JPH11145060A - Thin film manufacture device and photoelectric conversion element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To raise the air tightness between a film growth chamber and a common vacuum vessel so as to form a high-quality film and raise the photoelectric conversion efficiency of the photoelectric conversion element, by making the boundary between the film growth chamber and the common vacuum vessel air-tight, with each seal part in accordance across a board, and using inorganic material such as metal, ceramic, or the like as the seal part. SOLUTION: Band-shaped end plates 171 and 123 doubling as seal parts and a lip presser 172 are made of inorganic matter such as metal, ceramic, etc. low in degassification of Al, etc. In case that the width W of the sections to contact with a flexible board of the band-shaped ring end plates 171 and 123 doubling as seal parts installed in an upper film growth chamber wall body 22 and a lower film growth chamber 27 is made 10 mm or over, the air tightness can be secured. Furthermore, it is so arranged that the film growth chamber wall on one mobile side can bend and contact with the seal face precisely, when forming film growth chamber space across the board, thus the sealing property between the film growth chamber and the common chamber is ensured. Hereby, the leakage of gas to the common chamber at the time of having charged the film growth chamber with film growth gas can be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a thin film element having a plurality of layers on a flexible substrate such as a thin film photoelectric conversion element. The present invention relates to a stepping roll type thin film manufacturing apparatus having a plurality of thin films.

[0002]

2. Description of the Related Art For example, amorphous silicon (hereinafter referred to as a-
A thin film photoelectric conversion element or the like composed of a multilayer thin film including a photoelectric conversion layer mainly composed of Si) is formed on a flexible substrate made of a long polymer material or a metal such as stainless steel. The method of individualizing by cutting at is excellent in mass productivity.

[0003] As a method of forming a plurality of layers on a long flexible substrate, a roll-to-roll method in which a film is formed while continuously moving in each film forming chamber, and a film forming method in which the film is stopped in each film forming chamber. rear,
There is a stepping roll method in which a substrate portion on which film formation has been completed is sent out of a film formation chamber. For example, in the stepping roll method in which a film is formed by plasma enhanced chemical vapor deposition (hereinafter, referred to as CVD), a film forming chamber is opened, a substrate is moved by one frame, a film forming chamber is sealed, a source gas is introduced, a pressure is controlled, a discharge starts, and a discharge ends. The operation consisting of -stopping the source gas -degassing-opening the film forming chamber is repeated.

FIG. 6 is a side sectional view of a thin film manufacturing apparatus of a stepping roll film forming system having a plurality of film forming chambers in a common vacuum chamber. The substrate 1 is formed in several film forming chambers 80 while being unwound from the core 82 and wound around the core 83. The common chamber 81 houses a plurality of film forming chambers 80 therein. This apparatus can be used for manufacturing a thin film photoelectric conversion element, and a sputter deposition or a plasma CVD deposition is performed in a deposition chamber. The film forming apparatus adopting the stepping roll method is superior to the usual roll-to-roll film forming in the following points.

(1) There is no gas mutual diffusion between the adjacent film forming chambers. (2) The device is compact. The conventional technology related to the stepping roll type film forming apparatus is as follows.
JP-A-6-291349, JP-A-7-6953, JP-A-7-221025, JP-A-8-25
No. 0431, Japanese Patent Application Laid-Open No. 8-293493, and Japanese Patent Application Laid-Open No. 9-63970.

JP-A-6-291349 discloses a stepping roll type film forming apparatus and a method of manufacturing a thin film photoelectric conversion element using the apparatus. In a method for manufacturing a thin film photoelectric conversion element, in which a plurality of thin films having different properties are stacked on a strip-shaped flexible substrate to form a photoelectric conversion element, a plurality of film formation chambers arranged in one common vacuum chamber are provided. Through a flexible substrate, a film is formed on the surface of the substrate which is stopped in a predetermined vacuum atmosphere in a film forming chamber in which the entrance and exit of the substrate are kept airtight by a wall through a sealing material. It discloses that the operation of transporting the substrate separated from the film chamber wall to the next film formation position is repeated. And it is effective that the substrate surface is in a vertical plane.

Further, a voltage is applied between an electrode in contact with the substrate and an electrode facing the film-forming surface of the substrate in the film-forming chamber to form a film. Separating is effective. It is said that it is effective that the substrate used is a resin film having a conductive film applied on one surface, a metal film, or a metal film having a conductive film applied on one surface via an insulating film. .

Further, in a manufacturing apparatus for a thin film photoelectric conversion element in which a plurality of thin films having different properties are laminated on a strip-shaped flexible substrate to form a photoelectric conversion layer, the thin film photoelectric conversion elements are arranged near both ends in the longitudinal direction of a common vacuum chamber. A plurality of film forming chambers through which a flexible substrate that can be wound up from one of the rolls to the roll that has been unwound through the common vacuum chamber is provided. At the entrance and exit, it is separated by a wall that is in close contact with the substrate via a sealing material, and the sealing material on the film forming chamber wall can be retracted to a position away from the substrate, and the common vacuum chamber and each film forming chamber are connected to separate exhaust systems. Assume that they are connected. Further, it is effective to provide each deposition chamber with an electrode which is in contact with the substrate and which can be retracted to a position distant from the substrate, and a counter electrode of the electrode. Further, it is effective that the axes of both rolls and the electrode surfaces of both electrodes are vertical.

[0009] Japanese Patent Application Laid-Open No. 7-6953 is opposed to each other in parallel.
The high frequency electrode is applied to one of the two plate electrodes
To generate plasma in the deposition chamber space between the two electrodes.
To decompose the reaction gas and deposit a thin film on the substrate.
In the plasma CVD method, the reaction space is defined by parallel plate electrodes and side walls.
And the common chamber space side of the high-frequency electrode is 1 × 10 ^-3
Contact with a vacuum of Torr or less, or
The common room space side is brought into contact with the atmosphere. This plastic
The plasma CVD method prevents discharge on the back of the high-frequency electrode,
Uniformity of electricity can be obtained and the film quality can be improved.
In addition, there are multiple deposition chambers that contain discharges in one vacuum chamber.
Flexible to be placed, sent out in a vacuum chamber, and wound up
By sequentially forming films on a substrate, a roll-to-roll system
There is no need to provide a buffer vacuum chamber as in
Compact and lightweight, and
Discloses that a wide range of manufacturing costs can be reduced.
You.

Japanese Patent Application Laid-Open No. 7-2221025 discloses that a flexible substrate to be conveyed is stopped between two openings of a film forming chamber each having a box-shaped wall, and the substrate is moved to the film forming chamber. Between the open end faces of the walls of the two portions, the film forming space surrounded by one portion of the film forming chamber and the substrate is evacuated from the exhaust port communicating with the space, and the electrodes in the space are formed with the electrodes. In a manufacturing apparatus for a thin-film photoelectric conversion element in which a voltage is applied between the other part of the chamber and an electrode in a space surrounded by the substrate, a film is formed. The air passage is a flexible pipe, and the air passage is provided in a portion provided at a location where the flexible substrate does not pass through on the opening side of the wall of both portions of the film forming chamber. It is opened from the opening that is open and It is intended.

According to this manufacturing apparatus, it is possible to prevent gas accumulation in the space where the exhaust port is not provided, and to realize a clean film formation in which fresh raw material gas is always supplied. Also,
It discloses that even if a plurality of types of semiconductor layers are formed in the same film formation chamber, film formation with less influence of residual gas can be realized.
Japanese Patent Application Laid-Open No. 8-250431 discloses that a flexible substrate is brought into close contact with an end surface around an opening of a box-shaped film forming chamber wall, and a film forming space surrounded by the wall and the substrate is evacuated. In a method of manufacturing a thin-film photoelectric conversion element in which a thin film is formed on a substrate by applying a voltage to an electrode housed in the substrate, the outer periphery of the film-forming surface of the substrate is slid radially on the end surface around the opening of the wall of the film-forming chamber. Let
In addition, the substrate is pressed toward the electrode side by a pressing body located on the side opposite to the electrode to stretch the wrinkles of the substrate and form a film. In particular, the electrode housed in the film forming space as a pressing body It is said that it is effective to use the counter electrode of the above.

Further, the film forming space has an opening opposed to the opening of the box-shaped wall of the film forming chamber in which an electrode to which a voltage is applied is accommodated, and can be driven in the direction of the film forming chamber wall. An end face of the second box-shaped wall is provided with an elastic lip-like body inclined outwardly with respect to the surface of the flexible substrate that is in close contact with the wall of the film formation chamber;
The counter electrode accommodated in the second wall body can be driven to the inside of the opening surface of the wall body of the film forming chamber while pressing the substrate on the surface thereof, whereby the wrinkles of the flexible substrate are extended. It is disclosed that, if a film is formed, a film formation pattern does not shift and a film having a uniform film thickness can be formed.

Japanese Patent Application Laid-Open No. Hei 8-293349 discloses a method in which a first electrode is provided between two rows of flexible substrates conveyed in parallel, and a second electrode is provided on the outside of each substrate so as to face the first electrode. A thin-film photoelectric element is disposed to form a thin film on one surface of each substrate by generating a discharge by applying a voltage between the first and second electrodes in a deposition space formed between the first electrode and each substrate. In the device for manufacturing a conversion element, one first electrode is provided for each substrate, and the back surface of the first electrode parallel to the substrate surface is connected by an insulator. Each of the first electrodes has an opening on the back surface thereof, and a through hole communicating with the opening is formed in an insulator connecting the back surfaces of the first electrodes, and a vacuum exhaust port is opened on an inner surface of the through hole. I have. A sealing material that can be in close contact with the substrate is attached to the end surface of the first electrode.

A voltage application electrode and a ground electrode are arranged on both sides of the flexible substrate to be conveyed, and a discharge is generated by applying a voltage to the voltage application electrode in a film forming space formed between the voltage application electrode and the substrate. In a thin-film photoelectric conversion device manufacturing apparatus in which a thin film is formed on one surface of a substrate, the voltage application electrodes are insulated and air-tightly coupled to a conductive frame having a flat plate-like end face capable of air-tightly contacting the substrate. A conductive shield surrounding the back and side surfaces of the voltage applying electrode is conductively coupled to the conductive frame and grounded. Further, a voltage application electrode inside the substrate and a ground electrode outside the substrate are arranged to face each other with the two rows of flexible substrates conveyed in parallel, and both voltage application electrodes penetrate the shield body. They are connected by insulators. Each voltage applying electrode has an opening, and a through hole communicating with the opening is formed in an insulator connecting the two voltage applying electrodes, and a vacuum exhaust port is opened on an inner surface of the through hole. By such a thin-film photoelectric conversion element manufacturing apparatus, film formation is performed on two rows of flexible substrates conveyed in parallel by applying a voltage between the first and second electrodes provided for each of them. In addition, it is possible to separately control both film forming conditions, to reduce a difference in film formation between substrates, and to connect two first electrodes via an insulator to connect both substrates. Disclosed is a method of disposing the thin film photoelectric conversion element in a space between the thin film photoelectric conversion elements and forming the film formation space by airtightly contacting the end faces of the substrates.

[0015] Further, the shield body surrounding the back and side surfaces of the electrode to which a high voltage is applied is shielded by a conductive frame body which is insulated and coupled to the substrate side and forms a film forming space between the shield body and the substrate. Arrangement of a plurality of film forming chambers for sequentially forming films on one row of flexible substrates in the substrate transfer direction, and arrangement of a plurality of film formation chambers for forming films on a plurality of rows of flexible substrates in parallel in the substrate transfer direction On the other hand, it discloses that the arrangement in the horizontal direction can be performed with a narrow interval between the film forming chambers, and therefore, the manufacturing apparatus of the thin film photoelectric conversion element which needs to stack a plurality of thin films can be downsized. .

In Japanese Patent Application Laid-Open No. 9-63970, an end surface around an opening of a box-shaped film forming chamber wall of a flexible substrate is brought into close contact with an elastic sealing member, and is surrounded by the wall and the substrate. In a manufacturing apparatus of a thin film element for forming a thin film on a substrate by applying a voltage to an electrode housed in the space and applying a voltage to an electrode housed in this space, a seal member made of a fluororesin is disclosed. I have. Fluororesin has less adhesion to the surface of a flexible substrate made of a polymer material or a metal than fluororubber or the like, so that adhesion that hinders substrate transport does not occur.

Also, the flexible substrate is brought into close contact with the end surface around the opening of the box-shaped film forming chamber wall through an elastic sealing member, and the film forming chamber surrounded by the wall and the substrate is evacuated. West,
In a manufacturing apparatus of a thin film element for forming a thin film on a substrate by applying a voltage to an electrode housed in this space, the contact surface between the flexible substrate of the seal member and the elastic base material is smaller than that of the elastic base material. Also disclosed is one covered with a surface film made of a material having low adhesive force to the substrate.

Further, the flexible substrate is brought into close contact with an end surface around the opening of the box-shaped film forming chamber wall through an elastic sealing member, and the film forming chamber surrounded by the wall and the substrate is evacuated. ,
In a method of manufacturing a thin film element in which a thin film is formed on a substrate by applying a voltage to an electrode housed in this space, a thin film is formed, and after releasing the pressure for bringing the end face of the film forming chamber wall into close contact with the substrate, It discloses that the substrate is pressed from one surface side to the other surface side, thereby removing the substrate adhered to the seal member.

FIG. 7 is a cross-sectional view of a film forming chamber of a conventional stepping roll type thin film manufacturing apparatus.
(B) is the time of sealing. A box-shaped lower film-forming chamber wall 21 and an upper film-forming chamber wall 22 are arranged above and below the intermittently transported flexible substrate 1. A high voltage electrode 31 connected to the power supply 4 is provided in the lower film forming chamber, and a heater 33 is provided in the upper film forming chamber.
Is provided.

At the time of film formation (FIG. 7B), the upper film forming chamber wall 22 is lowered, and the ground electrode 32 is attached to the opening-side end face of the lower film forming chamber wall 21 while holding down the substrate 1. The contact is made to the sealing material 5 provided. As a result, an airtightly sealed film-forming space 6 communicating with the exhaust pipe 61 is formed by the lower film-forming chamber wall 21 and the substrate 1, and plasma is applied by applying a high-frequency voltage to the high-voltage electrode 31. And a source gas introduced from an introduction pipe (not shown) is decomposed to form a film on the substrate 1. In the figure, the outside of the film forming chamber is a common vacuum chamber.

FIG. 8 is a cross-sectional view of the seal portions of the lower and upper film forming chambers of the conventional film forming apparatus. On the end surface of the lower film forming chamber wall 21, two band-shaped end plates 23 and 24 are provided.
Also, two band-shaped end plates 2 are provided on the end surface of the upper film forming chamber wall 22.
5 and 26 are screwed, respectively, and hold the sealing material 5 in the dovetail groove formed therebetween so as not to fall off.
During film formation, the substrate 1 is sandwiched between the surfaces of the end plates 23 and 24 on the lower film formation chamber side and the sealing material 5 therebetween, and the surfaces of the end plates 25 and 26 on the upper film formation chamber side and the sealing material 5 therebetween. Thus, the spaces in the upper and lower film forming chambers are kept in a vacuum.

Another example is disclosed in Japanese Patent Application Laid-Open No. 8-250504.
There is also a method as shown in FIG. FIG. 9 is a cross-sectional view perpendicular to the direction of transport of a flexible substrate when a film forming chamber of a conventional thin film manufacturing apparatus for forming a film by plasma CVD is opened.
The flexible substrate 1 is transported in a direction perpendicular to the paper. The lower film forming chamber for accommodating the high-voltage electrode 31 includes the wall 21 and the top plate 27 having an opening, and is connected to the vacuum exhaust pipe 61. The upper film forming chamber for accommodating the ground electrode 32 including a heater (not shown) is composed of the wall body 22 and the housing 28, and the support tube 34 of the ground electrode 32 is fitted to the housing 28 so as to be vertically movable. . A moving plate 29 is attached to an end of the housing 28. The moving plate 29 is guided by the vertical drive guide 30 and is driven by the actuator 41 in the vertical direction as indicated by the arrow 51. The vertical drive guide 30 and the actuator 41 are fixed to a mount 42 and mounted on an upper flange 36 on a film forming chamber 35. The support tube 34 is cylindrical, and the upper end of the internal cavity communicates with the vacuum exhaust pipe 63, and the lower end communicates with the internal space of the upper film formation chamber through the through hole 37 at the lower end. The vacuum exhaust pipe 61 and the vacuum exhaust pipe 63 are connected by a flexible pipe 64. On the other hand, the support tube 34 of the ground electrode can be moved in the housing 28 via the moving plate 29, whereby the ground electrode 32 is driven up and down as shown by the arrow 52. A wrinkle-stretching structure is formed between the lower end of the wall 22 of the upper film forming chamber and the top plate 27 of the lower film forming chamber.

FIGS. 10A and 10B are enlarged cross-sectional views of a seal portion of a film forming chamber of a conventional thin film manufacturing apparatus (FIG. 9). FIG. 10A shows a state where the film forming chamber is opened, and FIG. is there. Top plate 2
The sealing material 5 is held between the end plates 23 and 24 on the portion close to the opening 45 of 7, as in FIG. On the other hand, the base of the lip (lip-like body) 7 made of rubber is inserted into the concave portion of the L-shaped packing 71 having a rectangular ring shape, and is sandwiched between the end face of the upper film forming chamber wall 22 and the lip retainer 72. Is held by The L-shaped packing 71 and the lip retainer 72 are fixed to the end surface of the wall 22 with screws, so that the lip 7 can be easily attached and detached. Lip 7
Is divided into four parts for each side of the rectangular wall 22.

When the film forming chamber is opened, the lip 7 is
Is inclined outward by 45 to 60 degrees, and projects downward about 5 mm from the lower end of the L-shaped packing 71. The edge of the lip retainer 72 is chamfered, for example, by 30 degrees. When the upper film forming chamber wall 22 starts to descend in the direction of the arrow 51, the tip of the lip 7 comes into contact with the substrate indicated by the chain line, and further presses the substrate 1 onto the surface of the end plates 23, 24 on the top plate 27. To reach. When the upper film forming chamber wall 22 descends in the direction of arrow 53 as it is, the tip of the lip 7 slides and deforms in the direction of arrow 54 in parallel to the surfaces of the end plates 23 and 24. Since the edge of the lip retainer 72 is chamfered, the end of the deformed lip 7 can escape to this chamfer.

At this time, the tip of the lip 7 and the sections 23, 2
4 causes friction between the substrate 1 and the substrate 1 on the arrow 54.
, The outer periphery of the substrate 1 is
The wrinkles are extended by sliding on the surfaces of 3, 24 in a radial direction from the center outward. Then, L continues to decrease,
The mold packing 71 presses the lower substrate 1 against the sealing material 5 and the end plates 23 and 24 to form a space surrounded by the film formation space 6 below the substrate 1 and the wall 22 above the substrate 1. Vacuum seal. Subsequently, the ground electrode 32
Is lowered in the direction of arrow 55, and the substrate 1 is forcibly moved to arrow 5
The wrinkles are further stretched by pulling in the direction of 6.
At this time, the pressing depth d of the ground electrode 32 into the substrate is 2.
It is effective that it is 0 to 2.5 mm.

In the above example, the upper film forming chamber can be evacuated. However, the present invention can also be carried out in a thin film photoelectric conversion device manufacturing apparatus in which only the lower film forming chamber accommodating the high voltage electrode is evacuated. .

[0027]

In the example shown in FIG. 9 or 10, since the ground electrode 32 has a built-in substrate heater 33, the wall 22 around the heater and the L-shaped packing 7 are provided.
1, the lip 7, the lip holder 72, the end plates 23 and 24, the top plate 27, and the sealing material 5 are heated. Usually, since the sealing material is made of fluoro rubber, the viscosity of the L-shaped packing 71, the lip 7, the lip presser 72, and the sealing material 5 is increased by heating. For this reason, in the example of FIG. 9, when the upper film formation chamber is lifted after the film formation is completed or after the film formation chamber is sealed, and the flexible substrate is transported and frame-fed,
The sealing material 5, in the example of FIG.
There was a problem that the flexible substrate could not be transported because it adhered to one of the L-shaped packings 71.

In order to solve this problem, as a sealing member which comes into contact with a flexible substrate on the outer periphery of the film forming chamber and seals the vacuum, instead of a fluorine-based rubber, a material having low adhesiveness, for example, Teflon (made by DuPont) is used. (Registered trademark name) or Daiflon (registered trademark name of Daikin Industries, Ltd.), or a material that reduces the adhesiveness to fluorine-based rubber, for example, a metal film such as Ag, Al, Ti, Cu, or Cr; Alternatively, metal oxides such as ZnO, ITO, and SnO ₂ , or fluorine-based compounds such as Teflon (registered trademark of DuPont), Daiflon (registered trademark of Daikin Industries, Ltd.), silicon-based compounds, and nitrides It was considered to coat the surface with boron or the like. Also, in order not to increase the adhesiveness itself of the seal member, it has been considered that the surroundings are cooled and the seal member is kept at 100 ° C. or lower, preferably 50 ° C. or lower, and the adhesiveness of the seal member is not increased.

However, when the seal is cooled, the temperature of the heater near the seal decreases, and it is difficult to make the temperature of the substrate on which the thin film is formed uniform over the entire film formation region. In addition, even when the seal portion is coated with various materials, if the temperature rises above the heat-resistant temperature of the seal material itself, the quality of the film formed by degassing deteriorates.

In the event that the flexible substrate adheres to the seal member, as a method for removing the sticking of the flexible substrate, a drivable pressing body in the upper film forming chamber is projected before the transfer so that the flexible member is attached to the seal member. There is a method of peeling off the sticky flexible substrate, but this method is a mechanical means, and the flexible substrate may be scratched or the formed thin film or the thin film photoelectric conversion element may be damaged. was there.

FIGS. 11A and 11B are cross-sectional views of a film forming chamber of a conventional thin film manufacturing apparatus for simultaneously forming a film on two substrates, wherein FIG. It is. High voltage electrode 2
In a film-forming chamber structure in which a frame 254 having the same potential as the ground electrode 222 containing the heater 21 and the heater 223 is insulated by an insulator 253, for example, quartz is used for the insulator 253, and the high-voltage electrode 221 and the quartz are used. , Frame 254 serving as ground electrode
The sealing material 252 is used to seal the airtightness of the quartz.
Alternatively, since the sealing material can also serve as an insulating material, a sealing material having a sufficient thickness to provide a necessary interval has been used in some cases. Further, the two high-voltage electrodes 221 are separated by an insulating block 209 so that films can be formed independently on two substrates. And the insulating block 2
09 is connected to the exhaust member 208 at the ground potential.

In the thin film manufacturing apparatus of this structure, both sides of the film forming chamber are surrounded by the ground electrode 222 having a built-in heater, the side wall is surrounded by vacuum, and the lower or upper part fixed to the common chamber is formed. Since only heat is transmitted and heat is released, the inside of the film forming chamber is sufficiently heated. For example, when the heater temperature is 250 ° C., the temperature inside the deposition chamber is about 150 ° C. to 20 ° C.
The temperature rose to about 0 ° C. Therefore, when the temperature inside the film formation chamber rises or falls, when quartz is used as the insulator, the frame 254 serving as a ground electrode or the high-voltage electrode 2 is used.
21. In addition, there was a case in which a force was applied to quartz due to thermal expansion and contraction of members (SUS, aluminum) constituting the film forming chamber, and the quartz was damaged. In this case, gas leaks from the film formation chamber to the common chamber, and the pressure at which stable discharge can be performed in the film formation chamber cannot be maintained, or the pressure of the common chamber increases,
Discharge occurs between the high voltage electrode and the ground electrode outside the deposition chamber,
It was not possible to stably discharge in the film forming chamber.

The insulator 253 is connected to the high voltage electrode 221.
And the ground electrode 222 and the frame 254 having the same electric potential, the high voltage electrode 221 or the ground electrode is required to replace the damaged insulator 253. The frame 254 had to be disassembled, requiring a great deal of labor and time. As another problem, in order to transport a flexible substrate, tension is applied in the transport direction of the substrate. Since the transport distance becomes longer, the number of rolls that support the flexible substrate must be increased, and the mechanical loss at the roll axis increases. As a result, the tension applied to the flexible substrate is reduced, and the substrate is wrinkled. Had occurred.

In addition, the outgassing from the sealing material was large, and the film quality was deteriorated. Further, when a thick sealing material was used for the insulator, the outgassing was further increased and the film quality was further deteriorated.
An object of the present invention is to provide a film forming chamber having a seal portion that is hardly adhered to a substrate even at a high temperature, has little degassing, is less susceptible to distortion of a film forming chamber wall, and has an easily replaceable seal portion. To provide a thin film manufacturing apparatus having the same.

[0035]

In order to achieve the above-mentioned object, a transport system for transporting a flexible substrate into one common vacuum chamber and a thin film formed on the flexible substrate are formed. A plurality of film forming chambers each provided with a means, and each of the film forming chambers includes two film forming section chambers each having an opening bounded by a flexible substrate, and each opening is provided with a seal portion. In a thin film manufacturing apparatus in which the seal portions are aligned with each other with the substrate interposed therebetween and the airtightness is formed between the film forming chamber and the common vacuum chamber, the seal portions are made of an inorganic material such as metal or ceramic.

[0036] The width of the portion of the seal portion that comes into contact with the substrate is preferably 10 mm or more. It is preferable that the movable film forming section chamber and the heater for heating the substrate in the film forming section chamber have an integral structure. It is preferable that the movable film forming section chamber and the sealing section are made of the same material and are integrated. It is preferable that the heater is larger than a film formation area on the flexible substrate.

The pressure of the seal portion is 1 × 10 ⁴ Pa or more and 5 ×
It is good to be 10 ⁵ Pa or less. Further, in one common vacuum chamber, there is provided a transport system for transporting a flexible substrate, and one or a plurality of deposition chambers provided with means for depositing a thin film on the flexible substrate. The film forming chamber is composed of two film forming section chambers having an opening bounded by a flexible substrate, and each opening is provided with a seal section, and each seal section is aligned with the substrate in between. In a thin-film manufacturing apparatus in which the space between the chamber and the common vacuum chamber is airtight, the sealing portion at the opening of one of the film forming section chambers is a foil or plate made of metal, and has an elasticity inclined toward the outside of the film forming section chamber. The lips have a lip.

Further, in one common vacuum chamber, there is provided a transfer system for transferring a flexible substrate, and one or a plurality of film forming chambers provided with means for forming a thin film on the flexible substrate. Each of the film forming chambers includes two film forming section chambers each having an opening bounded by a flexible substrate, and each opening is provided with a seal portion, and each seal portion is aligned with the substrate interposed therebetween. A thin-film manufacturing apparatus in which the space between the film-forming chamber and the common vacuum chamber is hermetically sealed, and one of the film-forming chambers includes a high-voltage electrode and a sealing portion around the periphery thereof. A flexible insulating sheet is used as an insulator between the high-voltage electrode and a portion that effectively becomes a ground potential.

It is preferable that the portion which is effectively at the ground potential is an exhaust member of the film forming chamber. It is preferable that the effective ground potential portion is a frame at the periphery of the ground electrode in the film forming chamber.
The insulating sheet is preferably fixed by a band-shaped fixing jig. The insulating sheet is preferably made of a polyimide resin or an aramid resin.

The thickness of the insulating sheet is preferably 10 μm to 500 μm. Further, a tension adjusting device for the substrate is provided between the film forming chambers. Then, it is assumed that at least a thin film photoelectric conversion element in which a photoelectric conversion layer and an electrode layer are laminated is manufactured by the above thin film manufacturing apparatus. According to the present invention, a metal is used as a sealing material for sealing a vacuum by contacting a flexible substrate and a substrate on the outer periphery of a film forming chamber space.
Alternatively, since it is made of an inorganic material such as ceramics, the adhesiveness to the substrate is low, and sticking between the seal portion and the substrate can be prevented. In addition, by using an inorganic substance such as metal or ceramic for the seal portion, degassing is reduced as compared with, for example, using a fluorine-based rubber or coating the same.

The width of the seal portion in contact with the flexible substrate is 10 mm
As a result, the airtightness was improved and the common chamber pressure was reduced to 3 × 10 ^-2
It can be kept at Pa or less, and a stable discharge can be obtained in the film forming chamber. Pressure on the substrate at the seal is 1 × 10 ⁴ Pa or more 5 × 10
^By setting the pressure to ⁵ Pa or less, even if inorganic materials such as metals and ceramics with low elasticity are used as sealing materials, the flexible substrate will not be torn and the common chamber pressure will be kept at 3 × 10 ^-2 Pa or less. And a stable discharge can be obtained in the film forming chamber.

When the film forming chamber space is formed with the flexible substrate interposed therebetween, the surface of one of the operating film forming chambers can be moved with respect to the seal surface, so that the surface can be brought into contact with the seal surface accurately, and Gas leakage into the chamber can be reduced. Since the flexible substrate and the seal portion that comes into contact with the substrate on the outer periphery of the film forming chamber and hermetically seals the vacuum are made of metal or inorganic material such as ceramic,
Eliminating the cooling of the seal portion prevents a decrease in the heater temperature in a portion close to the seal portion, makes the temperature of the substrate on which the thin film is formed uniform over the entire film formation region, and improves the uniformity of the film quality.

By using a metal foil for the lip, the lip can be attached without cooling, and the film can be formed by extending wrinkles of the flexible substrate. The high voltage electrode and the ground electrode are insulated from each other by using a film-forming chamber structure in which the high voltage electrode and the ground electrode are insulated from each other by using a flexible insulating sheet. By using a polyimide-based or aramid-based polymer film for the flexible insulating sheet substrate, a high-quality film with little outgassing, that is, a high-quality photoelectric conversion element can be formed.

The replacement is facilitated by fixing the insulator from these side surfaces instead of sandwiching it between the high voltage electrode and the ground electrode. Since the surface other than the sealing surface of the flexible insulating sheet is roughened, film peeling is less likely to occur.

[0045]

FIG. 1 is an enlarged sectional view of a sealing portion of a film forming chamber of a thin film manufacturing apparatus according to the present invention, wherein FIG. . The entire film forming chamber is the same as FIG. 1 and corresponds to the conventional seal partial view 10. Band-shaped end plates 171 and 123 serving also as seal portions provided on the upper film forming chamber wall 22 and the lower film forming chamber wall 27, respectively, and a lip retainer 172.
Uses an Al material. In this embodiment, the band-shaped end plates 171 and 123 also serving as a seal portion, and the lip holder 17 are provided.
Although Al was used for 2, any other inorganic material such as a metal or a ceramic with little outgassing may be used. The lip 7 is made of fluorine rubber. The flexible substrate used was a polyimide substrate having a thickness of 50 μm, on which metal or metal oxide-containing multi-layered electrode layers were formed on both surfaces. When the width W of the portion of the strip-shaped ring end plates 171 and 123 serving as the seal portions provided in the upper film forming chamber wall 22 and the lower film forming chamber wall 27 that comes into contact with the flexible substrate is set to 10 mm or more, airtightness is obtained. (Sealability) could be secured.

Further, when forming a film forming chamber space with a flexible substrate interposed therebetween, the movable film forming chamber wall on one side is flexed so as to be able to come into accurate contact with the sealing surface. The chamber seal was secured. As a result, the leakage of gas into the common chamber when the film forming gas was sealed in the film forming chamber space could be reduced. The pressure in the deposition chamber is 3 × 10 ^-1 to 5 × 10 ² P
When maintained in the range of a, the pressure in the common chamber could be kept at 3 × 10 ^-2 Pa or less, and stable discharge was possible in the film formation chamber.

When the thickness of the flexible substrate was changed,
At 25 μm or less, the gas leaked from the deposition chamber to the common chamber, and the common chamber pressure could not be maintained at 3 × 10 ⁻² Pa or less. Further, when a flexible metal foil substrate was used, the common chamber pressure could not be kept at 3 × 10 ⁻² Pa or less. When the pressure sandwiching the flexible substrate is 5 × 10 ⁵ Pa or more, the flexible substrate may be damaged and torn. Also, 1 × 10 ⁴ Pa
In the following cases, the pressure in the common chamber could not be maintained at 3 × 10 ⁻² Pa or less, and stable discharge could not be performed in the film formation chamber.

FIG. 2 is a graph showing the dependence of the photoelectric conversion efficiency of the photoelectric conversion element formed by the thin film manufacturing apparatus according to the present invention on the heater temperature during film formation. Curve a is an element in which an intrinsic semiconductor layer is formed in a film formation chamber of a metal seal portion according to the present invention, and curve b is an element in which an intrinsic semiconductor layer is formed in a film formation chamber of a conventional fluorine rubber seal portion. It is the characteristic of. When the fluorine rubber is used as the seal part, increasing the heater temperature will increase the temperature of the seal part, thus increasing the degassing of impurities.
When metal is used, degassing hardly increases. For this reason, when the sealing portion is made of metal, the outgassing from the sealing portion is small even when the film is formed by increasing the heater temperature, so that the intrinsic semiconductor layer has a good film quality and a high conversion efficiency, as compared with the case of the fluorine rubber. Decrease was small. Example 2 In the film forming chamber of Example 1 (FIG. 1), a metal (stainless steel) foil was used as a material of the lip 7. In the case of the metal foil, the pressure per contact area with the substrate is higher than that of the fluorine-based rubber, but the frictional force with the substrate is small. Therefore, the peripheral section of the lip 7 is bent in an arc shape to increase the contact area. The frictional force was increased, and the wrinkle extension by the lip 7 was improved. Embodiment 3 FIGS. 3A and 3B show a seal portion of a film forming chamber according to another embodiment of the present invention, in which FIG. 3A shows an opened state and FIG. 3B shows a sealed state. Example 2
The upper film forming chamber wall 22 in FIG. 1 and the high-voltage electrode 32 having a conventional heater 33 are integrally formed. In the present embodiment, the seal members 171 and 123 and the lip retainer 172 are made of Al, and the metal foil lip 7 is attached. In addition, in order to ensure the sealing between the film forming chamber and the common chamber, when forming the film forming chamber space with the flexible substrate interposed therebetween, the surface of one of the operating film forming chambers is positioned with respect to the sealing surface. Movable so as to be able to make accurate contact with the sealing surface.

In the case of this structure, the seal portion is entirely made of metal.
Since there is no softening or degassing, a cooling mechanism for the seal is required.
There is no need to reduce the heater temperature near the seal
The substrate temperature for forming a thin film is made uniform over the entire deposition area
And the peeling of the film adhered to the film forming chamber wall can be suppressed.
Therefore, deterioration of film quality due to peeling flakes does not occur,
The uniformity of the film quality was also improved. Example 4 In this example, the upper film forming chamber in Example 3 (FIG. 3) was used.
The wall 22 and the strip-shaped end plate 171 are made of the same material.
Body structure. Therefore, the temperature of the seal part and its vicinity
Temperature can be raised close to the substrate temperature, and substrate temperature uniformity
And the variation in characteristics within the substrate was reduced. Example 5: FIG. 4 shows a film forming apparatus for simultaneously forming films on two substrates.
3 is an enlarged cross-sectional view of a seal portion of a film forming chamber of FIG.
(B) is a conventional structure. This figure is shown in FIG.
In order to simplify the seal part of the structure shown in
It is. Conventionally, quartz and sealing material 2 are used as the insulator 253.
52 is made of a fluorine-based rubber or a seal
A thick fluorine-based rubber, which also serves as a material and an insulator, is used.
However, as the temperature rises, the photoelectric conversion element becomes impure.
Substance gas is degassed and causes deterioration of film quality.
I was In this embodiment, the high voltage electrode 221 and the ground electrode
Insulating sheet for insulating frame 254 having the same potential as 222
201 is a seamless (endless) 50μm thick
A polyimide sheet was used. Similarly, the exhaust member 208 and the high
The voltage electrode 221 was also connected by the insulating sheet 201. Absolute
The high voltage electrode 221 and the ground electrode of the edge sheet 201 are used.
The fixing to the frame body 254 is different from the conventional sandwich structure.
Differently, fix the fixing jig 260 with screws from the side and
The sheet 201 is sandwiched between the electrodes. This
The pressure in the common chamber is 3 × 10 ^-2Pa and below
It is possible to maintain stable discharge and uniform film formation.
I was able to.

The material is not limited to the polyimide sheet, and for example, an aramid resin can be used as long as the material is excellent in heat resistance and high-frequency insulation properties. In addition, since it is necessary to fit each electrode and the sealing surface shape without gaps,
It has been found that these insulating sheets preferably have a thickness of 10 to 500 μm. Since the film is formed also on the insulating sheet, it is possible to suppress film peeling by roughening a portion other than the seal portion by, for example, sandblasting, thereby forming a film having few defects such as pinholes. Was completed.

The seal between the high-voltage electrode 221 and the exhaust block 209 on the back surface thereof can also be made of the flexible insulating sheet 201. The film produced by the apparatus employing such a sealing method had high quality without being affected by degassing from the vacuum sealing material. Example 6 In a film forming chamber having a structure combining Example 3 and Example 5,
Fluorine-based rubber does not exist in the portion exposed to the film formation atmosphere, and all are metal except for the substrate on which the film is formed and the flexible insulating sheet for sealing the common chamber and the film formation chamber. In the film forming chamber having such a structure, it is not necessary to cool the seal portion. Therefore, there is no low-temperature portion in the film formation chamber, and a flake-like film that causes pinholes is hardly generated.

Further, since the space between the high voltage electrode and the ground electrode is a flexible and flexible insulating sheet, there is no influence of thermal distortion due to thermal expansion or thermal contraction of the film forming chamber. Furthermore, the device structure is simple and the cost can be kept low. Embodiment 7 FIG. 5 is a side sectional view of a thin film manufacturing apparatus of a stepping roll film forming system having a tension adjusting device according to the present invention. In order to transport the flexible substrate, tension is applied in the transport direction of the substrate. Since the transport distance becomes longer, the number of rolls that support the flexible substrate must be increased, and the loss of tension on the roll axis increases. As a result, the tension on the flexible substrate is reduced, and wrinkles of the substrate are reduced. Etc. easily occur. In this embodiment, the tension adjusting device T is arranged between the film forming chambers of the flexible substrate. The tension adjusting device T includes a driving roll R1 and a slack adjusting roll R2. The driving roll R1 pulls and conveys the substrate, and the slack adjusting roll R2 applies a pulling force that does not cause wrinkles. In this manner, the tension of the substrate was maintained at about 100 N / width, no wrinkles were generated, and no characteristic failure due to deformation of the substrate due to excessive tension was generated.

When a pin / pin two-layer tandem amorphous silicon solar cell was manufactured using a thin film manufacturing apparatus of the stepping roll type having the film forming chamber of this embodiment, the initial stage was smaller than that manufactured by the thin film manufacturing apparatus having the conventional structure. The photoelectric conversion efficiency was high and the light degradation rate was low. In particular, the structure of the film forming chamber of Example 6 was effective for the film forming chamber for forming the i-layer.

[0054]

According to the present invention, a transport system for transporting a flexible substrate into one common vacuum chamber, and one or more units provided with means for forming a thin film on the flexible substrate are provided. Each of the film forming chambers includes two film forming section chambers each having an opening bounded by a flexible substrate, and each opening is provided with a seal section. In a thin film manufacturing apparatus in which the film formation chamber and the common vacuum chamber are hermetically sealed with the substrate interposed therebetween, since an inorganic material such as metal or ceramic is used for the seal portion, a fluorine-based rubber that is frequently degassed is used. And there is no degassing compared to what is coated on this,
In addition, the airtightness between each of the film forming chambers and the common chamber was improved, so that a high-quality film could be formed, and the photoelectric conversion efficiency of the photoelectric conversion element was improved. Further, sticking of the flexible substrate to the seal portion can be prevented. As a result, trouble in transporting the flexible substrate has been eliminated.

Further, by using a metal foil for the lip, a cooling mechanism is not required, the temperature of the portion near the seal portion can be kept high, the substrate temperature can be made uniform over the entire film formation area, and the uniformity of film quality can be improved. did. Further, the cost of the apparatus can be significantly reduced. Since the high voltage electrode and the ground electrode are of a film forming chamber structure insulated by an insulator, and a flexible insulating substrate is used for the insulator, the manufacturing cost of the apparatus is reduced.

The replacement is facilitated by fixing the insulator not from the side between the high-voltage electrode and the ground electrode but from these side surfaces.

[Brief description of the drawings]

FIGS. 1A and 1B are enlarged cross-sectional views of a sealing portion of a film forming chamber of a thin film manufacturing apparatus according to the present invention, wherein FIG.

FIG. 2 is a graph showing the heater temperature dependence of the photoelectric conversion efficiency of the photoelectric conversion element formed by the thin film manufacturing apparatus according to the present invention during the film formation.

3A and 3B are enlarged cross-sectional views of a sealing portion of a film forming chamber according to another embodiment of the present invention, wherein FIG. 3A is open and FIG.

FIGS. 4A and 4B are enlarged cross-sectional views of a sealing portion of a film forming chamber of a film forming apparatus for simultaneously forming a film on two substrates, wherein FIG. 4A is a structure according to the present invention, and FIG.

FIG. 5 is a side sectional view of a thin film manufacturing apparatus of a stepping roll film forming method having a tension adjusting device according to the present invention.

FIG. 6 is a side sectional view of a thin film manufacturing apparatus of a stepping roll film forming system having a plurality of film forming chambers in a common vacuum chamber.

FIGS. 7A and 7B are cross-sectional views of a film forming chamber of a conventional stepping roll type thin film manufacturing apparatus, in which FIG.

FIG. 8 is a cross-sectional view of a seal portion of a lower and upper film forming chambers of a film forming chamber of a conventional thin film manufacturing apparatus.

FIG. 9 is a cross-sectional view perpendicular to the direction in which a flexible substrate is conveyed when a film forming chamber of a conventional thin film manufacturing apparatus for forming a film by plasma CVD is opened.

10 is an enlarged cross-sectional view of a sealing portion of a film forming chamber of a conventional thin film manufacturing apparatus (FIG. 9), where FIG.
(B) when the film forming chamber is sealed

11A and 11B are cross-sectional views of a film forming chamber of a conventional thin film manufacturing apparatus for simultaneously forming a film on two substrates, and FIG.
(B) when the film forming chamber is sealed

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Flexible substrate 21 Lower film forming chamber wall 22 Upper film forming chamber wall 27 Top plate 28 Housing 29 Moving plate 43 Moving plate 30 Vertical drive guide 31 High voltage electrode 32 Ground electrode 36 Common vacuum chamber wall 41 Actuator 44 Actuator 6 Film forming space 61 Vacuum exhaust pipe 64 Flexible piping 7 Lip 71 L-shaped packing 72 Lip holding 80 Film forming chamber 81 Common chamber 82 Core 83 Core 123 Band end plate 171 Band end plate 173 Lip holding 201 Insulating flexible Functional substrate 205 Deposition chamber 206 Plasma 208 Exhaust member 209 Exhaust block 210 Common chamber 221 High voltage electrode 222 Ground electrode 223 Heater 252 Seal material 253 Insulator 254 Frame 255 Seal material 258 Screw 260 Fixing jig 272 Vacuum exhaust port T tension Adjustment device First drive roll R2 slack adjustment roll

Claims (14)

[Claims] In a common vacuum chamber, there is provided a transfer system for transferring a flexible substrate, and one or a plurality of film forming chambers provided with means for forming a thin film on the flexible substrate. Each of the film forming chambers includes two film forming section chambers each having an opening bounded by a flexible substrate, and each opening is provided with a seal portion, and each seal portion is aligned with the substrate interposed therebetween. A thin-film manufacturing apparatus in which the space between the film forming chamber and the common vacuum chamber is airtight, wherein the seal portion is made of an inorganic material such as metal or ceramic. 2. The thin film manufacturing apparatus according to claim 1, wherein a width of a portion of the seal portion that contacts the substrate is 10 mm or more. 3. The thin film manufacturing apparatus according to claim 1, wherein a movable film forming section chamber of the film forming section chamber and a heater for heating a substrate have an integral structure. 4. The thin-film manufacturing apparatus according to claim 3, wherein the movable film-forming section chamber and the sealing section are made of the same material and are integrated. 5. The pressure of said seal portion is 1 × 10 ⁴ Pa or more and 5 ×
^5. The thin film manufacturing apparatus according to claim 1, wherein the pressure is 10 ⁵ Pa or less. 6. A common vacuum chamber having a transport system for transporting a flexible substrate and one or a plurality of deposition chambers having means for depositing a thin film on the flexible substrate. Each of the film forming chambers includes two film forming section chambers each having an opening bounded by a flexible substrate, and each opening is provided with a seal portion, and each seal portion is aligned with the substrate interposed therebetween. In a thin-film manufacturing apparatus in which the space between the film forming chamber and the common vacuum chamber is airtight, the sealing portion of the opening of one of the film forming section chambers is a metal foil or plate,
An apparatus for manufacturing a thin film, comprising: an elastic lip-shaped body inclined toward the outside of a film forming section chamber. 7. A common vacuum chamber having a transfer system for transferring a flexible substrate and one or more film forming chambers provided with means for forming a thin film on the flexible substrate. Each of the film forming chambers includes two film forming section chambers each having an opening bounded by a flexible substrate, and each opening is provided with a seal portion, and each seal portion is aligned with the substrate interposed therebetween. A thin-film manufacturing apparatus in which the space between the film-forming chamber and the common vacuum chamber is hermetically sealed, and one of the film-forming chambers includes a high-voltage electrode and a sealing portion around the periphery thereof. A thin-film manufacturing apparatus, wherein a flexible insulating sheet is used as an insulator between the high-voltage electrode and a portion that effectively becomes a ground potential. 8. The thin-film manufacturing apparatus according to claim 7, wherein the portion that effectively becomes the ground potential is an exhaust member of a film forming chamber. 9. The thin-film manufacturing apparatus according to claim 7, wherein the portion which becomes an effective ground potential is a frame around the periphery of the ground electrode in the film forming chamber. 10. The thin film manufacturing apparatus according to claim 7, wherein said flexible insulating sheet is fixed by a band-shaped fixing jig. 11. An apparatus according to claim 7, wherein said insulating sheet is made of a polyimide resin or an aramid resin. 12. The insulating sheet has a thickness of 10 μm to 500 μm.
The thin film manufacturing apparatus according to claim 11, wherein 13. The thin film manufacturing apparatus according to claim 1, further comprising a substrate tension adjusting device between said film forming chambers. 14. A thin-film photoelectric conversion device comprising at least a photoelectric conversion layer and an electrode layer laminated, wherein the thin-film photoelectric conversion device is manufactured by the thin-film manufacturing apparatus according to claim 1.