JP2003055095A - Thin film deposition process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for depositing a thin film having excellent crystal orientation properties on a long-length base material. SOLUTION: One or more kinds of particles forcedly flown in a specified direction in a varpor phase are collided against a base material 20 to deposit a crystalline thin film on the base material 20 from one or plural kinds of particles. The surface of the base material 20 with the thin film deposited is inclined by an angle of θ to a specified (arrow) direction. Also, the surface of the base material 20 consists of a polycrystal body having a structure in which a specified crystal plane is preferentially oriented.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a crystalline thin film, and more particularly to a method for efficiently forming a thin film having a specific crystal plane preferentially oriented on a polycrystalline substrate. Regarding

[0002]

Japanese Unexamined Patent Publication No. 7-291626 discloses a method of forming a thin film having a specific crystal orientation strongly oriented on a polycrystalline or amorphous substrate by a laser deposition method. In this method, as shown in FIG. 1A, a specific crystal orientation is oriented substantially perpendicular to the base material 11 in an arrangement in which the target 12 irradiated with the laser light 13 and the base material are substantially parallel to each other. Prepare the conditions for forming the film.
Under this condition, as shown in FIG. 1B, a film is vapor-deposited on the substrate 11 tilted at a predetermined angle θ with respect to the target 12. Under this specific condition, by tilting the substrate, it is possible to deposit a film in which a specific crystal axis is strongly oriented in a plane substantially parallel to the substrate surface. In this way, the evaporation method of tilting the substrate is ISD method (Inclined Subst
rate deposition).

Goyal et al., Appl. Phys. Lett. 69 (1
2), 16 September 1996, 1795-1797 discloses a method of growing an epitaxial YBa ₂ Cu ₃ O _x film on a substrate having a biaxial texture. Specifically, this method uses a Ni sheet in which a very sharp and well-developed cubic texture is formed by thermomechanical processing. The surface of this Ni sheet is
It has a strong {100} <001> cubic orientation. In this way, Pt,
A noble metal such as Pd or Ag is deposited on top of which Y
The Ba ₂ Cu ₃ O _x film is epitaxially grown. The obtained YBa ₂ Cu ₃ O _x film was 10 ^{5 at} 77K under zero magnetic field.
It has a critical current density (Jc) of A / cm ² . The biaxially textured substrate used here is RABiT (Rolling
-Assisted-Biaxially-Textured-Substrate).

[0004]

DISCLOSURE OF THE INVENTION The conventional ISD described above
According to the method, a single crystal film can be formed on a polycrystalline substrate, and the film forming speed is relatively high. Therefore, the ISD method is suitable for producing a wire by forming an oxide superconducting thin film on a long base material. However, in the oxide superconducting thin film prepared by the conventional ISD method, although the crystal grains are aligned in a specific direction to some extent, there is a deviation of the crystal orientation of about 20 ° on average. Jc of superconducting film having such misalignment
Is less than 10 ⁵ A / cm ² and does not reach 10 ⁶ A / cm ² .

On the RABiT, an oxide superconducting thin film having a relatively high Jc can be formed in a small area. However, in the conventional method, if there are pits or grooves between the crystal grains that form the base material, those portions significantly reduce the crystal orientation, and thus the quality of the epitaxial growth film. The longer the substrate is, the more likely the depressions and grooves are to be present in the substrate. Therefore, when an oxide superconducting thin film is formed on a long base material by the conventional method, the quality of the thin film is extremely deteriorated on the depressions and grooves existing on the base material surface. It is difficult to obtain a high Jc.

One object of the present invention is to provide on a long substrate,
It is to provide a method capable of forming a thin film having excellent crystal orientation.

A further object of the present invention is to provide a method capable of forming a thin film having excellent crystal orientation on a long substrate at a relatively high speed.

[0008]

According to the present invention, one or more kinds of particles, which are forcibly blown in a specific direction in a gas phase, are made to collide with a base material, and the particles are separated from the one or more kinds of particles. A method for forming a crystalline thin film on the substrate, wherein the surface of the substrate on which the thin film is formed is inclined with respect to the specific direction, and the surface of the substrate is Is characterized by being a polycrystal having a structure in which specific crystal planes are preferentially oriented.

In a preferred embodiment of the present invention, the specific crystal plane is a {100} plane in a cubic system, and the {100} plane is oriented substantially parallel to the surface of the base material. In another preferred embodiment of the present invention, the specific crystal plane is a {110} plane in a cubic system, and the {110} plane is preferably oriented substantially parallel to the surface of the substrate.

In the present invention, the base material may be made of silver, silver alloy, nickel, nickel base alloy, copper, copper base alloy, stainless steel, or a composite material in which any combination thereof is used. According to the present invention, at least one selected from the group consisting of yttria-stabilized zirconia, cerium oxide, magnesium oxide, yttrium oxide, ytterbium oxide, holmium oxide, gadolinium oxide, barium zirconia, samarium zirconia, zirconium garnate, and lanthanum garnate. A thin film of seed can be formed. On the other hand, according to the present invention, selected from the group consisting of yttria-stabilized zirconia, cerium oxide, magnesium oxide, yttrium oxide, ytterbium oxide, holmium oxide, gadolinium oxide, barium zirconia, samarium zirconia, zirconium garnate, and lanthanum garnate. You may form the thin film which consists of the 1st part which consists of at least 1 sort (s), and the 2nd part which consists of an oxide superconductor formed on it. Oxide superconductors are typically of the formula R ₁ Ba ₂ Cu ₃
It is represented by O ₇ (R is a rare earth element). In the formula, the rare earth element can be holmium or yttrium. On the other hand, in the formula, the rare earth element may be selected from the group consisting of neodymium, samarium, and ytterbium. When forming a thin film composed of the first part and the second part, silver, silver alloy, gold, gold alloy, platinum, platinum alloy, manganese, manganese alloy, palladium and palladium alloy are formed on the second part. It is preferable to form a thin film of at least one selected from the group consisting of

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The inventors of the present invention have made remarkable striking results by applying a polycrystalline base material having a structure in which specific crystal planes are preferentially oriented (oriented polycrystalline base material) to the above-mentioned ISD method. It was found that various effects can be obtained. The effects are as follows. (1) A thin film crystal in which a specific crystal plane is extremely strongly oriented,
It can be formed uniformly over a long base material. (2) Crystal growth on the base material is less susceptible to defects (grooves or depressions) on the surface of the base material. (3) A thin film having good crystallinity can be formed at a relatively high rate.

When a thin film is simply epitaxially grown on an oriented polycrystalline substrate as in the prior art, crystal growth is greatly affected by defects existing on the substrate. In the defect portion, the crystal quality is extremely deteriorated, and Jc may be zero when forming a thin film of an oxide superconductor, for example.
The longer the substrate, the more such locations. When it is desired to obtain properties that are almost equal over the entire length of the substrate, such as superconducting properties, the occurrence of such points is fatal. On the other hand, according to the present invention, the occurrence of such a place can be significantly suppressed. Although the mechanism is not clear, the epitaxy provided by the oriented polycrystalline substrate and the crystal orientation effect of tilting the substrate surface with respect to the direction of the flying particles act synergistically to prevent defects in the substrate. It is considered that crystal growth proceeds beyond the limit. In the present invention, since the crystal growth is promoted as described above, the crystal quality can be maintained high even when the film is formed at a relatively high speed.

In the present invention, a polycrystalline substrate having a structure in which specific crystal planes are preferentially oriented is used. Typically, such substrates are substrates that have a texture. Generally, in a polycrystalline body, the texture can be formed by plastic working and recrystallization (heat treatment, annealing). By these treatments, a structure in which crystals are arranged in a specific orientation can be obtained. When the crystal is plastically deformed, the orientation of the crystal changes. The crystal rotates so that the slip direction becomes closer to the tensile direction in the tensile deformation, and the slip surface becomes perpendicular to the compression direction in the compressive deformation. Thus, during the plastic deformation, each crystal grain of the polycrystalline aggregate rotates and is arranged in a crystallographically specific direction, so that a texture is formed as a whole. Further, when a polycrystalline body having a developed work texture through plastic working is annealed, recrystallization occurs, and as a result, crystals are arranged in an orderly manner and primary recrystallized texture is formed. A secondary recrystallization texture is formed by heating. In the present invention, the characteristics of the texture thus formed (the orientation of crystal orientation)
Make effective use of.

In the present invention, the material of the substrate is not particularly limited as long as it can form the above-mentioned texture. The material of the base material can be selected according to the crystal system and lattice constant of the thin film to be formed. For example, when it is desired to form a cubic thin film, the material of the surface of the base material is preferably a cubic crystal or a crystal having a lattice constant close to that of the thin film crystal.
In general, it is preferable that the surface of the substrate has the same crystal system as the crystal system of the thin film to be formed or has a lattice constant close to that of the thin film crystal to be formed.

Specifically, the material of the substrate is silver (Ag),
Silver alloy, nickel (Ni), nickel-based alloy, copper (C
u), copper alloys, stainless steel, and any combination thereof. The above-mentioned texture can be obtained by subjecting these materials having a predetermined shape to plastic working and / or heat treatment. The plastic working typically includes wire drawing and rolling. Such processing is
It may be performed cold or hot. The heat treatment is typically performed at a temperature that allows recrystallization of the material used. When a plurality of materials are combined, they can be bonded (clad) or compounded. For example, a composite substrate having a texture can be obtained by laminating two or more different sheet materials, rolling and heating. Alternatively, two or more different tube materials may be combined. In such a case, a tube with a small diameter is inserted into a tube with a large diameter, and the obtained superposed body is subjected to plastic working (for example, wire drawing and / or rolling) and, if necessary, recrystallization. A heat treatment is performed to obtain a composite base material having a texture. In such a composite, preferred material combinations include Ag-Ag alloys, Ni-Ni based alloys, combinations of two or more Ag alloys, Cu alloys-Ag, Cu alloys-Ag alloys, and stainless steels. Ag, Stainless Steel-Ag Alloy, Stainless Steel-C
u, stainless steel-Cu alloy, stainless steel-Ni, stainless steel-Ni base alloy. In particular, stainless steel −
The combination of stainless steel such as Ni and stainless steel-Ni-based alloy with other materials is preferable because non-magnetic stainless steel can be used and AC loss due to the base material can be suppressed.
When it is desired to reduce the magnetism of the base material as much as possible, it is preferable to use stainless steel, which is excellent in terms of workability, corrosion resistance, strength, cost, etc., but other non-magnetic materials may be used. Also in the case of compounding, as described above, the material of the substrate surface can be selected according to the crystal system and lattice constant of the thin film to be formed. For example, Ni or Ni
In a composite substrate in which the alloy is supported on stainless steel, the substrate surface on which the thin film is to be deposited preferably has a texture in which cubic Ni or Ni alloy crystals are preferentially arranged in a specific direction.

The specific crystal plane that is preferentially oriented on the surface of the substrate can be selected according to the crystal system and lattice constant of the thin film to be formed. Specifically, on a substrate, yttria-stabilized zirconia, cerium oxide, magnesium oxide, yttrium oxide, ytterbium oxide, holmium oxide, gadolinium oxide, barium zirconia, samarium zirconia, zirconium garnate, lanthanum garnate, R ₁ Ba. _When forming a thin film composed of an oxide superconductor such as ₂ Cu ₃ O ₇ (R is a rare earth element) or a combination thereof, the cubic {100} plane or the cubic {110} plane is the substrate surface. It is preferable to orient substantially parallel to. In this case, the substrate surface does not refer to the surface of the individual crystals in the polycrystalline body, but refers to a macroscopic surface that is composed of a large number of crystals and is regarded as continuous and uniform. When the {100} plane is oriented parallel to the substrate surface,
The 100> axis is oriented perpendicular to the substrate surface. In this case, <
The 010> axis and / or the <001> axis are preferably oriented parallel to the substrate surface. When the {110} plane is oriented parallel to the substrate surface, the <110> axis is oriented perpendicular to the substrate surface. In this case, the <011> axis and / or <
The 101> axis is preferably oriented parallel to the substrate surface. The specific crystal plane may be completely parallel to the surface of the base material, or may be formed with an appropriate off angle (eg, within ± 2 ° or within ± 1 °) with respect to the surface of the base material. Good.

In the present invention, in order to deposit the necessary chemical species on the substrate from the vapor phase, a method is used in which the chemical species are forced to fly in a specific direction and collide with the substrate. Such methods typically include laser deposition (laser ablation, pulsed laser deposition), electron beam evaporation, ion beam sputtering, DC and RF.
There is a sputtering method or the like.

In the present invention, the substrate surface is inclined at an appropriate angle with respect to the direction of the flying chemical species in the vapor deposition process. In FIG. 2A and FIG. 2B, the arrow indicates the flight direction of the chemical species in the vapor deposition process. For example, in the laser deposition method, the flight direction of the chemical species is the flight direction of the particles in the plume, usually the direction perpendicular to the target surface irradiated with the laser. In FIG. 2A, the substrate surface 20 is not inclined with respect to the flight direction of the chemical species, that is, the angle formed by the substrate surface 20 and the arrow is 90 °. On the other hand, in FIG. 2B, the substrate surface 20 is inclined at an angle θ with respect to the flight direction of the chemical species. This inclination angle θ can be selected according to the crystal system and lattice constant of the thin film to be formed.

In the present invention, the inclination of the substrate surface serves as a driving force for crystal orientation. That is, in the present invention, the substrate surface is tilted with respect to the direction of the flying chemical species in the vapor deposition process so that a specific crystal plane is preferentially oriented in a thin film formed under a predetermined condition. If the substrate surface is not inclined to the flight direction of the chemical species (if vertical),
The orientation of specific crystal planes becomes weak. The inclination of the surface of the base material and the oriented polycrystalline base material act as a driving force for a large crystal orientation, and the remarkable effects as described above are brought about.

In the present invention, a first specific arrangement is typically used in an arrangement in which the substrate surface is perpendicular to the flight direction of the chemical species (eg, in the case of laser deposition, the target surface and the substrate surface are parallel). Prepare film forming conditions that can form a film whose crystal orientation is almost perpendicular to the surface of the substrate,
Then, the base material surface is inclined at a predetermined angle with respect to the flight direction of the chemical species, the vapor deposition step is performed, and the first specific crystal orientation is oriented in the flight direction of the chemical species in the vapor-deposited film,
A single crystalline film can be formed by utilizing the tendency of the second specific crystal orientation to be oriented substantially perpendicular or parallel to the surface of the substrate. Here, the term "single crystallinity" means a state where a crystal having a specific orientation is predominant, and not only a single crystal having only a specific orientation but also a specific orientation in a state in which crystals having different orientations are mixed. It is also intended to mean a crystalline solid in which the crystals with are predominant.
In this case, for example, the predetermined tilt angle θ can be set to an angle of ± 20 ° formed by the first crystal orientation and the second crystal orientation. For example, if the first crystal orientation is <100>
By setting the tilt angle θ to 45 ° to 70 °, it is possible to deposit a cubic film in which <111> is oriented substantially parallel to the surface of the base material. Further, by setting the first crystal orientation to <110> and setting the tilt angle θ to 30 ° to 70 °, the tendency of <010> to be oriented as the second crystal orientation is utilized to form the substrate surface. Almost parallel <100
It is possible to deposit a cubic film in which> is oriented. Further, the first crystal orientation is set to <100> and the tilt angle θ is set to 30 ° to 70 ° to deposit a cubic film in which <110> is oriented substantially parallel to the substrate surface. You can Also, the first crystal orientation is <111>,
By setting the inclination angle θ in the range of 40 ° to 70 °, the tendency of <001> to be oriented as the second crystal orientation is utilized to make the cubic system in which <100> is oriented substantially parallel to the substrate surface. The film can be deposited. Regarding the laser vapor deposition method for inclining the surface of the substrate, reference can be made to JP-A-7-291626.

In the present invention, a specific crystal orientation is preferentially oriented in the flight direction of the chemical species in the vapor deposition step, and another specific crystal orientation is preferentially oriented by tilting the substrate surface, And epitaxy with oriented polycrystalline substrates provides a large driving force for the crystalline orientation of the film. Therefore, it is preferable to set the crystal orientation (texture) of the polycrystalline base material, the inclination angle of the base material surface, and the vapor deposition conditions so that these three driving forces are maximized. For example, when a base material whose cubic {100} plane is oriented substantially parallel to the base material surface is used, the inclination angle θ of the base material surface is 35 ° to 55 °, preferably 40 °.
It is preferable to set the vapor deposition condition such that it is set to -50 ° and <101> is oriented in the flight direction of the chemical species. Further, when a base material whose cubic {110} plane is oriented substantially parallel to the base material surface is used, the inclination angle θ of the base material surface is 35 ° to 55.
It is preferable to set it at 40 °, preferably 40 ° to 50 °, and set the vapor deposition condition in which <100> is oriented in the flight direction of the chemical species.

When the present invention is applied to the production of superconducting wires,
After forming a thin film of superconductor, it is formed of Ag, Au, P
It is preferably covered with a thin film of t, Mn, Pd, or an alloy thereof. Such a thin film can function as a stabilizer. Such a thin film can be formed, for example, by laser vapor deposition, electron beam vapor deposition, ion beam sputtering,
It can be formed by DC and RF sputtering.

[0023]

Example 1 Ni / SUS obtained by laminating stainless steel and nickel material, and rolling and heat-treating so as to have a texture.
A tape (thickness 100 μm, length 2 m) was used as a substrate for thin film formation. X-ray diffraction was performed on the surface of this Ni / SUS tape to obtain a pole figure, and as a result, the Ni {100} plane was preferentially oriented substantially parallel to the substrate surface, and therefore Ni <100 <nearly perpendicular to the substrate surface. It was found that the 001> axis was preferentially oriented. That is, Ni / S
The surface of the US tape has a Ni {100} <001> cubic texture. An X-ray φ scan was performed on this surface, and the half-value width (crystal orientation half-value width) of the peak attributable to the Ni {100} plane was determined. The result was 12 °.

On this Ni / SUS tape, a thickness of 1.5 μm
A yttria-stabilized zirconium (YSZ) thin film of m was formed by a laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) is 45
It was °. The conditions for forming the YSZ thin film are Ar
Atmosphere, pressure 13.3 Pa, tape heating temperature 500 ° C,
Laser energy 600 mJ, laser frequency 150 Hz
Met.

Next, a 1 μm thick Ho ₁ film was formed on the YSZ thin film.
A Ba ₂ Cu ₃ O ₇ thin film was formed by the laser deposition method. In this case, the tape was not tilted with respect to the direction the plume flew (it was vertical). Therefore, the tape surface was parallel to the target surface. The conditions for forming the Ho ₁ Ba ₂ Cu ₃ O ₇ thin film were an oxygen atmosphere, a pressure of 26.6 Pa, a tape heating temperature of 800 ° C., a laser energy of 600 mJ, and a laser frequency of 50 Hz.

After forming a Ho ₁ Ba ₂ Cu ₃ O ₇ thin film, an Ag thin film was formed as a stabilizing material on the Ho ₁ Ba ₂ Cu ₃ O ₇ thin film by a DC sputtering method to complete a superconducting tape.

Comparative Example 1 As a comparison, the tape surface and the target surface were made parallel without tilting the tape when the YSZ thin film was formed.
The film was formed under the same conditions as described above.

Y formed as in Example 1 and Comparative Example 1
An X-ray φ scan was performed on the surface of the SZ film {10
Full width at half maximum of the peak due to the 0} plane (full width at half maximum of crystal orientation)
I asked. Furthermore, regarding Example 1 and Comparative Example 1, Jc of the obtained superconducting tape was measured. Each measurement was carried out at 11 locations separated by 20 cm over a 2 m tape. The results are shown in Table 1. As can be seen from the table, when the tape is tilted to form the YSZ film,
A Jc of 10 ⁶ A / cm ² was obtained over the 2 m length of the tape. The Jc value is {100} <001>.
The value is higher than that when Ni tape having no texture (crystal grains are not arranged in a specific direction) is used as a substrate. On the other hand, when the tape was not tilted at the time of forming the YSZ film, 10 ⁶ A / cm ² was obtained at some points of the tape, but there was also a zero portion, and Jc was considerably large in the longitudinal direction of the tape. Variation was seen.

[0029]

[Table 1]

Example 2 The same Ni / SUS tape as in Example 1 was used as a substrate. 0.5 μm thick CeO on Ni / SUS tape
_Two thin films (first intermediate layer) were formed by the laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the CeO ₂ thin film are Ar atmosphere, pressure 6.7P.
a, tape heating temperature 550 ° C., laser energy 550
It was mJ and the laser frequency was 150 Hz.

Next, a 1 μm thick YSZ thin film (second intermediate layer) was formed on the CeO ₂ thin film by a laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the YSZ thin film were the same as the YSZ conditions of Example 1.

Next, a 1 μm thick Y ₁ B film was formed on the YSZ thin film.
An a ₂ Cu ₃ O ₇ thin film was formed by the laser deposition method. In this case, the tape was not tilted with respect to the direction the plume flew (it was vertical). Therefore, the tape surface was parallel to the target surface.

After forming a Y ₁ Ba ₂ Cu ₃ O ₇ thin film, an Ag thin film was formed thereon as a stabilizing material by a DC sputtering method to complete a superconducting tape. The conditions for forming the Y ₁ Ba ₂ Cu ₃ O ₇ thin film were an oxygen atmosphere, a pressure of 26.6 Pa, a tape heating temperature of 700 ° C., a laser energy of 600 mJ, and a laser frequency of 50 Hz.

Comparative Example 2 As a comparison, film formation was carried out under the same conditions as in Example 2 except that the tape surface was parallel to the target surface without tilting the tape when forming the CeO ₂ thin film and the YSZ thin film.

Formed Y for Example 2 and Comparative Example 2
An X-ray φ scan was performed on the surface of the SZ film {10
Full width at half maximum of the peak due to the 0} plane (full width at half maximum of crystal orientation)
I asked. Furthermore, regarding Example 2 and Comparative Example 2, Jc of the obtained superconducting tape was measured. Each measurement was carried out at 11 locations separated by 20 cm over a 2 m tape. The results are shown in Table 2. As can be seen from the table, when the tape is tilted to form the intermediate layer, the variation of the crystal orientation is reduced over the tape longitudinal direction, and the J of 10 ⁶ A / cm ² is measured over the entire length of 2 m of the tape.
c is obtained. Also, this Jc value is {100} <0
01> Higher value than the case where Ni tape having no texture (crystal grains are not arranged in a specific direction) is used as a base material. On the other hand, if the tape was not tilted when the intermediate layer was formed, at some points of the tape 10 ⁶ A / cm ²
However, a considerable variation was found in Jc in the longitudinal direction of the tape.

[0036]

[Table 2]

Example 3 The same Ni / SUS tape as in Example 1 was used as a substrate. 0.5 μm thick CeO on Ni / SUS tape
_Two thin films (first intermediate layer) were formed by the laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the CeO ₂ thin film were the same as those for CeO _{2 in} Example 2.

Next, a 1 μm thick YS film was formed on the CeO ₂ thin film.
The Z thin film (second intermediate layer) was formed by the laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the YSZ thin film were the same as the YSZ conditions of Example 1.

Next, on the YSZ thin film, a thickness of 0.2 μm is formed on the YSZ thin film.
Ho ₂ O ₃ thin film (third intermediate layer) was formed by laser deposition. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. Ho
The conditions for forming the ₂ O ₃ thin film are Ar atmosphere, pressure 1.3 Pa, tape temperature 500 ° C., laser energy 5
The laser frequency was 00 mJ and the laser frequency was 20 Hz.

Next, a 1 μm thick Y ₁ film was formed on the Ho ₂ O ₃ thin film.
A Ba ₂ Cu ₃ O ₇ thin film was formed in the same manner as in Example 2 by the laser deposition method. In this case, the tape was not tilted with respect to the direction the plume flew (it was vertical). Therefore,
The tape surface was parallel to the target surface.

After forming a Y ₁ Ba ₂ Cu ₃ O ₇ thin film, an Ag thin film was formed as a stabilizing material on the Y ₁ Ba ₂ Cu ₃ O ₇ thin film by a DC sputtering method to complete a superconducting tape.

Comparative Example 3 For comparison, a CeO ₂ thin film, a YSZ thin film and a Ho ₂ O ₃ thin film were used.
Film formation was performed under the same conditions as in Example 3 except that the tape surface was parallel to the target surface without tilting the tape during thin film formation.

H formed in Example 3 and Comparative Example 3
X-ray φ scan was performed on the surface of the o ₂ O ₃ film {10
Full width at half maximum of the peak due to the 0} plane (full width at half maximum of crystal orientation)
I asked. Furthermore, for Example 3 and Comparative Example 3, Jc of the obtained superconducting tape was measured. Each measurement was carried out at 11 locations separated by 20 cm over a 2 m tape. The results are shown in Table 3. As can be seen from the table, when the tape is tilted to form the intermediate layer, the variation of the crystal orientation is reduced over the tape longitudinal direction, and the J of 10 ⁶ A / cm ² is measured over the entire length of 2 m of the tape.
c is obtained. Also, this Jc value is {100} <0
01> Higher value than the case where Ni tape having no texture (crystal grains are not arranged in a specific direction) is used as a base material. On the other hand, if the tape was not tilted when the intermediate layer was formed, at some points of the tape 10 ⁶ A / cm ²
However, a considerable variation was found in Jc in the longitudinal direction of the tape.

[0044]

[Table 3]

Example 4 The same Ni / SUS tape as in Example 1 was used as a substrate. 0.5 μm thick Gd ₂ on Ni / SUS tape
An O ₃ thin film (first intermediate layer) was formed by the laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the Gd ₂ O ₃ thin film are Ar atmosphere and pressure 2.6P.
a, tape temperature 500 ° C, laser energy 500m
J, the laser frequency was 150 Hz.

Next, a 1 μm thick YSZ thin film (second intermediate layer) was formed on the Gd ₂ O ₃ thin film by a laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the YSZ thin film were the same as those for YSZ in Example 1.

Next, a C film having a thickness of 0.2 μm was formed on the YSZ thin film.
eO₂Thin film (third intermediate layer) is formed by laser deposition method
did. In the laser vapor deposition method, the direction of the plume
Then, the tape was tilted to form a thin film. In this case the tape
Angle between surface and target surface (tape surface and pull
The angle formed by the flying direction of the mu) was 45 °. CeO ₂
The conditions for forming the thin film are CeO of Example 2.₂Same as
It was the same.

Next, a 1 μm thick Nd ₁ film was formed on the CeO ₂ thin film.
A Ba ₂ Cu ₃ O ₇ thin film was formed by the laser deposition method. In this case, the tape was not tilted with respect to the direction the plume flew (it was vertical). Therefore, the tape surface was parallel to the target surface. The conditions for forming the Nd ₁ Ba ₂ Cu ₃ O ₇ thin film were an oxygen atmosphere, a pressure of 13.3 Pa, a tape temperature of 850 ° C., a laser energy of 600 mJ, and a laser frequency of 50 Hz.

After forming a Nd ₁ Ba ₂ Cu ₃ O ₇ thin film, an Ag thin film was formed as a stabilizing material on the Nd ₁ Ba ₂ Cu ₃ O ₇ thin film by DC sputtering to complete a superconducting tape.

Comparative Example 4 For comparison, Gd ₂ O ₃ thin film, YSZ thin film and CeO ₂ thin film
Film formation was performed under the same conditions as in Example 4, except that the tape surface was parallel to the target surface without tilting the tape during thin film formation.

C formed for Example 4 and Comparative Example 4
X-ray φ scan was performed on the surface of the eO ₂ film {10
Full width at half maximum of the peak due to the 0} plane (full width at half maximum of crystal orientation)
I asked. Furthermore, regarding Example 4 and Comparative Example 4, Jc of the obtained superconducting tape was measured. Each measurement was carried out at 11 locations separated by 20 cm over a 2 m tape. The results are shown in Table 4. As can be seen from the table, when the tape is tilted to form the intermediate layer, the variation of the crystal orientation is reduced over the tape longitudinal direction, and J ^{5 of} 10 ⁵ A / cm ² is observed over the entire length of 2 m of the tape.
c is obtained. Also, this Jc value is {100} <0
01> Higher value than the case where Ni tape having no texture (crystal grains are not arranged in a specific direction) is used as a base material. On the other hand, when the tape was not tilted during the formation of the intermediate layer, 10 ⁵ A / cm ² was obtained at many points of the tape, but there was a considerable variation in Jc in the longitudinal direction of the tape, and a point of zero. Was also seen.

[0052]

[Table 4]

Example 5 The same Ni / SUS tape as in Example 1 was used as a substrate. 0.5 μm thick CeO on Ni / SUS tape
_Two thin films (first intermediate layer) were formed by the laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the CeO ₂ thin film were the same as those for CeO _{2 in} Example 2.

Next, a 1 μm thick YSZ thin film (second intermediate layer) was formed on the CeO ₂ thin film by laser deposition. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the YSZ thin film were the same as those for YSZ in Example 1.

Next, on the YSZ thin film, a thickness of 0.2 μm is formed on the YSZ thin film.
CeO ₂ thin film (third intermediate layer) was formed by laser deposition. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. Ce
The condition for forming the O ₂ thin film is that the Ce of the first intermediate layer is
It was the same as O ₂ .

Next, a 1 μm thick Sm ₁ film was formed on the CeO ₂ thin film.
A Ba ₂ Cu ₃ O ₇ thin film was formed by the laser deposition method. In this case, the tape was not tilted with respect to the direction the plume flew (it was vertical). Therefore, the tape surface was parallel to the target surface. The conditions for forming the Sm ₁ Ba ₂ Cu ₃ O ₇ thin film were an oxygen atmosphere, a pressure of 13.3 Pa, a tape temperature of 800 ° C., a laser energy of 600 mJ, and a laser frequency of 50 Hz.

After forming an Sm ₁ Ba ₂ Cu ₃ O ₇ thin film, an Ag thin film was formed as a stabilizing material on the Sm ₁ Ba ₂ Cu ₃ O ₇ thin film by a DC sputtering method to complete a superconducting tape.

Comparative Example 5 For comparison, film formation was performed under the same conditions as in Example 5, except that the tape surface was parallel to the target surface without tilting the tape when forming the first to third intermediate layers. .

C formed for Example 5 and Comparative Example 5
X-ray φ scan was performed on the surface of the eO ₂ film {10
Full width at half maximum of the peak due to the 0} plane (full width at half maximum of crystal orientation)
I asked. Furthermore, regarding Example 5 and Comparative Example 5, Jc of the obtained superconducting tape was measured. Each measurement was carried out at 11 locations separated by 20 cm over a 2 m tape. The results are shown in Table 5. As can be seen from the table, when the tape is tilted to form the intermediate layer, the variation of the crystal orientation is reduced over the tape longitudinal direction, and J ^{5 of} 10 ⁵ A / cm ² is observed over the entire length of 2 m of the tape.
c is obtained. Also, this Jc value is {100} <0
01> Higher value than the case where Ni tape having no texture (crystal grains are not arranged in a specific direction) is used as a base material. On the other hand, when the tape was not tilted during the formation of the intermediate layer, 10 ⁵ A / cm ² was obtained at many points of the tape, but there was a considerable variation in Jc in the longitudinal direction of the tape, and a point of zero. Was also seen.

[0060]

[Table 5]

Example 6 A superconductor was replaced with Ho ₁ Ba ₂ C instead of Sm ₁ Ba ₂ Cu ₃ O _7.
A thin film was formed in the same manner as in Example 5 except that u ₃ O ₇ was used to obtain a superconducting tape. The conditions for forming the Ho ₁ Ba ₂ Cu ₃ O ₇ thin film were the same as in Example 1.

Comparative Example 6 A superconductor was replaced with Ho ₁ Ba ₂ C instead of Sm ₁ Ba ₂ Cu ₃ O _7.
A thin film was formed in the same manner as in Comparative Example 5 except that u ₃ O ₇ was used to obtain a superconducting tape. The conditions for forming the Ho ₁ Ba ₂ Cu ₃ O ₇ thin film were the same as in Example 1.

CeO ₂ in Example 6 and Comparative Example 6
For the film, when the half-width of crystal orientation was similarly obtained,
Results similar to those shown in Table 5 were obtained. Table 6 shows the Jc measurement results. If the tape is tilted when forming the intermediate layer,
It can be seen that 10 ⁵ A / cm ² is achieved over the entire length of 2 m. On the other hand, when the tape was not inclined at the time of forming the intermediate layer, 10 ⁵ A / cm ² was obtained in many parts, but the value showed a remarkable variation in the tape longitudinal direction.

[0064]

[Table 6]

Example 7 A superconductor is Y ₁ Ba ₂ Cu instead of Sm ₁ Ba ₂ Cu ₃ O _7.
A thin film was formed in the same manner as in Example 5 except that ₃ O ₇ was used to obtain a superconducting tape. The conditions for forming the Y ₁ Ba ₂ Cu ₃ O ₇ thin film were the same as in Example 2.

Comparative Example 7 A superconductor was replaced by Y ₁ Ba ₂ Cu instead of Sm ₁ Ba ₂ Cu ₃ O _7.
A thin film was formed in the same manner as in Comparative Example 5 except that ₃ O ₇ was used to obtain a superconducting tape.

CeO ₂ in Example 7 and Comparative Example 7
For the film, when the half-width of crystal orientation was similarly obtained,
Results similar to those shown in Table 5 were obtained. Table 7 shows the Jc measurement results. If the tape is tilted when forming the intermediate layer,
It can be seen that 10 ⁵ A / cm ² is achieved over the entire length of 2 m. On the other hand, when the tape was not inclined at the time of forming the intermediate layer, 10 ⁵ A / cm ² was obtained in many parts, but the value showed a remarkable variation in the tape longitudinal direction.

[0068]

[Table 7]

Example 8 The same Ni / SUS tape as in Example 1 was used as a substrate. 0.5 μm thick CeO on Ni / SUS tape
_Two thin films (first intermediate layer) were formed by the laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the CeO ₂ thin film were the same as those for CeO _{2 in} Example 2.

Next, a 1 μm-thick Zr ₂ Gd ₂ O ₇ thin film (second intermediate layer) was formed on the CeO ₂ thin film by the laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the Zr ₂ Gd ₂ O ₇ thin film are Ar.
The atmosphere, the pressure was 6.6 Pa, the tape temperature was 550 ° C., the laser energy was 500 mJ, and the laser frequency was 150 Hz.

Next, a CeO ₂ thin film (third intermediate layer) having a thickness of 0.2 μm was formed on the Zr ₂ Gd ₂ O ₇ thin film by the laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the CeO ₂ thin film were the same as for the CeO ₂ of the first intermediate layer.

Next, a 1 μm thick Ho ₁ film was formed on the CeO ₂ thin film.
A Ba ₂ Cu ₃ O ₇ thin film was formed in the same manner as in Example 1 by the laser deposition method. In this case, the tape was not tilted with respect to the direction the plume flew (it was vertical). Therefore,
The tape surface was parallel to the target surface.

After forming a Ho ₁ Ba ₂ Cu ₃ O ₇ thin film, an Ag thin film as a stabilizing material was formed on the Ho ₁ Ba ₂ Cu ₃ O ₇ thin film by a DC sputtering method to complete a superconducting tape.

Comparative Example 8 For comparison, film formation was performed under the same conditions as in Example 8 except that the tape surface was parallel to the target surface without tilting the tape when forming the first to third intermediate layers. .

C formed for Example 8 and Comparative Example 8
X-ray φ scan was performed on the surface of the eO ₂ film {10
Full width at half maximum of the peak due to the 0} plane (full width at half maximum of crystal orientation)
I asked. Furthermore, for Example 8 and Comparative Example 8, Jc of the obtained superconducting tape was measured. Each measurement was carried out at 11 locations separated by 20 cm over a 2 m tape. The results are shown in Table 8. As can be seen from the table, when the tape is tilted to form the intermediate layer, the variation of the crystal orientation is reduced over the tape longitudinal direction, and the J of 10 ⁶ A / cm ² is measured over the entire length of 2 m of the tape.
c is obtained. Also, this Jc value is {100} <0
01> Higher value than the case where Ni tape having no texture (crystal grains are not arranged in a specific direction) is used as a base material. On the other hand, when the tape was not tilted during the formation of the intermediate layer, 10 ⁶ A / cm ² was obtained at two points on the tape, but a considerable variation was found in Jc in the longitudinal direction of the tape.

[0076]

[Table 8]

Example 9 The same Ni / SUS tape as in Example 1 was used as a substrate. 0.5 μm thick CeO on Ni / SUS tape
_Two thin films (first intermediate layer) were formed by the laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the CeO ₂ thin film were the same as those for CeO _{2 in} Example 2.

Next, a 1 μm-thick Zr ₂ Sm ₂ O ₇ thin film (second intermediate layer) was formed on the CeO ₂ thin film by a laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the Zr ₂ Sm ₂ O ₇ thin film are Ar.
The atmosphere, the pressure was 6.6 Pa, the tape temperature was 500 ° C., the laser energy was 500 mJ, and the laser frequency was 150 Hz.

Next, a CeO ₂ thin film (third intermediate layer) having a thickness of 0.2 μm was formed on the Zr ₂ Sm ₂ O ₇ thin film by the laser deposition method. In the laser deposition method, the tape was tilted with respect to the plume flying direction to form a thin film. In this case, the angle between the tape surface and the target surface (the angle between the tape surface and the plume flying direction) was 45 °. The conditions for forming the CeO ₂ thin film were the same as for the CeO ₂ of the first intermediate layer.

Next, a 1 μm thick Ho ₁ film was formed on the CeO ₂ thin film.
A Ba ₂ Cu ₃ O ₇ thin film was formed in the same manner as in Example 1 by the laser deposition method. In this case, the tape was not tilted with respect to the direction the plume flew (it was vertical). Therefore,
The tape surface was parallel to the target surface.

After forming a Ho ₁ Ba ₂ Cu ₃ O ₇ thin film, an Ag thin film was formed as a stabilizing material on the Ho ₁ Ba ₂ Cu ₃ O ₇ thin film by a DC sputtering method to complete a superconducting tape.

Comparative Example 9 For comparison, film formation was performed under the same conditions as in Example 9 except that the tape surface was parallel to the target surface without tilting the tape when forming the first to third intermediate layers. .

C formed for Example 9 and Comparative Example 9
X-ray φ scan was performed on the surface of the eO ₂ film {10
Full width at half maximum of the peak due to the 0} plane (full width at half maximum of crystal orientation)
I asked. Furthermore, for Example 9 and Comparative Example 9, Jc of the obtained superconducting tape was measured. Each measurement was carried out at 11 locations separated by 20 cm over a 2 m tape. The results are shown in Table 9. As can be seen from the table, when the tape is tilted to form the intermediate layer, the variation of the crystal orientation is reduced over the tape longitudinal direction, and the J of 10 ⁶ A / cm ² is measured over the entire length of 2 m of the tape.
c is obtained. Also, this Jc value is {100} <0
01> Higher value than the case where Ni tape having no texture (crystal grains are not arranged in a specific direction) is used as a base material. On the other hand, when the tape was not tilted at the time of forming the intermediate layer, 10 ⁶ A / cm ² was obtained at one point of the tape, but there was a considerable variation in Jc in the longitudinal direction of the tape.

[0084]

[Table 9]

[0085]

According to the present invention, a thin film having excellent crystal orientation can be formed on a long substrate. Furthermore, according to the present invention, a thin film having excellent crystal orientation can be formed on a long base material at a relatively high speed. According to the present invention, an oxide superconducting wire having a large Jc can be manufactured. INDUSTRIAL APPLICABILITY The present invention is suitable for forming a thin film having good crystallinity on a large area or long substrate.

[Brief description of drawings]

1A and 1B are views for explaining a vapor deposition method in which a substrate is tilted.

FIG. 2A and FIG. 2B are views for explaining a state in which the surface of the base material is inclined with respect to the direction of particles that fly in the vapor deposition process.

[Explanation of symbols]

20 Base material surface

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4G077 AA03 BC53 DA03 ED04 EF01                       HA08 SA04                 4K029 AA02 AA25 BA50 BB02 BC04                       CA01 DB20 JA10 KA03                 5G321 AA02 AA04 AA07 CA04 CA21                       CA27

Claims (10)

[Claims] 1. A substrate is impinged with one or a plurality of types of particles forcibly propelled in a specific direction in a gas phase,
A method of forming a crystalline thin film from the one or more types of particles on the base material, wherein the surface of the base material on which the thin film is formed is inclined with respect to the specific direction. And a method for forming a thin film, wherein the surface of the substrate is a polycrystalline body having a structure in which specific crystal planes are preferentially oriented. 2. The specific crystal plane is a {100} plane in a cubic system, and the {100} plane is oriented substantially parallel to the surface of the base material. The method for forming a thin film as described in. 3. The specific crystal plane is a {110} plane in a cubic system, and the {110} plane is oriented substantially parallel to the surface of the base material. The method for forming a thin film as described in. 4. The base material is at least one selected from the group consisting of silver, silver alloys, nickel, nickel-base alloys, copper, copper-base alloys, stainless steel, and composite materials in which they are arbitrarily combined. The thin film forming method according to claim 1, wherein the thin film forming method comprises: 5. The thin film comprises yttria-stabilized zirconia, cerium oxide, magnesium oxide, yttrium oxide, ytterbium oxide, holmium oxide, gadolinium oxide, barium zirconia, samarium zirconia,
The thin film forming method according to claim 1, wherein the thin film forming method comprises at least one selected from the group consisting of zirconium garnate and lanthanum garnate. 6. The thin film comprises yttria-stabilized zirconia, cerium oxide, magnesium oxide, yttrium oxide, ytterbium oxide, holmium oxide, gadolinium oxide, barium zirconia, samarium zirconia,
A first portion made of at least one selected from the group consisting of zirconium garnate and lanthanum garnate, and a second portion made of an oxide superconductor formed on the first portion.
5. The method for forming a thin film according to claim 1, wherein the thin film forming method comprises: 7. The oxide superconductor has the formula R ₁ Ba ₂ Cu.
The thin film forming method according to claim 6, which is represented by ₃ O ₇ (R is a rare earth element). 8. The method of forming a thin film according to claim 7, wherein the rare earth element is holmium or yttrium. 9. The method for forming a thin film according to claim 7, wherein the rare earth element is selected from the group consisting of neodymium, samarium and ytterbium. 10. Silver, a silver alloy, on the second portion,
10. The method according to claim 6, further comprising the step of forming a thin film made of at least one selected from the group consisting of gold, gold alloys, platinum, platinum alloys, manganese, manganese alloys, palladium and palladium alloys. The method for forming a thin film as described in.