JPH10226877A - This film forming method and equipment therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently form a film, having uniform thickness and characteristics, on both sides of a base material by disposing at least a couple of solid raw materials with a base material between and irradiating these solid raw materials with a laser beam simultaneously or successively. SOLUTION: The inside of a chamber 1 is regulated so that partial pressure of oxygen becomes about 0.2Torr, and a couple of solid raw materials 2, 3 are rotated at a prescribed speed. Two excimer laser generators 4, 5 output laser beams simultaneously or successively by means of a laser control device 10. The outside peripheral surface of the solid raw material 2 is irradiated with the pulsed laser beam from the laser generator 4, and the outside peripheral surface of the solid raw material 3 is irradiated with the beam from the laser generator 5, and the solid raw materials 2, 3 are evaporated by the laser energies, respectively, and vapor deposition regions are formed in the positions at the prescribed distances, respectively. A loop-shaped silver tape 11 is moved by means of guide rollers 12 to 17 into the above state, heated by lamp heaters 18, 19, and then passed through the above vapor deposition region, by which films are formed on both sides of the loop-shaped silver tape 11.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to the production of superconducting wires having a superconducting thin film laminated on a substrate, or to the application to high-frequency equipment, and to the production of electronic members having various functional thin films laminated on a substrate. The present invention relates to a method and an apparatus for producing a thin film, in which a solid material is irradiated with a laser beam, and the energy is used to evaporate the solid material to produce a thin film on a substrate.

[0002]

2. Description of the Related Art As a device using a superconducting wire, for example, one of medical devices used for detecting abnormal cells in the body is a nuclear magnetic resonance diagnostic device (MRI: Magnetic Resin).
onanceImaing). The MRI utilizes a phenomenon in which a hydrogen nucleus absorbs an electromagnetic wave of a specific frequency in a magnetic field and resonates, and detects a resonance signal as a high-frequency signal in a MHz band and performs image processing by a computer.
The high frequency signal at this time is received using an antenna installed near the human body.

[0003] This antenna uses a highly conductive metal such as copper. However, in the case of observing a constantly moving organ such as the heart in real time or in the case of observing with a low magnetic field of 1 Tesla or less, etc. Therefore, it is necessary to increase the sensitivity of the antenna and to reduce the attenuation of the signal current as much as possible. For this reason, metals such as copper cannot cope. Therefore, attempts have been made to fabricate an antenna with a superconductor, and an oxide superconductor is being used because of its low cooling cost.

[0004]

However, since the material of this oxide superconductor is a ceramic, it is difficult to lengthen the material for application to MRI or the like. In many cases, Bi-based materials are used for silver tubes. Superconductors are packed and elongated through processes such as stretching and rolling.

However, the length of the superconductor wire elongated by such a method is because the superconductor is enveloped in silver,
There is a problem that high-frequency signals are shielded. Therefore, since there is no other suitable method, a part of silver was peeled off, and two silver sheets were laminated to produce an antenna. However, with this method, the productivity is poor, and the characteristics of the manufactured antenna are not sufficient for practical use.

On the other hand, some MRI antennas used closest to the body have an endless loop shape. In order to manufacture such an endless antenna with the above-mentioned wire, both ends of the wire must be connected by solder or the like, and the connection portion does not become superconducting, and the signal current decreases at this portion. Occurs.

When an endless antenna is manufactured, it is necessary to form a superconducting thin film on both sides of the base. However, it is difficult to form a thin film uniformly on both sides of the base with the current method. Therefore, an object of the present invention is to provide a method for producing a thin film and an apparatus therefor, which can efficiently produce a film having a uniform thickness and characteristics on both surfaces of a substrate.

[0008]

According to a first aspect of the present invention, there is provided a thin film forming method for irradiating a solid raw material with a laser beam to evaporate the solid raw material by the energy of the laser beam and depositing the solid raw material on a substrate to form a thin film. This is a method of producing a thin film in which at least a pair of solid raw materials are arranged with a substrate interposed therebetween, and the solid raw materials are irradiated with a laser beam simultaneously or sequentially to form a thin film on the substrate.

According to a second aspect, in the method for producing a thin film according to the first aspect, a long or endless substrate is moved between a pair of solid raw materials. According to the third aspect, in the method for producing a thin film according to the first aspect, the disk-shaped or cylindrical substrate is moved between a pair of solid raw materials while rotating.

According to a fourth aspect of the present invention, in the method for producing a thin film according to the third aspect, the center of the disk-shaped substrate is disposed at a predetermined distance from a line connecting the centers of the pair of solid raw materials. The substrate is moved between a pair of solid raw materials.

According to a fifth aspect of the present invention, in the method of manufacturing a thin film according to the first aspect, the film formation on the substrate is performed by using an oxygen partial pressure of 0.05 Torr to 1.0 Torr and an oxygen flow rate of 200 SCCM to 2,000 SCCM. Perform in an atmosphere.

According to claim 6, a chamber for circulating the reaction gas, at least one pair of solid raw materials disposed in the chamber, a substrate moving between the pair of solid raw materials, and a pair of solid raw materials. A pulsed laser oscillator that simultaneously or sequentially irradiates a laser beam to evaporate a solid material by its energy and deposits the solid material on both surfaces of a substrate to output the laser beam for producing a thin film,
This is an apparatus for producing a thin film comprising:

According to a seventh aspect of the present invention, in the thin film manufacturing apparatus according to the sixth aspect, when the substrate is endless, a plurality of guide rollers for moving the substrate between a pair of solid raw materials are provided. According to claim 8, in the thin film production apparatus according to claim 6, when the base is a disk, a holder for rotatably holding the base and the holder move between a pair of solid raw materials, A rotation mechanism for rotating the base held by the holder.

According to a ninth aspect of the present invention, in the thin film manufacturing apparatus according to the sixth aspect, the inside of the chamber has an oxygen partial pressure of 0.05 Torr to 1.0 Torr as a reaction gas and an oxygen flow rate of 200 SCCM to 2,000 SCCM. Oxygen atmosphere.

According to a tenth aspect, in the thin film manufacturing apparatus according to the sixth aspect, a high frequency heating means for performing high frequency heating on both surfaces of the substrate before moving the substrate between the pair of solid raw materials is added. did.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION

(1) Hereinafter, a first embodiment of the present invention will be described with reference to the drawings. In the method for producing a thin film of the present invention, a solid material is irradiated with a laser beam to evaporate the solid material by its energy, and the thin material is deposited on a substrate to produce a thin film. The substrate is disposed with the substrate interposed therebetween, and the solid material is irradiated with a laser beam simultaneously or sequentially to form a thin film on the substrate.

FIG. 1 is a block diagram of such an apparatus for producing a thin film. In the chamber 1, a pair of solid raw materials (targets)
A few are arranged. This pair of solid raw materials 2, 3
Is made of Y, Ba, and Cu, for example, in a disk shape with a diameter of 100 mm and a thickness of 10 mm.

These solid raw materials 2 and 3 are provided on rotating shafts 2a and 3a, respectively, and rotate at a predetermined speed. Outside the chamber 1, two excimer laser oscillators 4, 5 are arranged. A mirror 6 and a lens 7 are arranged on the optical path of one of the excimer laser oscillators 4 and 5, as shown in FIG. 2, and the laser beam of the pulse output from the excimer laser oscillator 4 is solid-state. The outer peripheral surface of the raw material 2 is irradiated.

A rotating mirror 8 and a lens 9 are arranged on the optical path of the other excimer laser oscillator 5, and a laser beam of a pulse output from the excimer laser oscillator 5 is applied to the outer peripheral surface of the solid material 3. It has become.

When only one excimer laser oscillator 5 is provided, the laser beam output from the excimer laser oscillator 5 is driven through the lens 9 by rotating the rotating mirror 8. And the irradiation of the solid raw material 2 through the mirror 6 and the lens 7 may be repeated.

The excimer laser oscillators 4 and 5 are connected to a laser controller 10 and controlled to output laser beams to a pair of solid raw materials 2 and 3 simultaneously or sequentially.

The excimer laser oscillators 4, 5
Are respectively the mirror 6 and the lens 7 or the rotating mirror 8
The fluence of the laser beam applied to the pair of solid materials 2 and 3 through the lens 9 is adjusted to be 1 J / cm ² or more.

More specifically, each of the excimer laser oscillators 4 and 5 has a width of 1 mm for irradiating the pair of solid materials 2 and 3 through the mirror 6 and the lens 7 or the rotating mirror 8 and the lens 9 respectively. , Length 10mm,
Average fluence is 1 J / cm ² , repetition frequency 5
It is adjusted to 0 Hz.

A loop-shaped substrate 11 (loop-shaped silver tape) is provided between the pair of solid raw materials 2 and 3 as described later.
In this case, for example, if the width of the loop-shaped base 11 is 20 mm or less, the pair of solid raw materials 2 and 3 include:
Thickness and either the same disk-shaped solid material 2,3 as shown in FIG. 3, or slightly irradiating a long laser beam Q _a.

When the width of the loop-shaped substrate 11 is wider than this, as shown in FIG. 4, the thickness of the solid raw materials 2 and 3 is reduced, and the width thereof is the same as this thickness or slightly longer. irradiating a laser beam Q _b.

By the way, the pair of solid raw materials 2 and 3 to be irradiated with the laser beam may be formed in a flat plate and may be moved in parallel on both sides of the loop-shaped base member 11. At least 25 mmR or more, preferably 50 mmR or more, more preferably 100 mmR
It is better to use a thin disk with a curvature of R or more because the laser beam has a vertically long shape, so that when irradiating a curved surface, a part deviating from the focus always occurs, but when the curvature is small, the deviation is larger. Fluence there.

The loop-shaped substrate 11 moves between the pair of solid raw materials 2 and 3 as described above. The loop-shaped base 11 is made of silver or polycrystalline YSZ or a superconductor such as YSZ, STO, CeO ₂ or the like on the surface and the base 1.
1 is a metal substrate on which an intermediate layer that plays a supplementary role of suppressing the reaction with 1 and orienting the crystal is laminated.

This loop-shaped substrate 11 is made of an endless material having both ends welded and polished so as to have a surface roughness of 1 S or less, and has a diameter of 1 m, a width of 20 mm and a thickness of 1 mm. It is a tape. Hereinafter, the base 1
1 is referred to as a loop-shaped silver tape 11.

The loop-shaped silver tape 11 is held by each of the guide rollers 12 to 17, and is driven at a constant speed, for example, 30 mm / min. It moves in the direction of the arrow (a) at a speed, that is, in the direction perpendicular to the arrangement direction of the pair of solid raw materials 2 and 3.

In the chamber 1, two lamp heaters 18 and 19 are arranged. These lamp heaters 1
Numerals 8 and 19 are disposed opposite to each other on the upstream side of the pair of solid raw materials 2 and 3 with the loop-shaped silver tape 11 interposed therebetween, and heat both sides of the loop-shaped silver tape 11 to a temperature of, for example, about 650 to 700 ° C. . The lamp heaters 18, 19
Are connected to power supplies 20 and 21, respectively.

On the other hand, the inside of the chamber 1 is in an oxygen atmosphere as a reaction gas. Since the oxygen partial pressure and the oxygen flow rate during the film formation in the chamber 1 affect the crystal orientation and superconductivity of the film formed on the loop-shaped silver tape 11, the Tc suitable for the application is high, and the surface property is high. In order to obtain a c-axis oriented film having a good value, these parameters must be carefully controlled.

Specifically, when the oxygen partial pressure is reduced, a c-axis oriented film can be obtained, but Tc tends to decrease. When the oxygen partial pressure is increased, a film having a high Tc can be obtained, but a-axis oriented grains are mixed. And the surface properties deteriorate.

When the flow rate of oxygen is lower, a c-axis oriented film can be easily obtained, but Tc tends to be reduced. When the flow rate is increased, a film having a higher Tc can be easily obtained, but a-axis oriented grains are more likely to be mixed. .

Therefore, the appropriate regions of the oxygen partial pressure and the oxygen flow rate are shown in the orientation of the film and the oxygen partial pressure dependence of Tc in FIG. 5, and the orientation of the film and the oxygen flow rate dependence of Tc in FIG. 6, respectively. . However, an appropriate oxygen flow rate is proportional to the size of the chamber 1.

For example, in the case of a 100-liter chamber 1, a flow rate of 20 to 200 SCCM is appropriate,
40-400 SCC for 0 liter chamber 1
The flow rate of M is appropriate.

Therefore, the oxygen flow rate shown here is normalized with the volume of the chamber 1 being 1 m ³ . Based on these results, the oxygen partial pressure was 0.05 Torr or more and 1.0 Torr.
r, preferably 0.1 Torr or more and 0.8 Torr or less, and an oxygen flow rate of 200 SCCM or more and 2000 SCCM or less, preferably 300 SCCM or more and 2000 SCCM or less. Alternatively, the ratio of the oxygen flow rate to the chamber volume is 2 ×
It is desired that the concentration be 10 ⁻⁴ or more and 2 × 10 ⁻³ or less, preferably 3 × 10 ⁻⁴ or more and 2 × 10 ⁻³ . Also, in other words,
The ratio of the volume occupied at 1 atmosphere and 20 ° C. by the oxygen flowing per minute to the chamber volume is 2 × 10 ⁻⁴ or more and 2 × 10 ⁴
It must be less than ^-3 . That is, if the volume of the chamber is 2 m ³ , the appropriate flow rate is doubled,
If m ³ becomes one-half.

Here, for example, oxygen is supplied to the chamber 1 at a flow rate of 1000 SCCM with respect to a container volume of 1 m ³ , and the exhaust speed is adjusted so that the oxygen partial pressure becomes 0.2 Torr.

Next, the operation of the above-configured device will be described. The chamber 1 has a container volume of, for example, 1 m ^3.
Oxygen is supplied at a flow rate of 1000 SCCM, and the exhaust gas is adjusted so that the oxygen partial pressure becomes 0.2 Torr.

In the chamber 1, Y, Ba, C
The pair of solid raw materials 2 and 3 formed from the compound u are rotated at a constant speed by the rotating shafts 2a and 3a, respectively. On the other hand, the two excimer laser oscillators 4 and 5 output laser beams simultaneously or sequentially under the oscillation control by the laser control device 10.

At this time, the repetition frequency of the laser beam output is adjusted to 50 Hz, and a pair of solid raw materials 2, 3
1mm width and 10m length laser beam
m, the average fluence was adjusted to 1 J / cm ² .

The laser beam of the pulse output from one of the excimer laser oscillators 4 irradiates the outer peripheral surface of the solid material 2 through the mirror 6 and the lens 7 as shown in FIG. The output pulse laser beam is applied to the outer peripheral surface of the solid raw material 3 through the rotating mirror 8 and the lens 9.

When each of the disk-shaped solid raw materials 2 and 3 is irradiated with a laser beam as described above, each of the disk-shaped solid raw materials 2 and 3 evaporates due to the laser energy, and the solid raw materials 2 and 3 are separated from the solid raw materials 2 and 3 by a predetermined amount. An evaporation region is formed at a distance.

At this time, a pair of disk-shaped solid raw materials 2 and 3
Are rotated at a constant speed by the rotating shafts 2a and 3a, respectively, and the laser beams are simultaneously or sequentially output from the two excimer laser oscillators 4 and 5, so that the outer periphery of each disk-shaped solid raw material 2 and 3 Each surface is scanned by each laser beam.

The laser beam is applied to each of the disk-shaped solid raw materials 2 and 3, and the deposition area is, for example, 10 times or more the area of the laser beam irradiation area. By irradiating the pair of disk-shaped fixed raw materials 2 and 3 with a laser beam simultaneously or sequentially in this manner, a wide vapor deposition region is obtained on both sides of the loop-shaped silver tape 11 in a strip shape.

In this state, the loop-shaped silver tape 11 is moved by each of the guide rollers 12 to 17, and first, both sides of the loop-shaped silver tape 11 are, for example, 650 to 700 by the respective lamp heaters 18 and 19.
Heated to about ℃.

The heated loop-shaped silver tape 11 is
For example, the YBCO superconducting film is formed on both surfaces of the substrate 11 through the deposition region obtained between the pair of solid materials 2 and 3 at a speed of, for example, 30 mm / min.

As described above, in the first embodiment, a pair of solid raw materials 2 and 3 are arranged with the loop-shaped silver tape 11 interposed therebetween, and the solid raw materials 2 and 3 are simultaneously or sequentially irradiated with a laser beam. The energy is used to evaporate the pair of solid raw materials 2 and 3 and deposit them on both sides of the loop-shaped silver tape 11, that is, the silver tape to form a thin film. A superconducting film having uniformity and characteristics can be efficiently produced.

The superconducting films thus formed on both sides of the silver tape can be formed as YBCO superconductors having a high Tc and excellent surface properties. When the silver tape on which the YBCO superconductor was formed, that is, the loop-shaped superconducting tape was used as a signal receiving coil for MRI, for example,
A high signal-to-noise ratio can be obtained, and it is possible to observe a constantly moving organ such as a heart in real time without using a strong magnetic field. (2) Next, a second embodiment of the present invention will be described.
The same parts as those in FIG. 1 are denoted by the same reference numerals, and detailed description thereof will be omitted.

FIG. 7 is a configuration diagram of an apparatus for producing a thin film. In the chamber 1, in addition to a pair of solid raw materials 2 and 3 made of Y, Ba, and Cu, a pair of solid raw materials 2 and 3 made of Sr and Ti Solid raw materials 30 and 31 are arranged.

The pair of solid raw materials 30 and 31 have a diameter of 100 mm and a thickness of 10 mm, for example, like the solid raw materials 2 and 3.
mm. These solid raw materials 30 and 31 are provided on rotating shafts 30a and 31a, respectively, and rotate at a predetermined speed.

Outside the chamber 1, two excimer laser oscillators 32 and 33 are arranged in addition to the two excimer laser oscillators 4 and 5. One of these excimer laser oscillators 32 and 33 is an excimer laser oscillator 32
The laser beam of the pulse output from is irradiated onto the outer peripheral surface of the solid raw material 30 through an optical system similar to the optical system shown in FIG. 2, and the laser beam of the pulse output from the other excimer laser oscillator 33 is also the same as described above. The outer peripheral surface of the solid raw material 33 is irradiated through an optical system.

These excimer laser oscillators 32 and 33
Is connected to a laser controller 10 and controlled so as to output a laser beam to the pair of solid raw materials 30 and 31 simultaneously or sequentially.

The excimer laser oscillators 32, 3
3 is adjusted so that the fluence of the laser beam applied to the pair of solid raw materials 30 and 31 is 1 J / cm ² or more. For example, these excimer laser oscillators 32 and 33 are a pair of solid materials 30 and 3 respectively.
The width of the laser beam irradiated to 1 is 1 mm and the length is 10
mm, the average fluence is adjusted to 1 J / cm ² , and the repetition frequency is adjusted to 50 Hz.

Next, the operation of the device configured as described above will be described. The chamber 1 has a container volume of, for example, 1 m ^3.
Oxygen is supplied at a flow rate of 1000 SCCM, and the exhaust gas is adjusted so that the oxygen partial pressure becomes 0.2 Torr.

In this chamber 1, Y, Ba, C
A pair of solid raw materials 2 and 3 formed from the compound u are rotated at constant speeds by rotating shafts 2a and 3a, respectively.
Further, the pair of solid raw materials 30 and 31 made of Sr and Ti are also rotated at a constant speed by the rotating shafts 30a and 31a, respectively.

On the other hand, two excimer laser oscillators 4, 5
Output laser beams simultaneously or sequentially.
The pulse laser beam output from one of the excimer laser oscillators 4 is applied to the outer peripheral surface of the solid raw material 2 in the same manner as described above, and the pulse laser beam output from the other excimer laser oscillator 5 is the solid laser 3. Is irradiated on the outer peripheral surface of the light emitting element.

When each of the disk-shaped solid raw materials 2 and 3 is irradiated with a laser beam as described above, each of the disk-shaped solid raw materials 2 and 3 evaporates due to the laser energy, and a predetermined amount of the solid raw materials 2 and 3 is generated. An evaporation region is formed at a distance.

At the same time, the other two excimer laser oscillators 32 and 33 output laser beams simultaneously or sequentially. One of the excimer laser oscillators 32
The pulsed laser beam output from the
And the other excimer laser oscillator 33
The pulsed laser beam output from the
Is irradiated on the outer peripheral surface of the light emitting element.

As described above, each of the disk-shaped solid raw materials 30, 31
Is irradiated with a laser beam, the respective solid-state raw materials 30, 31 evaporate due to the laser energy, and an evaporation region is formed at a position at a predetermined distance from the solid-state raw materials 30, 31.

In this state, the loop-shaped silver tape 11 is moved by the guide rollers 12 to 17, and firstly, both sides of the silver tape are, for example, 650 to 700 by the lamp heaters 18 and 19.
Heated to about ℃.

The heated loop-shaped silver tape 11 is
First, a pair of solid raw materials 2, 3 made of Y, Ba, Cu
For example, the YBCO superconducting film is formed on both surfaces of the loop-shaped silver tape 11 by passing through the deposition region obtained at a speed of, for example, 30 mm / min.

Subsequently, the loop-shaped silver tape 11 passes at a speed of, for example, 30 mm / min into the deposition region obtained between the pair of solid raw materials 30 and 31 composed of Sr and Ti, thereby forming a loop-shaped silver tape. SrTiO ₃ is formed on the YBCO superconducting film on both sides of the silver tape 11.

As described above, in the second embodiment, the pair of solid raw materials 2 and 3 made of Y, Ba and Cu and the pair of solid raw materials 30 and 31 made of Sr and Ti are combined with the loop-shaped silver tape 11. The solid raw materials 2 and 3 and the solid raw materials 30 and 31 are respectively irradiated with a laser beam simultaneously or sequentially, and the pair of solid raw materials 2 and 3 and the solid raw materials 30 and 31 are evaporated by the energy thereof,
This is deposited on both sides of the loop-shaped silver tape 11 to
Since a BCO superconducting film thin film was formed and SrTiO ₃ was formed on the YBCO superconducting film thin film, the thickness and the thickness of both sides of the loop-shaped silver tape 11 were changed in the same manner as in the first embodiment. A superconducting film having uniform characteristics can be efficiently produced.

Furthermore, YBCO superconductors are susceptible to acid and water and have a problem in environmental resistance. In addition, there is a problem that oxygen in a crystal is easily desorbed, in which case the characteristics are deteriorated. By coating the surface with a SrTiO ₃ film, the above problem is solved, and the characteristics do not deteriorate even if used for a long time.

On the other hand, YB
In the case where the SrTiO ₃ film is laminated on the YBCO superconductor by irradiating a laser beam to the solid raw materials 30 and 31 made of Sr and Ti arranged in pairs while forming the CO superconductor, the loop-shaped silver tape 11 The superconductor on either side contacts each of the guide rollers 12-17.

At this time, if the temperature of the loop-shaped silver tape 11 is high, depending on the material of each of the guide rollers 12 to 17,
A reaction may occur and the superconductor may deteriorate. Even if the reaction does not react at a low temperature, the surface of the superconductor is easily damaged because the hardness of the superconductor is not so high.

However, on the YBCO superconductor, SrTi
By continuously laminating O ₃ films, the surface of the YBCO superconductor can be protected, oxygen is not desorbed from the YBCO superconductor, and each of the guide rollers 12 to 1 can be protected.
There is no reaction with 7 and no damage.

When the substrate is conductive, the SrTiO ₃ film
The superconductor may be laminated from the end where the film is formed. However, in order for the superconductor to form a closed loop, it may be slightly at the end.
It is better to provide a portion where the protective film of the rTiO ₃ film is not laminated. When this portion has moved once, the superconductor may be laminated again to form a closed loop, and then the protective film may be laminated thereon. (3) Next, a third embodiment of the present invention will be described.
The same parts as those in FIG. 7 are denoted by the same reference numerals, and detailed description thereof will be omitted.

FIG. 8 is a diagram showing the configuration of a thin film manufacturing apparatus, in which a YBCO superconductor is formed on both sides of a long silver tape 40, and
An SrTiO ₃ film is formed on a BCO superconductor.

That is, when a pair of solid raw materials 2 and 3 made of Y, Ba and Cu are irradiated with a laser beam, each of the disk-shaped solid raw materials 2 and 3 is evaporated by the laser energy, and these solid raw materials 2 and 3 are evaporated. A vapor deposition region is formed at a position at a predetermined distance from 3.

At the same time, when a pair of solid raw materials 30 and 31 composed of Sr and Ti are irradiated with a laser beam, the disk-shaped solid raw materials 30 and 31 are evaporated by the laser energy, and these solid raw materials 30 and 31 are evaporated. , 31 at a predetermined distance from each other.

In this state, the long silver tape 40 is heated on both sides by, for example, 650 to 700 ° C. by the respective lamp heaters 18 and 19.
Is heated to about the temperature, and firstly, at a speed of, for example, 30 mm / min, through a deposition region obtained between the pair of solid raw materials 2 and 3, a YBCO superconducting film is formed on both surfaces of the long silver tape 40. The membrane is made.

Subsequently, the long silver tape 40 is placed, for example, in the vapor deposition region obtained between the pair of solid raw materials 30 and 31.
When passing through the YBCO superconducting film on both sides of the long silver tape 40, for example, about 1 μm of SrTiO ₃
Is formed.

As described above, in the third embodiment, the pair of solid raw materials 2 and 3 made of Y, Ba and Cu and the pair of solid raw materials 30 and 31 made of Sr and Ti are combined with the long silver tape 40. And these solid raw materials 2, 3
And a laser beam is simultaneously or sequentially irradiated onto the solid raw materials 30 and 31, respectively, and the energy is used to evaporate each pair of the solid raw materials 2 and 3 and the solid raw materials 30 and 31, and deposit them on both surfaces of the long silver tape 40. First, a YBCO superconducting thin film is formed, and Sr is formed on the YBCO superconducting thin film.
Since a TiO ₃ film was formed, a long silver tape 40
A superconducting film having a uniform thickness and properties can be efficiently produced on both surfaces of the film.

Further, SrTiO 3 was deposited on the YBCO superconducting thin film.
Since the film ₃ is formed, the environmental resistance of the YBCO superconductor to acid and water is improved, and even when the long silver tape 40 is continuously wound into a coil, the SrTiO ₃ functions as an insulating layer. Can be.

In the present invention, the material laminated on the YBCO is not limited to SrTiO ₃ , but can be widely applied as long as the material is excellent in insulation, environmental resistance such as humidity and temperature. (4) Next, a fourth embodiment of the present invention will be described.
The same parts as those in FIG. 1 are denoted by the same reference numerals, and detailed description thereof will be omitted.

FIG. 9 is a configuration diagram of an apparatus for producing a thin film. Between the pair of solid raw materials 2 and 3, three disk-shaped substrates 50 are held as holders by a holder 51, and move in parallel with the outer peripheral surfaces of the pair of solid raw materials 2 and 3 while rotating. That is, it moves at a constant speed in the direction of the arrow (a).

These substrates 50 are LaAlO ₃ substrates each having a diameter of, for example, 50 mm. FIG.
Is a configuration diagram of a holder 51 for holding a disk-shaped substrate 50, and FIG. 11 is a configuration diagram of the holder as viewed from the moving direction.

The holder 51 is formed in a flat plate shape.
Each ring-shaped rotation roller (or gear) 5 having a hole at the center for holding each substrate 50 along its longitudinal direction.
2a to 52c are attached.

The rotation rollers 52a-52
c denotes each bearing 53 attached to the holder 51.
a to 53c so as to be rotatable. A part of each of the rotation rollers 52a to 52c is
Protruding from the top of the

A rotation bar 54 is provided above the holder 51.
Is fixed, and the holder 51 is
A part of each of the rotation rollers 52a to 52c protruding is in contact with each other.

Each rotation roller 52 of this rotation bar 54
The portions that come into contact with a to 52c are subjected to a process for increasing the friction coefficient, or are formed with irregularities 54a that mesh with the gears.

The bottom of the holder 51 is also subjected to a treatment for increasing the friction coefficient, or formed with irregularities 55 so as to mesh with the gears. Each roller 56 a to 56 c is rotatably provided on the bottom of the holder 51 and is in contact with the unevenness 55 on the bottom of the holder 51.

Therefore, when the holder 51 moves in the direction of the arrow (a) in parallel, the rotation rollers 52a to 52c rotate by contact with the rotation bar 54, and in response to this, the three substrates 50 are respectively moved by the arrows. (B) It rotates in the direction. The rotation speed of these substrates 50 is determined according to the translation speed of the holder 51.

As shown in FIG. 9, a pair of solid raw materials 2,
In the case where the axial direction of each of the rotation shafts 2a, 3a and the moving direction (a) of each substrate 50 are the same, the center h of each substrate 50 is set to the pair of solid raw materials 2, 3 as shown in FIG. The substrate 50 is set apart from the center line f connecting them by a predetermined distance L, and is set so as to move each substrate 50 between the pair of solid raw materials 2 and 3.

That is, the pair of solid raw materials 2 and 3 are arranged such that the location where the distance from each substrate 50 is the shortest does not face the center of the substrate 50. With such a positional relationship between the pair of solid raw materials 2 and 3 and the substrate 50, a film having a uniform thickness and characteristics can be formed on both surfaces of each substrate 50.

In this case, the predetermined distance L is between 40% and 80% of the radius of each substrate 50, preferably between 50% and 70%.
% Or less. The pair of solid raw materials 2 and 3 and the substrate 50
Is displaced from the range of the predetermined distance L,
When the center h of 0 is closer to the center line f, the film thickness at the center of each substrate 50 increases, and when the center h increases, the film thickness at the center of each substrate 50 decreases, which is not preferable.

Next, the operation of the device configured as described above will be described. The chamber 1 has a container volume of, for example, 1 m ^3.
Oxygen is supplied at a flow rate of 1000 SCCM, and the exhaust gas is adjusted so that the oxygen partial pressure becomes 0.2 Torr.

In this chamber 1, Y, Ba, C
The pair of solid raw materials 2 and 3 formed from the compound u are rotated at a constant speed by the rotating shafts 2a and 3a, respectively. On the other hand, the two excimer laser oscillators 4 and 5 simultaneously or sequentially output laser beams under the oscillation control of the laser control device 10, and the laser beam of the pulse output from one of the excimer laser oscillators 4 is a solid material. The laser beam of the pulse applied to the outer peripheral surface of the solid material 2 and output from the other excimer laser oscillator 5 is
Is irradiated on the outer peripheral surface of the light emitting element.

The repetition frequency of the laser beam output at this time is adjusted to 50 Hz, and the width of the laser beam is adjusted to 1 mm, the length is adjusted to 10 mm, and the average fluence is adjusted to 1 J / cm ^2. ing.

When each of the disk-shaped solid raw materials 2 and 3 is irradiated with a laser beam as described above, each of the disk-shaped solid raw materials 2 and 3 evaporates due to the laser energy, and a predetermined amount of the solid raw materials 2 and 3 is generated. At the position of the distance, a wide evaporation region is formed in a band shape.

In this state, the three disc-shaped substrates 50 are
By being held by the holder 51 and moving in parallel in the direction of the arrow (a), the holder 51 responds to the rotation caused by the contact between the rotation rollers 52a to 52c and the rotation bar 54, and moves in the direction of the arrow (b), respectively. Rotate.

As described above, the three disk-shaped substrates 50 are held by the holder 51, and while rotating, first pass between the two lamp heaters 18 and 19, so that both surfaces of each substrate 50 are, for example, It is heated to a temperature of about 650-800 ° C.

Subsequently, each of these heated substrates 50 is
It passes through the deposition region obtained between the pair of solid raw materials 2 and 3 at a speed of, for example, 30 mm / min.
A YBCO superconducting film is formed on both surfaces of the substrate.

As described above, in the fourth embodiment, a pair of solid raw materials 2 and 3 are irradiated with a laser beam simultaneously or sequentially, and the energy of the laser beam is applied to the pair of solid raw materials 2 and 3.
3 was evaporated and passed through each disc-shaped substrate 50 held and rotated by the holder 51 between the solid raw materials 2 and 3 to form thin films on both surfaces of these substrates. A superconducting film having a uniform thickness and characteristics can be efficiently formed on both surfaces of the substrate 50. The superconducting films formed on both surfaces of the substrate 50 can be formed as YBCO superconductors having high Tc and excellent surface properties. (5) Next, a fifth embodiment of the present invention will be described.
9 to 11 are denoted by the same reference numerals, and a detailed description thereof will be omitted.

FIG. 12 is a configuration diagram of an apparatus for producing a thin film.
The rotating shafts 2a, 3a of the pair of solid raw materials 2, 3 are arranged in a direction perpendicular to the moving direction (a) of the holder 51. That is, the outer peripheral surfaces of these solid raw materials 2 and 3 are arranged to face each other via the holder 51.

On the other hand, two excimer laser oscillators 4, 5
A mirror 60 and a lens 61 are arranged on the optical path of one of the excimer laser oscillators 4 so that the laser beam of the pulse output from the excimer laser oscillator 4 is applied to the outer peripheral surface of the solid material 2. I have.

On the optical path of the other excimer laser oscillator 5, a mirror 62 and a lens 63 are arranged so that the laser beam of the pulse output from the excimer laser oscillator 5 is applied to the outer peripheral surface of the solid material 3. It has become.

Further, each rotating shaft 2 of the pair of solid raw materials 2 and 3
In the case where the axial directions of a and 3a are perpendicular to the moving direction (a) of each substrate 50, as shown in FIG.
Are arranged at _a predetermined distance La from a center line g connecting the pair of solid raw materials 2 and 3, and each substrate 50 is set to be moved between the pair of solid raw materials 2 and 3.

This is similar to the above, and a pair of solid raw materials 2, 3
Means that the location closest to each substrate 50 is the substrate 50
It is installed so as not to face the center of. With such a positional relationship between the pair of solid raw materials 2 and 3 and the substrate 50, a film having a uniform thickness and characteristics can be formed on both surfaces of each substrate 50.

[0102] In this case, the predetermined distance L _a, each substrate 5
30% or more and 80% or less of the radius of 0. Next, the operation of the apparatus configured as described above will be described.

In the chamber 1, for example, oxygen is supplied at a flow rate of 1000 SCCM with respect to a container volume of 1 m ³ , and the oxygen partial pressure is adjusted by evacuation so as to be 0.2 Torr. Are rotated at a constant speed by rotating shafts 2a and 3a, respectively.

On the other hand, two excimer laser oscillators 4, 5
Output laser beams simultaneously or sequentially under the oscillation control of the laser control device 10. Among them, the laser beam of the pulse output from one excimer laser oscillator 4 is applied to the outer peripheral surface of the solid raw material 2, and the other excimer laser is used. The pulsed laser beam output from the laser oscillator 5 is
The outer peripheral surface of the solid raw material 3 is irradiated.

As described above, when each of the disk-shaped solid raw materials 2 and 3 is irradiated with a laser beam, each of the disk-shaped solid raw materials 2 and 3 evaporates due to the laser energy, and a predetermined amount of the solid raw materials 2 and 3 is generated. At the position of the distance, a wide evaporation region is formed in a band shape.

In this state, the three disc-shaped substrates 50 are
By being held by the holder 51 and moving in parallel in the direction of the arrow (a), the holder 51 responds to the rotation caused by the contact between the rotation rollers 52a to 52c and the rotation bar 54, and moves in the direction of the arrow (b), respectively. Rotate.

As described above, the three disk-shaped substrates 50 are held by the holder 51, and while rotating, first pass between the two lamp heaters 18 and 19, so that both surfaces of each substrate 50 are, for example, It is heated to a temperature of about 650-800 ° C.

Subsequently, each of the heated substrates 50 is
It passes through the deposition region obtained between the pair of solid raw materials 2 and 3 at a speed of, for example, 30 mm / min.
A YBCO superconducting film is formed on both surfaces of the substrate.

As described above, in the fifth embodiment, the pair of solid raw materials 2 and 3 in which the rotating shafts 2a and 3a are arranged in the direction perpendicular to the moving direction of each substrate 50 held by the holder 51 is used. In the meantime, each disk-shaped substrate 50 which has been rotated is passed through, and thin films are formed on both surfaces of these substrates 50. Thus, a superconducting film having a uniform thickness and characteristics is formed on both surfaces of these substrates 50 efficiently. Can be manufactured well. These substrates 5
The superconducting films formed on both sides of the layer 0 can be formed as a YBCO superconductor having a high Tc and excellent surface properties. (6) Next, a sixth embodiment of the present invention will be described.
The same parts as those in FIG. 12 are denoted by the same reference numerals, and detailed description thereof will be omitted.

FIG. 14 is a configuration diagram of an apparatus for producing a thin film.
In the chamber 1, two high-frequency heating devices 70 and 71 are arranged to face each other, and two heat radiation plates 72 and 73 are arranged in a direction in which the high-frequency heating devices 70 and 71 face each other.

The heat radiating plates 72 and 73 receive heat from the high frequency heating devices 70 and 71, respectively, and apply the radiant heat to the respective substrates 50 passing between the heat radiating plates 72 and 73 to heat them, for example, 750. ° C, for example, 10 mm or less from the position where the substrate 50 passes,
It is preferably located at a distance of 5 mm or less, more preferably 1 mm or less.

Since high-frequency heating can heat only a conductive material, a metal holder 51 such as SUS may be heated, and the substrate 50 may be heated by heat conduction from the holder 51. As described above, the heat radiation plates 72 and 73
Is used because high frequency heating can only heat conductive materials.

Further, two auxiliary heaters 74 and 75 are arranged slightly downstream of the pair of solid raw materials 2 and 3 in the direction of movement (a) of the holder 51. These auxiliary heaters 74 and 75 heat the respective substrates 50 so that the temperatures of the respective substrates 50 passing through the deposition region formed by the pair of solid raw materials 2 and 3 do not decrease. Therefore, these auxiliary heaters 74 and 75 need to be arranged close to the pair of solid raw materials 2 and 3.

Next, the operation of the device configured as described above will be described. The chamber 1 has a container volume of, for example, 1 m ^3.
Oxygen is supplied at a flow rate of 1000 SCCM, and the exhaust gas is adjusted so that the oxygen partial pressure becomes 0.2 Torr.

In this chamber 1, Y, Ba, C
A pair of solid raw materials 2 and 3 formed from the compound u are rotated at constant speeds by rotating shafts 2a and 3a, respectively.
The two excimer laser oscillators 4 and 5 simultaneously or sequentially output laser beams under the oscillation control of the laser control device 10, and one of the excimer laser oscillators 4 and 5 outputs the laser beam.
The laser beam of the pulse output from is irradiated on the outer peripheral surface of the solid raw material 2, and the pulse laser beam output from the other excimer laser oscillator 5 is irradiated on the outer peripheral surface of the solid raw material 3.

The repetition frequency of the laser beam output at this time is adjusted to 50 Hz, the width of the laser beam is adjusted to 1 mm, the length is adjusted to 10 mm, and the average fluence is adjusted to 1 J / cm ^2. ing.

When each of the disk-shaped solid raw materials 2 and 3 is irradiated with a laser beam as described above, each of the disk-shaped solid raw materials 2 and 3 evaporates due to the laser energy, and a predetermined amount of the solid raw materials 2 and 3 is generated. At the position of the distance, a wide evaporation region is formed in a band shape.

In this state, the three disk-shaped substrates 50 are
By being held by the holder 51 and moving in parallel in the direction of the arrow (a), the holder 51 responds to the rotation caused by the contact between the rotation rollers 52a to 52c and the rotation bar 54, and moves in the direction of the arrow (b), respectively. Rotate.

As described above, the three disc-shaped substrates 50 are held by the holder 51, and first pass between the two heat radiation plates 72 and 73 while rotating. These heat radiation plates 7
2 and 73 are heated by the two high-frequency heating devices 70 and 71, so that both surfaces of each substrate 50 are heated to a temperature of, for example, about 650 to 700 ° C. by receiving the radiant heat.

Each of the heated substrates 50 passes through the deposition region obtained between the pair of solid raw materials 2 and 3 at a speed of, for example, 30 mm / min. The YBCO superconducting film is formed on both sides of the 50.

At this time, these substrates are connected to the auxiliary heaters 7.
4, 75, so as not to lower the temperature when passing through the deposition area. As described above, in the sixth embodiment, the pair of solid raw materials 2 and 3 are simultaneously or sequentially irradiated with the laser beam, and the energy is used to evaporate the pair of solid raw materials 2 and 3. 3, each disk-shaped substrate 50, which is rotated by being held by the holder 51 and heated by high-frequency heating, is passed therethrough. At this time, the temperatures of the respective substrates 50 are not reduced by the auxiliary heaters 74 and 75. As a result, a superconducting film having a uniform thickness and characteristics can be efficiently formed on both surfaces of each substrate 50. In addition, the superconducting films formed on both surfaces of these substrates 50 have a high Tc and excellent surface properties. It can be formed as a superconductor.

Then, for example, when the superconductor on one side of the substrate 50 is processed into a predetermined pattern to produce a stripline type microwave resonator, this microwave resonator becomes
Since the surface resistance of the superconductor was low, the Q value was extremely high.

The present invention is not limited to the first to sixth embodiments, but may be modified as follows.
For example, in the first to sixth embodiments, mainly the YBC
Although the O superconductor has been described, other Bi-based or Tl-based oxide superconductors may be formed.

In addition, metal oxides, nitrides and carbides (Si
_{3 N 4, SiC, TiN,} TiC, BN, BC , etc.), further SrTiO _3, BaTiO _3, dielectric film and Au of oxides such as PZT, Ag, broadly applicable to making a metal film such as Cu it can.

Further, each of the excimer laser oscillators 4 and 5 is used. Instead of this, a laser beam output from another laser oscillator such as a YAG laser oscillator is
3 may be irradiated.

[0125]

As described above, according to the present invention, it is possible to provide a method and an apparatus for manufacturing a thin film capable of efficiently forming a film having a uniform thickness and characteristics on both surfaces of a substrate.

[Brief description of the drawings]

FIG. 1 is a configuration diagram showing a first embodiment of a thin film manufacturing apparatus according to the present invention.

FIG. 2 is a diagram showing an optical system in the apparatus for irradiating a pair of disk-shaped solid raw materials with a laser beam.

FIG. 3 is a diagram showing a shape of a laser beam applied to a pair of solid raw materials.

FIG. 4 is a diagram showing a shape of a laser beam applied to a pair of solid raw materials.

FIG. 5 is a diagram showing the orientation of a film and the oxygen partial pressure dependence of Tc.

FIG. 6 is a view showing the orientation of a film and the oxygen flow rate dependence of Tc.

FIG. 7 is a configuration diagram showing a second embodiment of a thin film manufacturing apparatus according to the present invention.

FIG. 8 is a configuration diagram showing a third embodiment of a thin film manufacturing apparatus according to the present invention.

FIG. 9 is a configuration diagram showing a fourth embodiment of an apparatus for producing a thin film according to the present invention.

FIG. 10 is a configuration diagram of a holder for holding a disk-shaped substrate in the apparatus.

FIG. 11 is a diagram showing an arrangement of substrates for a pair of solid raw materials.

FIG. 12 is a configuration diagram showing a fifth embodiment of a thin film manufacturing apparatus according to the present invention.

FIG. 13 is a view showing an arrangement of substrates for a pair of solid raw materials.

FIG. 14 is a configuration diagram illustrating a thin film manufacturing apparatus according to a sixth embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Chamber, 2, 3 ... A pair of solid raw material (Y, Ba, Cu), 4, 5, 32, 33 ... Excimer laser oscillator, 11 ... Loop-shaped silver tape, 12-17 ... Guide roller, 18, 19 ... Lamp heater 30, 31: A pair of solid raw materials (Sr, Ti), 40: Long silver tape, 50: Disc-shaped substrate, 51: Holder, 70, 71: High frequency heating device, 72, 73: Heat radiation plate , 74, 75 ... Auxiliary heater.

Claims (10)

[Claims] 1. A method for producing a thin film by irradiating a solid material with a laser beam, evaporating the solid material by its energy, and depositing the solid material on a substrate to produce a thin film. And irradiating the solid material with the laser beam simultaneously or sequentially to form a thin film on the substrate. 2. The method according to claim 1, wherein the long or endless substrate is moved between a pair of the solid raw materials. 3. The method for producing a thin film according to claim 1, wherein said disk-shaped or cylindrical substrate is moved between a pair of said solid raw materials while rotating. 4. The method according to claim 1, wherein a center of the disk-shaped substrate is disposed at a predetermined distance from a line connecting centers of the pair of solid raw materials, and the substrate is moved between the pair of solid raw materials. 4. The method for producing a thin film according to claim 3, wherein: 5. The thin film according to claim 1, wherein the film is formed on the substrate in an oxygen atmosphere having an oxygen partial pressure of 0.05 Torr or more and 1.0 Torr or less and an oxygen flow rate of 200 SCCM or more and 2000 SCCM or less. Method of manufacturing. 6. A chamber for circulating a reaction gas, at least a pair of solid raw materials disposed in the chamber, a substrate moving between the pair of solid raw materials, and a pair of solid raw materials simultaneously or sequentially. A pulsed laser oscillator for irradiating a laser beam to evaporate the solid material by its energy, depositing the solid material on both surfaces of the substrate, and outputting the laser beam for producing a thin film. Thin film production equipment. 7. The thin film producing apparatus according to claim 6, further comprising a plurality of guide rollers for moving the substrate between the pair of solid raw materials when the substrate is endless. 8. When the substrate is disk-shaped, the holder rotatably holds the substrate, and the holder moves between the pair of solid raw materials, thereby moving the substrate held by the holder. The apparatus for producing a thin film according to claim 6, further comprising a rotation mechanism for rotating the thin film. 9. The reaction chamber according to claim 6, wherein the reaction gas has an oxygen partial pressure of 0.05 Torr to 1.0 Torr and an oxygen flow rate of 200 SCCM to 2,000 SCCM. Thin film production equipment. 10. The thin film as claimed in claim 6, wherein high-frequency heating means for performing high-frequency heating on both surfaces of the substrate is added before the substrate is moved between the pair of solid raw materials. Production equipment.