JP3392299B2 - Raw material solution vaporizer for CVD - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a CVD raw material provided in a thin film forming apparatus for forming an oxide material such as an oxide superconductor on a substrate by a chemical vapor deposition method (hereinafter referred to as a CVD method). The present invention relates to a solution vaporizer.

[0002]

2. Description of the Related Art In recent years, oxide superconductors having a critical temperature (Tc) higher than the liquid nitrogen temperature (about 77 K) have been used, for example, Y-Ba-Cu-O-based and Bi-Sr-Ca-Cu-O-based. ,
Oxide superconductors such as T1-Ba-Ca-Cu-O system have been discovered. Various studies have been conducted on these oxide superconducting thin films for the purpose of use in the fields of power cables, magnets, energy storage, generators, medical devices, current leads and the like. As one of the methods for producing such an oxide superconductor, there is known a method of forming an oxide superconducting thin film on the surface of a base material by a thin film forming means such as a chemical vapor deposition method (CVD method). It is known that the oxide superconducting thin film formed by this kind of thin film forming means has a large critical current density (Jc) and exhibits excellent superconducting properties. Further, among the CVD methods, the CVD performed by using an organic metal compound such as a metal complex or a metal alkoxide as a raw material.
The method is attracting attention as a means for forming a thicker film in a short time with a high film forming speed.

As a raw material compound usually used in such a method for producing an oxide superconductor by the CVD method, a β-diketone compound of each element constituting the oxide superconductor, a cyclopentadienyl compound or the like is used. For example, for producing a Y—Ba—Cu—O-based oxide superconductor, Y (thd) ₃ , Ba (thd) ₂ or Ba (th
d) Organic metal complex raw materials (MO raw materials) such as ₂ · phen ₂ and Cu (thd) ₂ are used (thd = 2,2.
6.6-Tetramethyl-3.5-heptanedione, phen = 1.10-phenanthroline). These organometallic complex raw materials are raw materials that are solid at room temperature and show high rate-of-increasing characteristics when heated to 200 to 300 ° C, but they are sublimated due to the purity of the raw materials and the surface area change of the charged raw materials with heating time. It is difficult to control the composition because the efficiency is greatly affected, but these solid complex raw materials are dissolved in an organic solvent such as tetrahydrofuran (THF), isopropanol, toluene, diglyme (2.5.8-trioxononane) to form a raw material solution. Was used.

As will be described later, these raw material solutions are further heated and vaporized by a vaporizer and fed into a reaction chamber together with a carrier gas to cause a chemical reaction in the reaction chamber, and a base material placed in the reaction chamber. By depositing the reaction product on the surface, the desired Y-Ba-Cu-O-based oxide superconductor can be obtained. By the way, when using the thing which melt | dissolved the organic metal complex raw material in the organic solvent as a raw material solution for CVD, the vaporization apparatus of the raw material solution for CVD had a problem.

FIG. 4 shows an apparatus for producing an oxide superconducting conductor provided with a conventional CVD source solution vaporizer used for producing an oxide superconducting conductor. The oxide superconducting conductor manufacturing apparatus is roughly composed of a CVD reaction apparatus 1 and a bubbling type raw material solution vaporizing apparatus 4 for CVD. The CVD reaction apparatus 1 includes a reaction chamber 2 that constitutes a CVD reaction generation chamber, a substrate transfer device 7 that transfers a long substrate 6 that forms an oxide superconducting layer, and a nozzle 8, and further a vacuum pump. 9 is connected, and a heater 10 for heating the substrate 6 by heating the entire reaction chamber 1 is provided outside. The nozzle 8 has a connecting pipe 11
The raw material solution vaporizer 4 for CVD is connected via the, and the oxygen gas supply source 13 is connected via the connecting pipe 12.

The raw material solution vaporizer 4 is provided on the vaporizer main body 15 filled with the raw material solution 14 in which the aforementioned organic metal complex is dissolved in an organic solvent, and on the outer peripheral portion of the vaporizer main body 15.
A heater 16 for heating the inside of the vaporizer body 15,
A carrier gas supply source 19 for supplying an inert gas such as argon gas into the raw material solution 14 in the vaporizer main body 15 through a carrier gas supply pipe 17 is mainly configured. The upper end of the carrier gas supply pipe 17 is connected to the carrier gas supply source 19, while the lower end is arranged so as to be located in the raw material solution 14 in the vaporizer main body 15. The end of the connecting pipe 11 on the side not connected to the reaction chamber 2 is disposed above the liquid surface of the raw material solution 14 filled in the vaporizer main body 15.

In order to manufacture a long oxide superconducting conductor using the oxide superconducting conductor manufacturing apparatus equipped with such a bubbling type raw material solution vaporizer 4, a substrate transfer device 7 is used.
The long base material 6 is fed into the reaction chamber 2 by means of the above, the pressure inside the reaction chamber 2 is reduced to several torr by the vacuum pump 9, and the argon gas from the carrier gas supply source 19 is used as the raw material of the vaporizer main body 15. It is continuously fed into the solution 14. At this time, heating is performed by the heater 16 according to the vapor pressure in the vaporizer main body 15. Then, the vaporizer body 1
Bubbles are generated in the raw material solution 14 filled in 5, and the raw material solution floating on the liquid surface is vaporized with the bubbles, and a raw material gas is generated. At this time, the inside of the vaporizer main body 15 is also in a reduced pressure state of several Torr, so that the raw material gas in the vaporizer main body 15 is supplied to the reaction chamber 2 through the connecting pipe 11 by the flow of argon gas and becomes a raw material gas atmosphere. . Immediately thereafter, the heater 10 heats the long base material 6 in the reaction chamber 2 to react the surrounding raw material gas, and an oxide superconducting thin film is deposited on the surface of the base material 6. Can be manufactured.

FIG. 5 shows another example of the conventional apparatus for producing an oxide superconducting conductor, which is different from the apparatus for producing an oxide superconducting conductor shown in FIG. The point is that the device uses steam. Reference numeral 20 in FIG. 5 indicates a vaporization apparatus for vaporizing a raw material solution for CVD. The difference between the raw material solution vaporizer 20 and the bubbling type raw material solution vaporizer 4 is that the lower end portion of the carrier gas supply pipe 17 is not disposed in the raw material solution 14 and vaporizes. The point is that it is arranged so as to be located in the void in the container body 15. A method for producing a long oxide superconducting conductor using such a vapor-utilizing raw material solution vaporizer 20 using an oxide superconducting conductor producing apparatus is a method for producing argon oxide from a carrier gas supply source 19 inside a vaporizer main body 15. And a method of manufacturing using the bubbling type raw material solution vaporizer 4 described above except that the raw material solution 14 is vaporized by heating the vaporizer main body 15 by the heater 16 to generate the raw material gas. It can be manufactured in a similar manner.

[0009]

By the way, in the case of producing an oxide superconducting conductor by using the conventional oxide superconducting conductor producing apparatus equipped with the raw material solution supplying device, the film forming rate of the oxide superconducting thin film is Depending on the vaporization rate of the raw material solution 14, the vaporization rate of the raw material solution can be controlled mainly by the flow rate of the carrier gas and the temperature in the vaporizer main body 15. However, when the flow rate of the carrier gas is increased in order to increase the film forming speed, the film forming efficiency reaches a peak at a certain speed, and thus the film forming efficiency is unsatisfactory. Further, when the flow rate of the carrier is changed to increase the film formation efficiency, the conditions such as the reaction pressure and the oxygen partial pressure in the reaction chamber 2 are changed, and the film quality and the superconductivity in the length direction of the base material 6 are changed. A good oxide superconducting thin film with stable characteristics cannot be obtained. Further, if the temperature inside the vaporizer main body 15 is raised too much, problems such as decomposition of the raw material gas occur, and there is a drawback that a good oxide superconducting thin film cannot be obtained.

The present invention has been made in view of the above circumstances, and it is possible to improve the efficiency of film formation and to form a thin film such as an oxide superconducting thin film having stable properties such as film quality. An object is to provide a vaporizer.

[0011]

According to a first aspect of the present invention, there is an outlet for spraying a mist-like raw material solution.
CVD raw material solution supply device and the mist-like raw material solution
So as to be sprayed into the vaporizer body.
Container-shaped carburetor body having an attachment port provided with a discharge port, a first heating means disposed outside the carburetor body, for heating the inside of the carburetor body, and the vaporization A CVD raw material solution supply device provided in the vessel main body, which is provided in front of an outlet of the CVD raw material solution supply apparatus and includes at least a second heating means for vaporizing a mist-like raw material solution. A raw material solution vaporizer was used as a means for solving the above problems. Further, in the invention according to claim 2, the cover for preventing the vaporized raw material solution from reaching the blowout port of the CVD raw material solution supply device provided in the vaporizer main body is a mounting port of the vaporizer main body. The raw material solution vaporizer for CVD according to claim 1 is provided as a means for solving the above-mentioned problems. In the invention according to claim 3, a blowout port is provided in the carburetor main body.
The VD raw material solution supply device is provided so as to surround a cylindrical raw material solution supply unit into which the raw material solution is supplied, and an outer periphery of the supply unit, and to supply the raw material solution in a gap between the raw material solution supply unit. The vaporizing apparatus for a CVD raw material solution according to claim 1 or 2, characterized in that the vaporizing apparatus for a CVD raw material solution is provided with a cylindrical and tapered atomizing gas supply portion to which atomizing gas for vaporization is supplied. The means.

The present inventor has conducted various studies and experiments to form an oxide superconducting thin film which can improve film forming efficiency and has stable film quality and superconducting properties in the longitudinal direction of the substrate. As a result, the conventional CVD raw material solution vaporizer is provided with both the raw material solution supply means and the raw material solution vaporization means, whereas the raw material solution supply means and the raw material solution vaporization means are separately provided. By feeding the raw material solution to the vaporizing means of the raw material solution while controlling the flow rate of the raw material solution from the independent raw material solution supply means, if the raw material solution can be sequentially vaporized,
I thought that I could solve the above problems.

Then, the problem is the constitution of the raw material solution supply means and the vaporization means of the raw material solution, but as the constitution of the independent raw material solution supply means, Japanese Patent Application No. 5-2135,
Japanese Patent Application No. 7-311363 proposes a raw material solution supply device for CVD, and in the present invention, an independent vaporizing means of the raw material solution is provided at the outlet of the raw material solution supply device for CVD for spraying a mist-like raw material solution. A container-shaped carburetor body having a mounting port for arranging, a first heating means arranged outside the carburetor body for heating the inside of the carburetor body, and inside the carburetor body. By providing a raw material solution vaporizer for CVD, which is provided in front of the blowout port of the raw material solution supply device for CVD and which is provided with at least a second heating means for vaporizing the mist-like raw material solution, Since the flow rate of a gas such as a carrier gas and the inside of the carburetor main body can be kept constant, it is possible to form a thin film such as an oxide superconducting thin film having stable properties such as film quality.
Even if the supply speed of the mist-like raw material solution sprayed from the outlet of the raw material solution supply device for D into the vaporizer main body is increased,
Since the mist-like raw material solution is contacted with the second heating means and immediately vaporized, it was clarified that the vaporization efficiency and the film formation efficiency can be improved, and the present invention was completed.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION An example of a CVD source solution vaporizer of the present invention will be described below with reference to the drawings. FIG. 1 shows an example of an oxide superconducting conductor manufacturing apparatus equipped with a CVD source solution vaporizer according to the present invention. This oxide superconducting conductor manufacturing apparatus includes a raw material solution supply device 30 for CVD.
, Stock solution supply device 40, and CVD source solution vaporizer 5
0 and a CVD reactor 60.

The raw material solution supply device 30 has a cylindrical raw material solution supply section 31 and a cylindrical and tapered atomized gas supply section 32 which is provided so as to surround the outer circumference of the supply section 31.
The atomized gas supply unit 32 has a triple-layered structure that is roughly configured by a cylindrical shield gas supply unit 33 that is provided so as to surround the outer periphery of the atomized gas supply unit 32 excluding the tip portion.

The raw material solution supply unit 31 is supplied with a raw material solution 34 fed from a stock solution supply device 40, which will be described later, and has a central portion provided with the supplied raw material solution 3.
A liquid pool 35 is provided to temporarily store the liquid 4 therein. The inner diameter of the liquid pool 35 is larger than the inner diameters of the upper and lower end portions of the raw material solution supply unit 31, and the raw material solution 34 fed from the raw liquid supply device 40 is continuously fed to the front end while being accumulated. It is like this. When such a liquid pool 35 is provided, the raw material solution 3
Even if bubbles etc. are mixed in 4, the bubbles etc.
Since it floats on the liquid surface of the raw material solution 34 accumulated in the above, it can be prevented from reaching the tip.

The atomizing gas supply unit 32 supplies the atomizing gas for atomizing the above-mentioned raw material solution 34 into the gap between the atomizing gas supply unit 32 and the raw material solution supply unit 31. At the upper part of the atomizing gas supply part 32, MFC for atomizing gas is provided.
Atomizing gas supply source 3 via (flow rate adjuster) 36a
6 is connected to the atomizing gas supply unit 32 so that the atomizing gas can be supplied. If a specific example of the atomizing gas used here is specified, it is argon gas, helium gas, nitrogen gas, or the like. In the raw material solution supply device 30 of this example, the nozzle 37 is composed of the tip portion of the atomizing gas supply portion 32 and the tip portion of the raw material solution supply portion 31. Blow-out port 3 from which the tip of the nozzle 37 sprays the mist-like raw material solution 34
7a.

The shield gas supply section 33 is provided in the gap between the atomized gas supply section 32 and the atomized gas supply section 3.
A shielding gas for cooling the nozzle 2 and shielding the nozzle 37 is supplied. A taper portion 38 protruding outward is provided in a portion below the central portion of the shield gas supply portion 33. Further, a shield gas supply source 39 is connected to an upper portion of the shield gas supply unit 33 via a shield gas MFC (flow rate adjuster) 39 a, and is configured so that the shield gas can be supplied into the shield gas supply unit 33. ing. Argon gas, helium gas, nitrogen gas, and the like are given as specific examples of the shield gas used here.

In the raw material solution supply device 30 having the above structure, the raw material solution 34 is fed into the raw material solution supply part 31 at a constant flow rate, and the atomized gas is supplied to the atomized gas supply part 32.
When the raw material solution 34 is sent to the liquid pool 35 at a constant flow rate,
While reaching the tip of the raw material solution supply part 31 while accumulating in it, since the atomized gas flows from the tip of the atomized gas supply part 32 outside the tip, when the raw material solution 34 is blown out from the blowout port 37a of the nozzle 37, Immediately atomized by the atomized gas, a fixed amount of mist-like liquid solution 34 can be continuously supplied into the vaporizer body 51 of the raw material solution vaporizer 50. Also,
Along with this, when the shield gas is sent to the shield gas supply unit 33 at a constant flow rate, the atomized gas supply unit 32 and the raw material solution supply unit 31 are cooled, so that the raw material solution 34 flowing in the raw material solution supply unit 31 is also cooled. It is possible to prevent the raw material solution 34 from being vaporized during the process. Furthermore, since the shield gas flows outside the nozzle 37 and from the tip of the upper shield gas supply unit 33, the periphery of the nozzle 37 is shielded by the shield gas and the raw material solution is vaporized in the CVD raw material solution vaporizer. 34
It is possible to prevent the vaporized raw material gas from adhering to the nozzle 37 and becoming a solid raw material to be re-precipitated.

In the raw material solution supply section 31 of the raw material solution supply apparatus 30 as described above, a stock solution supply apparatus 40 is provided with a raw material solution MF.
It is connected via a connecting pipe 41 having a C (flow rate adjuster) 41a. As the connecting pipe 41, a pipe having an excellent chemical resistance such as a pipe whose inner surface is coated with a fluororesin is used. The stock solution supply device 40 includes a storage container 42 and a pressure source 4
3, the raw material solution 34 is stored in the storage container 42. As the storage container 42, a container having excellent chemical resistance such as a glass bottle is used. The pressure source 43 pressurizes the storage container 42 by supplying He gas or the like into the storage container 42 to discharge the raw material solution 34 filled in the storage container 42 to the connection pipe 41 at a constant flow rate. It has become.

Raw material solution 3 stored in storage container 42
No. 4 is a mixture of a plurality of metal organic compounds such as an organometallic complex of a constituent metal element of a target compound to be formed and a metal alkoxide in a composition ratio of the target compound and dissolving in an organic solvent. If specific examples of these metal organic compounds and organic solvents are specified, Y-Ba-Cu-O
Y (th) used when forming a film-based oxide superconductor
d) ₃ , Ba (thd) ₂ or Ba (thd) ₂ · ph
en ₂ , Cu (thd) ₂ etc. (thd = 2,2,6,6-tetramethyl-
3,5-heptanedione) and organic solvents such as tetrahydrofuran (THF), isopropanol, toluene and diglyme (2,5,8-trioxononane).

On the other hand, a raw material solution vaporizer 50 is disposed below the raw material solution supply device 30. The raw material solution vaporizer 50 includes a container-shaped vaporizer main body 51. A mounting port 52 is formed in the upper part of the vaporizer main body 51, and the raw material solution supply device 30 is provided through the mounting port 52.
Carburetor body 5 from the central part of the nozzle to the nozzle 37 at the tip
1, the mist-like raw material solution 34 is sprayed into the vaporizer main body 51 from the blowout port 37a of the raw material solution supply device 30.

Outside the carburetor main body 51, a heater 53 is attached as a first heating means for heating the inside of the carburetor main body 51. Further, the second heating means 5 is provided in the center of the vaporizer body 51 in front of the outlet 37a of the raw material solution supply device 30 arranged in the vaporizer body 51.
4 are provided. The second heating means 54 is for vaporizing the mist-like raw material solution 34 sprayed from the blowout port 37a, and has a large number of lumps 54 having a large heat capacity.
The raw material solution 34 is composed of an aggregate of a.
Metals and ceramics that are inert to, and are stable to oxidation and heat are used. For example, stainless steel balls, Hastelloy spheres, Ag spheres, AU spheres, and alumina spheres can be used. Above all, it is preferable to use stainless steel balls from the viewpoint of low cost. The shape of the mass 54a is not particularly limited, and may be a square block shape, a column shape, a pyramid shape, or the like other than the spherical shape. The size of the lump 54a is
When it is spherical, the diameter is about 1 to 5 mm.

Since the second heating means 54 has a large heat capacity, when the inside of the vaporizer main body 51 is heated to a constant temperature higher than the vaporization temperature of the raw material solution 34 by the heater 53, the second heating means 54 is heated. The heating means 54 is also heated to a constant temperature equal to or higher than the vaporization temperature of the raw material solution 34, so that the mist-like raw material solution 34 is discharged from the outlet 37a of the raw material solution supply device 30.
When is sprayed, the mist-like raw material solution 34 comes into contact with the second heating means 53 and immediately vaporizes to obtain a raw material gas. Such second heating means 54 is used for the vaporizer main body 51.
If it is not disposed inside, if the supply rate of the mist-like raw material solution 34 supplied to the inside of the vaporizer main body 51 is increased, the raw material solution 34 cannot be vaporized sufficiently, and vaporization efficiency is greatly improved. In addition to being unable to do so, it is difficult to form a good oxide superconducting thin film for a long time.

The large number of lumps 54a are accommodated in a tray 55. The saucer 55 allows the raw material gas obtained by the raw material solution 34 coming into contact with the large number of lumps 54a to pass therethrough,
In order to allow efficient supply to the CVD reactor 60, a mesh shape is preferable. As a material of the tray 55, a metal that is inert to the raw material solution 34 and is stable to oxidation and heat is used.

Further, at the mounting port 52 of the vaporizer main body 51, the raw material solution supply device 3 disposed inside the vaporizer main body 51.
A cover 56 for preventing the raw material gas from reaching the 0 outlet 37a is provided. The cover 56 is a tubular member having a tip portion that spreads outward, and surrounds the central portion and the tip portion 37 of the raw material solution supply device 30 arranged in the vaporizer main body 51. This cover 5
As a material of 6, a metal that is inert to the raw material solution 34 and is stable to oxidation and heat is used.
In this oxide superconducting conductor manufacturing apparatus, the vaporizer main body 51
It is considered that a circulation vortex of the source gas or the like as shown by the arrow in FIG. 1 is formed in the vaporizer main body 51 because the outlet for extracting the source gas from the source to the CVD reaction device 60 is small. If the carver 56 is not provided, the circulating vortex of the raw material gas may adhere to the blowout port 37a and be reprecipitated as a solid raw material. Such a raw material solution vaporizer 50 uses the transport pipe 57 for CVD.
It is connected to the reactor 60.

This CVD reaction apparatus 60 has a reaction chamber 61 made of quartz, and this reaction chamber 61 is of a cylindrical type with both ends oblong, and is closed in order from the left side of FIG. 1 by partition walls (not shown). It is divided into a base material introducing section 62, a reaction generation chamber 63, and a base material deriving section 64. Further, the base material introducing section 62
An introducing hole for introducing the tape-shaped base material 65 is formed in the base material, and a lead-out hole for leading out the base material 65 is formed in the base material lead-out portion 64. Although not shown in the drawing, the gap between the holes is closed at the peripheral edge of the hole while the base material 65 is being passed therethrough.
2 is provided with a sealing member that holds the base material lead-out portion 64 in an airtight state. Further, a triangular gas diffusion portion 66 communicating with the reaction generation chamber 63 is attached to the ceiling of the reaction generation chamber 63.

On the other hand, outside the CVD reaction apparatus 60, the heater 6 covers the part of the base material introduction part 62 on the side of the reaction generation chamber 63 to the part of the base material lead-out part 64 on the side of the reaction generation chamber 63.
7 is provided, and the base material introducing section 62 is an inert gas supply source 68.
Further, the base material lead-out portion 64 is connected to the oxygen gas supply source 69, respectively. Further, a transport pipe 57 connected to the carburetor main body 51 is connected to the gas diffusion portion 66. A heater 57a is provided around the transport pipe 57 to prevent the raw material gas from becoming the raw material solution 34 and depositing. An oxygen gas supply source 58 is branched and connected to an intermediate part of the transport pipe 57 so that the oxygen gas can be supplied into the transport pipe 57.

Further, an exhaust pipe 70 is provided at the bottom of the CVD reaction device 60 and is connected to a pressure adjusting device 72 equipped with a vacuum pump 71.
The gas inside can be exhausted. Furthermore, C
The CV is provided on the side of the base material lead-out portion 64 of the VD reaction device 60.
A substrate conveying mechanism 75 including a tension drum 73 and a winding drum 74 for winding the substrate 65 passing through the D reaction device 60 is provided. In addition, the base material introduction unit 62
A base material transport mechanism 78 including a tension drum 76 and a delivery drum 77 for supplying the base material 65 to the CVD reaction device 60 is provided on the side of the substrate.

Next, a raw material gas obtained by vaporizing the raw material solution 34 is converted into a reaction chamber 61 by using an oxide superconducting conductor manufacturing apparatus having the raw material solution vaporizing apparatus 50 configured as described above.
And the tape-shaped base material 65 in the reaction chamber 61.
A case of forming an oxide superconducting thin film on the above and manufacturing an oxide superconducting conductor will be described.

To manufacture an oxide superconducting conductor using the manufacturing apparatus shown in FIG. 1, first, a tape-shaped base material 65 and a raw material solution 34 are prepared. As the base material 65, a long one can be used, but it is particularly preferable that the upper surface of a heat-resistant metal tape having a low coefficient of thermal expansion is coated with a ceramic intermediate layer. As a constituent material of the heat resistant metal tape, a metal material or alloy such as silver, platinum, stainless steel, copper, or Hastelloy (C276) is preferable. Besides the metal tapes, tapes made of various ceramics such as various glass tapes or mica tapes may be used. Next, the material forming the intermediate layer is YSZ (yttrium-stabilized zirconia) whose thermal expansion coefficient is closer to that of the oxide superconductor than that of metal,
SrTiO ₃ , MgO, Al ₂ O ₃ , LaAlO ₃ , LaG
Ceramics such as aO ₃ , YAlO ₃ , and ZrO ₂ are preferable, and among these, it is preferable to use one having a crystal orientation as regular as possible.

Next, the raw material solution 34 for producing the oxide superconductor by the CVD reaction is a composition of the target compound, which is a metal organic compound such as an organic metal complex of a constituent metal element of the target compound to be formed, a metal alkoxide or the like. It is possible to use a mixture of a plurality of types having a ratio and dissolving in an organic solvent such as THF. When such a raw material solution 34 is prepared, it is filled in the storage container 40.

When the tape-shaped base material 65 is prepared, it is fed into the reaction chamber 61 by the base material transfer mechanism 78 from the base material introduction section 62 at a predetermined moving speed and the base material transfer mechanism 75 is wound. It is wound up by the take-up drum 74, and the base material 65 in the reaction production chamber 63 is heated to a predetermined temperature by the heater 67. Before feeding the base material 65, an inert gas is fed from the inert gas supply source 68 into the reaction chamber 61 as a purge gas, and at the same time, the pressure adjusting device 72 is fed.
It is preferable that the inside of the reaction chamber 61 is cleaned by removing unnecessary gas such as air in the reaction chamber 61 by activating the above to remove the gas inside the reaction chamber 61.

Once the base material 65 has been fed into the reaction chamber 61, oxygen gas is fed from the oxygen gas supply source 69 into the reaction chamber 61, and the pressure source 43 and the MFC 4 are further fed.
The flow rate of the raw material solution 34 from the storage container 42 is set to 0.1 by 1a.
Liquid is fed into the raw material solution supply unit 31 at about 1.0 ccm,
At the same time, the atomized gas is supplied to the atomized gas supply unit 3
2 at a flow rate of about 200 to 300 ccm and the shield gas to the shield gas supply unit 33 at a flow rate of 200 to 300 ccm.
Send in about 300 cc. At the same time, the pressure adjusting device 72 is operated to exhaust the gas inside the reaction chamber 61. At this time, the temperature of the shield gas is adjusted to be about room temperature. Further, the heater 53 is used so that the internal temperature of the vaporizer main body 51 of the raw material solution vaporizer 50 becomes a constant temperature within a range of about 200 to 300 ° C. suitable for vaporizing the raw material having the highest vaporization temperature among the raw materials. By adjusting, the second heating means 54 also heats to a constant temperature within the range of about 200 to 300 ° C. suitable for vaporizing the raw material having the highest vaporization temperature.

Then, the raw material solution 34 reaches the tip of the raw material solution supply part 31 while accumulating in the liquid pool 35, and thereafter, when it is blown out from the blowout port 37a, it is immediately atomized by the atomized gas flowing from the atomized gas supply part 32. Therefore, the constant flow rate of the mist-like raw material solution 34 is continuously supplied into the vaporizer main body 51. Then, the mist-like raw material solution 34 sprayed from the outlet 37a into the vaporizer main body 51 comes into contact with the second heating means 54 and is immediately vaporized to obtain the raw material gas. Further, this raw material gas is continuously supplied to the gas diffusion portion 66 via the transportation pipe 57. At this time, the heater 57a is arranged so that the internal temperature of the transport pipe 57 becomes the optimum temperature of the raw material having the highest vaporization temperature among the raw materials.
Adjust according to. At this time, the oxygen gas supply source 5
The operation of supplying oxygen gas from 8 and mixing oxygen into the raw material gas is also performed.

Next, inside the reaction chamber 61, the source gas discharged from the outlet of the transport pipe 57 to the gas diffusion section 66 moves to the reaction generation chamber 63 side while diffusing, and inside the reaction generation chamber 63. And then moves near the base material 65 to be drawn into the gas exhaust pipe 70.
Therefore, the raw material gas is allowed to react on the upper surface side of the heated base material 65 to generate an oxide superconducting thin film. By continuously performing the above film forming operation for a predetermined time, it is possible to obtain the oxide superconducting conductor 80 including the oxide superconducting thin film having a desired thickness and stable film quality on the base material 65.

Since the above-mentioned apparatus for producing an oxide superconducting conductor is provided with the raw material solution vaporizer (raw material vaporizing means) 50 having the above-mentioned structure, the independent raw material solution supplying apparatus (raw material supplying means) 30 is blown out. Since the raw material solution 34 can be sequentially vaporized by sending the mist-like raw material solution 34 into the vaporizer main body 51 while controlling the supply amount from the port 37a, it is easy to control the deposition rate of the oxide superconducting thin film. A good oxide superconducting thin film can be formed over a long period of time. Further, in the raw material solution vaporizer 50, a heater 53 for heating the inside of the vaporizer main body 51 is provided outside the vaporizer main body 51, and a raw material solution supply provided in the vaporizer main body 51 is provided. Since the second heating means 54 is provided in front of the outlet 37a of the device 30, the inside of the carburetor main body 51 is heated by the heater 53 to form the raw material solution 3
When heated to a constant temperature equal to or higher than the vaporization temperature of No. 4, the second heating means 54 can also be heated to a constant temperature equal to or higher than the vaporization temperature of the raw material solution 34. When the raw material solution 34 is sprayed, the mist-like raw material solution 34 comes into contact with the second heating means 53 and immediately vaporizes, so that the vaporization efficiency is improved, and thus the supply rate of the raw material solution 34 is faster than in the conventional case. However, since the raw material solution 34 can be sufficiently vaporized, the film forming efficiency of the oxide superconducting thin film can be improved. Further, in the raw material solution vaporizer 50, when the raw material solution vaporizer 50 is provided in the apparatus for manufacturing an oxide superconducting conductor, the raw material solution 34 can be sufficiently vaporized as described above. By continuously supplying the mist-like raw material solution 34, the constant amount of the raw material gas can also be continuously supplied to the reaction chamber 61, so that the conditions such as the reaction pressure and the temperature of the reaction chamber 61 do not easily change. Therefore, an excellent oxide superconducting thin film having stable film quality and superconducting properties can be formed in the length direction of the base material 65. Further, in this raw material solution vaporizer 50, the cover 56 is provided at the attachment port 52 of the vaporizer main body 51, so that the raw material gas can be prevented from reaching the blowout port 37a of the raw material solution supply device 30. Therefore, the circulation vortex of the raw material gas does not adhere to the nozzle 37 to become a solid raw material and re-precipitate, and it is possible to prevent liquid clogging or the like from occurring at the blowout port 37a, and to continuously continue for a long time. Vapor deposition is possible. In addition, the raw material solution supply device 3 having the above-described configuration as a raw material solution means for supplying the raw material solution into the vaporizer main body 51
By using 0, the mist-like raw material solution 34 can be sent into the vaporizer main body 51 while controlling the supply amount, and a constant amount of the mist-like raw material solution 34 can be continuously supplied. .

[0038]

【Example】

(Example) An Y-Ba-Cu-O-based oxide superconductor was produced as follows using the apparatus for producing an oxide superconductor having the structure shown in FIG. The CVD source solution vaporizer used had the shape shown in FIG. As a raw material solution, Y (t
hd) ₃ , Ba (thd) ₂ , Cu (thd) ₂ mixed in a molar ratio of Y: Ba: Cu = 1.0: 2.4: 3.3, dissolved in a diglyme solution, and stored in a storage container (Thd = 2.2.6.6-tetramethyl-3.5-heptanedione). On the other hand, as the second heating means provided in front of the outlet of the raw material solution supply device arranged in the vaporizer main body, a large number of diameters of 5 mm are used.
A stainless steel ball of a degree was used. The raw material solution was continuously supplied to the raw material solution supply unit at a flow rate of 1.0 ml / min by a pressure source and a liquid trace amount MFC. At the same time, Ar is supplied as atomizing gas to the atomizing gas supply unit at a flow rate of 300.
Ar is supplied as a shield gas while being sent in about ccm
Was sent to the shield gas supply unit at a flow rate of about 300 ccm. By the above operation, a constant amount of mist-like raw material solution can be continuously supplied into the vaporizer main body, and the mist-like raw material solution supplied into the vaporization main body is immediately vaporized by contact with the stainless steel balls. A raw material gas was obtained, and the raw material gas could be continuously supplied to the reaction chamber in a fixed amount. At this time, the temperature of the carburetor body and the transport pipe is 2
The temperature was 40 ° C.

Substrate movement speed in the reaction chamber 1.2 m /
h, substrate heating temperature 760 ° C., reactor pressure 5 torr,
The flow rate of oxygen gas from the oxygen gas supply source is 50 to 100 ml.
/ Min, and a Y-Ba-Cu-O-based oxide superconducting thin film was continuously formed on the base material to produce a YBCO tape. As the base material here, one having a YSZ (yttrium-stabilized zirconia) in-plane orientation intermediate layer formed on a hastero tape by an ion beam assisted sputtering method (width 1 cm x length ~ 30 cm x thickness 0.02 cm) is used. I was there.

(Comparative Example) An oxide similar to the oxide superconducting conductor manufacturing apparatus of FIG. 1 except that a CVD source solution vaporizer having no second heating means is provided in the vaporizer body. Using an apparatus for producing a superconducting conductor, an oxide superconducting thin film was formed on a base material in the same manner as in the above-mentioned embodiment, and YBCO
A tape was made.

YBCO produced in Examples and Comparative Examples
A tape (tape-shaped Y-Ba-Cu-O-based oxide superconducting conductor) is applied to the central portion of the tape with Ag coating by a sputtering device, and Ag electrodes are formed on both end sides. After Ag coating, heat treatment was performed at 500 ° C. for 2 hours in a pure oxygen atmosphere to obtain a measurement sample. Then, these samples were cooled to 77 K with liquid nitrogen, and the critical current density (Jc) in each length direction of each sample was measured under the condition of an external magnetic field of 0 T (Tesla). The results are shown in FIG. In FIG. 2, the solid line indicates the critical current density for each position in the length direction of the oxide superconducting conductor obtained in the example, and the broken line indicates the length direction of the oxide superconducting conductor obtained in the comparative example. It shows the critical current density for each position.

As is clear from FIG. 2, the YBCO tapes obtained in the examples have little variation in the critical current density in the length direction, and the critical current density is 10 ⁵ A / cm ² ( It can be seen that an oxide superconducting thin film having excellent characteristics of 77 K, 0T) or more and having stable superconducting properties in the longitudinal direction of the substrate is formed. In addition, in the example, the thickness of the oxide superconducting thin film was 1 μm, and the production speed was 1.2 m / h, which was several times higher than the conventional production speed, which was excellent. It has become clear that a long oxide superconducting conductor having characteristics can be produced at high speed. On the other hand, the YBC obtained in the comparative example
The O-tape has a large variation in the critical current density in the length direction, and the critical current density is 10 ⁵ A in some places.
/ Cm ² (77K, 0T), the superconducting properties are unstable in the longitudinal direction of the base material.

Further, in Examples and Comparative Examples, Y- formed on the base material when the feed rate of the raw material solution fed into the vaporizer body of the raw material solution vaporizer was changed within the range of 0 to 10 ml / min. The result of measuring the thickness of the Ba-Cu-O-based oxide superconducting thin film is shown in FIG. In FIG. 3, the solid line shows the relationship between the feed rate of the raw material solution in the example and the thickness of the Y—Ba—Cu—O-based oxide superconducting thin film, and the broken line shows the raw material solution in the comparative example. It shows the relationship between the supply rate and the thickness of the Y-Ba-Cu-O-based oxide superconducting thin film.
As is clear from FIG. 3, in the example, the film thickness is linearly increased until the supply rate of the raw material solution reaches 10 ml / min, and the film formation rate is significantly improved. Further, in the example, even if the feed rate of the raw material solution is 10 ml / min,
It can be seen that the raw material solution is sufficiently vaporized and the production rate of the long oxide superconducting conductor can be increased several times faster than the conventional one. This is considered to be because, in the example, the mist-like raw material solution supplied into the vaporizer was in contact with the stainless steel balls and immediately vaporized, so that the vaporization efficiency was significantly improved. On the other hand, in the comparative example, there was a tendency that the film thickness did not increase when the feed rate of the raw material solution was 1 ml / min or more. This indicates that when the feed rate of the raw material solution was set to 1 ml / min or more, the liquid feed became excessive and the vaporization rates reached parallel.

[0044]

As described above, in the raw material solution vaporizer for CVD according to the first aspect of the present invention, by virtue of the above-mentioned constitution, the blowing of the independent raw material solution supply device (raw material supply means) is performed. By feeding the mist-like raw material solution from the mouth into the vaporizer body while controlling the supply rate, the raw material solution can be vaporized in sequence, so that the film formation rate of the oxide thin film can be easily controlled for a long time. Therefore, a good oxide thin film can be formed. Further, in this raw material solution vaporizer, a raw material solution supply device provided with a first heating means for heating the inside of the vaporizer main body outside the vaporizer main body and arranged in the vaporizer main body Since the second heating means is provided in front of the blowout port of the above, when the inside of the vaporizer main body is heated to a constant temperature equal to or higher than the vaporization temperature of the raw material solution by the first heating means, the second heating means also changes the raw material solution. Since it can be heated to a constant temperature equal to or higher than the vaporization temperature of, when the mist-like raw material solution is sprayed from the outlet of the raw material solution supply device, the mist-like raw material solution immediately contacts the second heating means. Since vaporization improves vaporization efficiency, the raw material solution can be sufficiently vaporized even if the supply rate of the raw material solution is higher than in the past, and thus the oxide thin film deposition efficiency can be improved. Further, when the raw material solution vaporizer is provided in the thin film forming apparatus, the raw material solution can be sufficiently vaporized as described above, so that a constant amount of mist-like raw material solution is continuously supplied into the vaporizer body. As a result, a certain amount of raw material gas can be continuously supplied to the reaction chamber, and conditions such as reaction pressure and temperature in the reaction chamber are less likely to change. A stable and good oxide thin film can be formed.

In the raw material solution vaporizer according to the second aspect, in particular, since the cover for preventing the raw material gas from reaching the outlet of the raw material solution supply device is provided at the attachment port of the vaporizer main body, The circulation vortex of the raw material gas does not adhere to the nozzle to become a solid raw material and re-precipitate, and it is possible to prevent the raw material gas from adhering to the nozzle and causing liquid clogging at the outlet for a long time. Continuous vapor deposition is possible over the entire length. In the raw material solution vaporizer according to claim 3, in particular, the raw material solution supply device in which a blowout port is arranged in the vaporizer main body is provided with a cylindrical raw material solution supply unit into which the raw material solution is supplied. And a cylindrical, constricted atomized gas supply portion that is provided so as to surround the outer periphery of the supply portion and that is supplied with atomized gas for atomizing the raw material solution in a gap with the raw material solution supply portion. Therefore, the mist-like raw material solution can be fed into the vaporizer main body while controlling the supply amount, and a constant amount of the mist-like raw material solution can be continuously supplied.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing an example of an oxide superconducting conductor manufacturing apparatus including a CVD source solution vaporizer according to the present invention.

FIG. 2 is a diagram showing critical current densities in the length directions of YBCO tapes obtained in Examples and Comparative Examples.

FIG. 3 is a diagram showing the relationship between the supply rate of a raw material solution and the thickness of a Y—Ba—Cu—O-based oxide superconducting thin film.

FIG. 4 is a configuration diagram showing an example of an oxide superconducting conductor manufacturing apparatus including a conventional CVD raw material solution vaporizer.

FIG. 5 is a configuration diagram showing another example of an apparatus for manufacturing an oxide superconducting conductor, which is provided with a conventional CVD source solution vaporizer.

[Explanation of symbols]

30 ... Raw material solution supply device, 37a ... Blow-off port, 34
... raw material solution, 50 ... raw material solution vaporizer, 51 ... vaporizer main body, 52 ... mounting port, 53 ... heater (first heating means), 54 ... second Heating means, 54a ... lump, 56
···cover.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Saito 1-5-1, Kiba, Koto-ku, Tokyo Inside Fujikura Ltd. (72) Inventor Shigeo Nagaya Kitakanyama, Otaka-machi, Midori-ku, Nagoya-shi, Aichi Prefecture Ground No. 1 Chubu Electric Power Co., Inc. Power Technology Research Laboratory (72) Inventor Takaaki Shimonosono No. 20 Kitakanzan, Otaka-cho, Midori-ku, Aichi Prefecture Nagoya City Chubu Electric Power Co., Inc. Power Technology Research Center (56) References JP 10-8255 (JP, A) JP 9-143738 (JP, A) JP 6-346243 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C23C 16/00-16/56 C30B 25/14 H01L 21/205 H01L 21/31

Claims (3)

(57) [Claims] 1. A blowout for spraying a mist-like raw material solution.
Raw material solution supply device for CVD having a mouth, and the above-mentioned mist
So that the raw material solution of is sprayed into the vaporizer body.
A container-shaped carburetor body having a mounting port in which a blow-out port of the solution supply device is disposed, and a first heating means disposed outside the carburetor body and for heating the inside of the carburetor body, A second heating means for vaporizing the mist-like raw material solution, which is provided in front of the outlet of the CVD raw material solution supply device provided in the vaporizer body. Characteristic CVD source solution vaporizer. 2. A cover for preventing the vaporized raw material solution from reaching the outlet of the CVD raw material solution supply device provided in the vaporizer main body is provided at the attachment port of the vaporizer main body. The CV according to claim 1, characterized in that
Raw material solution vaporizer for D. 3. A raw material solution supply device for CVD, in which a blowout port is provided in the vaporizer body, encloses a cylindrical raw material solution supply part into which a raw material solution is supplied and an outer periphery of the supply part. It is characterized in that it is provided with a cylindrical and tapered atomized gas supply portion to which atomized gas for atomizing the raw material solution is supplied in the gap between the raw material solution supply portion. CV according to claim 1 or 2.
Raw material solution vaporizer for D.