JP2003007146A - Oxide super conductor and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oxide superconductor and a method of manufacturing the same, the super conductor excellent in strength and a superconducting property with Ag used mainly as a base material. SOLUTION: The oxide superconductor SA comprises an oxide superconductor base TA composed of a tape-form metallic main material a and an Ag layer b possessing rolled texture formed on at least one surface side of the metallic main material a, a diffused layer c formed with Cu diffused on a surface layer part of the Ag layer b of the base TA, and an oxide superconducting layer d formed on the diffused layer c.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxide superconducting conductor which can be used in the fields of superconducting power cables, superconducting magnets, superconducting energy storage, superconducting power generators, medical MRI devices, superconducting current leads, and the like, and a method for producing the same. Is.

[0002]

2. Description of the Related Art As a conventional method for producing an oxide superconducting conductor, oxide superconducting powder or mixed powder having a composition capable of becoming an oxide superconducting material by heat treatment is pressed into a cylindrical shape, and this is inserted into a silver tube and expanded. The powder-in-tube method (P
In addition to the solid phase method such as the IT method), there is a film forming method for continuously forming an oxide superconducting layer on a long base material such as a metal tape by a vapor phase method such as a laser vapor deposition method and a sputtering method. Are known.

As a structure of an oxide superconducting conductor manufactured by a vapor phase method such as a laser deposition method or a CVD method, as shown in FIG. 7, a YBaCuO-based oxide is formed on an upper surface of a base material 191 made of a metal such as Ag. It is widely known that the object superconducting layer 193 is formed, and the surface protective layer 195 made of Ag is further formed on the oxide superconducting layer 193. In order to obtain excellent superconducting properties in the oxide superconducting conductor prepared by the vapor phase method such as the laser deposition method or the CVD method, the oxide superconducting layer 1 formed on the base material 191 is required.
It is important to realize the biaxial orientation of 93 (in-plane orientation). For that purpose, the lattice constant of the base material 191 is brought close to that of the oxide superconducting layer 193, and
It is preferable that the crystal grains forming the surface of are aligned in a pseudo single crystal.

Therefore, in order to solve this problem, FIG.
As shown in, a metal base material 19 such as Hastelloy tape
A polycrystalline intermediate layer 192 such as YSZ (yttria-stabilized zirconium) is formed on the upper surface of No. 1 by using a sputtering device, and an oxide superconducting layer 193 such as YBaCuO based is formed on the polycrystalline intermediate layer 192. Various attempts have been made to form an oxide superconducting conductor having excellent superconductivity by forming a stabilizing layer 194 of Ag thereon. Alternatively, an Ag base material having a texture formed by rolling and heat treatment, and a Ni base material having a texture formed by rolling and heat treatment and further having an oxide intermediate layer formed thereon have been studied.

Of these, Ag is the oxide superconducting layer 1
Since it has a low reactivity with 93 and is the only metal material capable of forming the oxide superconducting layer 193 directly on the base material 191, it is also nonmagnetic and has low resistance. It is possible to realize a wire rod structure in which the base material 191 itself also functions as a stabilizing layer.

The tape-shaped Ag base material having a texture formed by this rolling and heat treatment has (100)
Plane, Ag {100} <001> having a cubic texture in which <001> is preferentially oriented in the longitudinal direction, or the (110) plane is formed on the substrate surface and <110> in the longitudinal direction.
Having a cubic texture with preferentially oriented Ag {1
10} <110> and the like have been developed, and of these, an oriented Ag base material of Ag {110} <110> is promising in view of lattice matching with a YBaCuO-based oxide superconducting layer.

[0007]

In the oxide superconducting conductor in which the oxide superconducting layer 193 is formed on the polycrystalline intermediate layer 192 as shown in FIG. 8, the action of the polycrystalline intermediate layer 192 causes the oxide superconducting layer to be formed. Since the surface on which 193 is formed is excellent in smoothness and in-plane orientation, an oxide superconducting layer 193 having good in-plane orientation can be obtained.
It has been confirmed that a high Jc of / cm ² or more can be obtained. Further, since Hastelloy is used as the metal tape, a wire rod having sufficient strength can be manufactured.
However, the substrate provided with the polycrystalline intermediate layer 192 needs to use an advanced and expensive technique such as an ion beam sputtering method for its film formation, and the production rate of the substrate up to about 1 m / h has so far been reached. However, there is a problem that the manufacturing cost is extremely high.

On the other hand, the orientation A using the rolled texture of Ag
With the g base material, the productivity of the base material can be increased, the manufacturing cost is relatively low, and it is promising, but a high Jc of 100,000 A / cm ² or more was obtained using this oriented Ag base material. However, the lack of superconducting properties has been a problem. It is considered that this is because the continuity of the oxide superconducting layer is impaired by the unevenness in the crystal grain boundaries of the Ag base material. When an Ag base material is used, Ag itself is a very soft metal and is further softened by being heated to a high temperature during the formation of the oxide superconducting layer. In order to apply superconducting conductors to wires, etc., it is necessary to solve the problem of strength.

The present invention has been made to solve the above problems, and uses an Ag-based base material and has excellent strength and superconducting properties, and an oxide superconducting conductor and a method for producing the same. An object is to provide a base material for an oxide superconducting conductor.

[0010]

In order to solve the above problems, an oxide superconducting conductor of the present invention comprises a tape-shaped metal base material and a rolling texture formed on at least one surface side of the metal base material. A base material for an oxide superconducting conductor having an Ag layer, a diffusion layer formed by diffusing Cu in a surface layer portion of the Ag layer of the base material, and an oxide superconducting layer formed on the diffusion layer. It is characterized by having and.

That is, the oxide superconducting conductor of the present invention is
By using the double-structured base material having the Ag layer having the rolling texture on the metal base material, the strength is significantly improved as compared with the conventional Ag base material. Further, since the diffusion layer in which Cu is diffused is formed in the surface layer portion of the Ag layer, the diffusion of Cu from the oxide superconducting layer to the Ag base material can be effectively suppressed. Since the grain boundary growth on the surface of the Ag base material can be suppressed by this of the layer, the composition of the oxide superconducting layer is not disturbed and the crystal continuity is not impaired, and the oxide superconducting excellent in superconducting properties is obtained. It can be a conductor.

Next, in the oxide superconducting conductor of the present invention, it is preferable that the Ag layer has a thickness in the range of 10 μm to 100 μm. When the thickness of the Ag layer is less than 10 μm, the constituent element of the metal base material is A
It is not preferable because it diffuses through the g layer to the superconducting layer. On the other hand, when it exceeds 100 μm, the amount of Ag used is large and the cost of the base material is high, which is not preferable.

Next, the oxide superconducting conductor of the present invention may have a structure in which a barrier layer is provided between the Ag layer and the metal base material. With such a configuration, it is possible to suppress the elements constituting the metal base material from diffusing into the Ag layer and the oxide superconducting layer.
The texture of the layer and the crystal structure of the oxide superconducting layer can be kept good, and the crystal orientation and crystal continuity of the oxide superconducting layer formed on the Ag layer can be made good. .

In the oxide superconducting conductor having the barrier layer, the Ag layer has a thickness of 5 μm or more and 10 μm or more.
The structure can be set to be less than or equal to μm. That is,
The barrier layer can prevent the elements constituting the metal base material from diffusing into the Ag layer and the oxide superconducting layer formed on the Ag layer. Therefore, according to this configuration, Ag
Even if the layer is thin, an oxide superconducting layer having good crystal continuity can be formed, and an oxide superconducting conductor having excellent superconducting properties can be provided. Further, in the oxide superconducting conductor provided with this barrier layer, the film thickness of the Ag layer is
When the thickness is less than 5 μm, it is difficult to attach the Ag layer (Ag foil) to the barrier layer, which is not practical. Also 10μ
When it exceeds m, it is not preferable because the cost of the base material is increased.

Next, the base material for an oxide superconducting conductor of the present invention forms an oxide superconducting layer by chemically reacting the raw material gas of the oxide superconducting on at least one surface side to form an oxide superconducting conductor. Which is a tape-shaped base material, comprising a tape-shaped metal base material, and an Ag layer made of Ag having a rolling texture formed on at least one surface side of the metal base material, the Ag layer film Thickness is 10 μm or more 1
It is characterized in that the thickness is set to 00 μm or less.

That is, since the base material for an oxide superconducting conductor of the present invention has a double structure in which a layer made of Ag is formed on a metal base material, the strength which has been a problem of the conventional Ag base material is improved. It is a solution to the problem. In addition, since the technique used for forming or laminating Ag on the metal base material can be applied to the technique used in the conventional production of a clad material, a high-strength base material can be obtained at low cost, An oxide superconductor can be manufactured without impairing the advantages of Ag base materials.

Next, in the base material for an oxide superconducting conductor of the present invention, an oxide superconducting layer is formed by chemically reacting a raw material gas of the oxide superconducting material on at least one surface side to form an oxide superconducting conductor. Which is a tape-shaped base material, a tape-shaped metal base material, an Ag layer made of Ag having a rolling texture formed on at least one surface side of the metal base material, the metal base material and the Ag layer And a barrier layer formed between the Ag layer and the barrier layer, the Ag layer having a thickness of 5 μm or more 10
It is characterized in that it is set to be not more than μm.

Between the metal base material of the base material and the Ag layer,
With the configuration including the barrier layer, the constituent elements of the metal base material are diffused to the Ag layer side by the heat treatment for introducing the rolling texture into the Ag layer and the heating for forming the oxide superconducting layer. Can be suppressed. Therefore, if the base material for an oxide superconducting conductor of the present configuration is used, it is possible to prevent the crystal orientation and the crystal continuity of the oxide superconducting layer from being impaired by such diffusion, and thus it has excellent superconducting properties. An oxide superconducting conductor can be realized.

Next, the method for producing an oxide superconducting conductor of the present invention comprises an oxidation process comprising a tape-shaped metal base material and an Ag layer having a rolling texture formed on at least one surface side of the metal base material. Forming a diffusion layer in which Cu is diffused on the surface layer portion of the Ag layer of the base material for a superconducting conductor, and forming an oxide superconducting layer by chemically reacting a raw material gas of the oxide superconductor on the diffusion layer. And a step of forming a film.

With such a structure, the action of the diffusion layer suppresses the diffusion of Cu from the oxide superconducting layer to the Ag base material, and easily manufactures an oxide superconducting conductor having excellent superconducting properties. be able to. Moreover, unlike a polycrystalline intermediate layer such as YSZ, a diffusion layer in which Cu is diffused does not require the use of a high-priced and expensive film-forming technique, and can be easily formed by ordinary sputtering, vapor deposition, CVD, or the like. Can be formed. Therefore, according to this structure, an oxide superconducting conductor having excellent superconducting properties can be manufactured at low cost.

Next, in the method for producing an oxide superconducting conductor of the present invention, a raw material gas of the oxide superconducting conductor is chemically reacted with at least one surface side of the moving tape-shaped substrate to form an oxide superconducting thin film. A reactor for performing a CVD reaction for forming a film, a source gas supply device for an oxide superconducting conductor for supplying an oxide superconducting conductor source gas to the reactor, and a gas exhaust unit for exhausting gas in the reactor are provided, and the oxidation is performed. Raw material gas supply means of the oxide superconducting conductor, a raw material gas supply source of the oxide superconducting conductor, a raw material gas introduction pipe of the oxide superconducting conductor, an oxygen gas supply means for supplying oxygen gas, the reactor, the reactor, The base material introduction part, the reaction generation chamber, and the base material discharge part are respectively partitioned via partition walls, and a plurality of the reaction generation chambers are provided in series in the moving direction of the tape-shaped base material. A passage hole is formed, a base material transfer region that passes through the base material introduction part, the plurality of reaction generation chambers, and the base material extraction part is formed inside the reactor, and gas diffusion is performed in each of the plurality of reaction generation chambers. And a plurality of reaction production chambers are provided as a film formation region, and a raw material gas introduction pipe for the oxide superconductor is connected to the reaction production chambers via the gas diffusion unit. It is characterized in that the film is formed by using.

With this structure, the diffusion layers and the oxide superconducting layer can be continuously formed by a plurality of reaction generating chambers, so that the oxide superconducting conductor can be efficiently manufactured. Can be done. Therefore, it is possible to improve the product yield and reduce the manufacturing cost.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION A base material for an oxide superconducting conductor according to the present invention, an oxide superconducting conductor, a method for producing the same, and an apparatus used for carrying out this method will be described with reference to the drawings. .

(Substrate for oxide superconducting conductor) FIG. 1 (A)
FIG. 1 is a diagram showing a cross-sectional structure of one embodiment of a base material for an oxide superconducting conductor of the present invention, and FIG. 1 (B) shows another embodiment of the base material for an oxide superconducting conductor of the present invention. FIG.
A substrate 10 for an oxide superconducting conductor shown in FIG. 1A is composed of a metal base material 1 made of a high-strength metal material and an Ag foil (Ag layer) 2 bonded on the metal base material 1. Has been done. Base material 20 for oxide superconducting conductor shown in FIG.
Is composed of a metal base material 11, a barrier layer 13 formed on the metal base material 11, and an Ag foil (Ag layer) 12 bonded on the barrier layer 13. Incidentally, FIG.
Although only the cross-sectional structure of the oxide superconducting conductor is shown in FIGS. 1A and 1B, it is actually a tape shape extending in the direction perpendicular to the paper surface.

The metal base materials 1 and 11 are made of Hastelloy (N
(iCrMo alloy), Ni, Inconel, stainless steel, and the like, which are preferably made of a material having excellent high-temperature strength. By using these metal materials as the metal base material,
When the Ag layer is heat-treated to form a texture or is heated to a high temperature for forming the oxide superconducting layer, softening of the metal base material and diffusion of constituent elements of the metal base material are less likely to occur. Therefore, a good texture is formed in the Ag layer,
Since it can be maintained and good crystal orientation and crystal continuity can be realized in the oxide superconducting layer,
An oxide superconducting conductor having good superconducting properties can be produced. The thickness of the metal base materials 1 and 11 is
The thickness may be appropriately changed depending on the purpose, but is 50 μm to 200 μm.
It is preferable that the thickness is about μm.

The Ag foils 2 and 12 are made of Ag having a rolling texture. As the rolling texture of the Ag foils 2 and 12, a {100} plane is formed on the surface of the base material, and a cubic texture in which <001> is preferentially oriented in the longitudinal direction is {100} <001> texture, {11 on the surface of the substrate
0 plane, {110} <110> texture having a cubic texture in which <110> is preferentially oriented in the longitudinal direction, {110} plane on the substrate surface, and <001> in the longitudinal direction.
Having a cubic texture with preferentially oriented {11
0} <001> texture is preferable. By using an oriented Ag base material having these textures, particularly when forming a YBaCuO-based oxide superconducting layer, the crystal lattice constant of the base material surface and the lattice constant of the oxide superconducting layer are made close to each other. Therefore, it is possible to improve the crystallinity of the oxide superconducting layer to be formed and to provide excellent superconducting properties.

The rolling texture of the Ag foils 2 and 12 is a texture obtained by applying a rolled Ag foil to the metal base material 1 or the barrier layer 13 and then heat treating it. Alternatively, the rolled Ag foil may be heat-treated in advance to form a rolling texture in the Ag foil, and the Ag foil having the rolling texture may be used as the metal base material 1 or the barrier layer 1.
It may be formed by adhering to No. 3.

The film thickness of the Ag foil 2 on the substrate 10 having no barrier layer is in the range of 10 μm to 100 μm. When the film thickness of the Ag foil 2 is less than 10 μm, the constituent elements of the metal base material 1 pass through the Ag foil 2 and diffuse into the oxide superconducting layer formed on the Ag foil 2, which is not preferable. On the other hand, when it exceeds 100 μm, the amount of Ag used is large and the cost of the base material is high, which is not preferable.

On the other hand, in the base material 20 having the barrier layer 13, since the barrier layer 13 can suppress the diffusion of the elements of the metal base material 11, the Ag foil 12 should be made thinner. You can Therefore, the Ag foil 12
Is 5 μm or more and 10 μm or less. Ag foil 1
When the film thickness of 2 is less than 5 μm, it is difficult to attach the Ag foil 12 to the barrier layer 13, which is not preferable in practice. Further, if it exceeds 10 μm, the cost of the base material increases, which is not preferable.

In the barrier layer 13 shown in FIG. 1B, the elements constituting the metal base materials 1 and 11 are heat-treated for forming the above-mentioned rolling texture and heating for bonding the Ag foil to the metal base material. It is provided to prevent it from diffusing into the Ag foil and impairing the crystal orientation of the Ag foil. As a material forming the barrier layer 13, a metal such as Pt, Au, or Cu, or an oxide such as MgO, YSZ (yttria-stabilized zirconia), or CeO ₂ can be used.

The film thickness of the barrier layer 13 may be set to an optimum film thickness depending on the material constituting the barrier layer 13, but when a metal material is used, it is preferably about 0.2 to 5 μm, and when an oxide is used. In particular, it is preferably 0.1 to 0.2 μm. The barrier layer 13 made of a metal material has a thickness of 0.2
If it is less than μm, the effect of suppressing the diffusion of the element of the metal base material 11 cannot be sufficiently obtained, and if it exceeds 0.5 μm, the internal stress of the barrier layer tends to cause peeling. Further, also in the barrier layer 13 composed of an oxide, if the film thickness is less than 0.1 μm, the effect of suppressing the diffusion of elements of the metal base material 11 is not sufficient, and if it exceeds 0.2 μm, the barrier layer 13 is formed. In addition to the increase in the time required for the cost, the barrier layer 13 may be cracked by the stress when the base material is bent.

Substrate 1 for oxide superconducting conductor having the above structure
According to Nos. 0 and 20, since the Ag foils 2 and 12 are formed on the metal base materials 1 and 11 made of high-strength metal such as Hastelloy, the base material which has been a problem of the conventional Ag base material. The strength can be greatly improved, and the application to wires and the like can be facilitated. Further, since the Ag foils 2 and 12, which are the surface layers, have a structure having a rolling texture, the lattice matching with the oxide superconducting layer formed on the Ag foils 2 and 12 becomes good, It is possible to form an oxide superconducting conductor having excellent superconducting properties. Further, if the base materials 10 and 20 according to the present invention are used, the oxide superconducting layer can be directly formed on the Ag foils 2 and 12, so that the structure of the oxide superconducting conductor can be simplified and It also has the advantage of easy manufacture.

(Oxide Superconducting Conductor and Manufacturing Method Thereof) Next, a method for manufacturing an oxide superconducting conductor according to the present invention will be described below with reference to FIGS. The method for producing an oxide superconducting layer according to the present invention is shown in FIG.
The oxide superconducting base material 10 or 20 shown in (B) is used. Then, a diffusion layer in which Cu is diffused is formed on the surface layer portions of the Ag foils 2 and 12 of the base materials 10 and 20, and then a raw material gas of the oxide superconductor is chemically reacted on the diffusion layer. The oxide superconducting layer is formed.

[Oxide Superconducting Conductor] FIG. 2 shows an example of a sectional structure of an oxide superconducting conductor according to the present invention. The oxide superconducting conductor S _A shown in FIG. 2A is an example of an oxide superconducting conductor using the base material having the configuration shown in FIG.
When a metal one surface side of the base material a paste (the shown upper surface) combined the Ag foil (Ag layer) b consisting of base material T _A, an oxide superconducting layer is formed on the substrate T d And the surface layer portion of the Ag foil b of the base material T _A is C
A diffusion layer c in which u is diffused in Ag is formed, and an oxide superconducting layer d is formed on the diffusion layer c.

In the oxide superconducting conductor S _A having the above structure, the thickness of the Ag foil b is preferably 10 μm or more and 100 μm or less. If the film thickness of the Ag foil b is less than 10 μm, the constituent elements of the metal base material a pass through the Ag foil b and diffuse into the oxide superconducting layer d, which is a cause of deterioration of superconducting properties, which is not preferable. If it exceeds 100 μm,
This is not preferable because the cost of the base material increases.

On the other hand, the oxide superconducting conductor S _B shown in FIG. 2 (B) is an example of an oxide superconducting conductor using the base material having the structure shown in FIG. 1 (B). A barrier layer e bonded to one surface side (upper surface side in the drawing) of the metal base material a,
Ag foil (Ag layer) b bonded on the barrier layer e
Is different from the oxide superconductor S _A shown in FIG. 2 (A) in that it uses a base material T _B consisting of.

In the oxide superconducting conductor S _B having the above structure, the element forming the metal base material by the barrier layer e is A
It is possible to prevent diffusion into the oxide superconducting layer d on the g foil b or the Ag foil b. Therefore, according to this configuration, A
Even if the g-foil b is thinned, the oxide superconducting layer d having good crystal continuity can be formed. In the oxide superconducting conductor S _B including the barrier layer e, if the film thickness of the Ag foil b is less than 5 μm, it is difficult to attach the Ag foil b to the barrier layer e, which is not practical. Also, 10 μm
If it exceeds the range, the cost of the base material increases, which is not preferable.

The element diffused in the diffusion layer c is
Besides diffusing the Cu element, an alloy mainly containing Cu may be used. For example, in Cu, Pt, Au, Pd, Ba,
What added Y etc. can be used. This diffusion layer c can be formed by using a well-known film forming technique such as a sputtering method, a vapor deposition method or a CVD method, and can be formed at a high level such as an ion beam sputtering method such as YSZ which has been conventionally used as an intermediate layer. There is no need to use expensive film forming technology. Also,
Since the formation speed can be greatly improved by using a normal sputtering method or CVD method, it is possible to easily and efficiently perform the manufacturing.

The layer thickness of the diffusion layer is 100 nm or more and 30.
The range of 0 nm or less is preferable, and C of the diffusion layer c is
The u content is 50 μg / cm ² or more and 300 μg / cm ²
It is preferably within the range of cm ² or less. When the diffusion layer c is controlled within these ranges, the crystal orientation and crystal continuity of the oxide superconducting layer b can be improved, and an oxide superconductor having more excellent superconducting properties can be provided.
When the layer thickness of the diffusion layer is less than 100 nm or the Cu content is less than 50 μg / cm ^{2, the} amount of Cu contained in the diffusion layer is insufficient, so that the C from the oxide superconducting layer is insufficient.
It is not preferable because the diffusion of u cannot be prevented, and the layer thickness exceeds 300 nm or the Cu content is 300 μ.
If it exceeds g / cm ² , excess Cu reacts with the oxygen gas used to form the oxide superconducting layer and Cu
It is not preferable because it precipitates as an oxide such as O.

The oxide superconducting conductor S of the present invention having the above structure
_A and S _B have a diffusion layer formed by diffusing Cu in the surface layer portion of the Ag foil b as the base material, so that Cu contained in the oxide superconducting layer diffuses into the Ag foil b. To prevent
In the oxide superconducting conductor in which the oxide superconducting layer is formed on the Ag foil, a high Jc of 100,000 A / cm ² or more can be realized. In addition, the base materials T _A and T _B are A on the metal base material a.
Due to the double structure in which the g layer b is formed, the oxide superconducting conductor has excellent strength.

[Production method of oxide superconducting conductor]
The oxide superconductor S _A, and a manufacturing apparatus for manufacturing the S _B, the method of manufacturing an oxide superconducting conductor using the manufacturing apparatus will be described with reference to FIGS. 3 to 6 show an example of a device for manufacturing an oxide superconducting conductor according to the present invention. The manufacturing device of this example has three CVD units A having substantially the same structure as shown in FIG. , B,
C is incorporated so that an oxide superconducting layer can be laminated on at least one surface of the tape-shaped substrate T in the reaction generation chamber 35A of each CVD reaction device 30A.

This apparatus for manufacturing an oxide superconducting conductor has a cylindrical quartz reactor 31A whose both ends are horizontally long and closed. This reactor 31A has a partition wall 3 as shown in FIG.
2A and 33A in order from the left side of FIG.
4A, a reaction generation chamber 35A, and a base material lead-out portion 36A, and the reaction generation chamber 35A is divided by a plurality of partition walls 37A (four partition walls in the drawing) provided between the partition walls 32A and 33A. It is divided into multiple parts (three parts in the drawing), and each has a structure that is approximately equal to each other.
Two boundary chambers 38A are defined between the adjacent reaction generation chambers 35A and 35A (between the adjacent partition walls 37 and 37). Therefore, the reactor 31A is provided with a plurality of reaction reaction chambers 35A (three reaction generation chambers in the drawing) in series in the moving direction of the tape-shaped substrate T fed into the substrate transfer region R described later. It will be. The material forming the reactor 31A is not limited to quartz, but may be a metal having excellent corrosion resistance such as stainless steel.

The partition walls 32A, 37A, 37A, 37
As shown in FIGS. 5 and 6, a passage hole 3 through which a long tape-shaped base material T can pass is provided in the lower center of A, 37A, 33A.
9A are respectively formed, and inside the reactor 31A, a base material transfer region R is formed so as to cross the central portion thereof. Further, the base material introducing portion 34A is provided with an introduction hole for introducing the tape-shaped base material T, and the base material leading portion 36A is provided with a lead hole for guiding the base material T. . Further, the periphery of the introduction hole and the outlet hole is a seal for closing the gap between the holes while the base material T is being passed therethrough to keep the base material introduction part 34A and the base material extraction part 36A in an airtight state. A stop mechanism (not shown) is provided.

As shown in FIG. 5, a substantially pyramidal truncated gas diffusion portion 40 is attached to the ceiling portion of each reaction generation chamber 35A. These gas diffusion parts 40 include a gas diffusion member 45 attached to the reactor 31A and a gas diffusion member 45.
Gas introduction pipe 5 connected to the ceiling wall 44 of the above and supplying the raw material gas of the diffusion layer or the oxide superconductor to the gas diffusion member 45.
3A and a slit nozzle (not shown) provided at the tip of the gas introduction pipe 53A. Also,
The bottom surface of the gas diffusion member 45 has an elongated rectangular opening 4
6A, and the gas diffusion member 4 through the opening 46A.
5A is connected to the reaction generation chamber 35A.

As shown in FIG. 3, a cutoff gas supply means 38B is connected to the ceiling of the boundary chamber 38A through a supply pipe 38C, and the cutoff gas supply means 38B is provided on both sides of the boundary chamber 38A. A shutoff gas for shutting off 35A and 35A is supplied, and the supply pipe 38C is connected to the boundary chamber 38A via the shutoff gas ejection portion. Argon gas, for example, is selected as the blocking gas.

On the other hand, each reaction generation chamber 35A and boundary chamber 38
Below A, as shown in FIG. 6, an exhaust chamber 70A is provided along the lengthwise direction of the base material transfer region R so as to penetrate each reaction generation chamber 35A and boundary chamber 38A. As shown in FIG. 5, in the upper portion of the exhaust chamber 70A, elongated rectangular gas exhaust holes 70a, 70a are formed along the length direction of the tape-shaped base material T passed through the base material transfer region R, respectively. Gas exhaust holes 70a, 7 are formed on both sides of the base material T so as to penetrate the reaction generation chamber 35A and the boundary chamber 38A.
Both sides or ends of the base material transfer region R of the partition walls 32, 33, and 37 are in a penetrating state at 0a. Also, the exhaust chamber 70A
A plurality of (seven in the drawing) exhaust pipes 70b are connected to the lower part of each of the exhaust pipes 70b.
It is connected to a pressure adjusting device 72 having a vacuum pump 71 shown in FIG.

Further, the exhaust chamber 70A having the gas exhaust holes 70a, 70a formed therein, the plurality of exhaust pipes 70b having the exhaust holes 70c, 70e, the valve 70d, the vacuum pump 71, and the pressure adjusting device 72 are used. Gas exhaust means 80A
Is configured. Gas exhaust means 80 having such a configuration
A is capable of promptly exhausting the raw material gas, the oxygen gas, the inert gas, and the blocking gas inside the CVD reactor 30.

A heater 47A is provided outside the reactor 31A as shown in FIG. In the example shown in FIG. 3, the heating heater 47A is continuous over the three reaction generation chambers 35A, but this heating heater 47A is used for each CV.
It is also possible to have an independent structure with respect to the reaction generation chamber 35A of the D reaction device 30. Further, the base material introducing portion 34A of the reactor 31A is connected to the inert gas supply source 51A, and the base material leading portion 36A is connected to the oxygen gas supply source 51B.

Each source gas introduction pipe 5 connected to the ceiling wall 44 of the gas diffusion portion 40 provided in the CVD unit A
As shown in FIG. 3, 3A is connected to a vaporizer (raw material gas supply source) of raw material gas of a raw material gas supply means 50a for a diffusion layer, which will be described later, via a gas mixer 48, which will be described later.
Further, each source gas introduction pipe 5 connected to the ceiling wall 44 of each gas diffusion portion 40 provided in the CVD units B and C
3A is connected via a gas mixer 48 to a source gas vaporizer (source gas supply source) of a source gas supply means 50b for an oxide superconductor.

The raw material gas supply means 50a for the diffusion layer and the raw material gas supply means 50b for the oxide superconductor include a raw solution supply device 65 and a liquid raw material supply device 55 shown in FIG. Source 62). The vaporizer 62 accommodates a tip portion (lower portion in the drawing) of a liquid raw material supply device 55 described later. Further, a heater 63 is attached to the outer peripheral portion of the vaporizer 62, and the raw material gas is obtained by heating the raw material solution 66 supplied from the liquid raw material supply device 55 to a desired temperature by the heater 63 and vaporizing the raw material solution 66. It is designed to be used. A heat retaining member 62A is installed on the inner bottom of the vaporizer 62. The heat retaining member 62A may be any material as long as it has a large heat capacity and does not react with the liquid raw material 66, and a metal thick plate is particularly preferable. Stainless steel, Hastelloy, Inconel, etc. are preferred.

As shown in FIG. 4, the liquid raw material supply device 55 has a tubular raw material solution supply section 56 and a cylindrical carrier gas supply section 5 surrounding the outer circumference of the supply section 56.
7 and a double structure. The raw material solution supply unit 56 supplies a raw material solution 66 fed from a stock solution supply device 65 described later into the vaporizer 62. The carrier gas supply part 57 is for flowing a carrier gas for ejecting the above-mentioned raw material solution 66 into a gap between the raw material solution supply part 56. Then, the MFC for carrier gas is provided on the upper part of the carrier gas supply unit 57.
Carrier gas supply source 60 via (flow rate regulator) 60a
Are connected so that a carrier gas such as an argon gas, a helium gas, or a nitrogen gas can be supplied into the carrier gas supply part 57 (a gap with the raw material solution supply part 56).

Further, the inside of the carburetor 62 is vertically divided into two parts by a partition plate 62a, and the divided regions are communicated with each other on the lower side of the partition plate 62a. Gas introduction pipe 5 after the raw material gas has passed
3 is configured to be able to flow to the connected portion 53A.

In the above-mentioned liquid raw material supply device 55, when the raw material solution 66 is sent into the raw material solution supply part 56 at a constant flow rate and the carrier gas is sent to the carrier gas supply part 57 at a constant flow rate, the raw material solution 66 is supplied. Although reaching the tip portion of the portion 56, the carrier gas flows from the tip of the carrier gas supply portion 57 on the outer peripheral side of the tip portion, so that when the tip portion 59 is blown out, the raw material solution 66 is vaporized together with the carrier gas. The gas is introduced into the inside of the vaporizer 62, and is heated and vaporized while moving inside the vaporizer 62 until it reaches the bottom portion thereof, and becomes a raw material gas. Further, it reaches the heat retaining member 62A installed at the bottom of the vaporizer 62, and the heat retaining member 62A
As a result, further vaporization is performed, and the raw material solution is completely vaporized to be a raw material gas. In the structure of the present embodiment, the raw material solution is not atomized from the tip of the raw material solution supply unit 56 but is used as the raw material gas only by heating and mixing the carrier gas. It is preferable that the liquid source material does not collide with the inner wall of the vaporizer 62 before the source material gas is vaporized.

A stock solution supply unit 65 is connected to the stock solution supply unit 56 of the liquid source supply apparatus 55 through a connecting pipe 67 equipped with a pressurizing liquid pump 67a.
The stock solution supply device 65 includes a storage container 68 and a purge gas source 6
9, the raw material solution 66 is stored in the storage container 68. The raw material solution 66 is a pressurized liquid pump 67a.
Is sucked in, the flow rate of which is adjusted by the MFC 67b, and the raw material solution is fed to the raw material solution supply unit 56.

Further, as shown in FIG.
A base material transport mechanism 78 including a tension drum 76 and a delivery drum 77 for supplying the tape-shaped base material T to the CVD reaction apparatus 30A is provided on the side (front side) of the base material introduction unit 34A of A. It is provided. This tension drum 7
6 and the delivery drum 77 are configured to be rotatable in the forward and reverse directions.
A tension drum 73 for winding the tape-shaped base material T passing through the base material transfer region R in the reactor 31A is provided on the side portion (post-stage side) of the base material lead-out portion 36A of the reactor 31A, and a winding drum. Substrate transport mechanism 75 including the take-up drum 74
Is provided. The tension drum 73 and the winding drum 74 are also configured to be freely rotatable in the forward and reverse directions.

Next, a diffusion layer in which Cu is diffused is formed on the tape-shaped base material T by using the oxide superconducting conductor manufacturing apparatus having the CVD units A, B and C configured as described above. The case of forming an oxide superconducting layer on the diffusion layer to manufacture an oxide superconducting conductor will be described.

To manufacture an oxide superconducting conductor using the manufacturing apparatus shown in FIGS. 3 to 6, first, a tape-shaped base material T is used.
A raw material solution for the diffusion layer and a raw material solution for the oxide superconducting conductor are prepared. As the base material T, the one having the configuration shown in FIG. 1 described above can be used.

The raw material solution for forming the diffusion layer by the CVD reaction is preferably one in which the metal complex forming the diffusion layer is dispersed in a solvent. Specifically, when a diffusion layer made of Cu is formed, Cu (thd) ₂ or Cu (D
PM) ₂ etc. dissolved in a solvent such as tetrahydrofuran (THF), toluene, isopropanol, diglyme (2,5,8-trioxononane) can be used.
(Thd = 2,2,6,6-tetramethyl-3,5-heptanedione)

As the element to be diffused in the diffusion layer c, Cu element may be diffused or an alloy mainly containing Cu may be used. For example, Cu with Pt, Au, Pd, B
It is possible to use those to which a, Y, etc. have been added, and in the case of diffusing these, the metal complex of the element to be added may be added to the above raw material solution. The diffusion layer c can be formed by a CVD method as in the manufacturing method of the present embodiment, or can be formed by a known film forming technique such as a sputtering method or an evaporation method, and has been conventionally used as an intermediate layer. Unlike YSZ, it is not necessary to use an advanced and expensive film forming technique such as an ion beam sputtering method. Further, since the formation speed can be greatly improved by using the ordinary sputtering method, CVD method, or the like, it is possible to easily and efficiently carry out the production.

An oxide superconductor was produced by a CVD reaction.
The raw material solution for making the oxide is the metal that constitutes the oxide superconductor.
It is preferable that the complex is dispersed in a solvent. Specifically
Is Y ₁Ba₂Cu₃O_7-x-Based oxide superconductivity of the following composition
When forming a layer, Ba-bis-2,2,6,6-tetrame
Chill-3,5-heptanedione-bis-1,10-phenanthate
Lorin (Ba (thd)₂・ Phen₂) And Y (th
d)₂And Cu (thd)₂Metal complexes such as
Can be done (phen = phenanthroline), and Y-
Bis-2,2,6,6-tetramethyl-3,5-heptanedionate
(Y (DPM)₃) And Ba (DPM)₂, Cu (DP
M)₂Metal complexes such as

For the oxide superconducting layer, in addition to the above Y system, La represented by the composition formula La _2−x Ba _x CuO ₄ is used.
_{System, Bi 2 Sr 2 Ca n-} 1 Cu n O 2n + 2 Bi system (n is a natural number) is represented by a composition _{formula, Tl 2 Ba 2 Ca n-} 1 Cu n O
_Since many kinds of oxide superconducting layers such as Tl-based ones represented by the composition formula of _{2n + 2} (n is a natural number) are known, the above-mentioned CVD using a metal complex salt according to the intended composition is known.
The law can be implemented. Here, for example, in the case of producing an oxide superconducting layer other than Y-based oxide, depending on the required compositional system,
Triphenylbismuth (III), bis (dipivaloimethanato) strontium (II), bis (dipivaloimethanato) calcium (II), tris (dipivaloimethanato)
A metal complex salt such as lanthanum (III) can be appropriately used for production of the oxide superconducting layer of each system.

Next, the prepared raw material solution is stored as a raw material solution 66 in the storage container 68 of the raw liquid supply apparatus 65 shown in FIG. 4, and is connected to the liquid raw material supply apparatus 55. In this example, the source gas supply means 50a for the diffusion layer was connected to the CVD unit A, and the source gas supply means 50b for the oxide superconductor was connected to the CVD units B and C, respectively.

After the tape-shaped base material T is prepared, it is moved to the base material transfer region R in the oxide superconducting conductor manufacturing apparatus by the base material transfer mechanism 78 from the base material introducing section 34A at a predetermined moving speed. And is wound up by the winding drum 74 of the base material transport mechanism. Further, the base material T in the reaction generation chamber 35A is heated to a predetermined temperature by the heater 47A. Next, when the tape-shaped base material T is fed into the reactor 31A, the raw material solution 66 is supplied from the storage container 68 by the pressure type liquid pump 67a provided in the raw material gas supply means 50a and 50b to a flow rate of about 0.1 to 10 ccm. The carrier gas is fed into the raw material solution supply unit 56, and at the same time, the carrier gas is fed into the carrier gas supply unit 57 at a flow rate of about 200 to 550 ccm. Further, the vaporizer 62 is heated to the vaporization temperature of the raw material solution 66 or higher.

Then, the raw material solution 6 on the mist at a constant flow rate
6 is continuously supplied into the vaporizer 62, heated and vaporized by the heater 63 to become a raw material gas, and this raw material gas is supplied to each gas diffusion portion 45 of the CVD units A, B, C via the gas introduction pipe 53A. Supplied continuously. Next, the source gas that has moved to the reaction generation chamber 35A moves from the upper side to the lower side of the reaction generation chamber 35A, reacts on the heated base material T to deposit reaction products, and diffuses in the CVD unit A. Even in the case where a layer is formed on the substrate T, an oxide superconducting layer is formed on the diffusion layer in the CVD unit B.
In the unit C, an oxide superconducting layer is formed on the oxide superconducting layer. At this time, the control means 82A controls the CV
The gas partial pressures of the D units A, B, and C are independently controlled, and the raw material gas supply means 50a, 50b, 50b are maintained so as to maintain a predetermined gas partial pressure in each reaction generation chamber 35A.
To control. At this time, the control unit 82A determines that the gas partial pressure of the reaction generation chamber 35 on the downstream side in the moving direction of the tape-shaped base material T is higher than the gas partial pressure of the reaction generation chamber 35 in the moving direction of the tape-shaped base material T. Raw material gas supply means 50a, 50
It is preferable to control b and 50b. Then, the base material T on which these layers are formed is wound around the winding drum 74. After the formation of the oxide superconducting layer, a heat treatment for adjusting the crystal structure of the oxide superconducting thin film may be performed if necessary.

Finally, when a stabilizing layer made of silver or the like is further formed on the oxide superconducting conductor S formed as described above by sputtering or vapor deposition, the oxide superconducting conductor having the stabilizing layer is formed. An oxide superconducting conductor equivalent to S can be obtained. The stabilizing layer can also be formed by the CVD method in one or more of the reaction generation chambers 35A of the manufacturing apparatus shown in FIGS. With such a configuration, the oxide superconducting conductor having the stabilizing layer can be continuously manufactured in the above manufacturing apparatus.

When the oxide superconducting conductor S is manufactured by using the apparatus having the structure shown in FIGS. 3 to 6, the oxide superconducting conductor having the metal intermediate layer and the stabilizing layer is formed on the substrate T once. It can be manufactured by moving. Even in the oxide superconducting conductor obtained in this example, since the metal intermediate layer and the oxide superconducting layer having an appropriate thickness with the transport speed of the base material T in an appropriate range are laminated, It is considered to be an oxide superconducting conductor having excellent superconducting properties.

The substrate T is repeatedly reciprocated between the delivery drum 77 and the winding drum 74 by using the apparatus shown in FIGS. 3 to 6, and the oxide having a lamination number of 4 layers or 6 layers is stacked. The oxide superconducting conductor may be manufactured by stacking superconducting layers. In the above example, the metal intermediate layer is formed in the reaction generation chamber 35A of the first stage (CVD unit A), and the oxide is formed in the reaction generation chamber 35A of the second and third stages (CVD unit B, C) thereafter. Although the case of forming the superconducting layer has been described, the manufacturing method using the manufacturing apparatus of this example is not limited to this method. For example, in a state where all the three reaction generation chambers 35A are assigned to the film formation of the metal intermediate layer, the metal intermediate layer is first formed on the substrate T while moving the substrate T, and the film having the required length is formed. After the completion, this time, the supply means for supplying the raw material gas is replaced in the three reaction production chambers 35A so that the oxide superconducting layer can be formed, and the delivery drum 7 is replaced.
7 and the direction of rotation of the winding drum 74 are reversed to move the base material T from the base material lead-out portion 36A side toward the base material introducing portion 34A side, and the metal intermediate formed on the base material T. It is also possible to form an oxide superconducting layer on the layer.

[0068]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. (Example 1) [Liquid material and base material] In this example, tape-shaped Hastelloy was used as a metal base material, and {11
The oxide superconducting conductor was produced using the base material to which the Ag foil in which the 0} <110> texture was formed was stuck together. Also,
In this example, two types of base materials were used in which a metal base material having a size of ^W 10 mm × ^L 50 mm × ^t 0.09 mm and an Ag foil having a thickness of 10 μm and a thickness of 50 μm were attached to each other. In this example, the Ag foil with the texture formed is used, but the Ag rolled foil may be bonded to the metal base material and heat-treated to form the texture.

First, in order to form a Y-based oxide superconducting layer having a composition of Y ₁ Ba ₂ Cu ₃ O _7-x , Ba-bis-2,2,6,6-tetra was used as a raw material solution for CVD. Methyl-3,5-heptanedione-bis-1,10-phenanthroline (Ba (th
d) ₂ (phen) ₂ ), Y (thd) ₂ and Cu (t
hd) ₂ was used. For each of these, Y: Ba: Cu =
A liquid raw material (raw material solution) for the oxide superconducting layer, which was mixed at a molar ratio of 1.0: 3.0: 2.7 and added to a solvent of tetrahydrofuran (THF) so as to be 7.0% by weight. And Further, as a liquid material for the diffusion layer, Cu (t
hd) ₂ was added to a solvent of THF so as to be 7.0% by weight to prepare.

In this example, the manufacturing process of the oxide superconducting conductor is shown in FIG.
~ Using the manufacturing apparatus shown in Fig. 6, as a manufacturing method, first, a diffusion layer in which Cu is diffused is formed on the surface layer portion of the base material using the liquid raw material for the diffusion layer, and then the oxide superconductor A method of producing an oxide superconducting conductor by forming a film of the oxide superconducting conductor on this diffusion layer using a liquid raw material was adopted.

[Formation of Diffusion Layer] The above raw material solution for the diffusion layer is continuously supplied to the raw material solution supply unit of the liquid raw material supply device at a flow rate of 0.27 ml / min by a pressure type liquid pump (pressurizing source). Supplied. At the same time, Ar was fed as a carrier gas into the carrier gas supply section at a flow rate of about 300 ccm.
By the above operation, a certain amount of mist-like liquid raw material is continuously supplied into the vaporizer, and the raw material gas obtained by vaporizing the liquid raw material is continuously supplied to the gas diffusion member of the CVD reaction device through the gas introduction pipe in a certain amount. Supplied. The temperature of the vaporizer and the transport pipe at this time was 230 ° C.

The base material moving speed in the reactor of the base material moved from the sending drum side to the winding drum side is 6.0 m / h, the base material heating temperature is 700 ° C., and the reactor internal pressure is 5.0 Tor.
Setting to r (5.0 × 133 Pa), a Cu diffusion layer having a layer thickness of 200 nm was continuously formed on the surface layer of the base material, and film formation was performed until the transfer of the base material of a predetermined length was completed. . The Cu content in the surface layer of the base material on which the diffusion layer was formed was analyzed and found to be 100 to 200 μg per cm ² .

[Formation of Oxide Superconducting Layer] Next, after the movement of the base material of a required length to be moved from the sending drum side to the winding drum side is completed, the raw material solution for the diffusion layer is added to the oxide superconducting layer. The raw material solution of the layer was replaced. Then, 0.27 ml of the raw material solution of the oxide superconducting layer is applied by a pressure type liquid pump.
The liquid was continuously supplied to the raw material solution supply part of the liquid raw material supply device at a flow rate of / minute, and at the same time, Ar as a carrier gas was sent to the carrier gas supply part at a flow rate of about 300 ccm. By the above operation, a certain amount of mist-like liquid raw material is continuously supplied into the vaporizer, and the raw material gas obtained by vaporizing the liquid raw material is continuously supplied to the gas diffusion member of the CVD reactor through the gas introduction pipe in a certain amount. Supplied to. The temperature of the vaporizer and the transport pipe at this time was 230 ° C.

Then, the rotation speed of the feed drum and the take-up drum is reversed, and the base material moving speed in the reactor of the base material moved from the take-up drum side to the feed drum side is 1.0 m / m.
h, substrate heating temperature is 780 ° C., reactor pressure is 5.0
Torr (5.0 × 133 Pa), set oxygen partial pressure value is 1.43 to 1.53 Torr (1.43 × 133 to 1.
53 × 133 Pa) and set YB on the moving substrate.
An aCuO-based oxide superconducting layer was continuously formed, and film formation was performed until the movement of the base material of a predetermined length was completed. Through the above steps, an oxide superconducting conductor having a diffusion layer was obtained. The manufacturing conditions of the oxide superconducting conductor of Example 1 are shown in Table 1 below.

[0075]

[Table 1]

[Analysis / Evaluation] Next, 2 obtained above
For each type of oxide superconducting conductor, the Ag foil thickness is 10
The superconducting properties were evaluated by using a sample A having a thickness of μm and a sample B having a thickness of the Ag foil of 50 μm. The results are shown in Table 2. As shown in Table 2, when a base material in which a barrier layer was not provided and an Ag foil was directly laminated on a metal base material was used, the oxide superconducting conductor of Sample A having a Ag foil thickness of 50 μm was Jc. Was 130,000 A / cm ² , but the oxide superconducting conductor of Sample A in which the thickness of the Ag foil was 10 μm was
Jc was 32,000 A / cm ² . The difference of this Jc is A
It is considered that when the thickness of the g foil is 10 μm, the diffused Hastelloy constituent elements (Ni, Cr, Mo, etc.) pass through the Ag foil and reach the oxide superconducting layer, so that the superconducting characteristics are deteriorated.

[0077]

[Table 2]

Example 2 Next, using tape-shaped Hastelloy as a metal base material, a Pt foil having a thickness of 5 μm was stuck as a barrier layer on the metal base material, and a Pt foil having a thickness of 10 μm was applied on the Pt foil. A with {110} <110> texture
An oxide superconducting conductor was produced using a base material having a structure in which g foil was bonded. The diffusion layer other than the base material and the oxide superconducting layer were synthesized under the same conditions as in Sample A of Example 1 above. Table 3 shows these conditions. In this example, the barrier layer was formed by bonding Pt foils together, but a layer made of Pt may be formed as a barrier layer by a sputtering method or the like. Further, the texture of Ag foil may be formed by heat treatment after the Ag foils are bonded together.

[0079]

[Table 3]

[Analysis / Evaluation] The superconducting properties of the oxide superconducting conductor prepared as described above were evaluated as Sample C. The results are shown in Table 4. As shown in Table 4, the oxide superconducting conductor of Sample C in which the barrier layer was formed between the metal base material and the Ag foil had a Jc of 180,000 A / cm ² , which was the same as that of Sample A of Example 1 above. It was confirmed that Jc was significantly improved in comparison. It is considered that this is because the barrier layer provided on the metal base material effectively suppressed the diffusion of the Hastelloy constituent elements and formed an oxide superconducting layer having good crystal orientation on the Ag foil. To be

[0081]

[Table 4]

[0082]

As described in detail above, according to the present invention, a tape-shaped metal base material and an Ag layer having a rolling texture formed on at least one surface side of the metal base material are provided. A structure comprising an oxide superconducting conductor base material, a diffusion layer formed by diffusing Cu in the surface layer portion of the Ag layer of the oxide superconducting conductor, and an oxide superconducting layer formed on the diffusion layer. As a result, an oxide superconducting conductor having excellent strength and superconducting properties can be provided.

Next, the base material for an oxide superconducting conductor of the present invention is composed of a tape-shaped metal base material and an Ag having a rolling texture formed on at least one surface side of the metal base material.
Since the g layer is provided, the problem of strength, which has been a problem of the conventional Ag base material, is solved.
In addition, since the technique used for forming or laminating Ag on the metal base material can be applied to the technique used in the conventional production of a clad material, a high-strength base material can be obtained at low cost, An oxide superconductor can be manufactured without impairing the advantages of Ag base materials.

Further, between the metal base material and the Ag layer,
When the barrier layer is provided, the elements forming the metal base material can be suppressed from diffusing into the Ag layer or the oxide superconducting layer. Therefore, the texture of the Ag layer or the oxide superconducting layer can be suppressed. The crystal structure can be kept good, and the crystal orientation and crystal continuity of the oxide superconducting layer formed on the Ag layer can be made good.

Next, according to the method for producing an oxide superconducting conductor of the present invention, the above base material of the present invention is used and a diffusion layer in which Cu is diffused is formed on the surface layer portion of the Ag layer of the base material. Since the oxide superconducting layer is formed on the diffusion layer, diffusion of Cu from the oxide superconducting layer to the Ag base material is suppressed, and an oxide superconducting conductor having excellent superconducting properties can be easily manufactured. You can Therefore, according to the manufacturing method of the present invention, an oxide superconducting conductor having excellent superconducting properties and high strength can be manufactured at low cost.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a sectional structure of a base material for an oxide superconducting conductor according to the present invention, and FIG. 1 (A) is an example of a base material composed of a metal base material and an Ag foil. Fig. 1 (B)
Shows an example having a barrier layer between the metal base material and the Ag foil.

FIG. 2 is a diagram showing an example of a cross-sectional structure of an oxide superconducting conductor that can be produced by the method for producing an oxide superconducting conductor according to the present invention, and FIG.
FIG. 2B shows an example using the base material having the structure shown in FIG.
Shows an example using the base material having the configuration shown in FIG.

FIG. 3 is a diagram showing an overall configuration of an oxide superconducting conductor manufacturing apparatus according to the present invention.

FIG. 4 is a configuration diagram showing a structural example of a source gas supply device provided in the manufacturing apparatus shown in FIG.

5 is a perspective configuration diagram showing a structural example of a reactor provided in the manufacturing apparatus shown in FIG.

6 is a cross-sectional configuration diagram showing a structural example of a reactor provided in the manufacturing apparatus shown in FIG.

FIG. 7 is a sectional view showing an example of a conventional oxide superconducting conductor.

FIG. 8 is a cross-sectional view showing another example of a conventional oxide superconducting conductor.

[Explanation of symbols]

S _A , S _B ... Oxide superconducting conductor, a ... Metal base material, b ... Ag
Foil (Ag layer), c ... Diffusion layer, e ... Barrier layer, 38, T,
T _A , T _B ... Base material, d ... Oxide superconducting layer, A, B, C ... C
VD unit, 30A ... CVD reactor, 31A ... Reactor, 32A, 33A, 37A ... Partition wall, 34A ... Substrate introduction part, 36A ... Substrate extraction part, 38A ... Boundary chamber, 39A ...
Base material passage hole, 40 ... Gas diffusion portion, 53A ... Raw material gas introduction pipe, 80A ... Gas exhausting means, R ... Substrate transport area

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 39/24 ZAA H01L 39/24 ZAAB (72) Inventor Takashi Saito 1-5-1 Kiba, Koto-ku, Tokyo No. 20 Fuji Kitura Co., Ltd. (72) Inventor Naoji Kashima 1-20-20 Kitakaseyama, Otaka-cho, Midori-ku, Nagoya-shi, Aichi Chubu Electric Power Co., Inc. Electric Power Technology Research Institute (72) Shigeo Nagaya Midori, Nagoya, Aichi 1 of 20 Kitakanyama, Otakacho, Ward Chubu Electric Power Co., Inc. Electric Power Technology Laboratory F-term (reference) 4K030 AA11 AA14 BA42 CA02 CA17 DA02 EA06 GA14 HA04 KA08 LA03 4M113 AD35 AD36 BA18 BA28 CA33 CA34 CA35 CA36 4M114 AA29 BB08 BB09 CC03 CC05 DB02 5G321 AA01 BA01 BA03 CA24 CA27 CA28 DB33

Claims (8)

[Claims] 1. A tape-shaped metal base material, and Ag having a rolling texture formed on at least one surface side of the metal base material.
A base material for an oxide superconducting conductor including a layer, a diffusion layer formed by diffusing Cu in a surface layer portion of the Ag layer of the base material, and an oxide superconducting layer formed on the diffusion layer. An oxide superconducting conductor characterized by being provided. 2. The Ag layer has a thickness of 10 μm or more and 10 or more.
The oxide superconducting conductor according to claim 1, wherein the oxide superconducting conductor has a thickness of 0 μm or less. 3. The oxide superconducting conductor according to claim 1, wherein a barrier layer is provided between the Ag layer and the metal base material. 4. The thickness of the Ag layer is 5 μm or more and 10 μm or more.
The oxide superconducting conductor according to claim 3, wherein the oxide superconducting conductor has a thickness of m or less. 5. A tape-shaped base material for forming an oxide superconducting layer by chemically reacting a raw material gas of an oxide superconductor on at least one surface side, the tape-shaped base material comprising: And a Ag layer made of Ag having a rolling texture formed on at least one surface side of the metal base material, wherein the thickness of the Ag layer is 10 μm or more and 100 μm or less. A base material for an oxide superconducting conductor. 6. A tape-shaped substrate for forming an oxide superconducting layer by chemically reacting a raw material gas for an oxide superconductor on at least one surface side, the tape-shaped base material comprising: A metal base material, an Ag layer made of Ag having a rolling texture formed on at least one surface side of the metal base material, and a barrier layer formed between the metal base material and the Ag layer, A substrate for an oxide superconducting conductor, wherein the Ag layer has a thickness of 5 μm or more and 10 μm or less. 7. A tape-shaped metal base material, and Ag having a rolling texture formed on at least one surface side of the metal base material.
A step of forming a diffusion layer in which Cu is diffused on the surface layer part of the Ag layer of the base material for an oxide superconductor having a layer; and a raw material gas of the oxide superconductor is chemically reacted on the diffusion layer. And a step of depositing an oxide superconducting layer. 8. A reactor for performing a CVD reaction in which a raw material gas of an oxide superconducting conductor is chemically reacted with at least one surface side of a moving tape-shaped substrate to form an oxide superconducting thin film, and an oxide is provided in the reactor. A raw material gas supply means of an oxide superconducting conductor for supplying a superconducting conductor raw material gas, and a gas exhausting means for exhausting gas in the reactor are provided, and the raw material gas supply means of the oxide superconducting conductor is provided with an oxide superconducting conductor. A source gas supply source, an oxide superconducting conductor source gas introduction pipe, and an oxygen gas supply means for supplying oxygen gas are provided, and the reactor includes a base material introduction part, a reaction generation chamber, and a base material extraction part. Are partitioned via partition walls, a plurality of the reaction generation chambers are provided in series in the moving direction of the tape-shaped base material, a base material passage hole is formed in each partition wall, and a base material introduction part is provided inside the reactor. A base material transfer region that passes through the plurality of reaction generation chambers and the base material lead-out portion is formed, each of the plurality of reaction generation chambers is provided with a gas diffusion portion, and the plurality of reaction generation chambers are formed into a film. The region is defined as a region, and a film is formed by using a film forming apparatus in which a raw material gas introduction pipe of the oxide superconductor is connected to the reaction generation chamber through the gas diffusion unit. Manufacturing method of oxide superconducting conductor of.