may be formed of one or more layer: Exemplary buffer layer materials include, but are not limited to, Ce02, YSZ (yttria stabilized zirconia), Y203 and SrTi03.
Lave r 14 can be formed of any material capable of supporting layer 16. For example, l~;s er 14 can be formed of a buffer layer material. Examples of buffer layer materials in.- lode metals and metal oxides, such as silver, nickel, TbOX, GaOX, Ce02, yttria-stabi~;.cd zirconia (YSZ), Y203, LaAl03, SrTi03, LaNi03, Gd203, LaCu03, SrRu03, Iv ~i ~=,a0 ;, NdAl03 and nitrides as known in the art. A buffer material can be prepared u~in'T solution phase techniques, including metalorganic deposition, such as disclosed in.- for example, S.S. Shoup et al., J. Am. Cer. Soc., vol. 81, 3019; D. Beach et al., Mat. i:;a. Soc. Symp. Proc., vol. 495, 263 (1988); M. Paranthaman et al., Superconductor Sci. Tech., vol. 12, 319 (1999); D.J. Lee et al., Japanese J.
Appl.
Phys., vol. :'~S, L178 (1999) and M.W. Rupich et al., LE.E.E. Traps. on Appl.
Supercon. vol. 9, 1527.
H'T~ layers 16a and 16b are also preferably deposited epitaxially using one of the above-cicscribed methods. HTS layers 16a and 16b include any HTS material, for example, wurium-barium-copper-oxide superconductors (YBCO), bismuth-strontium-calcium-co;~per-oxide superconductors (BSCCO), and thallium based superconductors.

Can iavers 18a and 18b can each be formed of one or more layers as shown for example in :vii. 1B. Cap layers 18a and 18b preferably each include at least one noble metaiayer. "Noble metal", as used herein, is a metal whose reaction products are theremu;~iynamically unstable under the reaction conditions employed to prepare the HTS ta;>~. Exemplary noble metals include for example silver, gold, palladium and platniu~ ~.. Noble metals provide a low interfacial resistance between the HTS
layer and t1:.: cap layer. In addition, cap layers 18a and 18b can each include a second layer of normal metal (e.~. Cu or A1 or alloys of normal metals).
Th~~ ,ndividual conductors 1 la and l 1b are then joined at the respective layers using one ~:: a variety of methods. For example, and while not to be construed as limiting, e:: _~mplary joining techniques include soldering and diffusion bonding. An exemplary ,>lder embodiment is shown in shown in Figs. 1A and 1B, with the resulting sr!~ier layer between the cap layers 18a and 18b being illustrated as reference numeral 20 (or the interface in the case of diffusion bonding).
Alternatively, if no cap layers are used, an intervening layer, preferably metallic, may be bonded to the two HTS layers.
Re i ~ wing now to Figs. 2A and 2B, an alternative embodiment of the invention is illustrate;!. In this embodiment, conductor 10' includes conductors l la and l 1b are offset (i.e. :;«t registered at their respective edges as shown in the figures). The offset configurati~.,n shown in this embodiment may be preferable in some circumstances because it allows for direct current transfer into the superconducting filament or layers 16a and 1 c>i ~. for example, at splices and terminations, from the broad surface of the cap layers i ~a and l 8b, respectively, as compared to transfer from the edges of the supercond~~~:iin~ layers 1Ga and 16b.
Fi'~. ~C depicts another alternative embodiment in accordance with the present invention. '. n Fig. 2C, the benefits of the offset configuration as shown in Figs. 2A
and 2B are ~, urther extended to provide current transfer to the substrates 12a and 12b by extension ofthe cap layers 18a and 18b respectively along the edges ofthe individual ~:~pes 11 a and 1 1b, respectively. This provides additional stability to the conductor '-:. nllow~ing alternate current paths and heat transfer to the substrates and subsequena~ ~ to the cryo<ven in which the conductor 10" is immersed or exposed.

Fi ~~: . 3:~ and 3B illustrate another alternative embodiment of the invention.
Figs. 3A a~, _; ~ c3 depict a conductor 20 in which each of the superconducting layers 16a and l c~: ~ are divided into a plurality of narrower filaments 17a and 17b, respectivel_, . It will be appreciated that the filament widths in each of layers 16a and 16b need n-:~t be of equal dimension within each layer. Nor is it necessary that the width of t1;: f-ilaments in the opposing layers be of equal width. The filaments are separated l rc~m one another by regions 30 which can be for example normal (i.e. non-supercondu~::tinj) regions in the superconducting layers or normal (e.g. non-supercondu.~~in~J) metal inserted between the narrower filaments.
In ~:. ~ case of normal regions in the superconducting layers, the layers in region 30 w, ~~uld then formed of the same material as the HTS layer but treated by for example ie~:: bombardment to suppress superconductivity. This can be accomplished for exampi-~ ion bombardment prior to deposition of the cap layers 18a and 18b.
Alternativc.~.-, ion bombardment can be used following cap layer deposition.
In ,';c case of normal metal inserted in regions 30, the material from the supercondt;.'llll~ layer can be removed from region 30 prior to cap layer deposition and the cah layer material can be inserted therefor. This is typically done simultaneously with the cap layer deposition. It will be appreciated that some or all of the width o n reunions 30 can be varied (independent of one another) to increase the volume of :,~e normal metal alternative current paths.
prc.:ra;bly, the f laments in the opposing layers with be offset with respect to one anothc, . thereby providing current sharing between multiple filaments.
This can be implen~~, rated within each layer and/or opposing layers.
Fiy~,. 3.A and 3B further show edge layers 32 which may be formed of cap layer materials as described hereinabove. This is similar to the extension of the cap layers 18a :;od 18b discussed in connection with Fig. 2C. As discussed above, this provides a~.iitional stability to the conductor by allowing alternate current paths and heat transfer to the substrates and subsequently to the cryogen in which the conductor 10" is immersed or exposed.

Fiy. 4A and 4B illustrate yet another embodiment of the invention. In this embodime;,~. an additional stabilizer 70 is included along with cap layers 18a and 18b. This :.;lows a cost effective alternative in siutations where additional stabilizer may be de~;,rable or necessary. For example, stabilizer 70 can be formed of copper, aluminum :.r the like.
It i:, :mticipated that practical conductors can be produced by laminating two individual ropes face-to-face such that a conductive metal layer 18 is disposed between th~ superconducting filaments with the buffer layer and substrate on the outside of :~;~ stack up.
In 5,.~n~e embodiments, coated conductors can be fabricated in a way that minimizes :;asses incun-ed in alternating current applications. The conductors are fabricated v~ ith multiple conducting paths, each of which comprises path segments which extend across at least two conducting layers, and further extend between these layers.
Eac'n superconducting layer has a plurality of conductive path segments extending <<~ ross the width of the layer, from one edge to another, and the path segments aiso have a component of direction along the length of the superconducting layer. The oath segments in the superconducting layer surface are in electrically conductive ~~ommunication with interlayer connections, which serve to allow current to flow fi-on~ one superconducting layer to another. Paths, which are made up ofpath segments, are periodically designed, so that current flow generally alternates between two supercunducting layers in bilayered embodiments, and traverses the layers through imerlayer connections.
Sulo~rconducting layers can be constructed to contain a plurality of path segments v rich extend both across their widths and along their lengths. For example, supercondu~eing layers can be patterned so as to achieve a high resistivity or a fully insulating !surricr between each of the plurality of path segments. For example, a regular peri~>dic array of diagonal path segments can be imposed on the layer along the full lens h of the tape. Patterning of superconducting layers to give such arrays can be acc~ ~ n1 Iished by a variety of means known to those skilled in the art, including for examp(~=~, laser scribing, mechanical cutting, implantation, localized chemical treatment t ~ v ro a ~~h a mask, and other known methods. Further, the superconducting layers are :;~iapted to allow the conductive path segments in their surfaces to electrically :communicate with conducting interlayer connections passing between the layers, at o ~ near their edges. The interlayer connections will typically be normally conducting not superconducting) but in special configurations could also be superconducting. Interlayer connections provide electrical communication between supercondu~tin~~ layers which are separated by non-conducting or highly resistive material va~i.ch is positioned between the superconducting layers. Such non-conducting _~r highly resistive material can be deposited on one superconducting layer. Pasa:y~es can be fabricated at the edges of the insulating material to allow the introductio: ~ of interlayer connections, followed by deposition of a fitrther supercondu~ting layer. One can achieve a transposed configuration with coated conductors icy patterning a superconducting layer into filaments parallel to the axis of the tape any: winding the tape in a helical fashion around a cylindrical form.
Mo; :~ details are provided in commonly owned United States Patent Applicatio; ~ Serial No. 09/500,718, filed on February 9, 2000, and entitled "Coated Conductor.. with Reduced AC Loss," which is hereby incorporated by reference in its entirety.
The i~asic "face-to-face" architectures in accordance with the present invention provide a o~~~mber of significant benefits. For example, the HTS films are located near the center l t ne of the conductor cross section. During bending, for example during coil windin a or cable fabrication, the HTS films are near the lowest strain region in the conductor. Conventional mechanics of solids calculations show that the strain tolerance oi~this architecture will be significantly improved relative to open faced tapes.
In ~:~idition, the electrical stability of the conductor can be significantly improved <w~~er a single HTS layer configuration. While electrical current transport is much more Miff icult in normal metals (e.g. silver) relative to the HTS film, current can transfer ov. ,- some calculable length from one filament to another through the cap layer stn;~i~. ~~e. This cun-ent transfer allows the two face-to-face filaments to provide a redunda~ .' current path, improving the stability against quench and reducing the sensitivity .~~ local defects and variations in performance.
Moreover, it is expected that this architecture will also provide considerable benefits for some alternating current applications in which the magnetic field is S oriented pri magi 1y parallel to the plane of the conductor and the magnetic flux fully penetrates :.e entire conductor. For example, in ac superconducting coils such as supercondu~ ting transformers, magnetic fields in the coils are parallel to the surfaces of the tape ,~ncl actor, except at the coil ends. In addition, the amplitude of the magnetic l~~ _ !d is usually larger than the penetration field for the superconducting layers. A~ .;rcling to the Critical State Model, the hysteretic loss of a pair of superconci:: ~tin~~ layers without transport current in fully penetrating parallel fields is the sum o I . ;free terms, one of which is proportional to the ratio of distance between layers to lay ;:r height alld thickness. Using the following typical parameters (superconciucting layer of 2 microns, substrate of 50 microns, buffer layers of 0.6 microns, si l ver cap layer of 4 microns, solder layer of 15 microns, critical current density of 1 V1A/cm2, and peak-to-peak field amplitude of 0.1 Tesla), the ratio of hysteretic loss of a conductor with a face-to-face architecture to that of a conductor with a back-to-back architecture is calculated to be approximately 0.25. Lower loss is expected i u; uc power transmission cables with multiple layers of conductor when the current is c~~erated at sufficient levels so that the magnetic flux fully penetrates the entire cone;:~;;tor in the outer layers.
h: :' ;:-ect current applications, additional face-to-face wires would then be bundled or uacl;ed to provide for the required total ampacity and geometry for a given application.
The simple face-to-face geometry can be readily extended to provide additional ;;nctionality and application benefits. Other laminate layers may also be bonded to ~ ire outsides or substrates of the face-to-face structure. The laminate layer or layers c;«~ be chosen for a variety of purposes provided they keep the operational HTS layer within a neutral mechanical axis zone under bending. These purposes include the ::- electrical, magnetic, thermal, mechanical, environmental, or other properties. i~or example, the laminate layer can have high conductivity and so act as an effective additional electrical stabilizer and also as a means of electrical contact to the supercc:;;ductor, permitting compact terminations. Alternatively, the laminate layer can love high resistivity and high heat capacity, so as to provide thermal stabilization in a cuwent limiting event without shorting out the superconducting material in s ~s normal state. Further, the laminate layer can be chosen for high strength in :mechanically demanding applications, or for specific thermal expansion characters s t s cs to put the superconductor under precompression. In special cases, certain ma~~netic properties can be desirable. Multiple laminate layers can also be desirable, t:~r example, to mechanically and environmentally protect the insert from both sides. Laminates can be bonded to an underlying layer by means of a bonding layer such ;;s a thin layer of solder or glue (for example, an epoxy) or by a direct thermal or- ::Iechanical bonding process. A slight offset or overlap at one edge ofthe tape, a.S SIIO\V1.1 ill Figs. 2A and 2B, can be used to provide direct access to the film surface for enhanced current transfer into the tape at splices and/or edge terminations.
An additional embodiment would build on the offset configuration as shown in Fig. 3. I ; a th s s case the HTS film on the surface of the tapes could be treated to produce lo; eU breaks, nonsuperconducting regions or stripes in the HTS film only along the l~ngtl~ of the tape (in the current flow direction). The cap layer deposited onto the H~! S film would then serve to bridge the nonsuperconducting zones with a ductile normal metal region. An offset in the edge justification of the narrow stripes or filamenm. similar to a cunning bond brick pattern, would allow current to transfer to several ~,urrow superconducting filaments both across the cap layers and to adjacent filaments, further increasing the redundancy and improving stability.
Furthermore, this embo~innent is expected to provide additional protection against defects that can propagate :~;:ross the full tape width. The filament edges can act to stop cracks from running ar;r~ss the full width of the conductor. This functionality could also be achieved h ; arrangement of adjacent narrow tapes comprising the full substrate/h;; Cfer/HTS/cap stack up. This embodiment could further be extended to substitute :; :normal metal region along the length of the tape in place of one or more of the supcr~onciucting stripes. This normal metal strip would add stabilization and would prov i.~ie additional cross sectional area through which to effect splices or terminatio ~ : ~;. F i sally and as discussed above, Figure 4 shows the running bond configurat : . ; n w i th an additional stabilizing element such as copper.
In <<.I embodiments, a normal metal layer could be included along the edge of the conduc:or to hermetically seal the HTS films and to provide for current transfer into t<hP Hri ~ film and, if necessary from the HTS film to the substrate.
Th~ invention thus provides novel superconductors that allow the use of a slight offs~ ~ in stack up of coated conductor tape elements to provide for effective current tra: : ; fer from tape to tape. In addition, stability of the conductor is enhanced by current ,daring across filaments due to the insert of normal metal at interface. The invention i.,rther allows for increased mechanical integrity of conductor stack up due to positioni;~g of the HTS layers near the conductor center line and an ability to splice and termin~~te stacked HTS coated conductors without splitting.
It is to be understood that while the invention has been described i o conjunction with the detailed description thereof, the forgoing description is intende;o i l lustrate and not limit the scope of the invention, which is defined by the scope c; ~ the appended claims. Other aspects, advantages, and modifications are within the ,cope of the following claims.

Claims (33)

What is claimed is:
1. A multi-layer high temperature superconductor, comprising:
a first high temperature superconductor coated element, comprising:
a first substrate;
at least one first buffer deposited on the first substrate;
at least one first high temperature superconductor layer; and a first cap layer; and a second high temperature superconductor coated element, comprising:
a second substrate;
at least one second buffer deposited on the second substrate;
at least one second high temperature superconductor layer; and a second cap layer;
wherein the first and second high temperature superconductor coated elements are joined at the first and second cap layers.
2. The superconductor of claim 1, wherein the first substrate is biaxially textured.
3. The superconductor of claim 2, wherein the biaxial texturing is by deformation texturing.
4. The superconductor of claim 3, wherein the first substrate comprises nickel.
5. The superconductor of claim 4, wherein the first substrate comprises nickel-chromium nickel-copper, or nickel-vanadium alloys.
6. The superconductor of claim 5, wherein the first substrate comprises a nickel-chromium alloy.
7. The superconductor of claim 2, wherein the at least one first buffer is epitaxially deposited.
8. The superconductor of claim 1, wherein the at least one first buffer comprises metal oxides.
9. The superconductor of claim 8, wherein the metal oxides comprise cerium oxide and gadolinium oxide.
10. The superconductor of claim 8, wherein the first buffer further comprises yttria stabilized zirconia.
11. The superconductor of claim 1, wherein at least two buffers are sequentially deposited on the first substrate.
12. The superconductor of claim 11, wherein three buffers are sequentially deposited on the first substrate.
13. The superconductor of claim 1, wherein the first high temperature superconductor layer comprises metal oxide.
14. The superconductor of claim 1, wherein the first high temperature superconductor layer comprises rare earth oxides.
15. The superconductor of claim 14, wherein the rare earth oxides have the formula (RE)Ba2Cu3O7-8, wherein RE is selected from the group consisting of rare earth elements and yttrium, and ~ is a number greater than zero and less than one.
16. The superconductor of claim 1, wherein the first cap layer is deposited on the first high temperature superconducting layer.
17. The superconductor of claim 1, wherein the first and second substrates are of substantially identical composition.
18. The superconductor of claim 1, wherein the first and second buffers are of substantially identical composition.
19. The superconductor of claim 1, wherein the first and second high temperature superconducting layers are of substantially identical composition.
20. The superconductor of claim 1, wherein the first and second cap layers are of substantially identical composition.
21. The superconductor of claim 1, wherein the first and second high temperature superconductor coated elements are of substantially identical composition.
22. The superconductor of claim 1, wherein the first and second cap layers are continuously joined at their uppermost surfaces.
23. The superconductor of claim 1, wherein the first and second cap layers are a single continuous layer.
24. The superconductor of claim 1, wherein the superconductor is in the form of a tape.
25. The superconductor of claim 1, wherein the substrates are substantially untextured. and the buffers and high temperature superconductor layers are biaxially textured.
26. The superconductor of claim 24, wherein the first and second high temperature superconductor coated elements are registered at their respective edges.
27. The superconductor of claim 24, wherein the first and second high temperature superconductor coated elements are offset along their lengths.
28. The superconductor of claim 27, wherein at least one of the first and second cap layers extends along the edge of at least the first and second high temperature superconductor coated element.
29. The superconductor of claim 1, wherein the superconductor comprises a multifilamentary structure.
30. The superconductor of claim 29, wherein the first and second high temperature superconducting layers are divided into a plurality of filaments.
31. The superconductor of claim 1, further comprising a stabilizer, wherein the first aid second cap layers are joined to opposing surfaces of the stabilizer.
32. A multi-layer high temperature superconductor, comprising:
a first high temperature superconductor coated element, comprising:
a first substrate;
at least one first buffer deposited on the first substrate;

at least one first high temperature superconductor layer; and a first cap layer; and a second high temperature superconductor coated element, comprising:
a second substrate;
at least one second buffer deposited on the second substrate;
at least one second high temperature superconductor layer; and a second cap layer;
wherein the first and second high temperature superconductor coated elements are joined with an intervening metallic layer.
33. A multi-layer high temperature superconductor, comprising:
a first high temperature superconductor coated element, comprising:
a first substrate;
at least one first buffer deposited on the first substrate; and at least one first high temperature superconductor layer, and a second high temperature superconductor coated element, comprising:
a second substrate;
at least one second buffer deposited on the second substrate; and at least one second high temperature superconductor layer, wherein the first and second high temperature superconductor coated elements are joined with an intervening metallic layer.
CA002378833A 1999-07-23 2000-07-14 Enhanced high temperature coated superconductors Abandoned CA2378833A1 (en)

Applications Claiming Priority (16)

Application Number Priority Date Filing Date Title
US14546899P 1999-07-23 1999-07-23
US60/145,468 1999-07-23
US16614599P 1999-11-18 1999-11-18
US16629799P 1999-11-18 1999-11-18
US16614099P 1999-11-18 1999-11-18
US60/166,297 1999-11-18
US60/166,140 1999-11-18
US60/166,145 1999-11-18
US50070100A 2000-02-09 2000-02-09
US50071800A 2000-02-09 2000-02-09
US09/500,717 2000-02-09
US09/500,701 2000-02-09
US09/500,718 2000-02-09
US09/500,717 US6562761B1 (en) 2000-02-09 2000-02-09 Coated conductor thick film precursor
US09/616,810 US6893732B1 (en) 1999-07-23 2000-07-14 Multi-layer articles and methods of making same
PCT/US2000/019345 WO2001008233A2 (en) 1999-07-23 2000-07-14 Joint high temperature superconducting coated tapes

Publications (1)

Publication Number Publication Date
CA2378833A1 true CA2378833A1 (en) 2001-02-01

Family

ID=37761110

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002378833A Abandoned CA2378833A1 (en) 1999-07-23 2000-07-14 Enhanced high temperature coated superconductors

Country Status (7)

Country Link
US (2) US6669774B1 (en)
EP (3) EP1198846B1 (en)
JP (2) JP4041672B2 (en)
CN (2) CN1208850C (en)
AU (10) AU1325401A (en)
CA (1) CA2378833A1 (en)
WO (9) WO2001026165A2 (en)

Families Citing this family (92)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0010494D0 (en) * 2000-04-28 2000-06-14 Isis Innovation Textured metal article
MXPA02011319A (en) * 2000-05-15 2003-06-06 Pharma Mar Sa Antitumoral analogs of et 743.
US20020056401A1 (en) * 2000-10-23 2002-05-16 Rupich Martin W. Precursor solutions and methods of using same
US6821338B2 (en) 2000-12-15 2004-11-23 The Regents Of The University Of California Particle beam biaxial orientation of a substrate for epitaxial crystal growth
US6500568B1 (en) 2001-06-06 2002-12-31 3M Innovative Properties Company Biaxially textured metal substrate with palladium layer
EP1271666A3 (en) * 2001-06-22 2006-01-25 Fujikura Ltd. Oxide superconductor layer and its production method
US6809066B2 (en) 2001-07-30 2004-10-26 The Regents Of The University Of California Ion texturing methods and articles
US6797313B2 (en) * 2001-07-31 2004-09-28 American Superconductor Corporation Superconductor methods and reactors
US20030062126A1 (en) * 2001-10-03 2003-04-03 Scaggs Michael J. Method and apparatus for assisting laser material processing
US6794338B2 (en) 2001-11-16 2004-09-21 3M Innovative Properties Company Article with thermochemically stable, amorphous layer comprising tantalum or tantalum-containing material
US6745059B2 (en) * 2001-11-28 2004-06-01 American Superconductor Corporation Superconductor cables and magnetic devices
EP1479111B1 (en) * 2002-02-21 2008-04-23 Jochen Dieter Prof. Dr. Mannhart Improved superconductors and methods for making such superconductors
US6894289B2 (en) * 2002-02-22 2005-05-17 Xenogen Corporation Fluorescence illumination assembly for an imaging apparatus
JP3725085B2 (en) * 2002-03-05 2005-12-07 株式会社東芝 Superconducting layer and manufacturing method thereof
DE10223542B4 (en) * 2002-05-27 2005-04-21 Siemens Ag Process for the preparation of a fully transposed high-Tc composite superconductor and conductor produced by the process
US8153281B2 (en) * 2003-06-23 2012-04-10 Superpower, Inc. Metalorganic chemical vapor deposition (MOCVD) process and apparatus to produce multi-layer high-temperature superconducting (HTS) coated tape
US20040266628A1 (en) * 2003-06-27 2004-12-30 Superpower, Inc. Novel superconducting articles, and methods for forming and using same
US7774035B2 (en) 2003-06-27 2010-08-10 Superpower, Inc. Superconducting articles having dual sided structures
KR100529602B1 (en) * 2003-07-18 2005-11-17 한국산업기술대학교 Method for manufacturing metal organic deposition precursor solution using superconduction oxide and film superconductor
US20050016759A1 (en) * 2003-07-21 2005-01-27 Malozemoff Alexis P. High temperature superconducting devices and related methods
ITTO20030692A1 (en) * 2003-09-11 2005-03-12 Edison Termoelettrica Spa SUPERCONDUCTIVE COMPOSITE TAPE AND RELATIVE PROCEDURE.
WO2005035809A1 (en) * 2003-10-07 2005-04-21 Nikko Materials Co., Ltd. HIGH-PURITY Ni-V ALLOY, TARGET THEREFROM, HIGH-PURITY Ni-V ALLOY THIN FILM AND PROCESS FOR PRODUCING HIGH-PURITY Ni-V ALLOY
CN100365839C (en) * 2003-12-15 2008-01-30 北京有色金属研究总院 Multilayer biaxial orienting insulation layer structure and high-temperature superconductive coating conductor and preparing method thereof
US7365271B2 (en) 2003-12-31 2008-04-29 Superpower, Inc. Superconducting articles, and methods for forming and using same
US20050159298A1 (en) * 2004-01-16 2005-07-21 American Superconductor Corporation Oxide films with nanodot flux pinning centers
US7261776B2 (en) * 2004-03-30 2007-08-28 American Superconductor Corporation Deposition of buffer layers on textured metal surfaces
WO2005096322A1 (en) * 2004-03-31 2005-10-13 Industrial Research Limited Composite superconductor cable produced by transposing planar subconductors
US7718574B2 (en) * 2004-04-08 2010-05-18 Superpower, Inc. Biaxially-textured film deposition for superconductor coated tapes
JP2005322476A (en) * 2004-05-07 2005-11-17 Hitachi Metals Ltd Manufacturing method of oxide superconductor
US7496390B2 (en) 2004-08-20 2009-02-24 American Superconductor Corporation Low ac loss filamentary coated superconductors
US7463915B2 (en) 2004-08-20 2008-12-09 American Superconductor Corporation Stacked filamentary coated superconductors
US7582328B2 (en) 2004-08-20 2009-09-01 American Superconductor Corporation Dropwise deposition of a patterned oxide superconductor
WO2007001383A2 (en) 2004-09-22 2007-01-04 Superpower, Inc. Superconductor components
US7972744B2 (en) 2004-09-28 2011-07-05 GM Global Technology Operations LLC Fuel cell assembly
US7816303B2 (en) * 2004-10-01 2010-10-19 American Superconductor Corporation Architecture for high temperature superconductor wire
KR100910601B1 (en) * 2004-10-01 2009-08-03 아메리칸 수퍼컨덕터 코포레이션 Thick superconductor films with improved performance
EP1805817B1 (en) 2004-10-01 2016-11-16 American Superconductor Corporation Thick superconductor films with improved performance
CN101728019B (en) * 2004-12-23 2013-08-28 超导技术公司 Superconductor productions
US7226893B2 (en) * 2005-02-23 2007-06-05 Superpower, Inc. Superconductive articles having density characteristics
US7763343B2 (en) 2005-03-31 2010-07-27 American Superconductor Corporation Mesh-type stabilizer for filamentary coated superconductors
US7071148B1 (en) * 2005-04-08 2006-07-04 Superpower, Inc. Joined superconductive articles
CA2622384C (en) * 2005-07-29 2014-09-23 American Superconductor Corporation High temperature superconducting wires and coils
WO2007025062A2 (en) * 2005-08-25 2007-03-01 Wakonda Technologies, Inc. Photovoltaic template
KR100691061B1 (en) * 2005-08-30 2007-03-09 엘에스전선 주식회사 Substrate for superconducting wire and fabrication method thereof and superconducting wire
US7674751B2 (en) * 2006-01-10 2010-03-09 American Superconductor Corporation Fabrication of sealed high temperature superconductor wires
CN100365740C (en) * 2006-04-27 2008-01-30 西南交通大学 Buffer layer of high temp superconductive coated conductor
DE102006029947B4 (en) * 2006-06-29 2013-01-17 Basf Se Method for applying a metallic cover layer to a high-temperature superconductor
WO2008118127A1 (en) 2006-07-21 2008-10-02 American Superconductor Corporation Low resistance splice for high temperature superconductor wires
US7902120B2 (en) 2006-07-24 2011-03-08 American Superconductor Corporation High temperature superconductors having planar magnetic flux pinning centers and methods for making the same
KR100807640B1 (en) * 2006-12-22 2008-02-28 한국기계연구원 Synthesizing precursor solution enabling fabricating biaxially textured buffer layers by low temperature annealing
US7893006B2 (en) 2007-03-23 2011-02-22 American Superconductor Corporation Systems and methods for solution-based deposition of metallic cap layers for high temperature superconductor wires
US20080286587A1 (en) * 2007-05-16 2008-11-20 Seagate Technology Llc Apparatus Having Electric Circuitry and Method of Making Same
DE102008040087B4 (en) * 2008-07-02 2011-12-15 Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. Electrically conductive high-temperature superconductor layer structure and method for its production
US8195260B2 (en) 2008-07-23 2012-06-05 American Superconductor Corporation Two-sided splice for high temperature superconductor laminated wires
JP2010129465A (en) * 2008-11-28 2010-06-10 Sumitomo Electric Ind Ltd Composite superconducting wire
WO2010088366A1 (en) * 2009-01-28 2010-08-05 Wakonda Technologies, Inc. Large-grain crystalline thin-film structures and devices and methods for forming the same
US20100270653A1 (en) * 2009-04-24 2010-10-28 Christopher Leitz Crystalline thin-film photovoltaic structures and methods for forming the same
JP5096422B2 (en) * 2009-07-10 2012-12-12 住友電気工業株式会社 Substrate and superconducting wire manufacturing method
ES2389159T3 (en) * 2009-08-13 2012-10-23 Nexans Coated conductor
DE102009038920A1 (en) * 2009-08-26 2011-03-10 Siemens Aktiengesellschaft Multifilament conductor and method for its production
JP5427553B2 (en) * 2009-10-30 2014-02-26 公益財団法人国際超電導産業技術研究センター Base material for oxide superconducting conductor and method for producing the same, oxide superconducting conductor and method for producing the same
JP5481180B2 (en) * 2009-12-21 2014-04-23 株式会社フジクラ Base material for oxide superconductor and oxide superconductor
US8428671B2 (en) * 2010-03-31 2013-04-23 American Superconductor Corporation Thick oxide film by single coating
US8716188B2 (en) * 2010-09-15 2014-05-06 Superpower, Inc. Structure to reduce electroplated stabilizer content
WO2012111678A1 (en) * 2011-02-15 2012-08-23 古河電気工業株式会社 Super-conducting wire and method for producing super-conducting wire
JP6090794B2 (en) * 2011-05-31 2017-03-08 古河電気工業株式会社 Oxide superconducting thin film and superconducting fault current limiter
DE102012218251A1 (en) 2012-10-05 2014-04-10 Bruker Hts Gmbh Superconductor structure with chained tape pieces, which are each overlapped by immediately successive, further pieces of tape
KR101410841B1 (en) * 2012-11-26 2014-06-23 한국전기연구원 high temperature superconducting wire
JP6108888B2 (en) 2013-03-13 2017-04-05 古河電気工業株式会社 Peelable superconductor, method for manufacturing peelable superconductor, and method for repairing superconducting wire
EP2835838B1 (en) 2013-08-08 2017-02-15 Theva Dünnschichttechnik GmbH High temperature tape superconductor system
DE102013220141B4 (en) * 2013-10-04 2017-11-16 Bruker Biospin Gmbh An NMR spectrometer comprising a superconducting magnet coil with windings of a superconductor structure with chained band pieces, which are each overlapped by immediately successive, further band pieces
CN103515026B (en) * 2013-10-17 2016-02-03 西南交通大学 One prepares conductor of high-temperature superconductor coat La 0.7sr 0.3mnO 3the method of buffer layer thin film
US20170125924A1 (en) * 2014-04-25 2017-05-04 Brookhaven Science Associates, Llc Generation of a Splice Between Superconductor Materials
US9738054B2 (en) 2014-10-21 2017-08-22 The Boeing Company Tailored coefficient of thermal expansion of composite laminates using fiber steering
CN105632938B (en) * 2014-11-28 2019-02-05 深南电路有限公司 A kind of processing method and package substrate of metallic carrier
KR20170126961A (en) 2015-03-02 2017-11-20 바스프 에스이 Process for preparing crystalline tantalum oxide particles
US10450199B2 (en) 2015-03-02 2019-10-22 Basf Se Nanoparticles for the use as pinning centers in superconductors
ES2733898T3 (en) 2015-03-26 2019-12-03 Basf Se Production procedure for high temperature superconducting cables
JP6505565B2 (en) 2015-09-28 2019-04-24 株式会社東芝 Connection structure of high temperature superconducting conductor, high temperature superconducting coil and high temperature superconducting coil
CN105551681B (en) * 2016-02-05 2017-03-29 上海上创超导科技有限公司 A kind of multiple structure of barium copper oxygen conductor of high-temperature superconductor coat
US10280580B1 (en) * 2016-03-04 2019-05-07 Usa Intellectual Property Holding, Inc. Anti-corrosion structure anchor
RU2627130C1 (en) * 2016-10-11 2017-08-03 Акционерное общество "Государственный научно-исследовательский и проектный институт редкометаллической промышленности АО "Гиредмет" Method for producing multilayer high-temperature superconducting material
JP2020506154A (en) 2017-01-11 2020-02-27 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se Manufacturing method of nanoparticles
KR20200085773A (en) 2017-11-28 2020-07-15 바스프 에스이 Combined superconducting tape
CA3089491A1 (en) 2017-12-14 2019-06-20 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Fabrication of high-temperature superconducting striated tape combinations
CN112074750A (en) 2018-04-25 2020-12-11 巴斯夫欧洲公司 Apparatus for quality control of superconducting tape
CN108754485A (en) * 2018-06-23 2018-11-06 西安文理学院 A kind of coating process improving the Gear Processing hobcutter service life
US11167375B2 (en) 2018-08-10 2021-11-09 The Research Foundation For The State University Of New York Additive manufacturing processes and additively manufactured products
WO2020049019A1 (en) 2018-09-07 2020-03-12 Basf Se Process for producing nanoparticles
WO2020212194A1 (en) 2019-04-17 2020-10-22 Basf Se Sealed superconductor tape
WO2021063723A1 (en) * 2019-09-30 2021-04-08 Basf Se High-temperature superconductor tape with buffer having controlled carbon content
WO2022032048A1 (en) * 2020-08-06 2022-02-10 American Superconductor Corporation Electro-formed metal foils

Family Cites Families (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1393610A (en) 1971-06-15 1975-05-07 Siemens Ag Electrical conductors comprising both superconductive material and normally conductive material
US3763552A (en) 1972-03-16 1973-10-09 Nasa Method of fabricating a twisted composite superconductor
JPS5775564A (en) 1980-10-28 1982-05-12 Hitachi Ltd Exciter for superconductive rotary machine
US4442396A (en) 1983-03-31 1984-04-10 Sundstrand Corporation Generator system with fault condition excitation
US4508887A (en) * 1983-08-01 1985-04-02 Dow Corning Corporation Method and novel catalyst compositions for preparing polyorganosiloxanes
US4659973A (en) 1986-04-30 1987-04-21 Siemens Energy & Automation, Inc. Brushless exciter for controlling excitation of a synchronous machine
US4639298A (en) * 1986-05-05 1987-01-27 W. R. Grace & Co. Oxidation of organic compounds using ceric ions in aqueous methanesulfonic acid
US4692227A (en) * 1986-12-01 1987-09-08 W. R. Grace & Co. Oxidation of organic compounds using thallium ions
US4670108A (en) * 1986-10-10 1987-06-02 W. R. Grace & Co. Oxidation of organic compounds using ceric methanesulfonate in an aqueous organic solution
US4994433A (en) * 1987-05-22 1991-02-19 Massachusetts Institute Of Technology Preparation of thin film superconducting oxides
JPS63310366A (en) 1987-06-10 1988-12-19 Hitachi Ltd Synchronous machine
JPH0791055B2 (en) 1987-07-31 1995-10-04 三菱マテリアル株式会社 Manufacturing method of complex metal oxide
US5304533A (en) 1987-08-24 1994-04-19 Mitsubishi Denki Kabushiki Kaisha Process for producing an oxide superconductor from alkoxides
US4959347A (en) 1987-08-24 1990-09-25 Mitsubishi Denki Kabushiki Kaisha Forming homogeneous precursers of Bi-Sr-Ca-Cu via carboxylates in the presence of oxidizing agents
EP0308869B1 (en) 1987-09-21 1995-05-31 Kanegafuchi Chemical Industry Co., Ltd. Process of producing single crystalline LnA2Cu3O7-x thin films having three-layered perovskite structure
US5362711A (en) * 1987-09-21 1994-11-08 Kanegafuchi Chemical Industry Co., Ltd. Method for producing single crystal superconducting LnA2 Cu3 O7-x films
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
US4859652A (en) 1987-11-16 1989-08-22 W. R. Grace & Co.-Conn. Method for preparation of high temperature superconductors using trichloroacetates
US4882312A (en) 1988-05-09 1989-11-21 General Electric Company Evaporation of high Tc Y-Ba-Cu-O superconducting thin film on Si and SiO2 with a zirconia buffer layer
EP0387525B1 (en) 1989-03-15 1993-08-11 Asea Brown Boveri Ag Process for producing a crystal-oriented surface layer from a ceramic high temperature superconductor
DE59007031D1 (en) * 1989-06-14 1994-10-13 Asea Brown Boveri Process for reducing eddy currents in a superconductor belt and superconductor arrangement.
US5229358A (en) 1989-06-15 1993-07-20 Microelectronics And Computer Technology Corporation Method and apparatus for fabricating superconducting wire
JPH03159902A (en) 1989-11-13 1991-07-09 Kokusai Chiyoudendou Sangyo Gijutsu Kenkyu Center Multicomponent oxide for production of oxide superconductor and production of oxide superconductor
CA2029789A1 (en) 1989-12-04 1991-06-05 Kenton D. Budd Flexible superconductor coated zirconia fibers
US5073537A (en) 1990-02-06 1991-12-17 Eastman Kodak Company Electrically conductive article
US5231074A (en) * 1990-04-17 1993-07-27 Massachusetts Institute Of Technology Preparation of highly textured oxide superconducting films from mod precursor solutions
JP2968557B2 (en) * 1990-05-14 1999-10-25 株式会社フジクラ Substrate for oxide superconducting conductor
US5256636A (en) * 1990-09-21 1993-10-26 The Regents Of The University Of Calif. Microelectronic superconducting device with multi-layer contact
JPH04300292A (en) * 1991-03-26 1992-10-23 Sumitomo Electric Ind Ltd Film forming method for multicomponent oxide film superconducting film
EP0506582B1 (en) 1991-03-28 1997-05-28 Sumitomo Electric Industries, Ltd. Process for preparing layered thin films
JPH05109329A (en) * 1991-04-01 1993-04-30 General Electric Co <Ge> Method for forming oriented dielectric thin film on metal substrate and product manufactured by method thereof
EP0584410A1 (en) * 1991-07-05 1994-03-02 Conductus, Inc. Superconducting electronic structures and methods of preparing same
US5449659A (en) 1991-07-05 1995-09-12 Conductus, Inc. Method of bonding multilayer structures of crystalline materials
US5427055A (en) 1992-01-31 1995-06-27 Canon Kabushiki Kaisha Method for controlling roughness on surface of monocrystal
JP3269841B2 (en) * 1992-04-02 2002-04-02 株式会社フジクラ Oxide superconductor and method of manufacturing the same
US5484766A (en) 1994-02-14 1996-01-16 Electric Power Research Institute, Inc. Preparation of Bi-Pb-Sr-Ca-Cu-O (2223) superconductors
EP0669412B1 (en) 1994-02-25 2002-05-22 Sumitomo Electric Industries, Ltd. Aluminim nitride thin film substrate and process for producing same
US5866252A (en) 1994-06-16 1999-02-02 The United States Of America As Represented By The Secretary Of The Air Force Super conducting metal-ceramic composite
JP3245506B2 (en) 1994-09-07 2002-01-15 財団法人国際超電導産業技術研究センター Surface treatment method for LnBa2Cu3O7-x single crystal substrate
US5741377A (en) 1995-04-10 1998-04-21 Martin Marietta Energy Systems, Inc. Structures having enhanced biaxial texture and method of fabricating same
US6077344A (en) 1997-09-02 2000-06-20 Lockheed Martin Energy Research Corporation Sol-gel deposition of buffer layers on biaxially textured metal substances
WO1997005669A1 (en) * 1995-07-26 1997-02-13 Illinois Superconductor Corporation Method for producing highly textured yttrium barium cuprate for use in waveguides and transmission lines
JP3353871B2 (en) * 1996-03-22 2002-12-03 財団法人国際超電導産業技術研究センター Oxide superconductor thin film laminate and method for producing oxide superconductor thin film laminate
US5981445A (en) 1996-06-17 1999-11-09 Corporation De I'ecole Polytechnique Process of making fine ceramic powders from aqueous suspensions
DE69730591T3 (en) 1996-10-23 2015-05-21 Fujikura Ltd. METHOD FOR THE PRODUCTION OF POLYCRYSTALLINE THIN FILM, METHOD FOR THE PRODUCTION OF OXIDINE SUPER PLASTER AND DEVICE THEREFOR
WO1998058415A1 (en) 1997-06-18 1998-12-23 Massachusetts Institute Of Technology Controlled conversion of metal oxyfluorides into superconducting oxides
US6256521B1 (en) 1997-09-16 2001-07-03 Ut-Battelle, Llc Preferentially oriented, High temperature superconductors by seeding and a method for their preparation
US5964966A (en) 1997-09-19 1999-10-12 Lockheed Martin Energy Research Corporation Method of forming biaxially textured alloy substrates and devices thereon
US6027564A (en) 1997-09-23 2000-02-22 American Superconductor Corporation Low vacuum vapor process for producing epitaxial layers
US6022832A (en) * 1997-09-23 2000-02-08 American Superconductor Corporation Low vacuum vapor process for producing superconductor articles with epitaxial layers
CA2305646A1 (en) 1997-10-01 1999-04-08 Edward J. Siegal Substrates with improved oxidation resistance
US6428635B1 (en) 1997-10-01 2002-08-06 American Superconductor Corporation Substrates for superconductors
US6190752B1 (en) 1997-11-13 2001-02-20 Board Of Trustees Of The Leland Stanford Junior University Thin films having rock-salt-like structure deposited on amorphous surfaces
DE19800168A1 (en) 1998-01-06 1999-07-15 Aventis Res & Tech Gmbh & Co Process for the production of a homogeneous and stable suspension from oxide precursors
DE69806118T2 (en) * 1998-03-17 2003-03-27 Repsol Quimica Sa Improved process for the production of propylene oxide and styrene
US6765151B2 (en) * 1999-07-23 2004-07-20 American Superconductor Corporation Enhanced high temperature coated superconductors
US6624122B1 (en) 2000-06-21 2003-09-23 The Regents Of The University Of California High critical current superconducting tapes

Also Published As

Publication number Publication date
WO2001008233A9 (en) 2002-07-25
CN1364321A (en) 2002-08-14
WO2001008232A2 (en) 2001-02-01
JP2003526905A (en) 2003-09-09
WO2001008169A9 (en) 2002-09-06
EP1198846A2 (en) 2002-04-24
US6893732B1 (en) 2005-05-17
WO2001008169A2 (en) 2001-02-01
AU1325101A (en) 2001-02-13
EP1198847B1 (en) 2008-10-01
WO2001026164A2 (en) 2001-04-12
WO2001008235A1 (en) 2001-02-01
WO2001011428A8 (en) 2001-10-11
WO2001008169A3 (en) 2002-01-10
AU1750901A (en) 2001-03-05
WO2001011428A1 (en) 2001-02-15
WO2001008231A2 (en) 2001-02-01
JP4041672B2 (en) 2008-01-30
JP2003505887A (en) 2003-02-12
WO2001026165A2 (en) 2001-04-12
WO2001008170A3 (en) 2001-11-29
WO2001026165A9 (en) 2003-01-30
CN1364320A (en) 2002-08-14
EP1198849A2 (en) 2002-04-24
EP1198847A1 (en) 2002-04-24
WO2001008231A3 (en) 2001-08-30
EP1198846B1 (en) 2006-11-08
WO2001008170A2 (en) 2001-02-01
AU2915401A (en) 2001-05-10
WO2001008233A3 (en) 2001-05-17
AU771872B2 (en) 2004-04-01
WO2001008231A9 (en) 2001-09-20
AU2004200987A1 (en) 2004-04-01
CN1208850C (en) 2005-06-29
AU1186901A (en) 2001-02-13
AU6216200A (en) 2001-02-13
WO2001026164A3 (en) 2002-01-17
WO2001008233A2 (en) 2001-02-01
AU2915501A (en) 2001-05-10
AU1325301A (en) 2001-02-13
US6669774B1 (en) 2003-12-30
AU1325001A (en) 2001-02-13
WO2001008170A9 (en) 2002-07-25
WO2001008232A9 (en) 2002-08-08
AU1325401A (en) 2001-02-13
WO2001011428A9 (en) 2002-07-25
WO2001026165A3 (en) 2001-12-06
CN1364321B (en) 2010-06-02
WO2001008232A3 (en) 2001-11-29

Similar Documents

Publication Publication Date Title
AU771872B2 (en) Joint high temperature superconducting coated tapes
US6765151B2 (en) Enhanced high temperature coated superconductors
US6828507B1 (en) Enhanced high temperature coated superconductors joined at a cap layer
US6537689B2 (en) Multi-layer superconductor having buffer layer with oriented termination plane
US6730410B1 (en) Surface control alloy substrates and methods of manufacture therefor
US6673387B1 (en) Control of oxide layer reaction rates
US7939126B2 (en) Precursor solutions and methods of using same
US6974501B1 (en) Multi-layer articles and methods of making same
KR20020025957A (en) Enhanced High Temperature Coated Superconductors
AU2002216631A1 (en) Precursor solutions and methods of using same
KR101414430B1 (en) Thick Oxide Film by Single Coating

Legal Events

Date Code Title Description
EEER Examination request
FZDE Discontinued