JP3741860B2 - Manufacturing apparatus and manufacturing method of oxide superconducting conductor - Google Patents

Description

ここで、Ｉｃは臨界電流値、Ｊｃは臨界電流密度である。
【００８０】
上記の結果から、３つの反応生成室内部の酸素分圧を独立に制御して３段階に酸素分圧を上昇することにより、１つの反応生成室で形成した場合に比べて３倍の膜厚と３倍の臨界電流値Ｉｃを得た。一方、３つの反応生成室内部の酸素分圧を同等に設定した場合には、１つの反応生成室で形成した場合に比べて３倍の膜厚を得たが約１．５倍の臨界電流値Ｉｃを得るに留まった。
また、ガスミキサにより原料ガスと酸素ガスとを混合して反応生成室に供給した場合には、ガスミキサのない場合に比べ、厚さ１．１倍，Ｊ_C １．４倍となることがわかった。
また、遮断ガス供給手段により遮断ガスを境界室に供給して、各反応生成室のガス条件を厳密に独立状態とした場合には、遮断ガスのない場合に比べて、厚さ１．５倍，Ｊ_C １．６倍となることがわかった。
【００８１】
以上のことから、複数の反応生成室を直列にｎ段設け（ｎは自然数）、連続してＣＶＤ反応を行うことで、１つの反応生成室のみの製造時に比べて、ｎ倍の酸化物超電導薄膜の形成速度と、ｎ倍の酸化物超電導薄膜の膜厚を得ることができる。
また、ガスミキサにより反応ガスの供給状態の改善を図り、かつ、境界室下方の排気口により反応生成室と境界室の排ガスをおこなうことで、反応生成室内における原料ガスや酸素ガスなどのガスの状態を独立に制御しながらＣＶＤ反応を行うことができるので、テープ状の基材厚さの分布や組成が均一な酸化物超電導薄膜を形成することができ、臨界電流密度等の超電導特性の優れた酸化物超電導体を効率よく製造できることがわかる。
【００８２】
【発明の効果】
本発明の酸化物超電導導体の製造装置および製造方法によれば、以下の効果を奏する。
（１）複数の反応生成室を直列に並べ、各反応生成室内の原料ガス濃度および酸素分圧等のガス条件を独立に制御可能とすることにより、酸化物超電導薄膜の形成速度の向上と、形成される酸化物超電導薄膜の膜厚の向上を図ることができる。
（２）ガスミキサにより、原料ガスと酸素ガスとの混合状態を向上すること、および、境界室に遮断ガスを供給して、核反応生成室間のガス状態の干渉を排除することにより、反応ガスの供給状態の改善を図ることができる。
（３）上記の反応ガスの供給状態の改善により、厚さの分布や組成が均一な酸化物超電導薄膜を形成することができる。
（４）上記により、超電導特性の優れた酸化物超電導体を効率良く製造することができる。
【図面の簡単な説明】
【図１】 本発明における酸化物超電導導体の製造装置および製造方法の第１実施形態の酸化物超電導体の製造装置の全体構成を示す図である。
【図２】 図１の酸化物超電導体の製造装置に備えられたＣＶＤ反応装置の構造例を示す斜視図である。
【図３】 図２に示すＣＶＤ反応装置の詳細構造を示す側断面図である。
【図４】 図２に示すＣＶＤ反応装置の詳細構造を示す正断面図である。
【図５】 図２に示すＣＶＤ反応装置の詳細構造を示す平面図である。
【図６】 図１に示す原料ガス供給手段および反応生成室を示す図である。
【図７】 図１に示すガスミキサを示す断面図である。
【図８】 本発明の第２実施形態の酸化物超電導体の製造装置における原料ガス供給手段および反応生成室を示す図である。
【図９】 本発明の第３実施形態の酸化物超電導体の製造装置における原料ガス供給手段および反応生成室を示す図である。
【図１０】 本発明の第４実施形態の酸化物超電導体の製造装置における反応生成室およびシャワーノズルの詳細構造を示す斜視図である。
【図１１】 本発明の第５実施形態の酸化物超電導体の製造装置における反応生成室，シャワーノズルおよび恒温機構を示す図である。
【図１２】 図１１に示す反応生成室，シャワーノズルおよび恒温機構を示す正断面図である。
【図１３】 従来のＣＶＤ反応装置を用いてチップ状の基材の表面に薄膜を形成する方法の例を示す図である。
【図１４】 従来のＣＶＤ反応装置を用いてチップ状の基材の表面に薄膜を形成する方法のその他の例を示す図である。
【図１５】 長尺の基材の表面に酸化物超電導薄膜を形成する従来のＣＶＤ反応装置の詳細構造を示す断面図である。
【図１６】 図１５のＣＶＤ反応装置の詳細構造を示す平面図である。
【符号の説明】
Ａ，Ｂ，Ｃ…ＣＶＤユニット、Ｔ…基材、３０…ＣＶＤ反応装置、３１…リアクタ、３８…境界室、３８Ｂ…遮断ガス供給手段、４８…ガスミキサ、５０…原料ガス供給手段、５２…酸素ガス供給手段、５４…酸素ガス流量調整機構、７０ｂ…排気管、７０ｃ，７０ｅ，７０ｆ…排気口、７０ｄ…バルブ（流量調整機構）、７１…真空ポンプ、７２…圧力調整装置、８０…ガス排気機構、８２…制御手段、Ｔ１…酸化物超電導体。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an oxide superconductor manufacturing apparatus and manufacturing method, and relates to an oxide superconductor manufacturing apparatus using a CVD reactor that forms a thin film on a substrate and an oxide superconductor manufacturing method using the same. The present invention relates to a technique suitable for use.
[0002]
[Prior art]
Conventionally, oxide superconducting thin films have been used for power cables, magnets, energy storage, generators, medical equipment, current leads, etc., and chemical vapor deposition (CVD) has been used for their production. ing. Compared to physical vapor deposition methods (PVD method) such as sputtering and vapor deposition methods such as vacuum evaporation, this CVD method has fewer restrictions on the shape of the substrate and enables thin film formation on a large area substrate at high speed. It is widely known as a new technique. However, in this CVD method, the charge composition and supply speed of the source gas, the type of carrier gas and the supply amount of the reaction gas, or the control of the gas flow in the film formation chamber due to the structure of the reaction reactor, etc. Because it has many unique control parameters not found in other film formation methods, it has the disadvantage that it is difficult to optimize the conditions for forming a high-quality thin film using the CVD method. Yes.
[0003]
In general, this type of CVD reactor includes a reactor that forms a reaction generation chamber, a base material provided in the reactor, a heating device that heats the interior of the reactor to a desired temperature, and reaction generation in the reactor. The main component is a raw material gas supply device for supplying a raw material gas and an exhaust device for exhausting the gas after reacting inside the reactor.
Then, in order to form a target thin film on a substrate using the CVD reactor of this configuration, the inside of the reactor is set to a reduced pressure atmosphere and heated to a desired temperature, and the target gas supply device is used to respond to the target thin film. The raw material gas is introduced into the reactor, the raw material gas is decomposed in the reactor, the reaction product is stacked on the substrate, and the reacted gas is discharged by an exhaust device.
In addition, when a thin film having uniform characteristics and thickness is formed on the surface of a chip-like substrate using the CVD reactor having such a configuration, there is a method of forming a film while moving the chip-like substrate in a plane. For example, as shown in FIG. 13, a plurality of chip-like base materials 1 are placed on a disc-like base material holder 2 provided in a reactor (not shown) along the circumference thereof. Then, the film is formed while rotating with the central axis G of the substrate holder 2 as the rotation axis, or the chip-shaped substrate 1 is placed in the vertical direction (X₁-X₂Between) and lateral direction (Y₁-Y₂And a method of forming a film while the tip-shaped substrate 1 is rotated eccentrically. In FIG. 13 to FIG. 14, reference numeral 3 is a source gas supply nozzle, and 4 is a source gas 4 supplied from the nozzle 3.
[0004]
However, the method of rotating the substrate holder 2 in which a plurality of chip-shaped substrates 1 arranged as shown in FIG. 13 is suitable for mass production, but the film thickness distribution is concentrically with respect to the rotation axis G. Therefore, the distribution of the film thickness of the formed thin film is not uniform, and the superconducting characteristics vary. Further, the method of traversing the chip-shaped substrate 1 as shown in FIG. 14 vertically and horizontally or rotating eccentrically can obtain a thin film having a uniform thickness, but the film forming apparatus becomes large and the production is performed. There is a problem of inefficiency. When a long oxide superconductor is produced by depositing an oxide superconducting thin film on a tape-like substrate using a CVD reactor, the tape-like substrate is fed in one direction into the reactor. In addition, since it is necessary to form a thin film while winding, it is impossible to apply a method of forming a film while moving the substrate as described above in a plane.
[0005]
Therefore, conventionally, a long oxide superconductor has been manufactured using a CVD reactor 10 as shown in FIGS. This CVD reaction apparatus 10 has a cylindrical reactor 11, which is partitioned into a base material introduction part 14, a reaction generation chamber 15, and a base material lead-out part 16 by partition walls 12 and 13. Passing holes 19 through which the tape-like base material 18 can pass are respectively formed in the lower center of the partition walls 12 and 13. A gas diffusion unit 20 is attached to the reaction generation chamber 15. A supply pipe 20b having a slit nozzle 20a at the tip is connected to the gas diffusion section 20, so that source gas and oxygen can be supplied from the supply pipe 20b into the reaction generation chamber 15 through the gas diffusion section 20. ing.
Further, an exhaust chamber 17 is provided below the reaction generation chamber 15 in the reactor 11 along the length direction of the tape-like base material 18 passed through the reactor 11. In the upper part of the exhaust chamber 17, elongated rectangular gas exhaust holes 21 a and 21 a are formed along the length direction of the tape-like base material 18 passed through the reactor 11. Further, one end of two exhaust pipes 23 is connected to the lower part of the exhaust chamber 17, while the other end of the two exhaust pipes 23 is connected to a vacuum pump (not shown). The exhaust ports 23 a of the two exhaust pipes 23 are provided along the length direction of the tape-shaped base material 18 passed through the reactor 11.
[0006]
[Problems to be solved by the invention]
In the conventional CVD reactor 10, when producing a long oxide superconductor, the raw material gas introduced from the slit nozzle 20a forms a thin film on the tape-shaped substrate 18 in the reaction generation chamber 15, Since the unreacted gas (residual gas) is discharged out of the CVD reactor 10 from the exhaust ports 23a and 23a provided along the length direction of the tape-shaped substrate 18 introduced, An oxide superconducting thin film having a uniform thickness and composition with respect to the length direction of the tape-shaped substrate 18 can be formed. However, the thickness of the oxide superconducting thin film formed on the tape-shaped substrate 18 in the reaction generation chamber 15 is defined by the amount of reaction gas supplied to the reaction generation chamber 15, and the supplied raw material Since the amount of gas is defined by the shape and size of the reaction generation chamber 15, it is difficult to introduce a large amount of source gas. For this reason, the thickness of the oxide superconducting thin film to be formed and the formation speed of the oxide superconducting thin film are also limited, and the resulting superconducting characteristics such as critical current and critical current density are unsatisfactory. It was.
Moreover, since the supply state of the raw material gas introduced from the slit nozzle 20a cannot be controlled, the thickness distribution and composition of the oxide superconducting thin film vary, and this makes it critical for the width direction of the tape-shaped substrate 18, for example. Since the current density varies, the superconducting properties of the resulting oxide superconductor are unsatisfactory.
[0007]
The present invention has been made in view of the above circumstances, and intends to achieve the following object.
(1) To improve the formation rate of the oxide superconducting thin film.
(2) To improve the thickness of the oxide superconducting thin film to be formed.
(3) To improve the supply state of the reaction gas.
(4) An oxide superconducting thin film having a uniform thickness distribution and composition is formed.
(5) Efficient production of oxide superconductors with excellent superconducting properties.
[0008]
[Means for Solving the Problems]
  The present invention relates to a reactor for performing a CVD reaction in which a raw material gas of an oxide superconductor is chemically reacted to the surface of a moving tape-like substrate to deposit an oxide superconducting thin film, and a raw material gas for supplying the raw material gas to the reactor In the oxide superconductor manufacturing apparatus comprising a supply means, a gas exhaust means for exhausting the gas in the reactor, and a control means for controlling them, the reactor includes a base material introduction section, a reaction generation chamber And the base material lead-out part, respectively, are partitioned via a partition wall, a plurality of the reaction generation chambers are provided in series in the moving direction of the tape-shaped base material, and a boundary chamber is provided between these reaction generation chambers, A base material passage hole is formed in each partition wall, and a base material conveyance region that passes through the base material introduction portion, the reaction generation chamber, the boundary chamber, and the base material outlet portion is formed inside the reactor,The source gas supply means includes a source gas supply source and an oxygen gas supply means for supplying oxygen gas, and is provided for each reaction generation chamber of the reactor. The boundary chamber includes reaction reaction chambers on both sides. Shut-off gas supply means for supplying shut-off gas for shutting off each other is connected, and the gas exhaust means includes a plurality of exhaust pipes each provided with a flow rate adjusting mechanism for adjusting the amount of gas exhaust; An exhaust port of the plurality of exhaust pipes provided in the reactor along a length direction and a width direction of a tape-shaped base material, and the exhaust port includes the base material introduction part and the reaction generation chamber Is located on the upstream side of the partition wall that divides the reaction chamber, the downstream side of the partition wall that partitions the reaction generation chamber and the substrate outlet, and the partition walls on both sides of the boundary chamber, and is moved in the reactor by the control means The length of the tape-shaped substrate inside The apparatus for producing an oxide superconductor, characterized in that it is a controlled configurable gas flow conditions in the direction and the width direction is means for solving the above-described problem.
  Further, according to the present invention, the source gas supply means includes a source gas supply source, an oxygen gas supply means for supplying oxygen gas,A gas mixer comprising: a gas mixer provided immediately upstream of the reactor for mixing the raw material gas and oxygen gas; and a gas diffusion section provided on one side of each reaction generation chamber of the reactor connected to the gas mixer. A plurality of protrusions provided on the inner periphery of the gas flow path for mixing the gas, and heating means for heating the inside of the gas mixer, the gas exhaust means Is configured to include a gas exhaust hole provided on both sides of the base material transport region on the opposite side of the gas diffusion part forming side and a gas exhaust device connected to the gas exhaust hole, A gas diffusion part and the gas exhaust hole are opposed to each other with a base material conveyance region interposed therebetween, and a shutoff gas supply means for supplying a shutoff gas for shutting off reaction reaction chambers on both sides is provided in the boundary chamber. Connected and shielded Argon gas is selected as the gas, and at least one exhaust hole of the gas exhaust means is provided along the length direction and the width direction of the tape-shaped substrate moving in the reactor, and the shut-off gas A flow rate adjusting mechanism is provided at a position opposite to the jetting portion over a partition wall that divides the reaction generation chamber and the boundary chamber, and the gas exhaust means adjusts the exhaust amount of the gas exhausted from each exhaust hole. The gas flow state in the length direction and the width direction of the tape-shaped substrate moving in the reactor can be controlled by the control means, and each source gas supply means is independently controlled by the control means. It is possible to independently control the oxygen partial pressure in the raw material gas supplied to each reaction generation chamber, and the oxygen partial pressure in the reaction generation chamber upstream in the moving direction of the tape-shaped substrate is Tape-like substrate The apparatus for producing an oxide superconductor, characterized in that the oxygen partial pressure in the dynamic direction downstream of the reaction generation chamber is set high and the means for solving the above-described problem.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, a first embodiment of a manufacturing apparatus and a manufacturing method of an oxide superconducting conductor according to the present invention will be described with reference to the drawings.
[0010]
FIG. 1 shows an example of an apparatus for manufacturing an oxide superconductor according to the present invention. In the manufacturing apparatus of this example, three CVD units A, B, and C having substantially the same structure are incorporated, and each CVD is performed. The units A, B, and C incorporate a CVD reactor 30 whose detailed structure is shown in FIGS. 2 to 7, and an oxide superconducting thin film is formed on a tape-like substrate in the CVD reactor 30. It is like that.
The CVD reaction apparatus 30 shown in FIGS. 2 to 7 used in the manufacturing apparatus of this example has a cylindrical quartz reactor 31 whose both ends are horizontally long, and this reactor 31 is illustrated by partition walls 32 and 33. 2 is divided into a base material introduction part 34, a reaction generation chamber 35, and a base material lead-out part 36 in order from the left side, and the reaction generation chambers 35 and 35 are divided into three by a partition wall 37, each of which is the above-mentioned CVD unit. A part of A, B and C is formed, and a boundary chamber 38 is defined between the reaction generation chambers 35 and 35. The material constituting the reactor 31 is not limited to quartz but may be a metal having excellent corrosion resistance such as stainless steel.
[0011]
As shown in FIGS. 2 to 4, passage holes 39 through which a long tape-like substrate T can pass are formed in the lower center of the partition walls 32, 33, and 37, respectively. The base material conveyance area | region R is formed in the form which crosses the center part. Further, an introduction hole for introducing the tape-shaped base material T is formed in the base material introduction portion 34, and a lead-out hole for leading out the base material T is formed in the base material lead-out portion 36. A sealing mechanism (not shown) that holds the base material introduction part 34 and the base material lead-out part 36 in an airtight state by closing the gaps of the holes in the state where the base material T is passed, at the peripheral part of the hole and the lead-out hole. ) Is provided.
[0012]
As shown in FIG. 2, a truncated pyramid-shaped gas diffusion unit 40 is attached to the ceiling of each reaction generation chamber 35. The gas diffusion portion 40 includes trapezoidal side walls 41 and 41 arranged along the longitudinal direction of the reactor 31, front and rear walls 42 and 43, and a ceiling wall 44. The gas diffusion member 45 is mainly composed of a supply pipe 53 connected to the ceiling wall 44. A slit nozzle 53 a is provided at the distal end of the supply pipe 53. The bottom surface of the gas diffusion member 45 is a rectangular opening 46, and the gas diffusion member 45 communicates with the reaction generation chamber 35 through the opening 46.
[0013]
A shutoff gas supply means 38B is connected to the ceiling of the boundary chamber 38 via a supply pipe 38A, and the shutoff gas supply means 38B shuts off the reaction generation chambers 35, 35 on both sides of the boundary chamber 38. The connection portion of the supply pipe 38A is connected via a cutoff gas ejection portion 38a, and for example, argon gas is selected as the cutoff gas.
[0014]
On the other hand, below each reaction generation chamber 35 and the boundary chamber 38, exhaust is performed so as to penetrate the reaction generation chamber 35 and the boundary chamber 38 along the length direction of the substrate transport region R as shown in FIG. A chamber 70 is provided. As shown in FIGS. 2 and 4, elongated gas exhaust holes 70 a and 70 a are formed in the upper portion of the exhaust chamber 70 along the length direction of the tape-shaped substrate T passed through the substrate conveyance region R. The gas exhaust holes 70a and 70a are formed so as to penetrate the reaction generation chambers 35 and the boundary chambers 38, respectively. As shown in FIGS. The lower end portions on both sides of the region R are in a penetrating state.
In addition, one end of a plurality of exhaust pipes 70b (10 in the drawing) is connected to the lower portion of the exhaust chamber 70, while the other end of the plurality of exhaust pipes 70b is a pressure provided with a vacuum pump 71. The adjustment device 72 is connected. Further, as shown in FIGS. 4 to 5, the exhaust ports 70c and 70e of the plurality (four in the drawing) of the plurality of exhaust pipes 70b are passed through the base material transport region R. The exhaust port 70c is provided along the length direction of the tape-shaped substrate T, and the exhaust port 70c is upstream of the partition wall 32 in the length direction of the tape-shaped substrate T passed through the substrate conveyance region R in the exhaust chamber 70. And the lengthwise direction of the tape-shaped substrate T passed through the substrate transport region R so that the exhaust port 70e is located across the partition walls 37, 37 on both sides of the boundary chamber 38. Has been extended.
Further, among the plurality of exhaust pipes 70b, the exhaust ports 70f of the remaining (six in the drawing) exhaust pipes 70b are provided along the width direction of the tape-shaped base material T passed through the base material transport region R. It has been. Each of the plurality of exhaust pipes 70b is provided with a valve (flow rate adjusting mechanism) 70d for adjusting the exhaust amount of the gas. Therefore, an exhaust chamber 70 in which gas exhaust holes 70a and 70a are formed, a plurality of exhaust pipes 70b... Having exhaust ports 70c, 70e and 70f, a valve 70d, a vacuum pump 71, and a pressure adjusting device. 72 constitutes a gas exhaust mechanism 80. The gas exhaust mechanism 80 having such a configuration allows gas such as the source gas, oxygen gas, inert gas, and shut-off gas inside the CVD reactor 30 to pass through the gas exhaust holes 70a, 70a to the exhaust chamber 70, exhaust port 70c, 70e, 70f and exhaust pipe 70b can be used for exhausting.
[0015]
As shown in FIG. 1, a heater 47 that covers a portion from the reaction generation chamber 35 side of the base material introduction portion 34 to a portion of the base material outlet portion 36 side of the reaction generation chamber 35 is provided outside the CVD reaction apparatus 30. Is provided. In the example shown in FIG. 1, the heater 47 is in a continuous state over the three reaction generation chambers 35, but the heater 47 may be independent of each reaction generation chamber 35. .
Further, outside the CVD reaction apparatus 30, the base material introduction part 34 is connected to the inert gas supply source 51A, and the base material lead-out part 36 is connected to the oxygen gas supply source 51B. Further, as shown in FIGS. 1 and 6, a supply pipe 53 connected to the ceiling wall 44 of the gas diffusion section 40 is supplied with a raw material gas vaporizer of a raw material gas supply means 50 described later via a gas mixer 48 described later. (Source gas supply source) 55 is connected.
In the raw material gas supply means 50, an oxygen gas supply source 52 is branched and connected to the upstream portion of the gas mixer 48 in the supply pipe 53 via an oxygen gas flow rate adjusting mechanism 54, and the oxygen gas is supplied to the supply pipe 53. It is comprised so that it can supply. At this time, it is desirable that the gas mixer 48 and the oxygen gas supply source 52 be connected as downstream as possible from the supply pipe 53.
[0016]
In the source gas supply means 50, the source gas vaporizer 55 includes a spherical body 55a and a cylindrical head 55b, and the body 55a and the head 55b are partitioned by a partition wall 56. The body portion 55a and the head portion 55b are communicated with each other through a needle-like needle tube 57 provided through the partition wall 56. In addition, the raw material solution is supplied into the head portion 55b from the raw material solution tank 60 through the supply pipe 61, and the raw material solution in the head portion 55b reaches the vicinity of the upper end portion of the needle pipe 57. In addition, the upper end portion of the needle tube 57 is inclined and cut, and the raw material solution is supplied in the form of droplets from the inclined cut portion to the barrel portion 55a side.
5, reference numeral 62 denotes a flow meter connected to the head 55b of the vaporizer 55, 63 denotes a regulated gas tank connected to the flow meter 62, and 64 denotes a flow regulator connected to the Ar gas supply source 65, respectively. Show.
[0017]
Further, on the side of the base material lead-out portion 36 of the CVD reactor 30, a tension drum 73 for winding the tape-like base material 38 passing through the base material transport region R in the CVD reactor 30 and a winding A base material transport mechanism 75 including a drum 74 is provided. Further, on the side of the base material introducing portion 34, a base material transport mechanism 78 including a tension drum 76 and a feed drum 77 for supplying the tape-shaped base material 38 to the CVD reactor 30 is provided. .
[0018]
As shown in FIG. 7, the gas mixer 48 has a tube body having substantially the same diameter as the supply pipe 53 made of quartz, and the gas mixer 48 is disposed inside the flow path through which the gas flows, A plurality of protrusions 48 a for mixing a gas such as oxygen gas are provided, and a heater 48 b as a heating means for heating the inside of the gas mixer 48 is attached around the gas mixer 48. As shown in FIG. 7 (a), the protrusion 48a has a flat plate shape that is fixed to the inner wall of the tube in a curved state from the upstream to the downstream with respect to the gas flow direction indicated by the arrow G. Alternatively, as shown in FIG. 7B, a so-called drop shape that is a streamlined shape with respect to the gas flow direction indicated by the arrow G can be used.
The material constituting the gas mixer 48 is not limited to quartz, but may be a material having low reactivity with a raw material gas such as stainless steel (SUS304), Inconel, Hastelloy and the like.
[0019]
Further, a flow meter (not shown) for measuring the flow of a gas such as a raw material gas or oxygen gas is attached in the substrate transport region R of the reactor 31, and a control means 82 is electrically connected to the flow meter and the valve 70d. Connected. The control means 82 adjusts each valve 70d based on the measurement result of the flow meter, and the raw material gas, oxygen gas, etc. in the length direction and width direction of the tape-like base material 38 moving in the reactor 31. The gas flow state of the gas can be controlled, and the flow state of the cut-off gas supplied to the boundary chamber 38 can be controlled by being connected to the cut-off gas supply means 38B.
Further, the control means 82 is electrically connected to the oxygen gas flow rate adjusting mechanism 54, thereby adjusting the operation of the oxygen gas flow rate adjusting mechanism 54 based on the measurement result of the flow meter in the substrate transport region R, The amount of oxygen gas sent to the CVD reactor 30 via the supply pipe 53 can also be adjusted. In this source gas supply means 50, it is preferable that the amount of gas such as source gas and oxygen gas and the flow state can be controlled independently for each of the CVD units A, B and C.
[0020]
Next, an oxide superconducting thin film is formed on the tape-shaped substrate 38 using an oxide superconductor manufacturing apparatus having the CVD units A, B, and C having the CVD reactor 30 configured as described above. The case of manufacturing an oxide superconductor will be described.
[0021]
In order to manufacture an oxide superconductor using the manufacturing apparatus shown in FIG. 1, first, a tape-shaped substrate T and a raw material solution are prepared.
The substrate T can be a long one, and in particular, a substrate obtained by coating a ceramic intermediate layer on the upper surface of a heat-resistant metal tape having a low coefficient of thermal expansion. Constituent materials for the heat-resistant metal tape include silver, platinum, and stainless steel.
Metal materials and alloys such as copper and hastelloy (C276 etc.) are preferable. In addition to the metal tape, a tape made of various ceramics such as various glass tapes or mica tapes may be used.
Next, the material constituting the intermediate layer is composed of YSZ (yttrium stabilized zirconia), SrTiO whose thermal expansion coefficient is closer to that of the oxide superconductor than metal._Three , MgO, Al₂O_ThreeLaAlO_ThreeLaGaO_ThreeYAlO_Three, ZrO₂Ceramics such as these are preferable, and among these, it is preferable to use one having as much crystal orientation as possible.
[0022]
Next, the raw material solution for generating the oxide superconductor by the CVD reaction is preferably a solution in which a metal complex of each element constituting the oxide superconductor is dispersed in a solvent. Specifically, Y₁Ba₂Cu_ThreeO_7-xIn the case of forming a Y-based oxide superconducting thin film widely known in the composition, Ba-bis-2,2,6,6-tetramethyl-3,5-heptanedione-bis-1,10-phenanthroline (Ba (Thd)₂(Phen)₂) And Y (thd)₂ And Cu (thd)₂Other than that, Y-bis-2,2,6,6-tetramethyl-3,5-heptanedionate (Y (DPM)_Three) And Ba (DPM)₂And Cu (DPM)₂Etc. can be used.
[0023]
In addition to the Y-based oxide superconducting thin film, La_2-xBa_xCuO_FourLa-based, Bi represented by the composition of₂Sr₂Ca_n-1Cu_nO_{2n + 2}Bi type represented by the composition of (n is a natural number), Tl₂Ba₂Ca_n-1Cu_nO_{2n + 2}Since many types of superconducting thin films such as Tl-based materials represented by the composition (n is a natural number) are known, the CVD method may be carried out using a metal complex salt corresponding to the target composition.
Here, for example, when manufacturing an oxide superconducting thin film other than Y-based, triphenyl bismuth (III), bis (dipivalloymethanato) strontium (II), bis (di- Metal complex salts such as pivalloymethanato) calcium (II) and tris (dipivalloymethanato) lanthanum (III) can be appropriately used for the production of the respective oxide superconducting thin films.
[0024]
If the tape-shaped base material T as described above is prepared, it is transferred from the base material introduction part 34 to the base material transport region R in the oxide superconductor manufacturing apparatus by the base material transport mechanism 78 at a predetermined moving speed. In addition, the substrate T in the reaction generation chamber 35 is heated to a predetermined temperature by the heater 47 and the gas mixer 48 is set to a predetermined temperature by the heater 48b. Heat. Before feeding the substrate T, the inert gas is fed from the inert gas supply source 51A into the CVD reactor 30 as a purge gas, and the cutoff gas is sent into the boundary chamber 38 via the cutoff gas ejection part 38a. At the same time, the gas inside the CVD reactor 30 is removed from the gas exhaust holes 70a, 70a through the exhaust chamber 70, the exhaust ports 70c, 70e, 70f, and the exhaust pipe 70b by the pressure adjusting device 72. It is preferable to clean the inside by eliminating unnecessary gas.
[0025]
If the base material T is sent into the CVD reactor 30, the oxygen gas is sent from the oxygen gas supply source 51B into the CVD reactor 30, and the source solution is vaporized from the source solution tank 60 in each source gas supply means 50. The Ar gas is sent from the adjustment tank 63 to the head portion 55b of the vaporizer 55 as a carrier gas. At the same time, the gas inside the CVD reactor 30 is exhausted from the gas exhaust holes 70a, 70a through the exhaust chamber 70, the exhaust port 70c, and the exhaust pipe 70b by the pressure adjusting device 72. As a result, a difference is generated between the pressure in the head portion 55b of the vaporizer 55 and the pressure in the body portion 55a, and the raw material solution in the head portion 55b is drawn into the inside of the needle tube 57 from the tip of the needle tube 57 due to this atmospheric pressure difference. Thus, the raw material solution can be converted into droplets.
[0026]
Then, a raw material gas in which a droplet-like raw material is contained in the carrier gas can be generated by the above operation, and this raw material gas is supplied from the body portion 55a of the vaporizer 55 through the supply pipe 53 to the gas diffusion portion 40. To supply. At the same time, an operation of supplying oxygen gas from the oxygen gas supply means 52 and mixing oxygen into the raw material gas is also performed.
At this time, the raw material gas and oxygen gas described above are agitated and uniformly mixed by the projection 48a inside the gas mixer 48 in the middle of the supply pipe 53, and immediately, the slit nozzle at the tip of the supply pipe 53 From 53a, it is ejected to the gas diffusion part 40.
[0027]
Next, in the CVD reaction apparatus 30, the raw material gas that has flowed from the outlet portion of the supply pipe 53 to the gas diffusion portion 40 diffuses along the front wall 42 and the rear wall 43 of the gas diffusion portion 40, thereby generating a reaction. The heated substrate is moved by moving to the chamber 35 side, passing through the inside of the reaction generation chamber 35, and then moving the substrate T so as to cross up and down and being drawn into the gas exhaust holes 70a and 70a. The source gas is reacted on the upper surface side of 38 to deposit a reaction product.
Here, when depositing the reaction product on the substrate T, the control means 82 causes the pressure adjusting device 72 provided in the gas exhaust mechanism 80 to pass through the gas exhaust holes 70a and 70a to the exhaust chamber 70 and the exhaust ports 70c and 70e. 70f and the exhaust pipe 70b, and the valve 70d is adjusted to adjust the gas flow in each exhaust pipe 70b, whereby the length of the tape-like base material T moving in the base material transport region R is adjusted. The CVD reaction is performed while controlling the flow state of the source gas in the direction and the width direction. At the same time, a shutoff gas is supplied to the boundary chamber 38 by the shutoff gas supply means 38B and exhausted from the gas exhaust holes 70a and 70a through the exhaust chamber 70, the exhaust ports 70e and 70f, and the exhaust pipe 70b. The flow of the reaction gas between the 35 is cut off, and the independence of the gas state such as the oxygen partial pressure in the reaction generation chamber 35 is maintained.
Further, while the reaction proceeds in the CVD reactor 30, the flow state of the gas such as the source gas and oxygen gas in the length direction and the width direction of the tape-shaped substrate T moving in the substrate conveyance region R May change and adversely affect the oxide superconducting thin film. Therefore, the flow rate change of the gas is measured with the flow meter provided in the base material transport region R of the reactor 31, and based on the measurement result. The control means 82 adjusts the amount of oxygen gas supplied from each valve 70d and the oxygen gas supply means 52, and controls the gas flow state to always be a preferable flow state, whereby the length direction of the tape-like substrate T is controlled. In addition, an oxide superconducting thin film having a uniform thickness distribution and composition in the width direction can always be formed.
[0028]
Further, while the reaction proceeds in the CVD reaction apparatus 30, deposits increase in the reaction generation chamber 35 and the like, and when this deposit undergoes a decomposition reaction by heating to release gas, The oxygen gas partial pressure may be different from the target partial pressure. In such a case, since the oxygen concentration in the exhaust gas discharged through the exhaust pipe 70b changes, this change in concentration is detected by an oxygen concentration measuring device (not shown) provided in the middle of the exhaust pipe 70b. When the oxygen concentration decreases, the control means 82 increases the amount of oxygen gas sent to the CVD reactor 30 at a predetermined rate according to the shortage, and when the oxygen concentration increases, the control means 82 increases the predetermined amount according to the increase. At a rate, the control means 82 reduces the amount of oxygen gas sent to the CVD reactor 30. By such an action of the control means 82, the oxygen partial pressure in the reaction generation chamber 35 can be kept constant at all times, so that the CVD reaction can always occur at a constant oxygen partial pressure. Accordingly, a uniform oxide superconducting layer can be generated on the tape-shaped substrate 38.
Further, the control means 82 controls the oxygen partial pressure independently for each of the CVD units A, B, and C, and controls each source gas supply means 50 so as to maintain a predetermined oxygen partial pressure in each reaction generation chamber 35. Control. At this time, for example, the control means 82 is configured such that the oxygen partial pressure in the reaction generation chambers 35 and 35 of the respective CVD units A, B, and C is higher than the oxygen partial pressure in the reaction generation chamber 35 in the moving direction of the tape-shaped substrate T. The raw material gas supply means 50 are preferably controlled so that the partial pressure of oxygen in the reaction generation chamber 35 downstream in the moving direction of the tape-shaped substrate T is increased.
[0029]
In the oxide superconductor manufacturing apparatus of the present embodiment, the reactor 31 is provided with a plurality of reaction generation chambers 35, 35 in series in the moving direction of the tape-shaped substrate T, so that a plurality of CVD reactions are performed. Can be performed continuously. Further, since the boundary chamber 38 is provided between the reaction generation chambers 35 and 35 and the cutoff gas is supplied to the boundary chamber 38 by the cutoff gas supply means 38B, the reaction generation chambers 35 and 35 are shut off. Thus, thin film formation conditions such as the reaction gas concentration and oxygen partial pressure inside each reaction generation chamber 35 can be set independently, and each source gas supply means 50 can be controlled independently by the control means 82. Since the oxygen partial pressure in the raw material gas supplied to each of the reaction generation chambers 35 and 35 can be independently controlled, when an oxide superconductor is manufactured using this apparatus, While maintaining the CVD conditions such as different oxygen partial pressures on the tape-shaped substrate T moving in the reactor 31, a plurality of CVD reactions can be continuously performed.
Further, since the gas mixer 48 having the above-described configuration is provided immediately upstream of the reaction generation chamber 35 and the oxygen gas supply means 52 is connected immediately upstream of the gas mixer 48, the source gas is not required to be oxygen gas or the like during transportation. The possibility of reacting is reduced, and the raw material gas and oxygen gas supplied into the reaction generation chamber 35 are well mixed, and the possibility that the mixed state is not uniform is reduced. There is less risk of adverse effects such as non-uniform thin film formation.
[0030]
Further, in the gas exhaust mechanism 80 having the above configuration, since the gas exhaust ports 70e and 70f are located below the boundary chamber 38, the reaction generation chamber that discharges the blocking gas and is blocked by the boundary chamber 38 is provided. The unreacted gas and the like in 35 and 35 are discharged to the outside, and the film forming process can be performed without allowing the residual gas after the reaction to touch the substrate T for a long time.
[0031]
Therefore, according to the manufacturing apparatus and the manufacturing method of the oxide superconducting conductor of the present embodiment, the CVD reaction can be continuously performed by the plurality of reaction generation chambers 35 and 35, so that only one reaction generation chamber is manufactured. Compared to the case, the formation speed of the oxide superconducting thin film can be improved and the thickness of the oxide superconducting thin film to be formed can be improved. Further, the reaction state of the reaction gas is improved by the gas mixer 48, and the reaction product chamber 35 and the boundary chamber 38 are exhausted by the exhaust ports 70 e and 70 f below the boundary chamber 38. In addition, it is possible to reduce the mixing of unnecessary components and unnecessary gases that do not contribute to the film, and the film can be processed without allowing the residual gas after reaction to come into contact with the tape-shaped substrate T for a long period of time. Since the CVD reaction can be performed while controlling the flow state of gas such as source gas and oxygen gas in the length direction and width direction of the tape-shaped base material 38, the length direction of the tape-shaped base material T In addition, an oxide superconducting thin film having a uniform thickness distribution and composition in the width direction can be formed, and an oxide superconductor T1 excellent in superconducting characteristics such as critical current density can be efficiently manufactured.
[0032]
In the oxide superconductor manufacturing apparatus of the present embodiment, an apparatus having a configuration in which a horizontally long reactor is used and a reaction generation chamber is connected in a horizontal position has been described. However, a tape-like substrate moving in the reactor is described. If the gas flow state of the material can be controlled, the reactor may be a vertical type that is limited to a horizontal type, and the flow direction of the source gas may be a horizontal direction or an oblique direction that is limited to a vertical direction. Of course, the conveyance direction may be either the left-right direction or the vertical direction. In addition, the shape of the reactor itself is not limited to a cylindrical shape, and may be any shape such as a box shape, a container shape, and a spherical continuous shape.
The apparatus for manufacturing an oxide superconductor of the present invention can be suitably used for an apparatus for manufacturing an oxide superconductor. Moreover, the manufacturing method of the oxide superconductor of this invention can be used suitably for the manufacturing method of an oxide superconductor.
[0033]
Hereinafter, a second embodiment of an oxide superconducting conductor manufacturing apparatus and manufacturing method according to the present invention will be described with reference to the drawings.
[0034]
In the present embodiment shown in FIG. 8, the difference from the first embodiment shown in FIGS. 1 to 7 is that, in the raw material gas supply means 50 ′, the liquid raw material supply apparatus 100 has a cylindrical shape as shown in FIG. A raw material solution supply unit 102, a cylindrical and tapered atomized gas supply unit 103 provided to surround the outer periphery of the supply unit 102, and an outer periphery excluding the tip of the atomized gas supply unit 103 are provided. This is a triple structure generally composed of the cylindrical shield gas supply unit 104, and is that a heater 131 is provided outside the vaporizer 130.
[0035]
As shown in FIG. 8, the raw material solution supply unit 102 is supplied with a liquid raw material 111 fed from a raw liquid supply device 120 described later, and the supplied liquid raw material 111 is temporarily stored in the central portion. A liquid reservoir 105 is provided for the purpose of storage. The inner diameter of the liquid reservoir 105 is larger than the inner diameter of the upper and lower capillaries 102a of the raw material solution supply unit 102, and the liquid raw material 111 sent from the raw solution supply device 120 is continuously fed to the tip while collecting. . Further, a branch pipe 105 a is provided on the upper part of the liquid pool 105, and a filling gas supply source 105 b is connected to the branch pipe 105 a via a filling gas MFC (flow rate regulator) 105 c. Supply filling gas. Here, by supplying a filling gas such as argon gas, helium gas, nitrogen gas, etc., the pressure in the liquid pool 105 is maintained at a state close to atmospheric pressure.
[0036]
As shown in FIG. 8, the atomizing gas supply unit 103 is configured to supply atomizing gas for atomizing the liquid raw material 11 into the gap with the raw material solution supply unit 102. The atomizing gas used here is, for example, argon gas, helium gas, nitrogen gas, or the like. Further, an atomizing gas supply source 103 a is connected to the upper portion of the atomizing gas supply unit 103 via an atomizing gas MFC 103 b so that the atomizing gas can be supplied into the atomizing gas supply unit 103. In the liquid raw material supply apparatus 100 of this example, the nozzle 106 is constituted by the tip of the atomizing gas supply unit 103 and the tip of the raw material solution supply unit 102.
[0037]
As shown in FIG. 8, the shield gas supply unit 104 supplies a shield gas to a gap with the atomizing gas supply unit 103, and the atomizing gas supply unit 103 is cooled by the supply of the shielding gas and the nozzle 106. It is for shielding. Here, argon gas, helium gas, nitrogen gas, etc. are applied as the shielding gas. Further, a taper portion 107 protruding outward is provided at a portion below the central portion of the shield gas supply unit 104, and an upper portion of the shield gas supply unit 104 is provided via a shield gas MFC 104b. A shield gas supply source 104 a is connected, and the shield gas can be supplied into the shield gas supply unit 104.
[0038]
In the liquid raw material supply apparatus 100 having the above-described configuration, when the atomized gas is fed into the atomizing gas supply unit 103 at a constant flow rate and the liquid raw material 111 is fed into the raw material solution supply unit 102 at a constant flow rate, the liquid raw material 111 is stored in the liquid pool 105. As the atomized gas flows from the tip of the atomizing gas supply unit 103 outside the tip while reaching the tip of the raw material solution supply unit 102, the liquid source 111 is ejected at the tip of the nozzle 106 at the time of ejection. The atomized gas is immediately atomized, and a certain amount of mist-like liquid material 111 can be continuously supplied into the vaporizer 130.
The inside of the vaporizer 130 which is the tip portion of the nozzle 106 is depressurized to several Torr to several tens Torr, and the filling gas is supplied from the branch pipe 105 a to the liquid pool 105. Is kept in a state close to atmospheric pressure, and the liquid raw material 111 can be prevented from being vaporized in the liquid pool 105 or the capillary tube 102a.
Further, when the shielding gas flows from the tip of the upper shielding gas supply unit 104 outside the nozzle 106, the periphery of the nozzle 106 is shielded by the shielding gas, and the liquid raw material 111 is vaporized in the vaporizer 130. It is possible to prevent the deposited raw material gas from adhering to the nozzle 106 to be re-deposited as a solid raw material.
[0039]
As shown in FIG. 8, a raw solution supply device 120 is connected to a raw material solution supply unit 102 of such a liquid raw material supply device 100 via a connection pipe 121 including a liquid raw material MFC 121a. As the connecting pipe 121, 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 120 includes a storage container 122 and a pressurization source 123, and the liquid raw material 111 is stored inside the storage container 122. As the storage container 122, a glass bottle or the like having excellent chemical resistance is used. The pressurizing source 123 pressurizes the inside of the storage container 122 by supplying He gas or the like into the storage container 122 so that the liquid raw material 111 in the storage container 22 can be discharged to the connecting pipe 121 at a constant flow rate.
[0040]
The liquid raw material 111 stored in the storage container 122 is the same as that stored in the raw material solution tank 60 of FIG. 6 in the first embodiment.
[0041]
As shown in FIG. 8, a container-like vaporizer 130 is disposed below the liquid raw material supply apparatus 100, and the tip portion from the central portion of the liquid raw material supply apparatus 100 is accommodated in the vaporizer 130. The liquid raw material supply apparatus 100 and the vaporizer 130 are connected.
A heater 131 for heating the inside of the vaporizer 130 is attached to the outer peripheral portion of the vaporizer 130, and the mist-like liquid material 111 sprayed from the nozzle 106 by the heater 131 is brought to a desired temperature. It is heated and vaporized to obtain a raw material gas. The vaporizer 130 is connected to the reactor 30 via the supply pipe 53 and the gas mixer 48.
[0042]
Next, the source gas obtained by vaporizing the liquid source 111 is sent to the reaction generation chamber 35 using the oxide superconducting conductor manufacturing apparatus having the source gas supply means 50 ′ configured as described above. In 35, an oxide superconducting thin film is formed on the tape-shaped substrate T to produce an oxide superconducting conductor.
[0043]
The liquid raw material 111 is filled in the storage container 22, and the liquid raw material 111 is fed from the storage container 122 into the raw material solution supply unit 102 at a flow rate of about 0.1 to 1.0 ccm by the pressurization source 123 and the MFC 121 a and simultaneously atomized. The gas is fed into the atomizing gas supply unit 103 at a flow rate of about 200 to 300 ccm, and the shield gas is fed into the shield gas supply unit 104 at a flow rate of about 200 to 300 ccm. At this time, the temperature of the shielding gas is adjusted to be about room temperature. Further, the heater 131 is adjusted so that the internal temperature of the vaporizer 130 becomes the optimum temperature of the raw material having the highest vaporization temperature among the raw materials.
[0044]
Then, the liquid raw material 111 reaches the front end of the raw material solution supply unit 102 while accumulating in the liquid pool 105, and then is immediately atomized by the atomizing gas flowing from the atomizing gas supply unit 103 when blowing out from the nozzle 106. A mist-like liquid material 111 having a constant flow rate is continuously supplied into the vaporizer 130. The mist-like liquid raw material 111 supplied into the vaporizer 130 is heated and vaporized by the heater 131 to be a raw material gas, and this raw material gas is continuously supplied to the gas diffusion section 40 via the supply pipe 53. To be supplied. At this time, it is adjusted by the heating means so that the internal temperature of the supply pipe 53 becomes the optimum temperature of the raw material having the highest vaporization temperature among the raw materials. At this time, the operation of supplying the oxygen gas from the oxygen gas supply source 54 and mixing the source gas and the oxygen gas by the gas mixer 48 is also performed.
[0045]
Thereafter, the production of the oxide superconducting conductor in the CVD reactor 30 is performed in the same manner as in the first embodiment.
[0046]
In this embodiment, since the liquid raw material supply apparatus 100 having the above-described configuration is provided, the liquid raw material 111 is fed into the raw material solution supply unit 102 at a constant flow rate, and the atomized gas is fixed to the atomized gas supply unit 103. When fed at a flow rate, the liquid raw material 11 reaches the tip of the raw material solution supply unit 102 while accumulating in the liquid pool 105, and is immediately atomized by the atomizing gas flowing from the atomizing gas supply unit 103 when blowing out from the nozzle 106. A certain amount of mist liquid raw material 111 can be continuously supplied into the vaporizer 130. Further, the inside of the vaporizer 130 is depressurized to about several to tens of Torr, but since the filling gas is supplied from the branch pipe 105a to the liquid reservoir 105, the pressure in the liquid reservoir 105 is almost atmospheric pressure. It is possible to prevent the liquid raw material 111 from being vaporized in the liquid pool 105 or the capillary tube 102a. Further, since the periphery of the nozzle 106 is shielded by the shielding gas, it is possible to prevent the source gas from adhering to the nozzle 106 in the vaporizer 130 and being deposited as the liquid source 111.
[0047]
Therefore, according to the oxide superconducting conductor manufacturing apparatus of the present embodiment, the same effect as in the first embodiment is exhibited, and a certain amount of mist-like liquid material 111 is continuously stabilized in the vaporizer 130. Therefore, a certain amount of the source gas vaporized from the liquid source 111 can be continuously supplied to the reaction generation chamber 35, and the pressure and temperature of the reaction generation chamber 35 are less likely to fluctuate. A good oxide superconducting thin film having stable film quality and superconducting characteristics can be formed in the length direction of the substrate T.
Further, according to the manufacturing apparatus, since the liquid raw material 111 supplied into the vaporizer 130 is in a mist form, the vaporization efficiency is improved, so the supply speed of the liquid raw material 111 can be further increased, There is an advantage that the film forming efficiency is improved.
[0048]
Hereinafter, a third embodiment of an oxide superconducting conductor manufacturing apparatus and method according to the present invention will be described with reference to the drawings.
[0049]
The present embodiment shown in FIG. 9 differs from the first embodiment shown in FIGS. 1 to 7 in the raw material gas supply means 50 ″, in which the raw material solution supply device 230 is the liquid in the second embodiment shown in FIG. In the raw material supply apparatus 100, the structure is substantially the same except that the branch pipe 105a, the filling gas MFC (flow rate regulator) 105c, and the filling gas supply source 105b are not connected, and the raw material solution vaporizer 250 is provided.
[0050]
In the raw material solution supply device 230 configured as described above, when the raw material solution 111 is fed into the raw material solution supply unit 102 at a constant flow rate and the atomized gas is fed into the atomizing gas supply unit 103 at a constant flow rate, the raw material solution 111 is accumulated in the liquid pool 105. However, since the atomized gas flows from the tip of the atomizing gas supply unit 103 outside the tip, the raw material solution 111 is discharged from the outlet 237a of the nozzle 106. Thus, a certain amount of mist-like raw material can be continuously supplied into the vaporizer body 251 of the raw material solution vaporizer 250.
In addition, when the shielding gas is sent to the shielding gas supply unit 104 at a constant flow rate, the atomizing gas supply unit 103 and the raw material solution supply unit 102 are cooled, so that the raw material solution 111 flowing in the raw material solution supply unit 102 is also cooled. The raw material solution 111 can be prevented from being vaporized in the middle. Furthermore, since the shielding gas flows outside the nozzle 106 and from the tip of the upper shielding gas supply unit 104, the periphery of the nozzle 106 is shielded by the shielding gas, and the raw material solution is vaporized in the CVD raw material vaporizer. It is possible to prevent the source gas vaporized from 111 from adhering to the nozzle 106 to be re-deposited as a solid source.
[0051]
The raw solution supply device 120 is connected to the raw material solution supply unit 102 of such a raw material solution supply device 230.
On the other hand, a raw material solution vaporizer 250 is disposed below the raw material solution supply device 230.
The raw material solution vaporizer 250 includes a container-shaped vaporizer body 251 as shown in FIG. An attachment port 252 is formed in the upper part of the vaporizer body 251. The attachment port 252 is accommodated in the vaporizer body 251 from the central part of the raw material solution supply device 230 to the nozzle 106 at the front end portion of the raw material solution supply unit 251. A mist-like raw material solution 111 is sprayed into the vaporizer body 251 from the outlet 237a of the supply device 230.
[0052]
As shown in FIG. 9, a heater 253 is attached to the outside of the vaporizer body 251 as first heating means for heating the inside of the vaporizer body 251.
In addition, a second heating unit 254 is provided in the center of the vaporizer body 251 in front of the outlet 237a of the raw material solution supply apparatus 230 provided in the vaporizer body 251. The second heating means 254 is for vaporizing the mist-like raw material solution 111 sprayed from the blowout port 237a, and consists of an aggregate of a large number of masses 254a having a large heat capacity. Metals and ceramics that are inert to 111 and stable against oxidation and heat are used. For example, stainless steel balls, Hastelloy spheres, Ag spheres, Au spheres, and alumina spheres can be used. Among these, it is preferable to use a stainless steel ball from the viewpoint of low cost.
The shape of the lump 254a is not particularly limited, and may be a square block shape, a column shape, a cone shape, or the like other than a spherical shape. The size of the lump 254a is about 1 to 5 mm in diameter when it is spherical.
[0053]
Since the second heating means 254 has a large heat capacity, when the inside of the vaporizer body 251 is heated to a constant temperature equal to or higher than the vaporization temperature of the raw material solution 111 by the heater 253, the second heating means 254 is heated. Since 254 is also heated to a constant temperature equal to or higher than the vaporization temperature of the raw material solution 111, when the mist-like raw material solution 111 is sprayed from the outlet 237a of the raw material solution supply device 230, the mist-like raw material solution 111 is It immediately vaporizes upon contact with the heating means 253, and a raw material gas is obtained.
If such a second heating means 254 is not disposed in the vaporizer main body 51, when the supply speed of the mist-like raw material solution 111 supplied into the vaporizer main body 251 is increased, the raw material solution 111 is In addition to being unable to vaporize sufficiently, the vaporization efficiency cannot be improved so much, and it is difficult to form a good oxide superconducting thin film over a long period of time.
[0054]
The large number of lumps 254 a are accommodated in a tray 255. The tray 255 is preferably in a mesh shape so that the raw material gas obtained by the raw material solution 111 contacting the large number of lumps 254a can pass through and can be efficiently supplied to the CVD reactor 30. As the material of the tray 2255, a metal that is inert to the raw material solution 111 and is stable against oxidation and heat is used.
[0055]
Further, as shown in FIG. 9, the attachment port 252 of the vaporizer main body 251 is a cover that prevents the raw material gas from reaching the outlet 237 a of the raw material solution supply device 230 disposed in the vaporizer main body 251. 256 is provided. The cover 256 has a tubular shape having a distal end portion that spreads outward, and surrounds the central portion and the distal end portion of the raw material solution supply device 230 disposed in the vaporizer body 251. As the material of the cover 256, a metal that is inert to the raw material solution 111 and is stable against oxidation and heat is used.
In the present embodiment, since the outlet for taking out the source gas from the vaporizer body 251 to the CVD reactor 30 is small, a circulation vortex such as the source gas is formed in the vaporizer body 251 as indicated by the arrow in FIG. However, if the carver 256 as described above is not provided, the circulating vortex of the source gas may adhere to the outlet 237a and re-deposit as a solid source.
Such a raw material solution vaporizer 250 is connected to the CVD reactor 30 via a supply pipe 257.
As shown in FIG. 9, a heater 257 a is provided around the transport pipe 257 to prevent the source gas from being deposited as the source solution 111. An oxygen gas supply source 54 is branched and connected to a middle portion of the supply pipe 257 so that oxygen gas is supplied into the supply pipe 257 and a gas mixer 48 is connected so that the source gas and the oxygen gas can be mixed. It is configured.
[0056]
The raw material gas obtained by vaporizing the raw material solution 111 is sent to the reaction generation chamber 35 using the oxide superconducting conductor manufacturing apparatus including the raw material solution vaporizing apparatus 250 configured as in the present embodiment, and the same as in the first embodiment. Thus, an oxide superconducting thin film is formed on the tape-shaped substrate T in the reaction generation chamber 35 to produce an oxide superconducting conductor.
[0057]
The raw material solution 111 is fed from the storage container 122 into the raw material solution supply unit 102 at a flow rate of about 0.1 to 1.0 ccm by the pressurization source 123 and the MFC 121a, and at the same time, the atomized gas is supplied to the atomizing gas supply unit 103 at a flow rate of 200. While sending at about ~ 300 ccm, the shield gas is fed into the shield gas supply unit 104 at a flow rate of about 200 to 300 cc. At this time, the temperature of the shielding gas is adjusted to be about room temperature. Further, the heater 253 adjusts the internal temperature of the vaporizer body 251 of the raw material solution vaporizer 250 to 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 is also heated to a constant temperature within a range of about 200 to 300 ° C. suitable for vaporizing the raw material having the highest vaporization temperature.
[0058]
Then, the raw material solution 111 reaches the front end of the raw material solution supply unit 102 while accumulating in the liquid pool 105, and then is immediately atomized by the atomizing gas flowing from the atomizing gas supply unit 103 when the raw material solution 111 is blown out from the blowing port 237a. The mist-like raw material solution 111 having a constant flow rate is continuously supplied into the vaporizer body 251. And the mist-form raw material solution 111 sprayed in the vaporizer main body 251 from the blower outlet 237a contacts the 2nd heating means 254, and is immediately vaporized, and raw material gas is obtained. Further, the source gas is continuously supplied to the gas diffusion unit 40 via the supply pipe 257. At this time, the heater 257a is adjusted so that the internal temperature of the supply pipe 257 becomes the optimum temperature of the raw material having the highest vaporization temperature among the raw materials, and the gas mixer 48 is similarly adjusted to have the highest vaporization temperature of the raw materials. The temperature is adjusted by the extinction heater 48b so that the optimum temperature of the high raw material is reached. Further, an operation of supplying the oxygen gas from the oxygen gas supply source 54 and mixing the raw material gas and the oxygen gas by the gas mixer 48 is also performed.
[0059]
Next, in the same manner as in the first embodiment, the oxide superconducting thin film can be generated by reacting the raw material gas on the upper surface side of the heated tape-like substrate T.
By continuously performing the above film forming operation for a predetermined time, an oxide superconducting conductor T1 including a stable oxide superconducting thin film having a desired film quality on the base material T can be obtained.
[0060]
In the present embodiment, the same effect as that of the first embodiment is obtained, and the raw material solution vaporizer (raw material vaporization means) 250 having the above-described configuration is provided, so that an independent raw material solution supply apparatus (raw material supply means) is provided. Since the raw material solution 234 can be sequentially vaporized by feeding the mist-like raw material solution 234 into the vaporizer body 251 while controlling the supply amount from the outlet 237a of 230, the film formation rate control of the oxide superconducting thin film Therefore, a good oxide superconducting thin film can be formed over a long period of time.
In the raw material solution vaporizer 250, a heater 253 for heating the inside of the vaporizer main body 51 is provided outside the vaporizer main body 251, and the raw material solution supply provided in the vaporizer main body 251 is provided. Since the second heating means 254 is provided in front of the outlet 237a of the device 230, the heater 253 heats the inside of the vaporizer body 251 to a constant temperature equal to or higher than the vaporization temperature of the raw material solution 111. Since the means 254 can also be heated to a constant temperature equal to or higher than the vaporization temperature of the raw material solution 111, when the mist-like raw material solution 111 is sprayed from the outlet 237a of the raw material solution supply device 230, the mist-like raw material solution 111 is Since the vaporization immediately occurs upon contact with the second heating means 253, the vaporization efficiency is improved. Therefore, even if the supply speed of the raw material solution 111 is increased as compared with the conventional method, Since the solution 111 can be sufficiently vaporized, it is possible to improve the film-forming efficiency of the oxide superconducting thin film.
Furthermore, in the raw material solution vaporizer 250, when provided in the oxide superconductor manufacturing apparatus, the raw material solution 111 can be sufficiently vaporized as described above. By continuously supplying the mist-like raw material solution 111, the raw material gas can also be continuously supplied to the reaction generation chamber 35, so that conditions such as reaction pressure and temperature in the reaction generation chamber 35 vary. It becomes difficult to form a good oxide superconducting thin film having stable film quality and superconducting characteristics in the length direction of the tape-shaped substrate T.
Further, in the raw material solution vaporizer 250, the cover 256 is provided at the attachment port 252 of the vaporizer body 251, so that the raw material gas can be prevented from reaching the outlet 237a of the raw material solution supply device 230. Therefore, the circulating vortex of the raw material gas does not adhere to the nozzle 237 and re-deposit as a solid raw material, and it is possible to prevent liquid clogging and the like from occurring at the blowout port 237a, and continuously for a long time. Vapor deposition is possible.
Further, by using the raw material solution supply device 230 having the above-described configuration as the raw material solution means for supplying the raw material solution into the vaporizer main body 251, the mist-like raw material solution 111 is controlled in the vaporizer main body 251 while controlling the supply amount. A constant amount of mist-like raw material solution 234 can be continuously supplied.
[0061]
Hereinafter, a fourth embodiment of an apparatus and a method for manufacturing an oxide superconducting conductor according to the present invention will be described with reference to the drawings.
[0062]
In the present embodiment shown in FIG. 10, the difference from the first embodiment shown in FIGS. 1 to 7 is that, in the CVD reaction apparatus 30, the reactor 30 has a cubic shape instead of a cylindrical shape, and The shower nozzle 45a is provided.
[0063]
As shown in FIG. 10, a divergent truncated pyramid-shaped gas diffusion section 40 is attached to the ceiling of the reaction generation chamber 35 as in the first embodiment.
As shown in FIG. 10, the gas diffusion part 40 is composed mainly of a gas diffusion member 45 including trapezoidal side walls 41, 41, a front wall 42, a rear wall 43, and a ceiling wall 44. The plate-like shower nozzle 45a having the above-described raw material gas outlets 45b and a supply pipe 53 connected to the ceiling wall 44 are provided. The bottom surface of the gas diffusion member 45 is an elongated rectangular opening 46, and the gas diffusion member 45 communicates with the reaction generation chamber 35 through the opening 46.
In FIG. 10, the shower nozzle 45 a is provided with a large number of source gas ejection ports 45 b on a plate, and includes four sides of the shower nozzle 45 a, side walls 41, 41, a front wall 42, and a rear wall 43. The gas diffusion member 45 is fixed at an arbitrary position between the ceiling wall 44 and the reaction generation chamber 35 in contact therewith. The shower nozzle 45a is not limited to the above as long as it has two or more source gas outlets 45b. For example, it may be an engaging member in which a large number of wires are assembled vertically and horizontally with a certain interval.
[0064]
Next, when the thin film is formed on the tape-shaped substrate T using the CVD reactor 30 of the present embodiment, the source gas supply means 50 and the like are operated in the same manner as in the first embodiment.
In the CVD reaction apparatus 30, the source gas that has flowed from the outlet portion of the supply pipe 53 to the gas diffusion unit 40 reacts while diffusing along the ceiling wall 44, the front wall 42, and the rear wall 43 of the gas diffusion unit 40. It moves to the generation chamber 35 side and reaches the shower nozzle 45a. Since the shower nozzle 45a is fixed in contact with the side walls 41, 41, the front wall 42 and the rear wall 43 at any position between the ceiling wall 44 and the reaction generation chamber 35 as described above, the supply pipe The source gas that has moved from 53 passes through a number of source gas outlets 45b provided on the entire surface of the shower nozzle 45a. At this time, since the source gas is forcibly diffused over the entire surface of the shower nozzle 45a, the source gas is uniformly diffused over a wider range than in the case of the single-point concentrated slit nozzle. The raw material gas that has passed through the shower nozzle 45a passes through the inside of the reaction generation chamber 35 while further diffusing along the front wall 42 and the rear wall 43 of the gas diffusion section 40, and then moves so as to cross the substrate 35 up and down. By moving the gas exhaust holes 70a and 70a so as to be drawn, the raw material gas is reacted on the upper surface side of the heated tape-like substrate T to deposit reaction products.
[0065]
In the CVD reaction apparatus 30 of the present embodiment, the same effects as those of the first embodiment are obtained, and the source gas is uniformly distributed over a wide range in the reaction generation chamber 35 by the shower nozzle 45 a provided in the gas diffusion portion 40. Since the diffused source gas reacts on the upper surface side of the tape-shaped substrate T and the reaction product is deposited, the thickness and composition uniform in the width direction of the tape-shaped substrate T. Can be formed.
Further, since the source gas is uniformly diffused over a wide range in the reaction generation chamber 35 and reacts in the entire range on the upper surface side of the tape-shaped substrate T in the reaction generation chamber 35, the wide range A thin film can be generated across the surface, and the reaction efficiency of the raw material gas is increased, so that the generation speed of the thin film can be improved.
[0066]
Hereinafter, a fifth embodiment of an apparatus and a method for manufacturing an oxide superconducting conductor according to the present invention will be described with reference to the drawings.
[0067]
11 to 12 is different from the fourth embodiment shown in FIG. 10 in that the shower nozzle 45a is heated and kept at a predetermined temperature in the gas diffusion section 40 of the CVD reactor 30. The constant temperature mechanism 90 is provided.
[0068]
The constant temperature mechanism 90 shown in FIGS. 11 and 12 circulates a heated liquid medium in the vicinity of the shower nozzle 45a, conducts the heat of the medium to the shower nozzle 45a, and heats the shower nozzle 45a to a predetermined temperature. A heating circulation device 91 that heats and circulates the medium, a feed pipe 92 that feeds the heated medium to the vicinity of the shower nozzle 45a, and a feed pipe 92 that is in contact with the upper surface of the shower nozzle 45a and sent to the shower nozzle 45a. The heat exchanger 94 heats the shower nozzle 45 a by conducting the heat of the medium, and the return pipe 93 that sends the medium that has passed through the heat exchanger 94 to the heating circulation device 91.
The heat exchanger 94 is provided with a source gas passage hole 94a. This source gas passage hole 94a is provided so as to communicate with each of the source gas outlets 45b of the shower nozzle 45a, and the source gas supplied from the supply pipe 53 passes through the heat exchanger 94 and the shower nozzle 45a. It can pass through and be supplied to the reaction production chamber 35.
[0069]
The medium may be any liquid or gas, and for example, silicon oil, water (including water vapor) or the like is applied.
Here, the temperature of the shower nozzle 45a heated by the constant temperature mechanism 90 is set to be approximately equal to or lower than the temperature at which the raw material having the highest vaporization temperature among the raw materials becomes the optimum temperature.
[0070]
According to the above-described CVD reaction apparatus 30, since the shower nozzle 45a is heated to a predetermined temperature by the constant temperature mechanism 90, the source gas does not react and accumulate at the source gas outlet 45b, and the source gas outlet. Since clogging of 45b is prevented, the source gas can be stably supplied toward the reaction generation chamber 35.
The constant temperature mechanism 90 is not limited to the one described above, and any means may be used as long as it can heat the shower nozzle 45a. For example, instead of heating with a medium, a current is supplied to the resistor. It may be a means by Joule heat obtained by flowing.
[0071]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited only to these Examples.
(Example)
Y₁Ba₂Cu_ThreeO_7-xAs a raw material solution for CVD, Ba-bis-2,2,6,6-tetramethyl-3,5-heptanedione-bis-1, 10-phenanthroline (Ba (thd)₂(Phen)₂) And Y (thd)₂And Cu (thd)₂Was used. Each of these is mixed at a molar ratio of Y: Ba: Cu = 1.0: 1.9: 2.7, and added to a tetrahydrofuran (THF) solvent so as to be 3.0% by weight. It was set as the solution.
[0072]
The base tape is a kind of Ni alloy, Hastelloy C276 (trade name of Haynes Stellite Co., USA, Cr 14.5 to 16.5%, Mo 15.0 to 17.0%, Co 2.5% or less, W3.0-4.5%, Fe4.0-7.0%, C0.02% or less, Mn1.0% or less, composition of balance Ni) 100 mm in length, 10 mm in width, 0.2 mm in thickness Hastelloy tape is mirror-finished, and 0.5 μm thick YSZ (YSZ (Y₂O_ThreeStabilized zirconia) In-plane oriented interlayer film was used.
[0073]
Next, the CVD unit A, B, and C shown in FIG. 1 are manufactured as shown in FIG. 1 so that the quartz-made CVD reactor 30 having the structure shown in FIGS. The oxygen partial pressure in the reaction generation chamber 35 is independently controlled by the oxygen concentration measuring device under the following conditions using the apparatus incorporated in the reactor 31 and the gas in the reactor 31 is discharged from the exhaust port of the gas exhaust mechanism 80. 70c is evacuated and each valve 70d is adjusted to control the flow of the raw material gas in the length direction and width direction of the base tape T moving through the base material transport region R, thereby performing continuous vapor deposition. Y of 30 cm in length and 1 cm in width on the YSZ in-plane intermediate film using beam-assisted sputtering₁Ba₂Cu_ThreeO_7-xAn oxide superconducting thin film having the following composition was formed.
Gas vaporizer temperature; 230 ° C
Feed rate of raw material solution; 0.2 ml / min
Movement speed of base tape in CVD reactor: 1 m / hour
Base tape heating temperature: 800 ° C
Pressure in reactor 31; 5 Toor
Oxygen gas flow rate from oxygen gas supply source; 45-55 ccm
CVD unit A oxygen partial pressure; 1.5 Torr
CVD unit B oxygen partial pressure; 1.6 Torr
CVD unit C partial pressure of oxygen; 1.7 Torr
[0074]
(Comparative Example 1)
Under the same conditions as in the example, only the oxygen partial pressure was set to the following conditions to form a similar oxide superconducting conductor thin film.
CVD unit A oxygen partial pressure; 1.5 Torr
CVD unit B oxygen partial pressure; 1.5 Torr
CVD unit C oxygen partial pressure; 1.5 Torr
[0075]
(Comparative Example 2)
As in Comparative Example 1, the oxygen partial pressure was set to the following conditions, and an oxide superconducting conductor thin film was formed using only the one-stage reaction generation chamber 35.
CVD unit oxygen partial pressure; 1.5 Torr
[0076]
(Comparative Example 3)
An oxide superconducting thin film was formed using an apparatus in which the gas mixer 48 was not provided in the quartz CVD reactor 30 having the structure shown in FIGS.
[0077]
(Comparative Example 4)
The oxide superconducting conductor thin film was formed using the apparatus in which the cutoff gas supply means 38B was not operated in the quartz CVD reactor 30 having the structure shown in FIGS.
[0078]
In the oxide superconducting conductor obtained in the above example and the oxide superconducting conductor obtained in Comparative Examples 1 to 4, an Ag stabilizing layer having a thickness of 10 μm is formed by sputtering on the surface where the oxide superconducting thin film is laminated. Then, an Ag electrode was formed on the surface of the Ag stabilizing layer, and after the Ag coating, a heat treatment was performed at 500 ° C. for 2 hours in a pure oxygen atmosphere to obtain a measurement material, and a measurement experiment was performed under the following conditions.
External magnetic field: 0T
Temperature: 77K
[0079]
The results of measuring the thicknesses and critical current values of the oxide superconductor thin films of the oxide superconductors obtained in Examples and Comparative Examples 1 to 4 are shown below.

Here, Ic is a critical current value, and Jc is a critical current density.
[0080]
From the above results, by independently controlling the oxygen partial pressures in the three reaction product chambers and increasing the oxygen partial pressure in three stages, the film thickness is three times that in the case of forming in one reaction product chamber. 3 times the critical current value Ic was obtained. On the other hand, when the oxygen partial pressures in the three reaction production chambers were set to be equal, the film thickness was three times that in the case where the reaction reaction chambers were formed, but the critical current was about 1.5 times greater. Only stayed to obtain the value Ic.
Further, when the raw material gas and oxygen gas are mixed and supplied to the reaction generation chamber by the gas mixer, the thickness is 1.1 times that of the case without the gas mixer, J_CIt was found to be 1.4 times.
In addition, when the shut-off gas is supplied to the boundary chamber by the shut-off gas supply means, and the gas conditions in each reaction generation chamber are strictly independent, the thickness is 1.5 times that in the case of no shut-off gas. , J_CIt was found to be 1.6 times.
[0081]
From the above, n stages of reaction generation chambers are provided in series (n is a natural number), and the CVD reaction is continuously performed, so that n times the oxide superconductivity compared to the case of manufacturing only one reaction generation chamber. The formation speed of the thin film and the n-fold oxide superconducting thin film thickness can be obtained.
In addition, the state of gas such as source gas and oxygen gas in the reaction generation chamber is improved by improving the supply state of the reaction gas with the gas mixer and exhausting the reaction generation chamber and the boundary chamber with the exhaust port below the boundary chamber. Since the CVD reaction can be carried out while independently controlling the film, it is possible to form an oxide superconducting thin film with a uniform tape-like substrate thickness distribution and composition, and excellent superconducting properties such as critical current density It turns out that an oxide superconductor can be manufactured efficiently.
[0082]
【The invention's effect】
The oxide superconducting conductor manufacturing apparatus and manufacturing method of the present invention have the following effects.
(1) By arranging a plurality of reaction production chambers in series and independently controlling the gas conditions such as the raw material gas concentration and the oxygen partial pressure in each reaction production chamber, the formation speed of the oxide superconducting thin film is improved, The thickness of the oxide superconducting thin film to be formed can be improved.
(2) The reaction gas is improved by improving the mixed state of the raw material gas and the oxygen gas by the gas mixer, and supplying the cutoff gas to the boundary chamber to eliminate the interference of the gas state between the nuclear reaction generation chambers. The supply state can be improved.
(3) An oxide superconducting thin film having a uniform thickness distribution and composition can be formed by improving the supply state of the reaction gas.
(4) As described above, an oxide superconductor having excellent superconducting characteristics can be efficiently produced.
[Brief description of the drawings]
FIG. 1 is a diagram illustrating an overall configuration of an oxide superconductor manufacturing apparatus according to a first embodiment of an oxide superconductor manufacturing apparatus and a manufacturing method according to the present invention.
2 is a perspective view showing an example of the structure of a CVD reaction apparatus provided in the oxide superconductor manufacturing apparatus of FIG. 1; FIG.
FIG. 3 is a side sectional view showing a detailed structure of the CVD reaction apparatus shown in FIG.
4 is a front sectional view showing a detailed structure of the CVD reactor shown in FIG. 2. FIG.
5 is a plan view showing a detailed structure of the CVD reactor shown in FIG.
6 is a view showing a raw material gas supply means and a reaction generation chamber shown in FIG. 1. FIG.
7 is a cross-sectional view showing the gas mixer shown in FIG. 1. FIG.
FIG. 8 is a view showing source gas supply means and a reaction generation chamber in the oxide superconductor manufacturing apparatus according to the second embodiment of the present invention.
FIG. 9 is a view showing a raw material gas supply means and a reaction generation chamber in the oxide superconductor manufacturing apparatus according to the third embodiment of the present invention.
FIG. 10 is a perspective view showing a detailed structure of a reaction generation chamber and a shower nozzle in an oxide superconductor manufacturing apparatus according to a fourth embodiment of the present invention.
FIG. 11 is a diagram showing a reaction generation chamber, a shower nozzle, and a constant temperature mechanism in an oxide superconductor manufacturing apparatus according to a fifth embodiment of the present invention.
12 is a front sectional view showing a reaction generation chamber, a shower nozzle, and a thermostatic mechanism shown in FIG.
FIG. 13 is a diagram showing an example of a method for forming a thin film on the surface of a chip-like substrate using a conventional CVD reactor.
FIG. 14 is a diagram showing another example of a method for forming a thin film on the surface of a chip-like substrate using a conventional CVD reactor.
FIG. 15 is a cross-sectional view showing the detailed structure of a conventional CVD reactor for forming an oxide superconducting thin film on the surface of a long substrate.
16 is a plan view showing a detailed structure of the CVD reactor of FIG.
[Explanation of symbols]
A, B, C: CVD unit, T: base material, 30 ... CVD reactor, 31 ... reactor, 38 ... boundary chamber, 38B ... shutoff gas supply means, 48 ... gas mixer, 50 ... source gas supply means, 52 ... oxygen Gas supply means, 54 ... oxygen gas flow rate adjustment mechanism, 70b ... exhaust pipe, 70c, 70e, 70f ... exhaust port, 70d ... valve (flow rate adjustment mechanism), 71 ... vacuum pump, 72 ... pressure adjustment device, 80 ... gas exhaust Mechanism, 82 ... control means, T1 ... oxide superconductor.

Claims (6)

A reactor that performs a CVD reaction in which a raw material gas of an oxide superconductor is chemically reacted to the surface of a moving tape-like substrate to deposit an oxide superconducting thin film; and a raw material gas supply means that supplies the raw material gas to the reactor; In the oxide superconductor manufacturing apparatus comprising a gas exhaust means for exhausting the gas in the reactor and a control means for controlling these,
The reactor is divided into a base material introduction part, a reaction generation chamber, and a base material lead-out part via partition walls, and a plurality of the reaction generation chambers are provided in series in the moving direction of the tape-shaped base material. Boundary chambers are provided between the reaction generation chambers through partition walls, and base material passage holes are formed in each partition wall, and a base material introduction portion, a reaction generation chamber, a boundary chamber, and a base material outlet portion are provided inside the reactor. A base material conveyance region is formed, and
The source gas supply means comprises a source gas supply source and oxygen gas supply means for supplying oxygen gas, and is provided for each reaction generation chamber of the reactor,
The boundary chamber is connected to a cutoff gas supply means for supplying a cutoff gas for blocking the reaction generation chambers on both sides,
The gas exhaust means is provided in the reactor along a length direction and a width direction of the tape-shaped base material, and a plurality of exhaust pipes each provided with a flow rate adjusting mechanism for adjusting a gas exhaust amount. The exhaust ports of the plurality of exhaust pipes, wherein the exhaust port is upstream of a partition partitioning the base material introducing portion and the reaction generating chamber, and the reaction generating chamber and the base material outlet portion. Are located across the partition walls on both sides of the boundary chamber,
An apparatus for producing an oxide superconducting conductor, wherein the control means can control the flow state of the gas in the length direction and the width direction of the tape-like base material moving in the reactor. .    2. The oxide superconducting conductor manufacturing apparatus according to claim 1, wherein the raw material gas supply means includes a gas mixer which is provided immediately upstream of the reactor and mixes the raw material gas and the oxygen gas. .    2. The raw material gas supply means can be controlled independently by the control means, and the oxygen partial pressure in the raw material gas supplied to each reaction generation chamber can be controlled independently. Production equipment for oxide superconducting conductors.    When manufacturing the oxide superconductor using the manufacturing apparatus according to claim 1, the barrier gas supply means supplies a barrier gas for blocking the reaction generation chambers on both sides to the boundary chamber, A method for producing an oxide superconducting conductor, comprising producing an independent atmosphere.    5. The raw material gas supply means can be controlled independently by the control means, and the oxygen partial pressure in the raw material gas supplied to each reaction generation chamber can be controlled independently. Manufacturing method of oxide superconducting conductor. A reactor that performs a CVD reaction in which a raw material gas of an oxide superconductor is chemically reacted to the surface of a moving tape-like substrate to deposit an oxide superconducting thin film; and a raw material gas supply means that supplies the raw material gas to the reactor; In the oxide superconductor manufacturing apparatus comprising a gas exhaust means for exhausting the gas in the reactor and a control means for controlling these,
The reactor is divided into a base material introduction part, a reaction generation chamber, and a base material lead-out part via partition walls, and a plurality of the reaction generation chambers are provided in series in the moving direction of the tape-shaped base material. A base material is provided between the reaction generation chambers, a base material passage hole is formed in each partition wall, and the base material passes through the base material introduction section, the reaction generation chamber, the boundary chamber, and the base material outlet section inside the reactor. A transfer area is formed,
The source gas supply means comprises a source gas supply source and oxygen gas supply means for supplying oxygen gas, and is provided for each reaction generation chamber of the reactor,
The boundary chamber is connected to a shutoff gas supply means for supplying a shutoff gas for shutting off reaction reaction chambers on both sides, and the control means can control the flow state of the gas in the reactor. When manufacturing an oxide superconductor using an oxide superconductor manufacturing apparatus,
By supplying the shut-off gas for shutting off the reaction generation chambers on both sides to the boundary chamber by the shut-off gas supply means, and manufacturing each reaction generation chamber as an independent atmosphere,
Each source gas supply means can be controlled independently by the control means, and the oxygen partial pressure in the source gas supplied to each reaction generation chamber can be controlled independently.
Oxide superconductivity characterized in that the oxygen partial pressure in the reaction generation chamber downstream in the direction of movement of the tape-shaped substrate is set higher than the oxygen partial pressure in the reaction generation chamber upstream in the direction of movement of the tape-shaped substrate. A method for producing a conductor.

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