JP3115367B2 - CVD reactor - Google Patents

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 for forming a coating layer on a substrate by using a chemical vapor deposition method (CVD method). The present invention relates to a CVD reactor used for manufacturing a long oxide superconductor, which is being developed for transportation and the like by using a 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 reactor using a horizontally long reaction chamber as shown in FIG. 6 is used. The CVD reactor 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 source gas supply port 7 is formed at one end on the lower side of the reaction chamber 2.
Is connected to the source gas supply device 3 through the source gas supply pipe 8.
Is connected to A gas outlet 9 is formed at the other lower end of the reaction chamber 2, and the gas outlet 9 is connected to the exhaust pump 4 through a gas discharge pipe 10.

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

In order to manufacture a long SC body using the above-mentioned conventional CVD reactor 1, a long substrate 11 is fed into the reaction chamber 2 by a substrate transfer device 6, and a raw material gas supply pipe 8 is further connected. The raw material gas is introduced into the reaction chamber 2 from the raw material gas supply device 3 via the source gas, 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 an SC layer on the surface of the long substrate 11, thereby producing an SC body.

[0006]

However, when the above-mentioned conventional CVD reactor 1 is used, the long substrate 11 is
Since it is introduced into the inlet A of the reaction chamber 2 and is rapidly heated at a high temperature at the same time as being discharged from the outlet B, it is rapidly cooled by the outside air.
Abrupt temperature changes occur at the inlet and the outlet of the device, and severe stress such as expansion or contraction caused by the rapid temperature change is applied. Therefore, there has been a problem that this may cause "warp" or "bending" of the substrate to cause undulation on the film-forming surface of the substrate.

Further, after the SC layer is deposited on the substrate, the substrate is carried out from the outlet B as described above and is rapidly cooled by the outside air. This causes a difference in the expansion coefficient between the substrate and the SC layer. There is a problem that stress is applied to the SC layer, which causes defects such as cracks in the SC layer.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made in consideration of the above-described circumstances. When an elongated substrate is introduced into or removed from a reaction chamber, an SC layer deposited on the elongated substrate or on the substrate is used. The temperature change occurring in the substrate or the SC is reduced due to this temperature change.
An object of the present invention is to provide a CVD reactor capable of reducing stress such as expansion or contraction generated in a layer.

[0009]

An object of the present invention is to provide a laterally elongated reaction chamber for performing a CVD reaction for chemically reacting a source gas such as a source compound gas and depositing a product on a substrate surface, 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, A CVD reaction apparatus provided with a horizontally-long heating means disposed in a chamber, wherein the heating means heats the raw material gas to a reaction temperature at which a product is deposited on the surface of the substrate by a chemical reaction. A reaction region, a preheating region provided on the front side of the reaction region in the direction of substrate movement, and gradually heating the substrate to reach the reaction temperature until the substrate reaches the reaction region; Provided toward the rear side, it is solved by a configuration in which a slow-cooling region gradually cooling the substrate body is heated to the reaction temperature.

[0010] Further, the heating means includes a horizontally long heat conducting plate and a heater for heating a central portion thereof.
The central region of the heat conductive plate is the reaction region, the region of the central region on the front side in the substrate moving direction is the preheating region, and the region of the central region on the rear side in the substrate moving direction is the slow cooling region. Desirably,

Further, it is desirable that cooling means is provided at both ends of the horizontally long heat conducting plate.

[0012]

As described above, in the CVD reaction apparatus of the present invention, the heating means is provided with a reaction region for chemically reacting the source gas and heating to a reaction temperature for depositing the product on the substrate surface. A preheating region provided on the front side of the reaction region in the substrate moving direction and gradually heating so as to reach the reaction temperature until the substrate reaches the reaction region; and a preheating region provided on the rear side of the reaction region in the substrate moving direction. And a gradual cooling region for gradually cooling the substrate heated to the reaction temperature, so that when the substrate is introduced into or removed from the reaction region in the reaction chamber, Can be moderated, thereby reducing stress such as expansion or contraction generated in the substrate or a thin film deposited on the substrate due to the temperature change.

[0013]

The present invention will be described below in detail with reference to examples. FIG. 1 shows a first embodiment of a CVD reactor according to the present invention. In the figure, reference numeral 21 denotes a CVD reactor.
The CVD reaction apparatus 21 includes a horizontally long reaction chamber 2.
2. The material gas supply device 23, the exhaust pump 24, the substrate heating device 25, and the substrate transfer device 26 are configured as main components.

At the upper part of the reaction chamber 22, there is formed a source gas diffusion part 27 which tapers upward and has a source gas supply means 23 connected to the top. On the other hand, two gas outlets 28, 28 are formed below the reaction chamber 22, and these two gas outlets 28, 28 are connected to an exhaust pump 24 through a gas exhaust pipe 29.

The long substrate 30 in the reaction chamber 22
Is moved in the direction of the arrow in the figure by the substrate transfer device 26 and is fed. Further, a substrate heating device 25 is provided at a lower portion in the chamber 22,
The long substrate 30 fed into the reaction chamber 22 can be heated.

As shown in FIG. 2A, the substrate heating device 25 includes a horizontally long heat conducting plate 31, a heater 32 for heating a central portion of the heat conducting plate 31, and a heating temperature of the heater 32. a temperature sensor T ₁ for measuring the, based on the information of the temperature sensor T _1, and a temperature controller 33 for controlling the heater 32.

Further, the substrate heating device 25 having the above-described configuration is used.
As shown in FIG. 2 (b), a reaction region 25a heated to a reaction temperature when a source gas is chemically reacted and a product is deposited on the surface of the long substrate 30;
a, the long substrate 3
A preheating region 25b having a temperature gradient for gradually heating so as to reach the above-mentioned reaction temperature until 0 reaches the reaction region 25a.
And a slow cooling region 25c provided on the rear side of the reaction region 25a in the substrate moving direction and having a temperature gradient for gradually cooling the long substrate heated to the reaction temperature.

The heat conductive plate 31 includes:
Metal materials such as Inconel and Hastelloy, alumina,
A material obtained by processing a ceramic material such as quartz glass into a plate shape is preferable.

As described above, in the CVD reactor 21 of the present embodiment, the reaction region is heated to the reaction temperature at which the source gas is chemically reacted and the product is deposited on the surface of the long substrate 30. 25a and a preheating region 25b which is provided on the front side of the reaction region 25a in the substrate moving direction and has a temperature gradient for gradually heating so as to reach the reaction temperature until the long substrate 30 reaches the reaction region 25a. Using a substrate heating device 25 provided with a slow cooling region 25c provided on the rear side of the reaction region 25a in the substrate moving direction and having a temperature gradient for gradually cooling the long substrate heated to the reaction temperature. Therefore, the long substrate 30 is connected to the substrate heating device 25.
When the substrate is introduced into the reaction region 25a or when the substrate is carried out of the heating region, the temperature change occurring in the long substrate 30 can be moderated. The stress such as expansion or contraction generated in the thin film deposited on the substrate is reduced. Therefore, it is possible to suppress, for example, the occurrence of undulations on the film-forming surface of the substrate and the occurrence of cracks in the thin film deposited on the substrate, which are caused by these stresses.

To manufacture a long SC body using the CVD reactor 21 of the present embodiment, first, the SC body raw material is supplied from the raw material gas supply device 23 into the chamber 22 through the raw material gas diffusion section 27. The gas is introduced, and the two gas outlets 2 on the lower side of the chamber 22 are exhausted by the exhaust pump 24.
The reaction residual gas in the chamber 22 is exhausted from 8, 28.
At this time, the source gas supply unit 23 sends the source gas diffusion unit 27
The SC raw material gas sent into the inside is diffused as shown by the arrow in the figure. By the above series of operations, in the vicinity of the CVD reaction region of the long substrate 30 in the reaction chamber 22,
A predetermined uniform SC material gas atmosphere is obtained. At the same time, the substrate heating device 25 is turned on to perform a preheating operation.

Next, the atmosphere is adjusted to a predetermined source gas atmosphere,
The long substrate 30 is fed at a predetermined speed into the chamber 22 in which the preheating of the substrate heating device 25 has been completed. At this time, first, the long substrate 30 is brought into contact with the preheating region 25b, and before reaching the next reaction region 25a.
Heat gradually to a predetermined CVD reaction temperature. Next, the long substrate 30 heated to the reaction temperature is placed in the reaction region 25a.
, And while being continuously heated at the CVD reaction temperature,
The SC raw material gas supplied from above reacts on the heated long substrate 30, and S
Layer C is deposited. Further, the long substrate 30 on which the SC layer is deposited reaches the slow cooling region 25c and is gradually cooled.

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

FIG. 3 shows a second embodiment of the CVD reactor according to the present invention, in which reference numeral 41 denotes a CVD reactor. The same members as those used in the first embodiment will be denoted by the same reference numerals for simplification. The difference between this embodiment and the first embodiment is that a cooler for cooling both ends of the heat conductive plate 31 constituting the substrate heating device 25 used in the first embodiment is provided. Are all the same.

As shown in FIG. 4A, a substrate heating device 42 constituting the CVD heating device 41 of the present embodiment includes a horizontally long heat conducting plate 31 and a heater for heating a central portion of the heat conducting plate 31. 32, a cooler 43, 43 for cooling the both ends of the heat conducting plate 31, a temperature sensor T ₁ for measuring the heating temperature of the heater 32, a cooler 43, 43
A temperature sensor T ₂ to measure the cooling temperature, on the basis of these temperature sensors T _1, T ₂ of the information, and a temperature controller 33 for controlling the heater 32 and the cooler 43, 43.

[0025] The condenser 43, as shown in FIG. 5, a cooling pipe 44 for the internal cooling water passes, it comprises a pump 45 for supplying cold water to the cooling pipe 44, a temperature sensor T ₂ When it is detected that the temperature is higher than the predetermined temperature, the pump 45 is operated by the temperature control device 33, and the cooling water having the predetermined temperature or a temperature slightly lower than the predetermined temperature is supplied to the cooling pipe 44.
To be sent to Further, when the temperature sensor T ₂ is detected as equal to or lower than the predetermined temperature, the cooling pipes 4 in opposite
Water supply to 4 is stopped.

In this embodiment, water (cooling water) is used as a cooling medium in the cooling pipe 44. However, the cooling medium is not limited to water, and may be, for example, oil or air. What is necessary is just to be able to give and receive heat.

Further, the substrate heating device 42 having the above configuration
As shown in FIG. 4 (b), a reaction region 42a heated to a reaction temperature when a source gas is chemically reacted and a product is deposited on the surface of the long substrate 30;
a, the long substrate 3
A preheating region 42b having a temperature gradient for gradually heating so as to reach the above reaction temperature until 0 reaches the reaction region 42a.
And a slow cooling region 42c provided on the rear side of the reaction region 42a in the substrate moving direction and having a temperature gradient for gradually cooling the long substrate heated to the reaction temperature.

As described above, in the CVD reactor of this embodiment, the heat conducting plate 31, the heater 32 for heating the central portion of the heat conducting plate 31, and both ends of the heat conducting plate 31 Coolers 43, 43 for cooling
And a temperature sensor T for measuring the heating temperature of the heater 32.
_1, a temperature sensor T ₂ to measure the cooling temperature of the cooler 43, 43, on the basis of these temperature sensors T _1, T ₂ of the information,
Since the configuration includes the heater 32 and the temperature controller 33 for controlling the coolers 43, 43, both ends of the heat conductive plate 31 are cooled to a temperature sufficiently close to room temperature by the coolers 43, 43. Therefore, when the long substrate 30 is introduced into or unloaded from the reaction region 42a, the temperature change occurring in the long substrate 30 is different from that of the first embodiment having no cooler. Can be further moderated. Therefore, the effect described in the first embodiment is further amplified.

(Experimental Example 1) An SC body was manufactured by using the above-described CVD reactor 21 of the first embodiment according to the present invention.
First, a long Hastelloy C-276 having a length of 1 m, a width of 5 mm, and a thickness of 0.1 mm is transferred to the substrate transfer device 26 at a rate of 1 m / sec.
h into the reaction chamber 22 at a feed rate of h.
An SC raw material gas composed of PM) ₃ , Ba (DPM) ₂ , and Cu (DPM) ₂ was introduced. At the same time, the two gas outlets 2 on the lower side of the
The gas in the reaction chamber 22 was exhausted at a predetermined speed from 8, 28, and the long Hastelloy substrate was heated to 850 ° C. by the substrate heating device 25 to perform the CVD method. The specifications and heating mode of the substrate heating device 25 used in this embodiment are shown below.

Substrate heating device 25 Heat conductive plate 31 Material: Inconel Heat conductive plate 31 Size: length 50 cm, width 2c
m, thickness 0.5 cm Total length of reaction zone (L) = 10 cm Total length of preheating zone (M) = 20 cm Total length of slow cooling zone (N) = 20 cm Heating temperature of heater 32 = 850 ° C.

By the above operation, a long SC having a Y—Ba—Cu—O based SC layer formed on a long Hastelloy substrate
The body was made. In addition, the SC layer of the obtained long SC body,
The thickness was about 5 to 8 μm, and the composition was uniform. The critical temperature of the long SC body was 77.3K or more.

(Experimental Example 2) An SC body was manufactured using the above-described CVD reactor 41 of the second embodiment according to the present invention.
First, a long Hastelloy C-276 having a length of 1 m, a width of 5 mm, and a thickness of 0.1 mm is transferred to the substrate transfer device 26 at a rate of 1 m / sec.
h into the reaction chamber 22 at a feed rate of h, and further into the reaction chamber 22 from the raw material gas supply device 23, Y (D
An SC raw material gas composed of PM) ₃ , Ba (DPM) ₂ , and Cu (DPM) ₂ was introduced. At the same time, the two gas outlets 2 on the lower side of the
The gas in the reaction chamber 22 was exhausted at a predetermined speed from 8, 28, and the long Hastelloy substrate was heated to 850 ° C. by the substrate heating device 42 to perform the CVD method. The specifications and heating style of the substrate heating device 42 used in this embodiment are shown below.

Substrate heating device 42 Heat conductive plate 31 Material: Heat conductive plate 31 Size: Total length of reaction zone (L): Total length of preheating zone (M):
Total cooling zone length (N): Heating temperature of heater 32: All of the above are the same as in Experimental Example 1. Cooling temperature of cooler 43: 30 ° C.

By the above operation, a long SC having a Y-Ba-Cu-O-based SC layer formed on a long Hastelloy substrate
The body was made. In addition, the SC layer of the obtained long SC body,
The thickness was about 10 μm, and the composition was uniform. Also, the critical temperature of the long SC body is 85K or more,
The critical current density is 5000 A / cm ² (at 77K, 0
T).

[0035]

As described above, according to the CVD reactor of the present invention, the reaction area for heating the substrate to the reaction temperature for chemically reacting the raw material gas and depositing the product on the surface of the substrate by the heating means. The temperature change occurring in the substrate when introduced into the substrate or when the substrate is unloaded from the reaction area can be moderated, whereby the temperature change occurs in the substrate or a thin film deposited on the substrate. Stress such as expansion or contraction is reduced. Therefore, it is possible to suppress the occurrence of undulations on the film-forming surface of the substrate and the occurrence of cracks in the thin film deposited on the substrate, which are caused by the stress. For example, using the CVD reactor of the present invention, When an SC body is manufactured, a high-quality SC body having a high critical current density and a high critical temperature can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a first embodiment of a CVD reactor according to the present invention.

FIG. 2A is a diagram illustrating a detailed configuration of a substrate heating device indicated by reference numeral 25 in FIG. 1; FIG. 4B is a diagram schematically illustrating a temperature change in each of a preheating region, a reaction region, and a slow cooling region of the substrate heating device 25.

FIG. 3 is a view showing a second embodiment of the CVD reactor of the present invention.

FIG. 4A is a view for explaining a detailed configuration of a substrate heating device indicated by reference numeral 42 in FIG. 3; FIG. 4B is a diagram schematically illustrating a temperature change in each of a preheating region, a reaction region, and a slow cooling region of the substrate heating device 42.

FIG. 5 is a diagram illustrating a detailed configuration of a cooler indicated by reference numeral 43 in FIG.

FIG. 6 is a view showing a conventional CVD reactor.

[Explanation of symbols]

21, 41: CVD reactor, 22: reaction chamber, 2
3: Source gas supply device, 24: Exhaust pump, 25: Substrate heating device, 26: Substrate moving device, 30: Long substrate, 25
a, 42a: reaction zone, 25b, 42b: preheating zone, 2
5c, 42c: slow cooling region, 31: heat conduction plate, 32
... heater, 33 ... temperature controller, 43 ... cooler

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // H01B 12/06 ZAA H01B 12/06 ZAA H01L 21/31 H01L 21/31 B (72) Inventor Akira Kagawa Koto-ku, Tokyo 1-5-1 Kiba Inside Fujikura Electric Wire Co., Ltd. (72) Inventor Satoshi Kono 1-5-1 Kiba Koto-ku, Tokyo Inside Fujikura Electric Wire Co., Ltd. (72) Inventor Akira Aji Odaka Midori-ku, Nagoya-shi, Aichi Prefecture Chubu Electric Power Co., Inc. (72) Inventor Noboru Kuroda, Chubu Electric Power Co., Inc. 20 Chuichi Electric Power Co., Inc. Chubu Electric Power Co., Inc. In-house (72) Inventor Hiroshi Yoshida 20-1 Kita-Sekiyama, Odaka-cho, Midori-ku, Nagoya-shi, Aichi Electric Power Engineering Laboratory, Chubu Electric Power Co., Inc. (56) References JP-A-63-26312 (JP, A) JP-A-62-227075 (JP, A) JP-A-49-4977 (JP, A) JP-A-63-84017 (JP, A) JP-A-56-77375 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C23C 16/00-16/56 C30B 25/16 H01B 12/06 ZAA H01B 13/00 565 H01L 21/31 H01L 39/24

Claims (3)

(57) [Claims] 1. A horizontally elongated reaction chamber for performing a CVD reaction for chemically reacting a source gas such as a source compound gas and depositing a product on a substrate surface, and a source gas supply means for supplying the source gas into the reaction chamber Gas exhaust means for exhausting gas in the reaction chamber, substrate moving means for moving the long substrate to one side along the longitudinal direction of the reaction chamber, and a horizontally long part disposed in the reaction chamber A CVD reaction apparatus comprising: a reaction region for heating to a reaction temperature for chemically reacting the raw material gas to deposit a product on the substrate surface; and A preheating region provided on the front side in the substrate moving direction and gradually heating so as to reach the reaction temperature before the substrate reaches the reaction region; and a reaction temperature provided on the rear side of the reaction region in the substrate moving direction. And a slow cooling region for gradually cooling the substrate that has been heated each time. 2. The heating means comprises a horizontally long heat conductive plate and a heater for heating a central portion thereof, wherein a central region of the heat conductive plate is the reaction region, and 2. The CVD according to claim 1, wherein a region on the front side in the substrate moving direction is the preheating region, and a region on the rear side in the substrate moving direction in the central region is the slow cooling region.
Reactor. 3. At both ends of the horizontally long heat conducting plate,
3. The CV according to claim 2, further comprising cooling means.
D reactor.