JP2996568B2 - Method for producing polycrystalline thin film and method for producing oxide superconducting conductor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polycrystalline thin film having a uniform crystal orientation and a method for producing an oxide superconductor having a uniform crystal orientation.

[0002]

2. Description of the Related Art Oxide superconductors discovered in recent years are excellent superconductors having a critical temperature exceeding the temperature of liquid nitrogen. At present, this type of oxide superconductor is a practical superconductor. There are various problems to be solved in order to use this. One of the problems is that the critical current density of the oxide superconductor is low.

[0003] The problem that the critical current density of the oxide superconductor is low is largely due to the existence of electrical anisotropy in the crystal itself of the oxide superconductor. It is known that electricity easily flows in the a-axis direction and the b-axis direction of the crystal axis, but hardly flows in the c-axis direction. From such a viewpoint, in order to form an oxide superconductor on a base material and use it as a superconductor, an oxide superconductor having a good crystal orientation is formed on the base material, and It is necessary to orient the a-axis or b-axis of the crystal of the oxide superconductor in the direction in which electricity is to flow, and to orient the c-axis of the oxide superconductor in the other direction.

Conventionally, various means have been tried to form an oxide superconducting layer having good crystal orientation on a substrate such as a substrate or a metal tape. As one of the methods, MgO or SrT having a crystal structure similar to that of an oxide superconductor is used.
A method of forming an oxide superconducting layer on a single crystal substrate such as iO ₃ by a film formation method such as sputtering using a single crystal substrate such as iO ₃ has been practiced.

If a film forming method such as sputtering is performed using the single crystal base material of MgO or SrTiO ₃ , the crystal of the oxide superconducting layer grows on the basis of the crystal of the single crystal base material. It is possible to improve the orientation, and the oxide superconducting layer formed on these single-crystal substrates exhibits a sufficiently high critical current density of about several hundred thousand to several million A / cm ^2. It is known to

[0006]

By the way, in order to use an oxide superconductor as a conductor, it is necessary to form an oxide superconducting layer having good crystal orientation on a long base material such as a tape. There is. However, if an oxide superconducting layer is formed directly on a base material such as a metal tape, the metal tape itself is polycrystalline and its crystal structure is significantly different from that of the oxide superconductor. Layers cannot be formed at all. In addition, there is a problem in that the heat treatment performed when forming the oxide superconducting layer causes a diffusion reaction between the metal tape and the oxide superconducting layer, which breaks down the crystal structure of the oxide superconducting layer and deteriorates the superconducting characteristics.

Therefore, conventionally, on a base material such as a metal tape,
2. Description of the Related Art An intermediate layer such as MgO or SrTiO ₃ is coated by using a sputtering apparatus, and an oxide superconducting layer is formed on the intermediate layer. However, the oxide superconducting layer formed on this kind of intermediate layer by a sputtering apparatus has a critical current density (for example, several thousand to 10,000 A / cm ²⁾ which is much lower than that of an oxide superconducting layer formed on a single crystal substrate. Degree). This is considered to be due to the following reason.

FIG. 9 shows a sectional structure of an oxide superconducting conductor in which an intermediate layer 2 is formed on a base material 1 such as a metal tape by a sputtering device, and an oxide superconducting layer 3 is formed on the intermediate layer 2 by a sputtering device. It shows. In the structure shown in FIG. 9, the oxide superconducting layer 3 is in a polycrystalline state, and many crystal grains 4 are in a state of being randomly combined. Looking at each of these crystal grains 4 individually, the c-axis of the crystal of each crystal grain 4 is oriented perpendicular to the substrate surface, but the a-axis and b-axis are oriented in a random direction. It is thought that it is.

As described above, a for each crystal grain of the oxide superconducting layer
When the directions of the axis and the b-axis become disordered, it is considered that the quantum coupling of the superconducting state is lost at the crystal grain boundaries in which the crystal orientation is disordered, resulting in a decrease in superconducting properties, particularly, a critical current density. The oxide superconductor is in a polycrystalline state in which the a-axis and b-axis are not oriented because the intermediate layer 2 formed thereunder is in a polycrystalline state in which the a-axis and the b-axis are not oriented. This is probably because the oxide superconducting layer 3 grows so as to match the crystal of the intermediate layer 2 when the oxide superconducting layer 3 is formed.

By the way, other than the application field of the oxide superconductor, a technique of forming various alignment films on a polycrystalline base material is used. For example, in the field of optical thin films, the field of magneto-optical disks, the field of wiring boards, the fields of high-frequency waveguides, high-frequency filters, and cavity resonators. The problem is to form a good polycrystalline thin film. That is, if the crystal orientation of the polycrystalline thin film is good, the quality of the optical thin film, the magnetic thin film, the wiring thin film, etc. formed thereon is improved, and the crystal orientation is further improved on the base material. It is more preferable if a good optical thin film, magnetic thin film, thin film for wiring, etc. can be directly formed.

Further, as a core material of a magnetic head used in a high frequency band, a magnetic thin film such as permalloy or sendust which has high magnetic permeability and is thermally stable has been put to practical use. Conventionally, these magnetic thin films are formed on a predetermined substrate by vapor deposition or sputtering. However, if these magnetic thin films have low crystal orientation, it is difficult to control the magnetic anisotropy of the magnetic thin film. And the orientation of the crystal grains becomes disordered in the film plane, and there is a problem that the high frequency characteristics of the magnetic permeability are impaired. In addition, when the axial direction of the crystal axis in the film plane is disordered, local fluctuation called skew or ripple occurs in the in-plane magnetization, and the high-frequency characteristic of the magnetic permeability is impaired as described above. .

The present invention has been made to solve the above-mentioned problems, and has a crystal axis c perpendicular to a film-forming surface of a substrate.
The axis can be oriented, and at the same time, the a-axis and the b-axis of the crystal axes of the crystal grains can be aligned along a plane parallel to the film-forming surface, thereby providing a polycrystalline thin film having excellent crystal orientation. It is another object of the present invention to provide an oxide superconducting conductor including an oxide superconducting layer having excellent crystal orientation.

[0013]

In order to solve the above-mentioned problems, the invention according to claim 1 is characterized in that constituent particles of a target are beaten out by sputtering and deposited on a metal base material,
A method of forming a polycrystalline thin film on a metal substrate, wherein when the constituent particles are deposited on the base material, the constituent particles are beaten out of a target and deposited on a film-forming surface on the base material. Depositing the constituent particles on the substrate while irradiating the ion beam generated by the ion source at an incident angle in the range of 55 to 60 degrees from an oblique direction with respect to the normal to the film forming surface of the substrate, As the target, stabilized zirconia,
Using any one of MgO and SrTiO ₃ ,
Film with many crystal grains constituting the obtained polycrystalline thin film
It is characterized in that the grain boundary tilt angle formed between the specific crystal axes of the plane is within 25 degrees.

According to a second aspect of the present invention, there is provided a method for forming a polycrystalline thin film on a metal substrate by punching out constituent particles of a target by sputtering and depositing the particles on a metal substrate. a is, the configuration particles when deposited on the substrate, outside the constituent particles to be deposited hammered from the target to the deposition surface on a substrate, the substrate of the ion beam ion source caused The constituent particles are deposited on the base material while irradiating at an incident angle in the range of 55 to 60 degrees from an oblique direction with respect to the normal to the film forming surface, and stabilized zirconia, MgO, SrTiO is used as the target.
₃ , a polycrystalline thin film obtained by setting the current density of the ion beam at 20 μA / cm ² or more and the ion beam voltage at 150 V or more and less than 700 V.
Specific crystal in the direction of the film plane in many crystal grains constituting
The grain boundary inclination angle between the axes is set to be within 25 degrees.

According to a third aspect of the present invention, there is provided a method as set forth above, wherein the stabilized zirconia, M
cubic system composed of any of gO and SrTiO ₃
The c-axis of each crystal grain of the polycrystalline thin film is oriented perpendicular to the substrate deposition surface.
The grains formed by the a-axes or b-axes of each crystal grain
The field inclination angle is set to 25 degrees or less.

According to a fourth aspect of the present invention, an inert gas ion or a mixed ion of an inert gas and an oxygen gas is used as the ion according to the first , second or third aspect of the present invention. is there.

[0017] For the invention of claim 5, wherein to solve the above problems, by sputtering and hammered out the constituent particles of the target is deposited on a metal substrate, forming a polycrystalline thin film on a metal substrate, Next, a method for producing an oxide superconducting conductor in which an oxide superconducting layer is formed on the polycrystalline thin film is described .
Te, when depositing the constituent particles on a substrate, outside the constituent particles to be deposited hammered from the target to the deposition surface on a substrate, the substrate of the ion beam ion source caused deposition While irradiating the sputtered particles while irradiating at an incident angle in the range of 50 to 60 degrees from an oblique direction with respect to the normal to the surface, stabilized zirconia, Mg
O, many with one made of any of the SrTiO ₃
Between specific crystallographic axes in the film plane direction
A polycrystalline thin film having a grain boundary inclination angle of 25 degrees or less is formed, and an oxide superconducting layer is formed on the polycrystalline thin film.

[0018] For the invention of claim 6, wherein to solve the above problems, sputtering hammered out the constituent particles of the target is deposited on a metal substrate by, forming a polycrystalline thin film on a metal substrate, Next, a method for producing an oxide superconducting conductor in which an oxide superconducting layer is formed on the polycrystalline thin film is described .
Te, when depositing the constituent particles on a substrate, outside the constituent particles to be deposited hammered from the target to the deposition surface on a substrate, the substrate of the ion beam ion source caused deposition While irradiating the sputtered particles while irradiating at an incident angle in the range of 50 to 60 degrees from an oblique direction with respect to the normal to the surface, stabilized zirconia, Mg
O, using one made of any one of SrTiO _3, the ion beam current density of 20 .mu.A / cm ² or more, a number as less than 700V ion beam voltage above 150V
Between specific crystallographic axes in the film plane direction
A polycrystalline thin film having a grain boundary inclination angle of 25 degrees or less is formed, and an oxide superconducting layer is formed on the polycrystalline thin film.

[0019]

According to a seventh aspect of the present invention, in forming an oxide superconducting layer on the polycrystalline thin film according to the fifth or sixth aspect , the oxide of the polycrystalline thin film is formed with an oxide. It is characterized in that a superconductor crystal is epitaxially grown.

According to an eighth aspect of the present invention, in order to solve the above problems, an inert gas ion or a mixed ion of an inert gas and an oxygen gas is used as the ion according to the first aspect. And

[0022]

[Action] When depositing the sputtered particles hammered from a target onto a metal substrate by sputtering, also simultaneously irradiated ion beam obliquely 55-60 ° range with respect to the normal of the metal <br/> substrate since, as a result of the constituent particles is efficiently activated, c with respect to the film formation surface of the base material of the polycrystalline body
The a-axis orientation and the b-axis orientation are also improved in addition to the axis orientation.
As a result, even in a polycrystalline thin film in which many crystal grain boundaries are formed , all of the a-axis orientation, the b-axis orientation, and the c-axis orientation of each crystal grain on the metal base material are satisfactory. Thus, a polycrystalline thin film having improved film quality can be obtained on a metal substrate . In order to activate constituent particles at the time of sputtering, argon ions or mixed ions of argon ions and oxygen ions are preferable.

The inventors of the present invention assume the following as a factor for adjusting the crystal orientation of the polycrystalline thin film. Money
In the unit cell of the crystal of the cubic polycrystalline thin film formed on the substrate of the genus , the substrate normal direction is the <100> axis, and the other <010> and <001> axes are: <
100> direction orthogonal to the axis. Considering the ion beam incident obliquely with respect to the substrate normal with respect to these directions, 54% is incident on the diagonal direction of the unit lattice with respect to the origin of the unit lattice, that is, along the <111> axis. The angle of incidence is .7 degrees. Here exhibit good crystal orientation in a range of the incident angle is 5 5-60 degrees of the ion beam as described above, wherein the incident angle of the ion beam 5
It seems to be related that it coincides with or is around 4.7 degrees, and when these angles coincide or approximate, ion channeling occurs most effectively and deposits on the substrate. In the crystal, only the atoms having the arrangement relationship corresponding to the angle on the upper surface of the base material are apt to remain selectively, and the other disturbed atomic arrangements have the sputtering generated by the obliquely incident ion beam. It is presumed that as a result of the effect of being sputtered and removed, only crystals in which atoms with good orientation are aggregated remain selectively and deposited, and the crystal orientation is adjusted due to this.

Therefore, if the ion beam voltage is too low, the ion irradiation becomes insufficient and the above-mentioned effect is unlikely to be produced. If the ion beam voltage is too high, a sputtering effect is produced to disturb the crystal orientation. From the above, the current density of the ion beam is preferably ²⁰ μA / cm ² or more, and the ion beam voltage is preferably 150 V or more and less than 700 V.

Further, if the oxide superconducting layer is epitaxially grown on the polycrystalline thin film having good crystal orientation, the oxide superconducting layer grows along the crystal of the polycrystalline thin film. Good a-axis orientation, b-axis orientation and c-axis orientation can be obtained.

[0026]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows an embodiment in which the polycrystalline thin film of the present invention is formed on a substrate. In FIG. 1, A is a plate-like substrate, and B is a polycrystalline thin film formed on the upper surface of the substrate A. Is shown. As the base material A, various shapes such as a plate material, a wire material, and a tape material can be used.
Silver, platinum, stainless steel, a metallic material or alloy such as copper
Or it is Ranaru thing.

In the polycrystalline thin film B, a large number of fine crystal grains 20 having a cubic crystal structure are joined and integrated with each other via a crystal grain boundary. The c-axis is oriented at right angles to the upper surface (film-forming surface) of the substrate A, and the a-axis and b-axis of the crystal axes of the crystal grains 20 are oriented in the same direction and are in-plane oriented. I have. The c-axis of each crystal grain 20 is oriented at right angles to the (upper surface) deposition surface of the substrate A. And each crystal grain 2
The 0 a-axis (or b-axis) are joined and integrated with each other at an angle (grain boundary tilt angle K shown in FIG. 2) of 30 degrees or less.

Next, an apparatus for producing the polycrystalline thin film B will be described. FIG. 3 shows an example of an apparatus for producing the polycrystalline thin film B. The apparatus in this example has a configuration in which an ion gun for ion beam assist is provided in a sputtering apparatus.

The apparatus of this embodiment comprises a substrate holder 11 for holding the substrate A horizontally, a plate-like target 12 disposed diagonally above the substrate holder 11 at a predetermined interval, and
An ion gun 13 disposed diagonally above the substrate holder 11 at a predetermined interval and spaced apart from the target 12, and a sputter beam irradiation device disposed below the target 12 and toward the lower surface of the target 12. 14 as a main component. Reference numeral 15 in the drawing indicates a target holder holding the target 12.

The apparatus of the present embodiment is housed in a vacuum vessel (not shown) so that the periphery of the substrate A can be maintained in a vacuum atmosphere. Further, an atmosphere gas supply source such as a gas cylinder is connected to the vacuum vessel, and the inside of the vacuum vessel is kept in a low pressure state such as a vacuum, and an inert gas atmosphere containing argon gas or another inert gas atmosphere or oxygen. The atmosphere can be set.

When a long metal tape (a tape made of Hastelloy or stainless steel) is used as the base material A, a feeding device and a winding device for the metal tape are provided inside the vacuum vessel, and a continuous feeding device is provided from the feeding device. Preferably, the substrate A is preferably sent to the substrate holder 11 and then wound up by a winding device so that a polycrystalline thin film can be continuously formed on the tape-shaped substrate. The base material holder 11
Is provided with a heater therein so that the substrate A positioned on the substrate holder 11 can be heated to a required temperature. An angle adjusting mechanism D is attached to the bottom of the substrate holder 11. The angle adjusting mechanism D is provided with the substrate holder 1
1, a lower support plate 6 pin-connected to the upper support plate 5, and a lower support plate 6
Is mainly constituted by a base 7 that supports. The upper support plate 5 and the lower support plate 6 are configured to be rotatable with respect to each other via a pin connection portion, so that the horizontal angle of the base material holder 11 can be adjusted. In the present embodiment, the angle adjusting mechanism D for adjusting the angle of the substrate holder 11 is provided. However, the angle adjusting mechanism D is attached to the ion gun 13 to adjust the inclination angle of the ion gun 13 and adjust the incident angle of the ion beam. You may do it. Further, the angle adjusting mechanism is not limited to the configuration of the present embodiment, and it is needless to say that various configurations can be employed.

The target 12 is for forming a target polycrystalline thin film, and has the same composition or an approximate composition as the target polycrystalline thin film.
Specifically, as the target 12, MgO or Y ₂
Zirconia (YSZ), MgO, Sr stabilized with O ₃
TiO ₃ or the like is used, but is not limited to this, and a target suitable for the polycrystalline thin film to be formed may be used.

The ion gun 13 has a structure in which an evaporation source is housed in a container and an extraction electrode is provided near the evaporation source. Then, a part of the atoms or molecules generated from the evaporation source is ionized, and the ionized particles are controlled by an electric field generated by an extraction electrode and irradiated as an ion beam. There are various methods for ionizing particles, such as a DC discharge method, a high-frequency excitation method, a filament method, and a cluster ion beam method. The filament type is a method in which a tungsten filament is energized and heated to generate thermoelectrons, which are collided with evaporated particles in a high vacuum to be ionized. In the cluster ion beam method, clusters of aggregated molecules coming out of vacuum from a nozzle provided at an opening of a crucible containing raw materials are bombarded with thermal electrons to be ionized and emitted. In this embodiment, an ion gun 13 having the internal structure shown in FIG. The ion gun 13 has a cylindrical container 16.
Is provided with an extraction electrode 17, a filament 18, and an introduction tube 19 for Ar gas or the like, so that ions can be irradiated in parallel from the tip of the container 16 in a beam shape.

As shown in FIG. 3, the ion gun 13 has its center axis S incident on the upper surface (film-forming surface) of the substrate A at an incident angle θ (perpendicular line (normal line) and center line S of the substrate A). Angle)
Therefore, they face each other at an angle. Is preferably in the range of 50 to 60 degrees, and most preferably in the range of 55 to 60 degrees. Therefore, the ion gun 13 is arranged so that the ion beam can be incident on the upper surface of the substrate A at an inclination angle θ. The ion beam applied to the base material A by the ion gun 13 is He ⁺ , Ne ⁺ , A
An ion beam of a rare gas such as r ⁺ , Xe ⁺ , Kr ⁺ , or a mixed ion beam of these and oxygen ions may be used. However, in order to adjust the crystal structure of the polycrystalline thin film,
Considering that a certain amount of atomic weight is required and that the effect is reduced with extremely light ions, it is preferable to use ions such as Ar ⁺ and Kr ⁺ .

The sputter beam irradiator 14 has the same structure as the ion gun 13 and can irradiate the target 12 with an ion beam to strike out constituent particles of the target 12. In the apparatus of the present invention, it is important that the constituent particles of the target 13 can be beaten out. Therefore, a voltage is applied to the target 12 with a high-frequency coil or the like so that the constituent particles of the target 12 can be beaten out. The sputter beam irradiation device 14 may be omitted.

Next, using the apparatus having the above structure, Y
The case where the polycrystalline thin film B of SZ is formed will be described.
In order to form the polycrystalline thin film B on the base material A, a target of YSZ is used, and the angle adjustment mechanism D is adjusted so that the ion beam irradiated from the ion gun 13 is applied to the upper surface of the base material holder 50 by 50 to 60 degrees. Irradiation at an angle in the range of Next, the inside of the container storing the substrate A is evacuated to a reduced pressure atmosphere. Then, the ion gun 13 and the sputter beam irradiation device 14 are operated.

When the target 12 is irradiated with an ion beam from the sputtering beam irradiation device 14, the constituent particles of the target 12 are beaten out and fly over the substrate A. And
At the same time as depositing the constituent particles struck out of the target 12 on the base material A, a mixed ion beam of Ar ions and oxygen ions is irradiated from the ion gun 13. The incident angle θ at the time of this ion irradiation is most preferably 50 to 60 degrees. If θ is 90 degrees, the c-axis of the polycrystalline thin film is oriented at right angles to the deposition surface of the substrate A, but the (111) plane stands on the deposition surface of the substrate A, which is not preferable. . When θ is 30 degrees, the polycrystalline thin film does not even have c-axis orientation. If the ion beam is irradiated at an angle in the preferable range as described above, the (100) plane of the crystal of the polycrystalline thin film stands.

By performing sputtering while performing ion beam irradiation at such an incident angle, the a-axis and the b-axis of the crystal axes of the YSZ polycrystalline thin film formed on the substrate A can be oriented. However, this is considered to be due to the result that the sputtered particles being deposited are efficiently activated by being irradiated with the ion beam at an appropriate angle.

The inventors of the present invention assume the following as factors that make the crystal orientation of the polycrystalline thin film B uniform.
The unit cell of the crystal of the YSZ polycrystalline thin film B is shown in FIG.
Is cubic, and in this crystal lattice,
The substrate normal direction is the <100> axis, and the other <010> and <001> axes are all the directions shown in FIG. 4B. Considering the ion beam incident obliquely with respect to the substrate normal with respect to these directions, the diagonal direction of the unit cell with respect to the origin O in FIG.
When incident along the axis, the incident angle is 54.7 degrees. Here, as described above, exhibiting good crystal orientation in the range of the incident angle of 50 to 60 degrees means that when the incident angle of the ion beam coincides with or becomes about 54.7 degrees, ion channeling is performed. Most effectively occurs, and in the crystals deposited on the substrate A, only the atoms having the arrangement relationship corresponding to the angle on the upper surface of the substrate A are likely to remain selectively, and other disordered atoms It is presumed that as a result of the arrangement, as a result of being sputtered and removed by the sputtering effect of the ion beam, only crystals in which atoms with good orientation are collected selectively remain and are deposited.

From the above, if the ion beam voltage at the time of irradiating the ion beam is too low, the ion irradiation becomes insufficient and the above-mentioned effect is hardly produced, and if the ion beam voltage is too high, the sputtering effect becomes high and the crystal orientation becomes poor. It will be disturbed. From the above, the current density of the ion beam is 20 μm.
A / cm ² or more is preferable, and the ion beam voltage is preferably 150 V or more and less than 700 V.

FIGS. 1 and 2 show a substrate A on which a YSZ polycrystalline thin film B is deposited by the above method. Although FIG. 1 shows a state in which only one crystal grain 20 is formed, it is needless to say that a multilayer structure of the crystal grains 20 may be used.

Next, FIGS. 5 and 6 show an embodiment of the oxide superconductor according to the present invention. It comprises a polycrystalline thin film B formed on the upper surface of the base material A, and an oxide superconducting layer C formed on the upper surface of the polycrystalline thin film B. The base material A and the polycrystalline thin film B are made of the same material as the material described in the previous example, and the crystal grains 20 of the polycrystalline thin film B are
As shown in FIG. 1 and FIG. 2, the crystal orientation is performed so that the grain boundary inclination angle is within 30 degrees.

Next, the oxide superconducting layer C is formed of a polycrystalline thin film B
The c-axis of the crystal grains 23 is oriented at right angles to the upper surface of the polycrystalline thin film B, and the a-axis and b-axis of the crystal grains 23. As in the case of the thin film B, it is oriented in-plane along a plane parallel to the upper surface of the base material, and the grain boundary inclination angle K ′ formed by the crystal grains 23 is set within 30 degrees. Oxide superconductor constituting the oxide superconductor _{layer, Y 1 Ba 2 Cu 3 Ox} , Y 2 Ba 4 Cu 8 Ox, Y 3 Ba 3 Cu 6
Ox composition or (Bi, Pb) ₂ Ca ₂ Sr ₂ Cu _{3
Ox, (Bi, Pb) 2} Ca 2 Sr 3 Cu 4 Ox having a composition, _{or, Tl 2 Ba 2 Ca 2 Cu} 3 Ox, Tl 1 Ba 2 Ca 2 C
u ₃ Ox, a high oxide superconductor critical temperature typified _{Tl 1 Ba 2 Ca 3 Cu 4} Ox a composition.

Next, an apparatus for forming the oxide superconducting layer C will be described. FIG. 7 shows an example of an apparatus for forming an oxide superconducting layer by a film forming method, and FIG. 7 shows a laser vapor deposition apparatus. The laser deposition apparatus 30 of this example has a processing vessel 31, and the deposition processing chamber 3 inside the processing vessel 31.
2, a substrate A and a target 33 can be installed. That is, a base 34 is provided at the bottom of the vapor deposition processing chamber 32, and the base material A can be installed horizontally on the upper surface of the base 34, and a support holder 36 is provided diagonally above the base 34. The target 33 supported by is provided in an inclined state. The processing container 31 is provided with the exhaust hole 3
7 is connected to a vacuum evacuation device (not shown) so that the inside can be depressurized to a predetermined pressure.

The target 33 is made of a composite oxide sintered body or oxide superconducting material having a composition equivalent to or close to that of the oxide superconducting layer C to be formed, or containing a large amount of components that easily escape during film formation. It is composed of a plate such as a body. The base 34 has a built-in heater and can heat the substrate A to a desired temperature.

On the other hand, a laser light emitting device 38, a first reflecting mirror 39, a condenser lens 40, and a second reflecting mirror 41 are provided on the side of the processing container 31, and a laser beam generated by the laser light emitting device 38 is provided. Can be condensed and radiated onto the target 33 via a transparent window 42 attached to the side wall of the processing container 31. The laser light emitting device 38 is
If it is possible to strike out constituent particles from
Any of an AG laser, a CO ₂ laser, an excimer laser and the like may be used.

Next, the case where the oxide superconducting layer C is formed on the YSZ polycrystalline thin film B will be described. After the YSZ polycrystalline thin film B is formed on the base material A as described above, an oxide superconducting layer is formed on the polycrystalline thin film B. When forming the oxide superconducting layer on the polycrystalline thin film B,
In this example, a laser vapor deposition device 30 shown in FIG. 7 is used.

The substrate A on which the polycrystalline thin film B is formed is placed on a base 34 of a laser vapor deposition device 30 shown in FIG. 7, and the pressure in the vapor deposition chamber 32 is reduced by a vacuum pump. Here, if necessary, an oxygen gas may be introduced into the vapor deposition processing chamber 32 to make the vapor deposition processing chamber 32 have an oxygen atmosphere. Further, the heater of the base 34 is operated to heat the substrate A to a desired temperature.

Next, the laser beam generated from the laser light emitting device 38 is focused and irradiated on the target 33 in the vapor deposition processing chamber 32. Thereby, the constituent particles of the target 33 are extracted or evaporated, and the particles are deposited on the polycrystalline thin film B. Here, when the constituent particles are deposited, the polycrystalline thin film B is preliminarily oriented in the c-axis and also in the a-axis and the b-axis, so that the crystal c of the oxide superconducting layer C formed on the polycrystalline thin film B The axis, a-axis and b-axis are also epitaxially grown and crystallized so as to match the polycrystalline thin film B. Thereby, the oxide superconducting layer C having good crystal orientation is obtained.

The oxide superconducting layer C formed on the polycrystalline thin film B is in a polycrystalline state. In each of the crystal grains of the oxide superconducting layer C, as shown in FIG. The c-axis, through which electricity does not easily flow, is oriented in the thickness direction of the substrate A, and the a-axis or the b-axis is oriented in the longitudinal direction of the substrate A. Therefore, the obtained oxide superconducting layer has excellent quantum coupling properties at the crystal grain boundaries and has little deterioration in superconductivity at the crystal grain boundaries, so that it is easy to conduct electricity in the plane direction of the base material A, and the critical current density is excellent. Things are obtained.

FIG. 8 shows another example of an apparatus for producing a polycrystalline thin film. In the device of this example, the same components as those of the device shown in FIG. 3 are denoted by the same reference numerals, and their description is omitted. The apparatus of this example is different from the apparatus shown in FIG.
This is a point that three high frequency power supplies 29 are connected to the base material A and the target 12 by providing three sputter beam irradiation devices 14.

In the apparatus of this example, three targets 1
2, 12, and 12, different types of particles can be beaten out and deposited on the base material A to form a composite film, so that a polycrystalline film having a more complicated composition can be manufactured. Further, the high frequency power supply 30 is operated to set the target 12
Can also be sputtered. When the above method is performed using the apparatus of this example, a polycrystalline thin film having excellent orientation can be obtained as in the case of the apparatus shown in FIG.

(Production Example) An apparatus having the structure shown in FIG. 3 was used, and the inside of the container accommodating this apparatus was evacuated to 3.0 × 10 ^-4 torr by a vacuum pump. Base material is width 1
Hastelloy C, 0mm, 0.5mm thick, 10cm long
276 tape was used. A target made of YSZ (stabilized zirconia) was used, and a sputtering voltage of 1000 was used.
V, sputter current 100 mA, the ion source beam incident angle was set to 55 degrees, and the ion source assist voltage was set to 30.
0V, the current density of the ion beam is 10-70 μA / c
m ² , and ion irradiation is performed simultaneously with sputtering on the substrate to form a 0.3 μm thick YSZ film.
A layer was formed. Here, the current density of the ion beam is a value measured by a current density measuring device grounded near the sample.

An X-ray diffraction test was performed on each of the obtained YSZ polycrystalline thin film samples by the θ-2θ method using CuKα radiation. 10 to 13 show the angle of incidence 55 of the ion source.
The current density of the ion beam is 10 μA / cm ² , 20 μA / cm ² , 40 μA / c at an ion beam voltage of 300 V.
m ^2, and shows a diffraction intensity of a sample were measured to 70μA / cm ^2. From the results shown in FIGS. 10 to 13, in the sample in which the current density of the ion beam was set to ²⁰ to 70 μA / cm ² , the (200) plane or (40)
A peak on the (0) plane was observed, indicating that the (1)
00) plane can be presumed to be oriented along a plane parallel to the substrate surface, and the YSZ polycrystalline thin film
It was found that the shaft was oriented with the axis perpendicular to the upper surface of the substrate. From the results shown in FIG. 10, YS was obtained for the sample in which the ion beam current density was 10 μA / cm ^2.
No Z peak is observed. Therefore, it was found that if the ion beam current density was too low, the crystal orientation of the polycrystalline thin film could not be controlled.

Next, FIGS. 14 to 17 show pole figures of the respective samples. As is clear from these figures, the current density of the ion beam was set to 10 μA / cm.
^In the sample of No. ² , no c-axis orientation was observed, and FIGS.
The result equivalent to the result shown in 3 was obtained. From the above, the current density when irradiating the ion beam is 20 μA /
It was found that more than cm ^{2 was} required.

FIGS. 18 to 20 show the incident angle 9 of the ion source.
It is a figure which shows the diffraction intensity of the sample measured by changing ion beam voltage and ion beam current suitably at 0 degree. Here, the beam current shown in each figure indicates the load current of the ion gun used in the experiment. From the results shown in FIGS.
Even if the incident angle of the ion source is set to 90 degrees, the YSZ (2)
00) peak and (400) peak,
As for c-axis orientation, sufficient orientation was observed.

Next, it was measured whether or not the a-axis or the b-axis of the YSZ polycrystalline thin film was oriented in each of the c-axis oriented samples as described above. Figure 2
As shown in FIG. 1, the YSZ polycrystalline thin film formed on the base material A is irradiated with X-rays at an angle θ, and 2θ (58.7) with respect to the incident X-rays in a vertical plane including the incident X-rays.
The X-ray counter 25 is installed at the position of the angle (degrees), and the value of the horizontal angle φ with respect to the vertical plane including the incident X-ray is appropriately changed, that is, the rotation angle of the substrate A is changed as shown by an arrow in FIG. By measuring the diffraction intensity obtained by rotating by φ, the orientation of the a-axis or the b-axis of the polycrystalline thin film B was measured. The results are shown in FIGS.
Shown in

As shown in FIG. 22, in the case of the sample manufactured by setting the incident angle of the ion beam to 55 degrees, the diffraction peak does not appear, and when φ is set to 90 degrees and 0 degrees, that is, the rotation angle φ The peak of the (311) plane of YSZ appears every 90 degrees. This corresponds to the (011) peak of YSZ in the substrate plane, and it became clear that the a-axes or b-axes of the YSZ polycrystalline thin film are oriented. On the other hand, as shown in FIG. 23, in the case of the sample manufactured by setting the ion beam incident angle to 90 degrees, no special peak is observed, and the directions of the a-axis and the b-axis may be disordered. found.

From the above results, the polycrystalline thin film of the sample manufactured by the above-mentioned apparatus has not only c-axis orientation but also a-axis
Further, it was clarified that the b-axes were aligned. Therefore, it was clarified that a polycrystalline thin film such as YSZ having excellent orientation can be manufactured.

On the other hand, FIG. 24 shows the results of using the sample of the YSZ polycrystalline thin film used in FIG. 22 and testing the crystal orientation of each crystal grain of the polycrystalline layer of this sample. In this test, when performing X-ray diffraction by the method described above based on FIG. 21, the diffraction peak was measured when the angle of φ was set to a value of −10 degrees to 45 degrees in increments of 5 degrees. is there. FIG.
It is clear from the results shown in that the diffraction peak of the obtained YSZ polycrystalline thin film appears within a grain boundary inclination angle of 30 ° but disappears at 45 °. Therefore, it was found that the grain boundary inclination angle of the crystal grain of the obtained polycrystalline thin film was within 30 degrees, and it was revealed that the thin film had good orientation.

Next, the ion beam voltage was increased to 500 V, 700 V, 200 V, 15
Set the respective values of 0V, 40μA / cm ² and current density of the ion ^{beam, 50μA / cm 2, 20μA /} cm
^{2. An} X-ray diffraction test was performed on samples manufactured with the respective values of 30 μA / cm ² and 30 μA / cm ² . The results are shown in FIGS.

FIG. 30 shows the relationship between the ion beam voltage and the ion beam current density obtained from the test results shown in FIGS. 25 to 29 and the relationship between the crystal orientation of the polycrystalline thin film. From the results shown in FIG. 30, it is inappropriate that both the ion beam voltage and the ion beam current density are too high or too low, and the ion beam voltage needs to be 150 V or more and less than 700 V, and It was found that the current density of the ion beam was required to be ²⁰ μA / cm ² or more.

Next, the ion beam voltage was set to 300 V, the current density of the ion beam was set to 40 μA / cm ² , the ion beam energy was set to 300 eV, and the angle of incidence of the ion beam was changed from 0 ° to 65 ° to make a polycrystalline thin film. FIG. 3 shows the measurement results of the relationship between the incident angle and the full width at half maximum in the distribution of the crystals of the obtained polycrystalline thin film in the (111) direction .
It is shown in FIG. Incidentally, the half-value full-width for each sample obtained, obtains the pole figure as shown in FIG. 16, 16 to the end portion of the figure drawn in the pole figure from the center of the pole figure 1
When two auxiliary lines were drawn as indicated by the dashed line, the angle was determined at half the angle a formed by these two auxiliary lines, that is, at half the peak ratio. The value of the full width at half maximum is
Most of the crystal grains in the crystal thin film
It is an indicator of the direction of existence.
This is a measured value that can be regarded as the grain boundary tilt angle of most crystal grains.
You. From the results shown in FIG. 31, it has become clear that the crystal orientation becomes good when the angle of incidence of the ion beam is in the range of 50 to 60 degrees. In particular, by setting the incident angle of the ion beam to 55 to 60 degrees, the full width at half maximum, in other words,
It was also clarified that the grain boundary tilt angle of the crystal thin film could be reduced to a minimum value of about 25 degrees.

Next, an oxide superconducting layer was formed on the polycrystalline thin film using a laser vapor deposition apparatus having the structure shown in FIG.
As a target, using a target made of an oxide superconductor of _{Y 0.7 Ba 1.7 Cu 3.0 O 7} -x a composition. Also,
The inside of the deposition chamber was evacuated to 10 ^-6 Torr, and laser deposition was performed at room temperature. An ArF laser having a wavelength of 193 nm was used as a laser for target evaporation. Then 40
Heat treatment was performed at 0 ° C. for 60 minutes in an oxygen atmosphere.
The obtained oxide superconductor has a width of 0.5 mm and a length of 10 c.
m.

The oxide superconductor was cooled, and the critical temperature and the critical current density were measured.
K, critical current density = 500000 A / cm ² ,
It was confirmed that it exhibited extremely excellent superconducting characteristics.

[0066]

As described above, according to the method for producing a polycrystalline thin film of the present invention, constituent particles struck out of a target made of stabilized zirconia, MgO, or SrTiO ₃ by sputtering are formed on a metal substrate. when deposited on top oblique direction 55 degrees with respect to the normal to the substrate deposition surface -
Since the ion beam is irradiated at an angle of 60 degrees, the constituent particles can be efficiently activated.
It is possible to obtain a polycrystalline thin film having a grain boundary inclination angle of 25 degrees or less in which the a-axis orientation and the b-axis orientation are improved in addition to the axis orientation. In the above-mentioned polycrystalline thin film, diffraction peaks of X-ray diffraction obtained by rotating the polycrystalline thin film appear every 90 degrees, so that the in-plane orientation of the crystal grains constituting the polycrystalline thin film in the a-axis and the b-axis is good. And the range of appearance of the peak is 0 to
Since the range is 30 degrees, it is apparent that the grain boundary inclination angle is 30 degrees or less. Further, since the incident angle of the ion beam is in a preferable range of 55 to 60 degrees, a large number of results are obtained.
The specific grain boundary inclination angle of the crystal axis each other forms the film surface direction can be obtained the crystalline orientation of good polycrystalline thin film was less than 25 degrees in Akiratsubu.

Further, the current density of the ion beam at the time of manufacturing the polycrystalline thin film is set to 20 μmA / cm ² or more, the ion beam voltage is set to 150 V or more and less than 700 V, and stabilized zirconia, MgO, By using any one of SrTiO ₃ , the grain boundary tilt angle of the crystal grains of the polycrystalline thin film obtained on the metal substrate can be kept within 25 degrees, and the polycrystalline thin film having good crystal orientation can be obtained. Can be reliably produced on a substrate . Note that the ion used as the ion beam is preferably an inert gas ion or a mixed ion of an inert gas ion and oxygen gas.

[0068] Then, according to the method of manufacturing an oxide superconductor according to the present invention, as described above at an incident angle of 5 5 to 60 degrees of the ion beam relative to the normal of the substrate film-forming surface on a metal substrate A polycrystalline thin film having good crystal orientation is formed, and an oxide superconducting layer is formed thereon. Since the X-ray diffraction peak obtained by rotating the polycrystalline thin film appears every 90 degrees, even if the polycrystalline thin film is formed on a metal substrate , The in-plane orientation of the constituting crystal grains is good, and the oxide superconducting layer is formed thereon, so that the oxide superconducting layer with good crystal orientation can be formed. Further, the grain boundaries between the a-axis and the b-axis of the crystal grains of the oxide superconducting layer
Since the inclination angles can be adjusted well, an oxide superconductor having a high critical current density can be obtained. Further, the angle of incidence of the ion beam is set to 55 to 55
By setting the angle to 60 degrees, the crystal orientation can be properly adjusted, and a polycrystalline thin film having a good crystal orientation within a grain boundary inclination angle of 25 degrees at a specific crystal axis in the film plane direction is formed on the substrate.
It is possible, that the oxide superconducting layer to be stacked can be obtained having excellent crystal orientation, it is possible to obtain an oxide superconductor exhibiting excellent critical current density.

Further, the current density of the ion beam during the production of the polycrystalline thin film was set to 20 μmA / cm while the ion beam was incident on the metal substrate at an incident angle of 50 ° to 60 ° with respect to the normal to the substrate deposition surface. ² or more and the ion beam voltage is 15
More than 0V and less than 700V, many
The grain boundary tilt angle of a specific crystal axis in the film plane direction
A polycrystalline thin film having good crystal orientation at 25 degrees or less can be reliably produced on a substrate, and by forming an oxide superconducting layer based on this, a critical current having excellent crystal orientation can be obtained. An oxide superconducting conductor having a high density can be reliably obtained. Also , if a long metal substrate is used,
A long superconducting conductor can be obtained. The ion used as the ion beam is preferably an inert gas ion or a mixed ion of an inert gas ion and oxygen gas.

[Brief description of the drawings]

FIG. 1 is a configuration diagram showing a polycrystalline thin film formed by the method of the present invention.

FIG. 2 is an enlarged plan view showing crystal grains of the polycrystalline thin film shown in FIG. 1, their crystal axis directions and grain boundary tilt angles.

FIG. 3 is a block diagram showing an example of an apparatus for producing a polycrystalline thin film on a substrate by performing the method of the present invention.

FIG. 4 is a sectional view showing an example of the ion source of the apparatus shown in FIG.

FIG. 5 is a configuration diagram showing an oxide superconducting layer formed on the polycrystalline thin film shown in FIG.

6 is an enlarged plan view showing crystal grains of the oxide superconducting layer shown in FIG. 5, the crystal axis direction thereof, and the grain boundary tilt angle.

FIG. 7 is a configuration diagram showing an example of an apparatus for forming an oxide superconducting layer on a polycrystalline thin film.

FIG. 8 is a configuration diagram showing another embodiment of the device of the present invention.

FIG. 9 is a configuration diagram showing a polycrystalline thin film manufactured by a conventional apparatus.

FIG. 10 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 300 V, and an ion beam current density of 10 μA.
6 is a graph showing the result of X-ray diffraction of a polycrystalline thin film manufactured at a density of / cm ² .

FIG. 11 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 300 V, and an ion beam current density of 20 μA.
6 is a graph showing the result of X-ray diffraction of a polycrystalline thin film manufactured at a density of / cm ² .

FIG. 12 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 300 V, and an ion beam current density of 40 μA.
6 is a graph showing the result of X-ray diffraction of a polycrystalline thin film manufactured at a density of / cm ² .

FIG. 13 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 300 V, and an ion beam current density of 70 μA.
6 is a graph showing the result of X-ray diffraction of a polycrystalline thin film manufactured at a density of / cm ² .

FIG. 14 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 300 V, and an ion beam current density of 10 μA.
FIG. 2 is a pole figure of a polycrystalline thin film manufactured at a rate of / cm ² .

FIG. 15 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 300 V, and an ion beam current density of 20 μA.
FIG. 2 is a pole figure of a polycrystalline thin film manufactured at a rate of / cm ² .

FIG. 16 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 300 V, and an ion beam current density of 40 μA.
FIG. 2 is a pole figure of a polycrystalline thin film manufactured at a rate of / cm ² .

FIG. 17 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 300 V, and an ion beam current density of 70 μA.
FIG. 2 is a pole figure of a polycrystalline thin film manufactured at a rate of / cm ² .

FIG. 18 shows an ion beam incident angle of 90 degrees, an ion beam voltage of 300 V, an ion beam current of 25 mA and 4
5 is a graph showing an X-ray diffraction result of a polycrystalline thin film manufactured at 5 mA.

FIG. 19 is an ion beam incident angle of 90 degrees, an ion beam voltage of 500 V, an ion beam current of 15 mA,
It is a graph which shows the X-ray-diffraction result of the polycrystalline thin film manufactured at 5 mA and 35 mA.

FIG. 20 is a graph showing an X-ray diffraction result of a polycrystalline thin film manufactured at an ion beam incident angle of 90 degrees, an ion beam voltage of 700 V, and an ion beam current of 25 mA.

FIG. 21 is a configuration diagram for describing a test performed for examining a-axis and b-axis orientations of a polycrystalline thin film.

FIG. 22 shows (311) of the produced polycrystalline thin film.
It is a graph which shows the diffraction peak of a surface.

FIG. 23 shows (311) of the produced polycrystalline thin film.
It is a graph which shows the diffraction peak of a surface.

FIG. 24 is a graph showing diffraction peaks of the obtained polycrystalline thin film at every rotation angle of 5 degrees.

FIG. 25 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 500 V, and an ion beam current density of 40 μA.
6 is a graph showing the result of X-ray diffraction of a polycrystalline thin film manufactured at a density of / cm ² .

FIG. 25 is an ion beam incident angle of 55 degrees, an ion beam voltage of 700 V, and an ion beam current density of 40 μA.
6 is a graph showing the result of X-ray diffraction of a polycrystalline thin film manufactured at a density of / cm ² .

FIG. 27 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 200 V, and an ion beam current density of 50 μA.
6 is a graph showing the result of X-ray diffraction of a polycrystalline thin film manufactured at a density of / cm ² .

FIG. 28 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 200 V, and an ion beam current density of 20 μA.
6 is a graph showing the result of X-ray diffraction of a polycrystalline thin film manufactured at a density of / cm ² .

FIG. 29 shows an ion beam incident angle of 55 degrees, an ion beam voltage of 150 V, and an ion beam current density of 30 μA.
6 is a graph showing the result of X-ray diffraction of a polycrystalline thin film manufactured at a density of / cm ² .

FIG. 30 is a diagram showing a relationship between an ion beam voltage and an ion beam current density and the crystal orientation of a manufactured polycrystalline thin film.

FIG. 31 is a graph showing the relationship between the angle of incidence of the ion beam and the full width at half maximum of the obtained polycrystalline thin film.

[Explanation of symbols]

A: substrate, B: polycrystalline thin film,
C: oxide superconducting layer, K, K ': grain boundary tilt angle, θ: incident angle,
φ: rotation angle, 11: substrate holder, 12: target, 1
3: ion gun, 20: crystal grain, 22: oxide superconducting conductor, 2
3 ... crystal grains,

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C30B 28/12 C30B 28/12 29/22 501 29/22 501K H01B 13/00 565 H01B 13/00 565D H01L 39/24 ZAA H01L 39/24 ZAAB (56) Reference JP-A-2-544757 (JP, A) JP-A-4-72062 (JP, A) JP-A-2-311398 (JP, A) Patent 2721595 (JP, B2) ( 58) Field surveyed (Int.Cl. ⁷ , DB name) C23C 14/00-14/58 C30B 28 / 12,29 / 22 C01G 3/00 H01B 13/00 H01L 39/24

Claims (8)

(57) [Claims] 1. A method of forming a polycrystalline thin film on a metal substrate by punching out constituent particles of a target by sputtering and depositing the constituent particles on a metal substrate, wherein the constituent particles are deposited on the base material. In addition, the ion beam generated by the ion source is placed at an angle of 55 ° from an oblique direction with respect to the normal to the film forming surface of the substrate, in addition to the constituent particles which are beaten from the target and deposited on the film forming surface of the substrate. The constituent particles are deposited on the substrate while irradiating at an incident angle in the range of ６０60 °, and stabilized zirconia, MgO, Sr
Using any one of TiO ₃ , specifying the film surface direction of many crystal grains constituting the obtained polycrystalline thin film
A polycrystalline thin film, characterized in that the tilt angle of the grain boundary formed by the crystal axes is 25 degrees or less. 2. A sputtering hammered out the constituent particles of the target is deposited on a metal substrate by a method of forming a polycrystalline thin film on a metal substrate, depositing the constituent particles on a substrate In addition, the ion beam generated by the ion source is placed at an angle of 55 ° from an oblique direction with respect to the normal to the film forming surface of the substrate, in addition to the constituent particles which are beaten from the target and deposited on the film forming surface of the substrate. The constituent particles are deposited on the substrate while irradiating at an incident angle in the range of ６０60 °, and stabilized zirconia, MgO, Sr
Using any one of TiO ₃ , the film surface direction in a large number of crystal grains constituting a polycrystalline thin film obtained by setting the current density of the ion beam to 20 μA / cm ² or more and the ion beam voltage to 150 V or more and less than 700 V Identification
A polycrystalline thin film, characterized in that the tilt angle of the grain boundary formed by the crystal axes is 25 degrees or less. 3. Stabilized zirconia, MgO, SrTiO
The c-axis of each crystal grain of the cubic polycrystalline thin film made of any one of ₃ is oriented perpendicular to the substrate deposition surface, and a
3. The method for producing a polycrystalline thin film according to claim 1, wherein a grain boundary inclination angle between the axes or between the b axes is set to 25 degrees or less. 4. A method for producing an oxide superconductor, comprising using an inert gas ion or a mixed ion of an inert gas and an oxygen gas as the ion according to claim 1, 2 or 3. 5. hammered out the constituent particles of the target are deposited on a substrate of metals by sputtering, a polycrystalline thin film is formed on a metal substrate and then an oxide superconducting layer on the polycrystalline thin film In the manufacturing method of the oxide superconducting conductor to be formed
There, at the time of depositing the constituent particles on a substrate, outside the constituent particles to be deposited hammered from the target to the deposition surface on a substrate, forming an ion beam ion source caused the substrate with depositing sputtered particles while irradiating with an incident angle in the range of 5 5-60 degrees from the oblique direction with respect to the normal line of the film plane,
As the target, stabilized zirconia, MgO, S
Numerous crystals using any one of rTiO ₃
Grain boundary tilt between specific crystal axes in the film plane direction in grains
A method for producing an oxide superconducting conductor, comprising: forming a polycrystalline thin film having an angle of 25 degrees or less, and forming an oxide superconducting layer on the polycrystalline thin film. 6. sputtering hammered out the constituent particles of the target is deposited on a metal substrate by, forming a polycrystalline thin film on a metal substrate, then forming an oxide superconducting layer on the polycrystalline thin film in oxide superconductor manufacturing method of
There, at the time of depositing the constituent particles on a substrate, outside the constituent particles to be deposited hammered from the target to the deposition surface on a substrate, forming an ion beam ion source caused the substrate with depositing sputtered particles while irradiating with an incident angle in the range of 5 5-60 degrees from the oblique direction with respect to the normal line of the film plane, as the target, stabilized zirconia, M
gO, used made of either of SrTiO _3, the ion beam current density of 20 .mu.A / cm ² or more, the multi as less than 700V ion beam voltage above 150V
Between certain crystal axes in the film plane direction
A method for producing an oxide superconducting conductor, comprising: forming a polycrystalline thin film having a grain boundary inclination angle of 25 degrees or less, and forming an oxide superconducting layer on the polycrystalline thin film. When 7. forming an oxide superconducting layer on a polycrystalline thin film according to claim 5 or 6, wherein, oxide, characterized in that the epitaxial growth of crystals of the oxide superconductor to the crystal of the polycrystalline thin film Of manufacturing superconductors. As 8. ions, inert gas ions or, method of manufacturing an oxide superconductor according to claim 5, 6 or 7, wherein the use of mixed ions of an inert gas and oxygen gas.