JPH0544043A - Cvd reactor - Google Patents

Abstract

PURPOSE:To prevent undulations on a formed film surface and cracks from occurring by providing a preheating zone and a slow cooling zone on the front side and the rear side of a reaction zone where the product is deposited on the surface of a substrate respectively and by feeding inert gas to both the zones. CONSTITUTION:A reaction chamber 22 is divided in three: a reaction zone 25a where a substrate 32 is heated to a reaction temp. at which feed gas is given chemical reaction to deposit the product on the surface of the substrate 32; a preheating zone 25b where the substrate 32 is gradually heated provided on the front side of the reaction zone 25a; and a slow cooling zone 25c where the substrate 32 is gradually cooled, provided on the rear side of the reaction zone 25a. Partition plates 27 prevent the atmospheres of three zones from being mixed, and inert gas is fed to the preheating zone 25b and the slow cooling zone 25c, causing the temp. change of the substrate 32 to be relaxed, preventing undulations on the formed film surface of the substrate 32 and cracks on the thin film vapor-deposited on the substrate 32 from occurring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a CVD reactor used when a coating layer is formed on a substrate by a chemical vapor deposition method (CVD method). More specifically, the present invention relates to a superconducting magnet coil and electric power. The present invention relates to a CVD reactor used when a long oxide superconductor, which is being applied and developed for transportation, is manufactured by the CVD method.

[0002]

2. Description of the Related Art Conventionally, when a long oxide superconductor is manufactured by a CVD method, for example, a CVD reaction apparatus using a horizontally long reaction chamber as shown in FIG. 2 is used. The CVD reaction apparatus 1 includes a horizontally long reaction chamber 2, a source gas supply device 3, an exhaust pump 4, a substrate heater 5, and a substrate transfer device 6 as main components.

A raw material gas supply port 7 is formed at one end on the lower side of the reaction chamber 2, and the raw material gas supply port 7 is formed.
Is the source gas supply device 3 through the source gas supply pipe 8.
Connected with. A gas exhaust port 9 is formed at the other end of the reaction chamber 2 on the lower side, and the gas exhaust port 9 is connected to an exhaust pump 4 through a gas exhaust pipe 10.

The long substrate 1 in the reaction chamber 2 is also used.
1 is moved by the substrate transfer device 6 in the direction of the arrow in the figure and is fed. Further, a substrate heater 5 is further provided in the lower part of the chamber 2 so that the long substrate 11 fed into the reaction chamber 2 can be heated.

In order to fabricate a long SC body using the above-mentioned conventional CVD reaction apparatus 1, a long substrate 11 is fed into the reaction chamber 2 by the substrate transfer apparatus 6, and the source gas supply pipe 8 is further connected. A raw material gas is introduced into the chamber 2 from the raw material gas supply device 3 via the raw material gas supply apparatus 3 and the inside of the reaction chamber 2 is set to a predetermined raw material gas atmosphere. Immediately thereafter, the long substrate 11 in the chamber 2 is immediately heated by the substrate heater 6 to deposit the SC layer on the surface of the long substrate 11, and thereby the SC layer is formed.
The body can be made.

[0006]

However, when the conventional CVD reactor 1 is used, the long substrate 11 is
Upon being introduced into the inlet A of the reaction chamber 2, it is rapidly heated at a high temperature, and when it is carried out of the outlet B, it is rapidly cooled by the outside air.
A sudden temperature change is caused at the inlet and the outlet, and severe stress such as expansion or contraction due to the abrupt temperature change is applied. Therefore, there is a problem that "warping" or "bending" occurs in the substrate due to this, and there is a possibility that the film-forming surface of the substrate may be uneven.

The present invention has been made in view of the above circumstances, and an SC layer vapor-deposited on a long substrate at the time of introducing the long substrate into the reaction chamber and carrying it out of the reaction chamber. By slowing down the temperature change that occurs in the
A CV capable of reducing stress such as expansion or contraction generated in a layer and efficiently forming a CVD vapor deposition layer having a uniform and stable composition on this long substrate.
It is intended to provide a D reactor.

[0008]

Means for Solving the Problems The above problem is to provide a horizontally elongated reaction chamber for performing a CVD reaction in which a source gas such as a source compound gas is chemically reacted to deposit a product on the surface of a substrate, and a source material in the reaction chamber. Source gas supply means for supplying gas, gas exhaust means for exhausting gas in the reaction chamber, substrate moving means for moving a long substrate to one side along the longitudinal direction of the reaction chamber, and the reaction A CVD reactor provided with a horizontally-long heating means arranged in a chamber, wherein the heating means chemically reacts the raw material gas to deposit a product on the surface of the base material at a reaction temperature. A reaction region for heating the substrate, a preheating region provided on the front side of the reaction region in the moving direction of the substrate to gradually heat the substrate to reach the reaction temperature before the substrate reaches the reaction region, and the reaction region. A slow cooling region which is provided on the rear side of the substrate in the moving direction of the substrate and gradually cools the substrate heated to the reaction temperature, and a shielding means is provided in the reaction chamber in proximity to both ends of the reaction region, The problem can be solved by dividing the inside of the reaction chamber into a reaction part, a preheating part, and a slow cooling part, and providing an inert gas supply means for feeding an inert gas into the preheating part and the slow cooling part. ..

[0009]

As described above, in the CVD reaction apparatus of the present invention, the heating means is a reaction region for heating the substrate to a reaction temperature at which the raw material gas is chemically reacted to deposit the product on the surface of the substrate. And a preheating region that is provided on the front side of the reaction region in the moving direction of the substrate, and that gradually heats the substrate so that the substrate reaches the reaction temperature before reaching the reaction region,
When the substrate is introduced into the reaction region in the reaction chamber, it is provided on the rear side of the reaction region in the substrate moving direction and has a slow cooling region for gradually cooling the substrate heated to the reaction temperature. Alternatively, the temperature change that occurs in the substrate when it is carried out from the reaction region can be made gradual, and as a result, expansion or contraction that occurs in the substrate or the thin film deposited on the substrate due to this temperature change, etc. Stress is reduced.

Further, a shielding means is provided in the reaction chamber in the vicinity of both ends of the reaction region, the reaction chamber is divided into a reaction section, a preheating section and a slow cooling section, and the preheating section and the slow cooling section are provided. Since the inert gas supply means for feeding the inert gas is provided in the section, the raw material gas is supplied only to the reaction section, and the inert gas is supplied to the preheating section and the slow cooling section.
For this reason, since a film is not formed on a region such as a preheating region and a gradual cooling region, which are insufficient heating conditions where a good thin film cannot be obtained, a defective thin film is not formed on the substrate.

[0011]

The present invention will be described in detail below with reference to examples. FIG. 1 shows an embodiment of a CVD reaction apparatus of the present invention, in which reference numeral 21 is a CVD reaction apparatus. The CVD reactor 21 includes a horizontally long reaction chamber 22,
The raw material gas supply device 23, the exhaust pump 24, the substrate heating device 25, and the substrate transfer device 26 are provided as main components.

The reaction chamber 22 is provided with two partition members 27, 27 provided therein, and a reaction section 22a located at the center of the reaction chamber 22 in the longitudinal direction and a front side of the reaction section 22a in the substrate moving direction. Preheating part 2 located on the side
2b and a slow cooling part 22c located on the rear side of the reaction part 22a in the substrate moving direction. Further, a raw material gas diffusion portion 28, which is narrowed upward and connected to the raw material gas supply means 23 at the top thereof, is formed in the upper portion of the reaction portion 22a, and the upper portion of the preheating portion 22b and the slow cooling portion 22 are formed.
An inert gas supply device 29 is connected to the upper part of c. Further, two gas discharge ports 30, 30 are formed immediately below the lower ends of the two partition members 27, 27, and these two gas discharge ports 30, 30 are connected to the exhaust pump 24 through a gas discharge pipe 31. Has been done.

Long substrate 32 in the reaction chamber 22
Is moved in the direction of the arrow in the figure by the substrate transfer device 26, and moves in the reaction chamber 22 from the preheating section 22b to the reaction section 2
2a-> the slow cooling part 22c is passed in this order.
In addition, a preheating unit 22 is provided in the lower portion of the chamber 22.
A long substrate 32 is provided with a substrate heating device 25 extending from b to the slow cooling unit 22c and fed into the reaction chamber 22.
It can be heated.

The substrate heating device 25 includes a horizontally long heat conduction plate 33, a heater 34 for heating the central portion of the heat conduction plate 33, and coolers 35, 35 for cooling both ends of the heat conduction plate 33. , And a temperature controller 36 for controlling the heater 34 and the coolers 35, 35.

Further, the substrate heating device 25 having the above structure
Is a reaction region 25a that heats the long substrate 32 at a reaction temperature when the raw material gas is chemically reacted in the reaction unit 22a to deposit a product on the surface of the long substrate 32, and in the preheating unit 22b, The long substrate 30 is the reaction part 22a.
A preheating region 25b for gradually heating the long substrate 32 so as to reach the above-mentioned reaction temperature before reaching the reaction region 25a therein.
And a slow cooling region 25c for slow cooling the long substrate 32 heated to the reaction temperature in the slow cooling section 25c.

As described above, in the CVD reaction apparatus 21 of this example, the substrate heating apparatus 25 is set to a long reaction temperature at which the raw material gas is chemically reacted to deposit the product on the surface of the long substrate 32. A reaction region 25a for heating the substrate 32 and a long substrate 32 which is provided on the front side of the reaction region 25a in the substrate moving direction and gradually reaches the reaction temperature until the long substrate 32 reaches the reaction region 25a. Since the preheating region 25b for heating and the slow cooling region 25c provided on the rear side of the reaction region 25a in the substrate moving direction for gradually cooling the long substrate 32 heated to the reaction temperature are provided, When the substrate 32 is introduced into the reaction region 25a in the reaction chamber 22 or is carried out from the reaction region 25a, the temperature change occurring in the long substrate 32 can be moderated. Due to the temperature change long substrate 32
Alternatively, stress such as expansion or contraction generated in the thin film deposited on the long substrate 32 is reduced. Therefore,
It is possible to suppress the occurrence of undulations on the film formation surface of the substrate and the generation of cracks in the thin film deposited on the substrate, which are caused by these stresses. In addition, the slow cooling unit 2
By introducing O ₂ gas into the region 2c and performing in-situ oxygen treatment, a more excellent superconducting tape can be obtained.

Further, partition members 27, 27 are provided in the reaction chamber 22 in proximity to both ends of the reaction region 25a,
The inside of the reaction chamber 22 is divided into a reaction part 22a, a preheating part 22b and a slow cooling part 22c, and the preheating part 22b and the slow cooling part 2 are divided.
Inert gas supply device 29 for feeding an inert gas into 2c
Since the structure is provided, the raw material gas is supplied only to the reaction part 22a, and the inert gas is supplied to the preheating part 22b and the slow cooling part 22c. For this reason, since a film is not formed on regions such as the preheating region 25b and the slow cooling region 25c, which are insufficient heating conditions in which a good thin film cannot be obtained, a defective thin film is formed on the long substrate 32. Inconveniences such as being caused are prevented.

In order to manufacture a long SC body using the CVD reactor 21 of the present embodiment, first, the SC body is introduced from the source gas supply device 23 into the reaction section 22a through the source gas diffusion section 27. At the same time that the source gas is introduced, an inert gas supply device 29 supplies an inert gas such as argon into the preheating section 22b and the slow cooling section 22c. Further, the exhaust pump 24 exhausts the reaction residual gas in the reaction part 22a and the inert gas in the preheating part 22b and the slow cooling part 22c from the two gas outlets 30, 30 on the lower side of the chamber 22. At this time, the inside of the reaction section 22a is in a uniform SC body material gas atmosphere, and the preheating section 22b and the gradual cooling section 22c.
The inside is an inert gas atmosphere.

Next, the long substrate 32 is fed into the reaction chamber 22, and the preheating section 22b → reaction section 22a → slow cooling section 22c.
Pass through each part in order. First, the long substrate 32 that has entered the preheating section 22b in the inert gas atmosphere is first moved to the long substrate 32 by the preheating region 25a of the substrate heating device 25.
The part that is being heated by the preheating part 22b and the reaction part 22
It is gradually heated to reach the CVD reaction temperature until the boundary of a is reached. Subsequently, the long substrate 32 inserted into the reaction part 22a in the source gas atmosphere is subjected to CV by the reaction region 25a of the substrate heating device 25 before reaching the next slow cooling part 22c.
The SC body material gas, which is continuously heated at the reaction temperature D, reacts on the heated long substrate 32, and the long substrate 3
An SC layer is deposited on top of 2. Further, the long substrate 32 on which the SC layer is deposited is sent to the slow cooling unit 22c and is gradually cooled by the slow cooling region 25c of the substrate heating device 25.

A suitable SC body material for producing an SC body using the CVD reactor according to the present invention is, for example, a Y-Ba-Cu-O-based SC body prepared by using Y- Bis-2,2,6,6-tetramethyl-3,5-heptanedionate (abbreviation: Y (DPM) ₃ ) and Ba-bis-2,2,6,6
-Tetramethyl-3,5-heptanedionate (abbreviation: Ba)
(DPM) ₂ ) and Cu-bis-2,2,6,6-tetramethyl-3,5-
SC body raw materials such as heptane dionate (abbreviation: Cu (DPM) ₂ ) are suitable.

(Experimental Example 1) An SC body was produced by using the CVD reactor 21 of the above-mentioned embodiment. First, from the source gas supply device 23, Y (DPM) ₃ , B is introduced into the reaction part 22a.
The SC body material gas composed of a (DPM) ₂ and Cu (DPM) ₂ was introduced, and the inert gas supply device 29 supplied the argon gas into the preheating section 22b and the slow cooling section 22c. At the same time, the gas in the reaction part 22a and the gas in the preheating part 22b and the slow cooling part 22c are exhausted from the two gas outlets 30, 30 at a predetermined speed by the exhaust pump 24, and the inside of the reaction part 22a is made into a raw material gas atmosphere, The inside of the preheating part 22b and the slow cooling part 22c was made into an argon gas atmosphere. Next, according to the above-mentioned operation, the length is 1 m, the width is 5 mm, and the thickness is 0.1.
mm long Hastelloy C-276 was passed in the order of preheating section 22b → reaction section 22a → slow cooling section 22c to prepare an SC body in which an SC layer was vapor-deposited on the above long Hastelloy. The moving speed of the Hastelloy is 1 m / h, and
The heating temperature of the heater 34 of the substrate heating device 25 was set to 850 ° C., and the cooling temperature of the cooling devices 35 and 35 was set to 30.

By the above operation, a long SC having a Y-Ba-Cu-O system SC layer formed on a long Hastelloy substrate.
The body was made. Also, the SC layer of the obtained long SC body is
When the SC film composition was examined by X-ray diffraction at a film thickness of about 10 μm, the composition was uniform. Also, the critical temperature of the long SC body is 85 K or higher,
The critical current density is 5000 A / cm ² (at 77K, 0
T).

[0023]

As described above, in the CVD reactor of the present invention, the heating means heats the substrate to a reaction temperature at which the raw material gas is chemically reacted to deposit the product on the surface of the substrate. Reaction region, a preheating region provided on the front side of the reaction region in the moving direction of the substrate, and a preheating region for gradually heating the substrate so that the substrate reaches the reaction temperature before reaching the reaction region, and the substrate of the reaction region. Provided on the rear side in the moving direction,
Since the structure is provided with a slow cooling region for gradually cooling the substrate heated to the reaction temperature, when the substrate is introduced into the reaction region in the reaction chamber or is carried out from the reaction region, The temperature change that occurs can be moderated, and this reduces the stress such as expansion or contraction that occurs in the substrate or the thin film deposited on the substrate due to this temperature change. Therefore, it is possible to suppress the occurrence of undulations on the film formation surface of the substrate and the generation of cracks in the thin film deposited on the substrate, which are caused by the above-mentioned stress. For example, using the CVD reactor of the present invention, SC
When the body is manufactured, a high-quality SC body having a high critical current density and a high critical temperature can be obtained.

Further, a shielding means is provided in the reaction chamber in the vicinity of both ends of the reaction region, the reaction chamber is divided into a reaction section, a preheating section and a slow cooling section, and the preheating section and the slow cooling section are provided. Since the inert gas supply means for feeding the inert gas is provided in the section, the raw material gas is supplied only to the reaction section, and the inert gas is supplied to the preheating section and the slow cooling section.
For this reason, since a film is not formed on a region such as a preheating region and a gradual cooling region, which is an insufficient heating condition where a good thin film cannot be obtained, there is a problem that a defective thin film is formed on the substrate. Is prevented. Thus, for example, the CVD of the present invention
When an SC body is produced using a reactor, the critical current density,
A good quality SC body with a high critical temperature can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing an embodiment of a CVD reaction apparatus of the present invention.

FIG. 2 is a diagram showing a first example of a conventional CVD reactor.

[Explanation of symbols]

21 ... CVD reactor, 22 ... Reaction chamber, 22a ...
Reaction part, 22b preheating part, 22c ... slow cooling part, 23 ... raw material gas supply device, 24 ... exhaust pump, 25 ... substrate heating device,
25a ... Reaction region, 25b ... Preheating region, 25c ... Slow cooling region, 26 ... Substrate transfer device, 27 ... Partition member, 29 ... Inert gas supply device, 32 ... Long substrate

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location H01L 39/24 ZAA B 8728-4M // H01B 12/06 ZAA 8936-5G H01L 21/31 B 8518 -4M (72) Inventor Akira Kagawa 1-5-1, Kiba, Koto-ku, Tokyo Within Fujikura Electric Line Co., Ltd. (72) Inventor, Satoshi Kono 1-5-1, Kiba, Koto-ku, Tokyo Inside Fujikura Electric Line Co., Ltd. (72) Inventor Akira Saji 1 20-20 Kitasekiyama, Otaka-cho, Midori-ku, Aichi Prefecture Chubu Electric Power Co., Inc. Electric Power Research Laboratory (72) Inventor Noboru Kuroda Kita-kanzan, Otaka-cho, Midori-ku, Nagoya City, Aichi Prefecture No. 20 1 Chubu Electric Power Co., Inc. Electric Power Research Laboratory (72) Inventor Hiroshi Yoshida Kitakanyama, Otaka-cho, Midori-ku, Aichi Prefecture Nagoya No. 20 No. 1 Chubu Electric Power Co., Electric Power Research Laboratory

Claims (1)

[Claims] 1. A horizontally long reaction chamber for performing a CVD reaction in which a raw material gas such as a raw material compound gas is chemically reacted to deposit a product on a substrate surface, and a raw material gas supply means for supplying the raw material gas into the reaction chamber. A gas exhaust means for exhausting the gas in the reaction chamber, a substrate moving means for moving a long substrate to one side along the longitudinal direction of the reaction chamber, and a horizontally long substrate arranged in the reaction chamber. And a reaction region for heating the substrate to a reaction temperature at which the raw material gas is chemically reacted to deposit a product on the surface of the substrate. A preheating region that is provided on the front side of the reaction region in the moving direction of the substrate and that gradually heats the substrate so that the substrate reaches the reaction temperature before reaching the reaction region, and a rear side of the reaction region in the moving direction of the substrate. And a gradual cooling region for gradual cooling of the substrate heated to the reaction temperature, wherein a shielding means is provided in the reaction chamber in proximity to both ends of the reaction region.
A CVD method characterized in that the inside of the reaction chamber is divided into a reaction part, a preheating part and a slow cooling part, and an inert gas supply means for feeding an inert gas into the preheating part and the slow cooling part is provided.
Reactor.