JPH07187614A - Production of superconducting oxide and superconductor device - Google Patents

Abstract

PURPOSE:To convert a nonsuperconductor into a superconductor by irradiation with corpuscular beams or electromagnetic radiation, to increase the Tc and Jc of the superconductor having low characteristics and to produce a superconducting coil or circuit without carrying out working. CONSTITUTION:A multiple oxide having a spinel or perovskite type structure or a structure analogous to it is irradiated with oxygen ions or with electron beams, laser beams or IR in an oxygen atmosphere to form irradiation defects in the resulting superconducting oxide and the critical current density of the superconducting oxide in a magnetic field is increased or minute irradiation defects are introduced by irradiation with electrons or ions having higher energy than energy required to sputter atoms from the superconducting oxide. The wiring layer of a superconductor device with the wiring layer at a prescribed position of the surface of the superconductor element is made of a superconducting oxide layer and a prescribed circuit is formed while interposing a nonsuperconducting oxide layer in a plane shape or a superconducting coil made of a superconducting oxide layer is disposed while interposing a nonsuperconducting oxide layer in a plane shape to obtain a superconducting coil of a spiral circuit.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a superconducting oxide formed by irradiating a particle beam or electromagnetic radiation and a method for producing the same, and particularly to a superconducting oxide and a superconductor suitable for constituting a superconducting device or a superconducting element. The present invention relates to devices and manufacturing methods thereof.

[0002]

2. Description of the Related Art Conventionally, only three kinds of superconducting materials such as Nb ₃ Sn have been put into practical use in superconducting devices such as superconducting coils, and the critical temperature at which superconductivity is reached is 23 K (Nb ₃ Ge) at the maximum.
It was. For this reason, expensive liquid helium must be used as a coolant for these superconducting substances, and the cooling efficiency was low. In order to improve the cooling efficiency, it is necessary to use a substance that exhibits superconducting properties at as high a temperature as possible, and up to now, research has been conducted on more than one thousand kinds of substances such as element / alloy compounds, ceramics, and organic substances. Of these, most recently, perovskite-based composite oxides, especially layered perovskite-based oxides, have a significantly higher critical temperature T than before.
It was revealed to have c. These are La-B
a-Cu-O system, La-Sr-Cu-O system or Y-B
It is a layered perovskite-based composite oxide that is different from a-Cu-O-based, etc., and has a Tc of 30 K or more, especially Y-Ba-Cu-.
O-type shows 90K or more and is cheap as a coolant, such as liquid hydrogen, liquid neon or liquid nitrogen (1/1 of liquid helium)
(10 price) can be used, and when liquid nitrogen is used, the cooling efficiency can be increased by 20 times that of liquid helium.

These oxides having a high Tc are, for example,
Physical Review Letters Volium 58, Number 4 (1987), pages 405 to 407 (Physical
Review Letters Vol. 58, No. 4 (1987) pp405
-407) for La-Ba-Cu-O-based substances, and Physical Review Letters Vol. 58, No. 4 (1987), pages 408 to 410 (Physical Review Letters Vol. 58, No. 4 (1987)).
pp. 408-410), the La-Sr-Cu-O-based substance is further described in Physical Review Letters.
Volium 58, (1987) pp. 908 (Physical Revie
w Letters Vol. 58, (1987) p908) Y-B
The a-Cu-O based materials are discussed.

[0004]

There are three problems with these oxides. First, the superconducting characteristics, especially the critical temperature Tc, vary even if the same oxide system is manufactured by the same manufacturing method. The above-mentioned composite oxide is prepared by various firing methods such as reaction sintering, pressureless sintering, gas pressure sintering, HP,
In addition to HIP, powder preparation methods such as gas phase method, liquid phase method and solid phase method, vacuum vapor method, MBE method, reactive vapor deposition method,
Ion plating method, cluster ion beam method,
It can be produced by a thin film method such as an ion sputtering method, a thermal spraying method, or a liquid quenching method, but in any case, it is necessary to perform heat treatment before or after forming the final shape such as a powder, pellet or film. In the superconducting oxide prepared by these methods, it is relatively easy to adjust the ratio (composition) of components other than oxygen, but it is difficult to adjust the oxygen concentration, and the heat treatment is However, even if it is performed at the same temperature and the same time in the same atmosphere, there is a large difference in oxygen concentration between each heat treatment charge and within the same charge, and there is a problem in practical use that Tc varies widely or remains a non-superconductor. is there.

Secondly, the workability of the composite oxide is extremely poor. When making a circuit which is an element such as a magnet of a superconducting device element or a superconducting element, it is always required to process it. For example, although the wire material constituting the magnet needs to be coiled, the complex oxide is significantly brittle and difficult to process as compared with the conventional metal-based ones, and is not suitable for coiling. Further, as a method for producing a circuit, there is a patterning process by reactive ion etching which has been used in the semiconductor process so far. However, since the composite oxide has a composition of three or more components, reactive ion etching or the like is used. There is a problem that ordinary fine processing becomes extremely difficult.

Thirdly, the critical current density Jc of the composite oxide in a magnetic field is extremely low. Since the conventional metal-based superconductor has a coherence length of about micrometer, a pinning center having a size of micrometer order such as grain boundaries and precipitates pin the magnetic flux lines to prevent the Jc in the magnetic field. However, since the coherence length of the composite oxide is about three orders of magnitude lower than that of the conventional one, the conventional pinning center is effective in pinning the magnetic flux lines penetrating in the magnetic field. However, there is a problem that Jc in the magnetic field becomes low.

The object of the present invention is to make a non-superconductor a superconductor by irradiating a particle beam or electromagnetic radiation to improve Tc and Jc of a superconductor having a low characteristic, and further to process a superconducting coil or a circuit. It is to provide a method of manufacturing without.

[0008]

The present invention uses a non-superconductor as a superconductor, and in order to achieve an improvement in Tc of the superconductor, a non-superconducting oxide or a superconducting oxide is subjected to a particle beam or electromagnetic radiation. Is applied to adjust the oxygen concentration for enriching the oxygen concentration at the crystal lattice position.

Further, according to the present invention, in order to manufacture an element circuit such as a magnet of a superconducting device element or a superconducting element without a working process, a non-superconducting oxide is irradiated with a particle beam or an electromagnetic radiation to be irradiated. This is achieved by forming the above portion as a superconducting oxide, and forming a part or all of the superconducting oxide in a planar shape in a state of being embedded in a non-superconducting oxide. As another manufacturing method, the superconducting oxide is irradiated with a particle beam or electromagnetic radiation, the irradiated portion is made into a non-superconducting oxide, and a part or all of the non-superconducting oxide in a planar shape is used in the superconducting oxide. It is achieved by being formed in a state of being embedded in the. By these manufacturing methods, the superconducting oxide used for the coil or circuit used in the superconducting magnet can be applied by irradiation without processing the shape of the magnet, the circuit or the like among the non-superconducting oxides.
The method of converting a superconducting oxide into a non-superconducting oxide by irradiating these particle beams or electromagnetic radiation may be a method of reducing the oxygen concentration at the crystal lattice position by the irradiation.

Further, according to the present invention, the improvement of the critical current density Jc of the superconducting composite oxide in the magnetic field is achieved by the electron or ion which can give higher energy than the ejection energy of the atoms of the superconducting oxide. Irradiate,
This can be achieved by introducing irradiation defects with controlled nanometer order size.

Upon irradiation with the particle beam or electromagnetic radiation in the present invention as described above, heating can be performed by another heating means at the same time as irradiation, or heat treatment can be performed after irradiation. In particular, it is more effective when the non-superconductor is made to be a superconductor or the oxygen concentration at the crystal lattice position is enriched. The temperature at that time is T, which is the complete solution temperature of the irradiated oxide.
If it is (k), it is preferably T (k) or less and T / 3 (k) or more.
However, when the superconducting oxide is changed to a non-superconducting oxide, the heat treatment is not necessary.

Examples of the particle beam or electromagnetic radiation in the present invention include ions, electrons, neutrons, lasers, etc., and it is preferable to irradiate a preferable particle beam or electromagnetic radiation according to each purpose of the present invention. .

Particle beams suitable for irradiating a non-superconductor or a superconductor to convert the non-superconductor into a superconductor and to enrich the oxygen concentration at the crystal lattice position are oxygen ions and electrons, which are suitable electromagnetic waves. Radiation is laser light, infrared light, or the like. However, in the case of irradiating with electrons, laser light, and infrared light, the atmosphere is preferably oxygen. When the particle beam or the electromagnetic radiation is irradiated into the non-superconducting oxide layer to form the superconducting oxide, the particle beam or the electromagnetic radiation suitable for use is the same as the above.

Particle beams suitable for irradiating a superconductor to reduce the oxygen concentration at the crystal lattice position are ions, electrons and neutrons. However, the energy of these particle beams needs to be equal to or higher than the energy that can repel oxygen at the crystal lattice position of the oxide, but this is not the case only for hydrogen ions. The particle beam and electromagnetic radiation for irradiating the superconductor to make it non-superconductor are the same as above, but it is preferable that the atmosphere for irradiating the electromagnetic radiation is not oxygen. When the non-superconducting oxide is formed by irradiating the superconducting oxide with the particle beam or the electromagnetic radiation, the particle beam or the electromagnetic radiation suitable for use is the same as above.

Ions that can be used to both enrich or reduce the oxygen concentration at the crystal lattice positions described above are oxygen ions. Therefore, in the case of irradiating oxygen ions, the non-superconductor can be made to be a superconductor or Tc can be improved by appropriately selecting the temperature and the irradiation amount, while the superconductor can be made to be a non-superconductor. When hydrogen ion irradiation is used to reduce the oxygen concentration at the crystal lattice position or when the superconductor is changed to a non-superconductor, hydrogen has the action of reducing oxygen in the oxide, so compared to other ions, There are advantages such as a small irradiation dose.

It is electrons and then ions that are suitable as a particle beam for use in introducing fine irradiation defects into the superconducting oxide to improve Jc. The reason for this is that irradiation with neutrons increases activation of oxides and irradiation time, but irradiation times of electrons and ions are short, and the size and distribution of irradiation defects introduced can be controlled accurately. Most preferably, the irradiation dose is about 60 to 200% of the value at which Tc (onset) starts to decrease due to irradiation.

Ions suitable for irradiating a superconductor to reduce the oxygen concentration at the crystal lattice position or to make it a non-superconductor are those having energy capable of repelling oxygen at the crystal lattice position of the oxide. In addition to oxygen, Ti, Zr, Hf, C, Si, Ge, Sn, Pb,
V, Cr, Mn, Fe, Co, Ni, Zn, N, Al,
It is also possible to use Mg ions.

Various accelerators can be used for ion irradiation. For example, Kotsk Croft-Walton type accelerator, van de Graaff type accelerator, tandem type accelerator, Kauffman type accelerator and the like. For electron irradiation, in addition to the Kotsk Croft-Walton accelerator or the like, a lineat or a cyclotron accelerator or the like can be used.

A specific application example of the present invention is as follows. According to the present invention, in a semiconductor device having a wiring layer at a predetermined position on the surface of a semiconductor element, the wiring layer is made of a superconducting oxide layer, and a predetermined circuit is formed in a planar shape via a non-superconducting oxide layer. In a semiconductor device.

The present invention relates to a semiconductor device having a wiring made of a superconducting oxide layer, wherein the wiring has a planar shape and a predetermined circuit is formed via a non-superconducting oxide layer. is there.

The present invention resides in a superconducting coil made of a superconducting oxide, which is characterized in that a spiral circuit is formed in a planar shape via a non-superconducting oxide.

[0022]

[Function] Details of a method of irradiating a non-superconducting oxide or a superconducting oxide with a particle beam or electromagnetic radiation to enrich the oxygen concentration at the crystal lattice position to adjust the oxygen concentration and a method of converting the non-superconductor into a superconductor I will describe.

The oxygen-deficient layered perovskite oxide is
As shown in FIG. 1, depending on the oxygen concentration at the lattice position that constitutes the crystal, it exhibits non-superconductivity or superconductivity.
The inventors of the present invention have made such a non-superconducting oxide into a superconducting body and further raising the critical temperature Tc of the superconducting oxide by oxygen ion irradiation or electron, laser beam or infrared light irradiation in an oxygen atmosphere. We discovered that irradiation was effective and reached the present invention.

FIG. 2 is a diagram showing the relationship between the oxygen ion dose and Tc. When the state of the non-superconducting region A of the triple-layered perovskite in which oxygen is significantly deficient is irradiated with oxygen ions, the state transitions to the superconducting state at a certain dose or more, and the critical temperature Tc appears (enters the region B in FIG. 2). Further, Tc rises as the dose of oxygen ions increases. However, when oxygen ion irradiation is continued, Tc shows the maximum value, and thereafter, Tc decreases as the ion irradiation amount increases, and finally Tc becomes a non-superconductor (entering the C region in FIG. 2). Oxygen ion irradiation at which Tc shows the maximum value is affected by irradiation temperature and irradiation speed,
It's not uniquely decided. The higher the irradiation temperature or irradiation rate, the larger the oxygen ion irradiation dose at which Tc shows the maximum. On the other hand, the reason why Tc begins to drop above a certain dose is that oxygen atoms at the crystal lattice positions are preferentially ejected due to irradiation damage during oxygen ion irradiation, and the oxygen concentration at the lattice positions decreases. This was clarified from the result of observing a lattice image during irradiation of oxygen ions by using an apparatus in which an ion accelerator is combined with a 200 KeV electron microscope. Therefore, the curve showing the relationship between Tc and oxygen ion irradiation dose in FIG. 2 has a peak because of the competition between the reaction in which oxygen introduced by irradiation enters the lattice position and the reaction in which oxygen at the lattice position is ejected during irradiation. It is considered to be the result. Therefore, in order to improve Tc by enriching oxygen concentration, it is preferable to irradiate oxygen ions up to the irradiation dose at which Tc in FIG. 2 shows a peak. On the other hand, in order to reduce the oxygen concentration at the lattice position of the superconducting oxide of the present invention, Tc of FIG.
Can be achieved by irradiating with oxygen at a dose higher than that at which the peak shows a peak. Further, in order to make the superconducting oxide of the present invention a non-superconducting oxide, irradiation with oxygen ions up to the dose corresponding to the region C in FIG. Can be achieved.

On the other hand, as a method of converting the non-superconducting oxide in the state of the non-superconducting region A in FIG. 2 into a superconductor and further increasing the Tc of the superconducting oxide, the electron, laser beam or infrared light in an oxygen atmosphere is used. Irradiation is effective. FIG. 3 is a diagram showing the relationship between the energy density of laser light and the like and Tc. When a triple-layered perovskite (state of non-superconducting region D) in which oxygen is significantly deficient is irradiated with an electron beam, a laser beam, or infrared light in an oxygen atmosphere, it transitions to a superconducting state at a certain energy density or more, and a critical temperature appears ( This corresponds to the area E in FIG. 3). If this energy density is further increased, Tc increases, but there is a range of energy density in which Tc can be increased. If the energy density is too high, Tc sharply decreases, or Tc becomes non-superconductor (region of FIG. 3). Equivalent to F). The mechanism in which the non-superconductor becomes a superconductor by irradiation with an electron beam, a laser beam, infrared light, or the like, and the superconductor Tc rises is that the irradiation raises the temperature of the irradiated portion of the non-superconductor or the superconductor. , Introduction of oxygen from the atmosphere (: oxidation)
It is considered that this is because enrichment of oxygen concentration at the crystal lattice position is achieved by. On the other hand, when the energy density of irradiated particles becomes too high, Tc decreases or non-superconductor formation (state of region F in FIG. 3) occurs. This is because the temperature of the irradiated portion rises and the superconductor structure is increased. It is considered that the change in structure is caused by the evaporation of elements, the melting of superconductors or the formation of amorphous.

FIG. 4 is a diagram summarizing the results of the ICP analysis showing that the composition changes depending on the temperature of the YBa ₂ Cu ₃ O ₇ _ _x superconductor when the superconductor is irradiated with a laser beam. However, YBa ₂ Cu ₃ O _{7 — x} is a thin film formed on the MgO substrate by RF magnetron sputtering. It can be seen that when the temperature exceeds 700 ° C. by laser beam irradiation, the compositional variation becomes remarkable.

By the way, the oxygen concentration at the lattice position of the superconducting oxide of the present invention can be reduced by irradiating with an electron or laser having an energy density higher than the energy density at which Tc in FIG. 3 shows a peak. The oxide can be made into a non-superconducting oxide by irradiating with an electron or laser having an energy density corresponding to the region F in FIG.

As described above, the non-superconducting oxide in the non-superconducting region (A or D) shown in FIG. 2 or 3 is made into a superconductor by the method of enriching the oxygen concentration of the present invention. An oxide can be formed. Also, by the above method, the superconducting oxide formed in the non-superconducting oxide is combined with the superconducting coil, the superconducting circuit, the superconducting wiring, etc., and further, the semiconductor element is formed to form the superconducting circuit or the superconducting wiring. Can be made.

Oxygen ions, various ions, electrons, neutrons, etc. are caused by the ejection of oxygen at the oxide crystal lattice position by particle beam irradiation, but hydrogen ion irradiation is caused by a special mechanism other than the ejection of the crystal lattice position. The oxygen concentration can be reduced. That is, the hydrogen introduced into the oxide by hydrogen ion irradiation preferentially cuts off the bond between copper and oxygen, which are considered to contribute to superconductivity, and easily reduces oxygen in the superconducting oxide. effective. The fact that oxygen reduction of the oxide superconductor is caused by the hydrogen ion irradiation will be described by way of example with reference to changes in the X-ray diffraction pattern of FIG. FIG. 5 shows a thin film of YBa ₂ Cu ₃ O ₇ _ _x (thickness 10 μm produced by RF magnetron sputtering).
m) before irradiation with hydrogen ions (400 KeV) (upper figure) and after irradiation with 2.3 × 10 ¹⁷ H + / cm ² at room temperature (lower figure), the crystal structures of the films were analyzed by X-ray diffraction (CuKα). Line used)
It is the result of examination by. Before the irradiation, a single orthorhombic YBa ₂ Cu ₃ O ₇ _ _x was formed, but after the irradiation, a phase transition was made to a tetragonal YBa ₂ Cu ₃ O ₇ _ _x , and Y ₂ BaCuO ₅
And a CuO phase is newly formed. The transition from orthorhombic to tetragonal is a phenomenon that occurs when oxygen in YBa ₂ Cu ₃ O _{7 — x} decreases, and it can be seen that hydrogen ion irradiation reduces oxygen. This is shown in the following chemical reaction formula.

The _{YBa 2 Cu 3 O 7 _ x} ( orthorhombic) + y (2H) → YBa 2 Cu 3 O 7 _ x ( _{tetragonal) + yH 2 O ... (1} ) i.e., hydrogen was introduced in the hydrogen ion irradiation Reduced oxygen to induce the orthorhombic to tetragonal transition.
However, according to the equation (1), H ₂ O should be generated. H ₂ O is newly generated by irradiation with hydrogen ions to produce Y ₂ B.
It can be rationalized from the fact that aCuO ₅ and CuO were produced. That is, the reaction between H ₂ O and YBa ₂ Cu ₃ O ₇ _ _x is
When the convenience X = 0.5, can be expressed as _{3H 2 O + 2YBa 2 Cu 3} O 6. 5 → Y 2 BaCuO 5 + 3Ba (OH) 2 + 5CuO ... (2). Therefore, Y ₂ BaCuO ₅ and CuO were produced by the reaction between YBa ₂ Cu ₃ O _{7 — x} and H ₂ O. Since Ba (OH) ₂ is not crystallized here, it is considered that it does not appear in the diffraction peak of FIG.
Thus, by irradiating the superconducting oxide with hydrogen ions, the oxygen concentration at the crystal lattice position can be easily reduced by the reducing action. FIG. 6 shows YBa ₂ Cu ₃ described in FIG.
It is the result of measuring the electric resistance-temperature curve showing that a thin film of O _{7 — x} can be changed from a superconductor to a non-superconductor by hydrogen ion irradiation.

In the superconducting oxide in the state of the superconducting region B or E of FIG. 2 or 3, the above-described method for reducing the oxygen concentration of the present invention or the crystal composition or crystallinity of the superconducting oxide is destroyed. A non-superconducting oxide can be formed by the method. Also, in this superconducting oxide, a superconducting magnet or superconducting circuit formed by forming a non-superconducting oxide by this manufacturing method, a superconducting device such as a superconducting wiring, or a semiconductor element combined with a semiconductor element,
It is possible to obtain a semiconductor device having a superconducting circuit and superconducting wiring formed therein.

When performing the oxygen concentration adjusting method of irradiating the non-superconducting oxide or the superconducting oxide of the present invention with a particle beam or electromagnetic radiation to enrich the oxygen concentration at the crystal lattice position, during or after adjustment. Assuming that the complete solution temperature of the oxide is T (k), the temperature of
3 (k) or more is preferable, but T (k) is particularly preferable.
Hereinafter, the range of 4T / 5 (k) or more is preferable. The reason for this is that the range is suitable for recovering the disorder of crystallinity due to irradiation of a particle beam or electromagnetic radiation.

FIGS. 7 and 8 show Bi produced by a spatter.
FIG. 4 is a diagram showing electric resistance-temperature curves and changes in the critical current density Jc in a magnetic field when a thin film (thickness 5 μm) of SrCaCu ₂ O _x was irradiated with 2 MV electrons at room temperature. The thin film is almost a single crystal. Tc by electron irradiation
Tends to decrease (FIG. 7), but Jc in the magnetic field increases with the irradiation dose (FIG. 8). It is considered that this is because fine irradiation defects introduced by electron irradiation function as pinning centers of magnetic flux lines.

The oxide to which the present invention is applied is mainly a composite oxide having a spinel type structure, a perovskite type structure or a structure similar to this. Figure 9 shows the spinel structure AB ₂
The schematic diagram of O ₄ is shown. For example, LiTi ₂ O ₄ is typical, and Li enters the A site and Ti enters the B site in FIG.
Is an oxide containing. 10 to 13 are schematic diagrams of crystal structures of perovskite oxides (oxides having a perovskite structure or a structure similar thereto). Figure 1
0 shows a schematic diagram of a perovskite type structure ABO ₃ .
Is represented _{BaPb 1 _ x Bi x O 3} , Ba, Pb-or Bi to B site enters the A site. FIG. 11 is a schematic diagram of the layered perovskite structure K ₂ NiF ₄ . La ₂ CuO ₄ is a typical one, and has a structure in which La is located at the K site, Cu is located at the Ni site, and O is located at the F site. FIG. 12 is a schematic diagram of an oxygen-deficient (triple) layered perovskite structure, which is represented by YBa ₂ Cu ₃ O _{7 — x} . FIG. 13 shows a schematic view of a multilayer perovskite structure, for example, Bi ₄ Sr ₃ C
It is represented by a ₃ Cu ₄ O _{16 and the} like.

The oxide having a layered perovskite structure, in addition to La ₂ CuO _4, for example, _{La 2 _ x M x CuO 4} _ y
And divalent Ca represented by M at the La ³ + position.
An oxide in which ² +, Sr ² +, and Ba ² + can be substituted and inserted, and an oxide in which Cu is substituted with Ag or Hg is also an object of the present invention. Examples of oxides having an oxygen-deficient layered perovskite structure include YBa ₂ Cu ₃ O ₇ _ _x and YSr ₂ Cu.
₃ O ₇ _ _x , YBa ₂ Cu ₃ _ _x Ni _x O ₇ _ _y , YBa ₂ Cu ₃ _ _x Ag _x O _{7
_ Y, YBaCaCu 3 O 7 _} y, Y 0. 75 Sc 0. 25, Ba 2 Cu 3 O 7
_ _y , YBa ₂ Cu ₃ F ₂ O _y , LnBa ₂ Cu ₃ O ₇ _ _x (however, Ln
Is La, Dy, Md, Sm, Eu, Gd, Ho, E
r, Tm, Yb, etc.) and the like. An oxide having a multi-layer perovskite structure is Bi-Sr-Ca-Cu-
Other than O-based materials, Tl-Ba-Ca-Cu-O-based materials and the like can also be mentioned.

[0036]

【Example】

[Example 1] An example of enriching or reducing the oxygen concentration at the crystal lattice position of a non-superconducting oxide or a superconducting oxide by irradiation of oxygen ions will be described. Tables 1 to 3 show the test materials and the manufacturing method thereof. The value of x in the table is 0.05,
A total of 60 test materials were prepared with 6 kinds of composition ratios so as to be 0.1, 0.2, 0.3, 0.4 and 0.5. Oxygen ions were injected into these test materials at 1 × 10 ¹⁷ ions / cm ² using a Kotsk Croft-Walton ion accelerator.
Operating conditions of the ion accelerator accelerating voltage 0.4MeV, degree of vacuum in the vacuum chamber is a sample chamber 10 ~ ⁶ ~10 ~ ⁷ torr, the temperature is 870～1100K. FIG. 14 is a diagram showing the external appearance of this ion accelerator, and FIG. 15 is a conceptual diagram further showing the structure of this device and the path 4 of the ion beam. This will be described in detail. The oxygen to be ion-implanted is supplied to the ion source 6 by the oxygen bottle 5, where a high voltage is applied to generate oxygen ions. The ion beam includes an accelerator 1 composed of an ion source 6, a mass analyzer 7, and an accelerating tube 8, a quadrupole lens 2, a deflector 9, and a slit 10.
After that, the test material 11 in the vacuum chamber 3 is irradiated and driven. However, oxygen ions can be similarly generated by using a carbon dioxide bolt instead of the oxygen bottle. Further, the electromagnet 12, the accelerating tube current 13, the quadrupole lens power source 14, the deflector current 15, the slit ammeter 16, the target ammeter 17, and the temperature measurement control system 18 are connected to a micro computer 19, which are connected by the micro computer 19. The driving conditions are controlled to be constant. Oxygen ion implantation was performed under the same conditions from both sides of the thin film sample except for the classifications C and D in Tables 1 to 3.

After the above oxygen ion implantation, the sample was cooled to the liquid helium temperature, and the inductance change in the process was measured by the inductance method to examine the critical temperature Tc. FIG. 16 shows an example thereof (results obtained by measuring a test piece corresponding to x = 0.1 of sample material No. 1 in Tables 1 to 3). The horizontal axis of FIG. 16 represents the absolute temperature and the vertical axis represents the inductance change. In this example, Tc can be read as 35K.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

Table 4 shows the T of the test materials treated in the above steps.
It is a result showing whether c increased or decreased as compared with the critical temperature measured by the same method before oxygen ion implantation. In the case of the decreased amount, Tc was improved by annealing after irradiation.

[0042]

[Table 4]

Table 5 shows a ratio of how much the maximum value Tc, max of Tc obtained when the above oxygen ions are injected by the accelerator is higher than the critical temperature Tc ⁰ when no ion injection is performed. It is shown in. Also, this value
Although (Tc, max-Tc ⁰ ) / Tc ⁰ varies depending on the value of x of each test material, it can be seen that the value of Tc can be increased by the method of the present invention for any of the test materials. Furthermore, the superconducting substances of Table 5 having Tc higher than Tc ⁰ obtained by adjusting the oxygen concentration using the method of the present invention are the products of the present invention.

[0044]

[Table 5]

[Embodiment 2] An example of another test material by oxygen ion irradiation similar to that of Embodiment 1 will be described. The test material is R
YBa ₂ Cu was produced by F magnetron spa ivy ₃ O _{6. 2,
YBa 2 Cu 3 O 6. 6} , ErBa 2 Cu 3 O 6. 5 of the thin film (thickness 1
2 μm, using MgO substrate). Oxygen ion irradiation was carried out at 1110 ± 30K at 75 KeV by means of the Kotsk Croft-Walton accelerator shown in FIGS. FIG. 17 shows the change in Tc (offset) of the test material with respect to the oxygen ion irradiation dose. However, before the oxygen ion _{irradiation, YBa 2 Cu 3 O 6.} 2 is _{non-superconductor, YBa 2 Cu 3 O 6.} 6
The superconductor offset _{54K, ErBa 2 Cu 3 O 6} . 5 is a superconductor offset 51K. By irradiation with oxygen ions, the non-superconductor becomes a superconductor, and the superconductor T
As shown in the figure, c increased to a certain dose. When the irradiation amount is further increased, Tc starts to decrease due to the ejection of oxygen atoms due to the irradiation damage described above. Again 1
Irradiation with 0 ¹⁹ , O + / cm ² made it possible to make any of the test materials a non-superconductor.

[0046] [Embodiment 3] FIG. 18 Cu ₃ O ₆ YBa ₂ non superconductor fabricated in oxide mixing method. ₂ (dimensions 25mm length,
This is a graph showing a change in critical temperature with respect to energy density when a test material having a width of 6 mm and a thickness of 3 mm) is irradiated with a carbon dioxide laser or an electron beam in an oxygen stream (5 l / min). However, electron beam irradiation is 50 to 100
A beam of kV and 3 to 4 mmφ was used. Similar results were obtained with both carbon dioxide laser irradiation and electron beam irradiation. Irradiation with an energy density of about 1 × 10 ² J / cm ² or more caused a transition from non-superconducting to superconducting, and Tc could be increased by increasing the energy density. When further increasing the energy density of about ² × 10 ³ J / cm 2 than Tc begins to decrease, that is the test material at approximately 4.3 × 10 ³ J / cm ² and begins to melt non-superconductor did it.

[Embodiment 4] FIG. 19 shows a YBa ₂ Cu ₃ O ₇ _ _x thin film (thickness: 5 μm) produced by an RF magnetron sputtering device.
m, MgO substrate was used), and the effect of hydrogen ion irradiation dose on the electric resistance-temperature curve when irradiated with 400 KeV hydrogen ions was examined. Irradiation was carried out at room temperature using a Kotsk Croft-Walton accelerator. 10 ¹⁵
H + / cm ² order Tc offset begins to decrease at the irradiation amount of, can be non-superconducting embodied in irradiation amount of 10 ¹⁷ H + / cm ² order.

[Embodiment 5] This embodiment will be described with reference to FIG. (100) to form a semi-insulating layer 22 having a Yotsute Ba ₂ YCu ₃ O _{5. 0} becomes composition Supatsutaringu method on the substrate 21 made of Si single crystal in the crystal orientation. Semi-insulating layer 22
Has a thickness of about 200 nm. This in vacuum, 100
After heating at a temperature of 0 ° C. for about 1 hour, it is cooled.
Next, in pure oxygen at a pressure of 1 atm, a part of the semi-insulating layer 22 is locally heated to 800 to 500 ° C. by using laser light 24 or infrared light from a CO ₂ laser 25, and at least 500 ° C. At the above temperature, the heated portion is oxidized to form a superconductor 23 having a composition of Ba ₂ YCuO ₇ .
The shape of the superconductor 23 can be made arbitrary by moving the beam spot 26 of the laser light 24. This can be achieved either by moving the substrate 21 or by sweeping the laser light using an optical system. According to this embodiment, the semi-insulating substrate is automatically realized by the semi-insulating layer 22. Further, since the superconductor 23 is embedded in the semi-insulating layer 22 and the surface of the circuit using the same is flat, no step is generated and high integration is possible. Further, the minimum size of the superconductor 23 is mainly determined by the beam spot diameter of the laser light 24, but the size can be reduced to 1 μm or less.

In this embodiment, heating by laser light in oxygen was used for local oxidation of the semi-insulating layer 22, but heating at 800 to 500 ° C. by high frequency instead of laser light may be used. . The pressure of oxygen is not limited to 1 atm, and may be lower than this, but in order to promote the oxidation efficiently, the pressure of 800 to 50 at 1 atm or more is applied.
It is desirable to perform local heating at 0 ° C. The cooling rate after heating can be changed according to the sweep speed of the spot of the laser light, but from the viewpoint of reducing the crystal defects in the superconductor 23, the sweep speed should be made as slow as possible for cooling. Is required, and it is desirable to keep the cooling state at about 5 deg / min up to about 500 ° C.
In the example shown in FIG. 20, the superconductor 23 can be used as wiring for a circuit.

[Embodiment 6] This embodiment will be described with reference to FIG. In the fifth embodiment, the semi-insulating layer 22 was formed in advance, but conversely, the superconductor 23 was previously formed on the substrate 21, and the hydrogen ion source 2 was added to this.
It is also possible to inject the hydrogen ion beam 220 from 30 and reduce the superconductor 23 at the portion of the beam spot 210 to form this portion as the semi-insulating layer 22. In this embodiment, the wiring made of the superconductor 23 is formed by this method. When implanting the hydrogen ion beam 220,
The substrate is preferably heated to about 500 ° C., but it is not essential. Here, the superconductor 23
A hydrogen ion beam was used to form the semi-insulating layer 22. However, an ion beam having other reducing properties may be used instead of the hydrogen ion beam, and a laser beam or a high frequency wave at 800 ° C. may be used in vacuum. Needless to say, the object of the present invention can be achieved because oxygen is dissociated even by heating above.

[Embodiment 7] This embodiment will be described with reference to FIG. The present embodiment is a superconducting tunnel element using the superconductor of the present invention. On the substrate made of Si or sapphire, Ba ₂ YCu ₃ O was formed by the sputtering method.
_A semi-insulating layer 22 of _5.0 is formed. Its thickness is about 200
nm. This is heat-treated in oxygen according to the same method and conditions as shown in Example 5 to form the superconductor 23 as shown in FIG. The width of the superconductor 23 is about 20 μm, but there is no special limitation. Next, hydrogen ions are implanted by the same method and conditions as in Example 6 to form the tunnel portion 31 (see FIG. 22 (b)). The ion beam is focused so that the width of this portion is about 10 to 50 nm. The tunnel portion 31 can be a semi-insulator or a normal conductor depending on the implantation amount of hydrogen ions. Even in the case of, it can be used as a superconducting weak bond. In this way, a superconducting weakly coupled device having a flat structure can be constructed without using a photolithography or etching process.

[Embodiment 8] This embodiment will be described with reference to FIG. On the substrate 21 made of sapphire, Ba ₂ YCu ₃ O
_5. To form a semi-insulating layer 22 having a ₀ a composition. The forming method and conditions may be the same as those described in the fifth embodiment.
In the same manner as in Example 5, 800 to 800
Local heating at 500 ° C. is performed to form a superconductor to form the superconductor wiring 41 of the first layer. Then this upon, again Ba ₂ YCu ₃ O _{5. 0} to form a semi-insulating layer 20, again means pursuant local oxidation by the laser beam, the superconducting wire 42 of the second layer to form a superconductor . This makes it possible to easily realize a two-layer superconductor wiring. Further, as is clear from FIG. 23, since each layer is flattened, multilayer wiring of two or more layers can be realized and the performance of the circuit can be improved.

These superconductor wirings are semiconductor devices,
It goes without saying that it may be used together with a MOS transistor, for example. Further, an oxide superconductor material having a composition of Ba ₂ YCu ₃ O ₇ -δ was used as the material of the superconductor or the semi-insulating layer, but instead of Ba, it is replaced by Sr or Ca, Y, and Gd, Lu, Eu. , Sc, Ce, Sm, Nd, Yb, T
The same effect can be obtained by using b and Ho.

[Example 9] The test material was Y-Ba-Cu produced by the sputtering method (RF, magnetron).
-O-based oxide (however, the target material was Ba ₂ Cu ₃ O ₃ and Y ₂ O ₃ , the substrate was sapphire, SrTiO ₃ , quartz, and the substrate temperature was 700 ° C. or lower) and molecular beam epitaxy. The single-crystal La-Sr-Cu-O-based oxide having a thickness of about 0.5 to 1 [mu] m. 24 and 25 show the test materials Y-Ba-Cu-O and La-, respectively.
It is a diagram which shows the specific resistance of Sr-Cu-O type oxide, and the relationship of temperature.

Table 6 shows the contents of the non-superconducting treatment according to the manufacturing method of the present invention, the presence or absence of the non-superconductor and the presence or absence of the insulator. Even those that did not become insulators showed values several orders of magnitude higher than the specific resistance values shown in FIG. 25 by controlling the ion species and the doping amount thereof. The Kokcroft type ion accelerator and the tandem type accelerator were used for the ion doping, and they were used according to the acceleration voltage.

[0056]

[Table 6]

FIG. 26 is a sectional view showing an example of a semiconductor device having each layer wiring substrate of the present invention. The manufacturing process of this substrate is based on the wiring manufacturing method of the present invention. That is, the oxide superconductor 70 is formed on the insulating film 60 on the semiconductor element 50 by sputtering (71 is also a superconductor at this stage). After that, a portion to be a wiring is masked, and ion doping is selectively performed to form an insulator 7
1 is formed. By repeating this process, a multilayer wiring can be manufactured as shown in FIG. However, the insulators 81 and 82 are formed in the subsequent ion doping step. In addition, these steps also include an ion doping step of manufacturing the resistor 80.

[Embodiment 10] FIG. 27 shows that a normal conductor or an oxide insulator 91 is formed by ion doping on an oxide superconducting layer 90 formed by a sputtering method, a vacuum deposition method, or a chemical vapor deposition method. It is sectional drawing of the composite_body | complex which laminated | stacked 91 by 2 layers by repeating these processes to the 3 layer structure. Therefore, as shown in FIG. 27, it is possible to manufacture a composite having a structure of two or more layers in which an oxide superconductor and an oxide of the same kind are integrated.

[Embodiment 11] An embodiment of manufacturing a superconducting coil using irradiation will be described with reference to FIG. Y, B
Y ₂ O ₃ , B such that the atomic ratio of a and Cu is 1: 2: 3.
aCO ₃ and CuO were weighed and mixed, calcined at 900 ° C. for 24 hours, and then pulverized. The calcined powder is kneaded with pine oil and an organic binder to form a paste, which is applied to the outer peripheral surface of a non-superconductor, for example, a Zr cylindrical tube 510, and 950 in an oxygen atmosphere.
Heat treatment was performed at 1 ° C. for 1 hour to form a superconducting layer 610 (FIG. 28A). Next, the cylinder coated with the superconducting layer shown in FIG. 7A was irradiated with the particle beam 710 locally while moving in one direction 730 at the same time as rotation 720 was applied as shown in FIG. 710 may be any particle that can give radiation damage to 610, for example, ions or electrons can be used. 710 may also be an electromagnetic radiation such as a laser, especially with an energy density value of 10 ³ J
/ Cm ² order is preferable. The portion of 610 illuminated by 710 is shown in Examples 2-6 and 8-1.
The non-superconductor is made into a non-superconductor by the same action as any of 0, and finally, the portion of the non-superconductor 810 is formed in a spiral shape as shown in the left side of FIG. As a result, the unirradiated portion 900
Can be a coiled superconductor. (C) As shown in FIG.
By superimposing the above superconducting coils 910 on the central axes of the coils and integrating them with 900, a superconducting magnet element can be manufactured.

The cylinder coated with the superconducting layer shown in FIG.
Of course, there is no limitation that it is produced by the coating method. That is, 610 may be produced by solidification from a molten state, or the outer surface portion of the non-superconductor 510 may be made into a superconductor by using irradiation as in Examples 1 to 3.

[Embodiment 12] A superconducting magnet manufactured by the method of the present invention will be described with reference to FIG. (A)
The hollow disk-shaped superconducting oxide 190 shown in (1) is irradiated with the same particle beam or electromagnetic radiation as in any one of Examples 2 to 6, 8 to 11 to the pole portion 100 of (b). Irradiation of the spiral 100 can also be achieved by masking the pole portion 101, or the irradiation beam 1
It was also possible to achieve this by a method of sweeping the beam to the 00 part. By this irradiation, the pole portion 100 selectively becomes a non-superconductor, so that the remaining portion 101 can form the superconducting coil 191. Further, in the same manner (c)
A superconducting coil 192 having a reverse spiral shape to that shown in FIG. In (b) and (c), the same coil is formed in any cross section perpendicular to the thickness direction. Then (b)
Except for the tip position 103 of the outer circumference of the coil, the surface portion of the coil is made non-superconductor by using the same irradiation as above to form the coil 193 as shown in (d). However, in the back surface of (d), only the front surface is made non-superconductor except the tip position 102 of the inner peripheral portion of the coil. The coil 192 of (c)
As shown in (e), except for the tip position 104 of the coil inner peripheral portion, the surface portion is made into a non-superconductor by irradiation similar to the above,
The back surface of the coil 194 is made non-superconducting by irradiating the front surface except the coil outer peripheral tip position 105. Finally 102 on the back of coil 193 and 1 on the front of 194
Coils 193 and 194 were coupled so that 04 was in contact with each other, and the coupling coil was used as one unit to laminate the coupling coils in multiple layers as shown in (f) to produce a long superconducting coil. However, the coil coupling could be achieved by an appropriate heat treatment in which the non-superconductor did not undergo superconducting transition. The coupling coils are arranged so that 105 of (e) and 103 of (d) are in contact with each other (f).
It was made to couple in the order shown in.

[Embodiment 13] A non-inductive winding coil using the method of the present invention will be described with reference to FIG. Figure 30 (a)
29D is the same coil 193 as that in FIG. 29D, which is manufactured by irradiation in Example 12. FIG. 30 (b) is similar to FIG.
9 (b), except for the tip position 205 on the inner circumference of the coil 191, the surface is made non-superconductor by the above irradiation, and the back surface is made non-superconductor by irradiation except the tip position 206 on the outer circumference. is there. 102 of 193 and 2 of 195
No. 05 was bonded by the same heat treatment as in Example 12, and then 1
The non-induced superconducting coil was produced by repeating the above-described two coil joinings in the order of joining the coil outer peripheral tip positions 103 of 206 and 193 of 95. By using this non-induction coil for the superconducting coil 211 of the permanent current switch shown in FIG. 31, when the switch 212 is cut, the electrical resistance of the 211 becomes large, so that a high-performance persistent current switch with good cut resistance is produced. did it. However, 2
Reference numeral 13 indicates a DC power source.

[Embodiment 14] Two long coils having different dimensions of the coil shown in FIG. 29F or the number of laminated coils 193 and 194 shown in FIG. 29 are used as the primary side coil and the secondary side coil, respectively. And confirmed the operation of the superconducting transformer.

[Embodiment 15] FIG. 32 shows an embodiment in which the shielding effect of the superconducting magnetic shield is improved by the method of the present invention. Reference numeral 221 in FIG. 32 (a) shows a YBa ₂ Cu ₃ O _{7 — x} magnetic shield made of a superconducting oxide. 22
2 MeV electrons 222 at 250K at 7 × 10 ¹⁷ e /
The shield body of (b) in which the irradiation defect 223 was introduced was produced by irradiation with cm ² . The Jc of 221 was increased from 800 A / cm ² by about 1.8 times, and the shield effect when a magnetic field was applied was improved.

[Embodiment 16] FIG. 33 shows an embodiment in which the performance of the superconducting power transmission line is improved by the method of the present invention. Figure 3
231. 3 (a) was prepared in the superconducting oxide (La _{0. 9} Sr
_0.1) a transmission line ₂ CuO _3. 231 was irradiated with ² MeV electrons 232 at 250 K at 5 × 10 ¹⁷ e / cm ² to produce a transmission line (b) in which an irradiation defect 233 was introduced.
The Jc of (b) was about 1.5 times that of (a) 280 A / cm ² , and the characteristics of the transmission line could be improved. The cooling medium Lig.
He is shown at 234.

[0066]

According to the present invention, the non-superconducting oxide can be made into a superconducting oxide, and the critical temperature Tc and the critical current density Jc of the superconducting oxide can be stably improved. Further, according to the present invention, there is an effect that superconducting devices such as superconducting coils and superconducting elements such as superconducting circuits and wirings can be manufactured without a working process.

[Brief description of drawings]

FIG. 1 is the oxygen temperature at the crystal lattice position of the oxide and the critical temperature T.
It is a figure which shows the relationship of c.

FIG. 2 is a diagram showing a relationship between an oxygen ion irradiation dose and a critical temperature Tc.

FIG. 3 is a diagram showing the relationship between the energy density of an electron beam, a laser beam, and infrared light and the critical temperature Tc.

FIG. 4 is a diagram showing a relationship between a rising temperature and composition of YBa ₂ Cu ₃ O _{7 — x} by laser beam irradiation.

FIG. 5 is a diagram showing changes in the X-ray diffraction pattern of YBa ₂ Cu ₃ O _{7 — x} due to hydrogen ion irradiation.

FIG. 6 is a diagram showing the effect of hydrogen ion irradiation on the electric resistance-temperature curve of YBa ₂ Cu ₃ O ₇ — _x .

FIG. 7 is a diagram showing the effect of electron irradiation on the electric resistance-temperature curve of BiSrCaCuO _x .

FIG. 8 is a diagram showing the effect of electron irradiation on Jc in a magnetic field of BiSrCaCu ₂ O _x .

FIG. 9 is a schematic view of a spinel structure.

FIG. 10 is a schematic diagram of a perovskite structure.

FIG. 11 is a schematic view of a layered perovskite structure.

FIG. 12 is a schematic view of an oxygen-deficient layered perovskite structure.

FIG. 13 is a schematic diagram of a multilayer perovskite structure.

FIG. 14 is an external view of an ion accelerator.

FIG. 15 is a schematic diagram showing a configuration of an ion accelerator and an ion beam path.

FIG. 16 is a diagram showing an example of a measurement result of Tc by the inductance method.

FIG. 17 is a diagram showing the relationship between the oxygen ion irradiation dose and the critical temperature Tc.

FIG. 18 is a diagram showing the relationship between the energy density of particles or electromagnetic radiation and the critical temperature Tc.

FIG. 19 is a diagram showing an electric resistance-temperature curve for each dose of hydrogen ions.

FIG. 20 is a diagram showing a method for manufacturing a superconductor device which is the fifth embodiment of the present invention.

FIG. 21 is a diagram showing a method for manufacturing a superconductor device which is the sixth embodiment of the present invention.

22A and 22B are views showing a seventh embodiment of the present invention, in which FIG. 22A is a sectional view in which a superconductor is formed, and FIG. 22B is a sectional view in which a tunnel portion is further formed.

FIG. 23 is a diagram showing an eighth embodiment of the present invention.

FIG. 24 is a diagram showing the relationship between the specific resistance and the temperature of a Y—Ba—Cu—O-based oxide.

FIG. 25 is a diagram showing the relationship between the specific resistance and temperature of a La—Sr—Cu—O-based oxide.

FIG. 26 is a cross-sectional view showing an example of a multilayer wiring substrate manufactured by the manufacturing method of the present invention.

FIG. 27 is a cross-sectional view showing an example of the composite body of the present invention.

FIG. 28 is a diagram showing a method for manufacturing a superconducting coil of the present invention, wherein (a) to (c) are diagrams showing respective steps.

FIG. 29 is a diagram showing a method for manufacturing a superconducting magnet of the present invention, wherein (a) to (f) are diagrams showing respective steps.

FIG. 30 is a diagram showing a method of manufacturing a non-inductive winding coil,
(A) And (b) is a figure of the coil manufactured by a different method, respectively.

FIG. 31 is a circuit diagram showing a persistent current switch.

FIG. 32 is a schematic diagram showing a method for manufacturing a superconducting shield of the present invention, wherein (a) and (b) are diagrams showing respective steps.

FIG. 33 is a schematic view showing the method for manufacturing a superconducting power transmission line of the present invention, in which (a) and (b) are diagrams showing respective steps.

[Explanation of symbols]

 1 Ion Accelerator 21 Substrate 22 Semi-insulating Layer 23 Superconductor 24 Laser Light 25 Laser 26, 210 Beam Spot 220 Hydrogen Ion Beam 230 Hydrogen Ion Source 41, 42 Superconducting Wiring 31 Tunnel Part 50 Base 60 Insulating Layer 70 Superconducting Wiring 71, 81 , 82 Insulator 80 Resistor 90 Superconducting layer 91 Insulating layer, 510 Non-superconducting cylindrical tube 610 Superconducting layer 710 Particle beam or electromagnetic radiation 810 Non-superconducting part 900,910 Superconducting coil 190 Hollow superconducting disc 191,192,193 , 194 Superconducting coil element 195 Non-inductive winding coil 211 Non-inductive winding coil 212 Permanent current switch 213 DC power source 221,223 Superconducting magnetic shield 231,233 Superconducting power transmission line 222,232 Electron beam 234 Cooling medium

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location // C01G 3/00 ZAA H01B 13/00 565 D H01L 39/12 ZAA C (31) Claiming priority Number Japanese Patent Application Sho 62-104283 (32) Priority Date Sho 62 (1987) April 30 (33) Priority Claim Country Japan (JP) (72) Inventor Masahiro Ogihara 4026 Kuji Town, Hitachi City, Ibaraki Japan Hitachi Research Laboratory (72) Inventor Jiro Kuniya 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Hitate Manufacturing Co., Ltd. (72) Inventor Yutaka Misawa 4026 Kuji Town, Hitachi City, Ibaraki Hitachi Research Co., Ltd. In-house (72) Yuzo Kozono 4026 Kuji Town, Hitachi City, Hitachi, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi, Ltd. (72) Inheihei Matsuda 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi, Ltd. (72) Masateru Suwa 4026 Kuji Town, Hitachi City, Hitachi, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi, Ltd. (72) Toshikazu Nishino 1-280, Higashi Renegoku, Kokubunji, Tokyo Hitachi, Ltd. (72) Inventor, Ushio Kawabe 1-280, Higashi Koikekubo, Kokubunji, Tokyo Metropolitan Institute, Hitachi, Ltd. (72) Haruhiro Hasegawa 1-280, Higashi Koikeku, Kokubunji, Tokyo, Hitachi, Ltd. (72) Inventor Kazumasa Takagi 1-280, Higashi Koikekubo, Kokubunji, Tokyo, Central Research Laboratory, Hitachi, Ltd. (72) Tokkai Fukasawa 1-280, Higashi Koikeku, Kokubunji, Tokyo, Hitachi, Ltd. Central Research Center (72) ) Inventor Katsumi Miyauchi 1-280, Higashi Koigokubo, Kokubunji, Tokyo Inside the Central Research Laboratory, Hitachi, Ltd.

Claims (9)

[Claims] 1. A method of irradiating a superconducting oxide with electrons or ions to form irradiation defects in the superconducting oxide by the irradiation, thereby increasing the critical current density of the superconducting oxide in a magnetic field. A method for producing a superconducting oxide. 2. A method for producing a superconducting oxide, which comprises irradiating a superconducting oxide with electrons or ions having an energy higher than the ejection energy of atoms of the oxide to introduce fine irradiation defects. . 3. A semiconductor device having a wiring layer at a predetermined position on the surface of a semiconductor element, wherein the wiring layer is made of a superconducting oxide layer, and a predetermined circuit is formed in a plan view via a non-superconducting oxide layer. A semiconductor device characterized by the above. 4. A superconducting wire having a wire made of a superconducting oxide layer, wherein the wire has a planar shape and a predetermined circuit is formed via a non-superconducting oxide layer. 5. A superconducting coil made of a superconducting oxide, wherein the coil has a spiral circuit formed in a planar shape via a non-superconducting oxide. 6. A superconductor device comprising a superconducting oxide layer and a non-superconducting layer which are alternately formed in a plan view, and a predetermined circuit including the superconducting oxide layer is formed. 7. The superconductor device according to claim 6, wherein the superconductor device is formed on an insulating film. 8. The superconductor device according to claim 6, wherein two or more superconducting oxides and non-superconducting oxides are alternately laminated. 9. At least one of a superconducting magnet, a superconducting power transmission line, a superconducting transformer, a superconducting shield, a persistent current switch, and a weak electric element is formed by the superconducting oxide produced by the manufacturing method according to claim 1. A superconductor device configured.