JP2722115B2 - Method and apparatus for continuously forming large-area functional deposition film by microwave plasma CVD - Google Patents

Description

Description: TECHNICAL FIELD [0001] The present invention uses a novel microwave energy supply device capable of generating uniform microwave plasma over a large area, and a plasma reaction caused by the device. The present invention relates to a method and an apparatus for continuously forming a large-area functional deposition film by decomposing and exciting a source gas.

More specifically, there is provided a method and apparatus capable of dramatically increasing the utilization efficiency of the raw material gas and capable of continuously forming a functional deposition film having high uniformity at high speed over a large area. Can realize mass production of large-area thin-film semiconductor devices such as photovoltaic elements at low cost.

[Description of Prior Art]

In recent years, the demand for electric power has rapidly increased worldwide, and the problem of environmental pollution has become more serious as electric power production has been activated to meet such demand.

However, it is expected as a power generation method to replace thermal power generation,
In nuclear power, which has already entered the practical period,
Serious radioactive contamination, which is typified by the Chernobyl nuclear power plant accident, harms the human body and invades the natural environment, threatening the future spread of nuclear power generation. There are even countries that have banned laws.

In addition, the use of fossil fuels, such as coal and petroleum, is steadily increasing in order to meet the increasing demand for electricity even with thermal power generation. It raises the concentration of greenhouse gases such as carbon dioxide and causes global warming, and the annual average temperature of the earth is steadily rising.
The Energy Agency) has proposed reducing CO2 emissions by 20% by 2005.

Against this background, the artificial increase in developing countries and the accompanying increase in electricity demand are inevitable.
The power supply problem must be considered on a global scale, coupled with an increase in power consumption per capita due to the further promotion of electronics in lifestyles in advanced countries.

Under such circumstances, the power generation method using solar cells using sunlight does not cause the above-mentioned problems such as radioactive contamination and global warming, and the sunlight falls all over the earth. Energy sources are less unevenly distributed, and relatively high power generation efficiency can be obtained without the need for complicated large-scale facilities, so that it can respond to future increases in power demand without causing environmental destruction. Attention has been paid to a clean power generation system, and various research and developments have been made for practical use.

By the way, for a power generation method using a solar cell, in order to establish it as one that meets the power demand, the solar cell to be used has sufficiently high photoelectric conversion efficiency and excellent characteristic stability, and It is basically required to be mass-produced.

By the way, in order to supply necessary electricity in a general household,
Where a solar cell with an output of about 3 kW per household is required, if the photoelectric conversion efficiency of the solar cell is, for example, about 10%, the area of the solar cell for obtaining the required output is about 30 m ² Becomes For example, in order to supply necessary electric power to 100,000 households, a solar cell having an area of 3,000,000 m ² is required.

For this reason, a gaseous raw material gas such as silane, which is easily available, is used, and is decomposed by glow discharge to deposit a semiconductor thin film such as amorphous silicon on a relatively inexpensive substrate such as glass or a metal sheet. Solar cells that can be manufactured by such a method are attracting attention because of their high mass productivity and the possibility that they can be manufactured at a lower cost than solar cells manufactured using single-crystal silicon or the like. Has been made.

In a power generation system using a solar cell, a form in which unit modules are connected in series or in parallel to obtain a desired current and voltage by unitization is often adopted, and disconnection or short circuit does not occur in each module. Is required. In addition, it is important that there is no variation in output voltage or output current between the modules. For this reason, it is required that the uniformity of the characteristics of the semiconductor layer itself, which is the largest characteristic determining factor, be ensured at least at the stage of manufacturing the unit module. From the viewpoint of facilitating module design and simplifying the module assembling process, the provision of a semiconductor deposition film having excellent uniformity of characteristics over a large area enhances mass productivity of solar cells, Required to achieve significant reductions in production costs.

As for the solar cell, a semiconductor layer, which is an important component, has a semiconductor junction such as a so-called pn junction or a pin junction. These semiconductor junctions are formed by sequentially laminating semiconductor layers of different conductivity types, implanting dopants of different conductivity types into a semiconductor layer of one conductivity type by ion implantation, or diffusing them by thermal diffusion. Achieved.

Looking at this point, solar cells using thin-film semiconductors such as amorphous silicon, which have attracted attention,
In the production, phosphine (PH ₃ ), diborane (B
A semiconductor film having a desired conductivity type is obtained by mixing a source gas containing an element serving as a dopant such as ₂ H ₆ ) with silane or the like as a main source gas and subjecting the mixture to glow discharge decomposition. It is known that a semiconductor junction can be easily achieved by sequentially laminating the semiconductor films. For this reason, in order to manufacture an amorphous silicon-based solar cell, a method has been proposed in which an independent film formation chamber for forming each semiconductor layer is provided, and each semiconductor layer is formed in the film formation chamber. ing.

By the way, U.S. Pat.
A continuous plasma CVD apparatus employing a roll-to-roll system is disclosed. According to this apparatus, a plurality of glow discharge regions are provided, and a sufficiently long flexible substrate having a desired width is arranged along a path through which the substrate sequentially passes through each of the glow discharge regions. It is stated that the element having a semiconductor junction can be continuously formed by continuously transporting the substrate in the longitudinal direction while depositing and forming a conductive semiconductor layer required in the discharge region. In this specification, a gas gate is used to prevent a dopant gas used for forming each semiconductor layer from diffusing and mixing into another glow discharge region. Specifically, each of the glow discharge regions is
Separated from one another by a slit-shaped separation passageway, and is employed further the separation passage, for example, Ar, means for forming a flow of scavenging gas such as H _2. From this, it can be said that this roll-to-roll system is suitable for mass production of semiconductor devices.

However, since the formation of each semiconductor layer is performed by a plasma CVD method using RF (radio frequency), it is naturally a limit to improve the film deposition rate while maintaining the characteristics of a continuously formed film. There is. That is, for example, even when a semiconductor layer having a thickness of at most 5000 ° is formed, it is necessary to always generate a predetermined plasma over a large area and maintain the plasma uniformly. However, doing so requires considerable skill and it is difficult to generalize the various plasma control parameters involved. In addition, the decomposition efficiency and utilization efficiency of the film-forming source gas used are not high, which is one of the factors for raising the production cost.

In addition, Japanese Patent Application Laid-Open No. 61-288074 discloses a deposited film forming apparatus using an improved roll-to-roll method. In this apparatus, a hollow continuous portion is formed in a part of a flexible continuous sheet-like substrate installed in a reaction vessel, and active species generated in an activation space different from that of the reaction vessel in this, and It is characterized in that another source gas is introduced as required and a chemical interaction is caused by thermal energy to form a deposited film on the inner surface of the sheet-like substrate forming the holo-like slack portion. By depositing on the inner surface of the holo-like sag as described above,
The device can be made compact. Further, since active species that have been activated in advance are used, the film forming speed can be increased as compared with a conventional deposited film forming apparatus.

However, this apparatus utilizes a deposited film forming reaction due to chemical interaction in the presence of thermal energy, and in order to further improve the film forming rate, the amount of active species introduced and the thermal energy must be reduced. Although it is necessary to increase the supply amount, there is also a limit to a method for supplying a large amount of heat energy uniformly, and a method for generating a large amount of highly reactive active species and introducing it to the reaction space without loss.

On the other hand, a plasma process using microwaves has recently attracted attention. Since the microwave has a short frequency band, the energy density can be increased as compared with the case of using the conventional RF, and is suitable for efficiently generating and sustaining the plasma.

For example, U.S. Pat.Nos. 4,517,223 and 4,50
No. 4,518 discloses a method of depositing and forming a thin film on a substrate having a small area in a microwave glow discharge plasma under a low pressure. Not only can high-quality deposited films be prevented by preventing the polymerization of active species that cause a decrease in film characteristics, but also the generation of powders such as polysilane in plasma can be suppressed.
Although it is said that the deposition rate can be dramatically improved, no specific disclosure has been made in forming a uniform deposited film over a large area.

On the other hand, U.S. Pat.No. 4,729,341 discloses a low-pressure microwave plasma CVD for depositing and forming a photoconductive semiconductor thin film on a large-sized cylindrical substrate by a high-power process using a pair of radiation-type waveguide applicators. Although a method and an apparatus are disclosed, the large-area substrate is limited to a cylindrical substrate, that is, a drum as a photoreceptor for electrophotography, and is applied to a large-area and long substrate. Absent.

By the way, since plasma using microwaves has a short microwave wavelength, energy non-uniformity is likely to occur, and there are various problems that must be solved for increasing the area.

For example, an effective means for equalizing microwave energy is the use of a slow-wave circuit, which has an abrupt microwave coupling to the plasma as the microwave applicator increases in lateral distance. It has a unique problem that a drop occurs. Therefore, as a means for solving this problem, a method of changing the distance between the object to be processed and the slow wave circuit to make the energy density near the surface of the substrate uniform has been attempted. For example, U.S. Pat.
No. 4,521,717 discloses such a method. In the former, it is described that the slow-wave circuit needs to be inclined at a certain angle with respect to the substrate, but the transmission efficiency of microwave energy to plasma is not satisfactory. Further, in the latter, it is disclosed that two slow wave circuits are provided in a plane parallel to the base body in a non-parallel manner. That is, it is desirable that the planes perpendicular to the center of the microwave applicator cross each other in a plane parallel to the substrate to be processed and on a straight line perpendicular to the moving direction of the substrate. In order to avoid interference between the two applicators, each of them is displaced laterally to the direction of movement of the substrate by half the length of the waveguide crossbar.

Some proposals have been made to maintain plasma uniformity (ie, energy uniformity). The proposals are, for example, from the Journal of Vacuum Technology.
Science Technology) B-4 (January-February 1986) 295
Page-298 and B-4 of the magazine (January-February 1986) 126
See page-130. According to these reports, microwave plasma disk sources (MP
A microwave reactor called DS) has been proposed.
That is, the plasma has a disk-like or tablet-like shape, and its diameter is a function of the microwave frequency. And those reports disclose the following contents. That is, first, the plasma disk source can be changed by the microwave frequency. However, in the microwave plasma disc source which is designed to operate at 2.45 GHz, the plasma confinement diameter is at most about 10 cm, a most 118cm ³ about even if the plasma volume, the large area I can't say at all. The report also states that
In systems designed to operate at frequencies as low as 5 MHz, the lower frequency provides a plasma diameter of about 40 cm and a plasma volume of 2000 cm ³ . The report further reports that the lower frequency, e.g., 400 MHz
It is said that the discharge can be expanded to a diameter of more than 1 m by operating at. However, a device which achieves this content requires a very expensive specific device.

In other words, a large-area plasma can be achieved by lowering the frequency of the microwave, but a high-power microwave power supply in such a frequency range has not been generalized and is difficult to obtain. Very expensive, if at all. Also, it is more difficult to obtain a variable-power high-power microwave power supply.

Similarly, as a means for efficiently generating high-density plasma using microwaves, a method of arranging an electromagnet around a cavity resonator and satisfying ECR (Electron Cyclotron Resonance) conditions is disclosed in Japanese Patent Laid-Open No. 55-141729. Japanese Patent Application Laid-Open No. 57-133636 and Japanese Patent Application Laid-Open No. 57-133636, and various reports have been made by academic societies and the like that various types of semiconductor thin films are formed using this high-density plasma. Microwave EC
R plasma CVD equipment has been commercialized.

However, in these methods using ECR, since a magnet is used to control the plasma, the non-uniformity of the plasma due to the wavelength of the microwave and the non-uniformity of the magnetic field distribution are also added. It is technically difficult to form a uniform deposited film on a substrate having a large area. In addition, when the device is enlarged for the purpose of increasing the area, the electromagnets naturally used also increase in size, resulting in an increase in weight and space,
Further, there are various problems that must be solved for practical use, such as measures against heat generation and the necessity of a DC stabilized power supply with a large current.

Furthermore, the characteristics of the deposited film formed are not at a level that can be said to be equivalent to those formed by the conventional RF plasma CVD method, and the deposited film is formed in a space where ECR conditions are satisfied. The characteristics and the deposition rate are extremely different between a deposited film formed in a so-called divergent magnetic field space outside the ECR condition and a deposited film formed outside the ECR condition. Therefore, this method is particularly suitable for the fabrication of semiconductor devices requiring high quality and uniformity. It can not be said.

The aforementioned U.S. Pat.Nos. 4,517,223 and 4,729,3
In the specification of No. 41, regarding obtaining a high density plasma,
It is disclosed that there is a need to maintain a very low pressure. That is, a process under a low pressure is indispensable to increase the deposition rate and increase the gas use efficiency. However, neither the slow-wave circuit nor the electron cyclotron resonance disclosed in the aforementioned patents is sufficient to maintain the relationship between high deposition rate, high gas utilization efficiency, high power density and low pressure. Things.

Accordingly, there is a need for an early provision of a new microwave applicator that solves the various problems of the microwave means described above.

By the way, thin-film semiconductors have a large area or a long size, such as thin-film transistors (TFTs) for driving pixels of a liquid crystal display and photoelectric conversion elements and switching elements for contact-type image sensors, in addition to the above-mentioned applications for solar cells. It is also suitably used for the production of thin film semiconductor devices that need to be used, and is partially used as a key component for the image input / output device. By providing a deposited film formation method,
It is expected that it will become more widely spread.

[Object of the invention]

The present invention overcomes the above-mentioned problems in the conventional thin film semiconductor device forming method and apparatus and provides a novel method and apparatus for forming a functional deposition film uniformly and at high speed over a large area. The purpose is to do so.

Another object of the present invention is to provide a method and an apparatus for continuously forming a functional deposition film on a belt-shaped member.

A further object of the present invention is to provide a method and apparatus capable of dramatically increasing the utilization efficiency of a source gas for forming a deposited film and realizing mass production of thin film semiconductor devices at low cost.

Yet another object of the present invention is to provide a microwave applicator that can generate a substantially uniform microwave plasma over a large area and a large volume.

Still another object of the present invention is to provide a novel method and apparatus for forming a photovoltaic device having a high efficiency and a high photoelectric conversion efficiency continuously on a relatively wide and long substrate. Is what you do.

[Structure and effect of the invention]

The present inventors have solved the above-mentioned problems in the conventional thin film semiconductor device forming apparatus, and have conducted intensive research to achieve the object of the present invention. A state in which microwave applicator means for emitting or transmitting with directivity in one vertical direction is included in a microwave transmitting member, and the inner peripheral wall of the microwave applicator means is not in contact with the microwave applicator means. When a microwave is supplied from a microwave power supply to the microwave applicator means, a raw material gas for forming a deposited film is introduced into the film formation chamber, and a predetermined pressure is maintained. It has been found that uniform microwave plasma can be generated in the longitudinal direction of the applicator means in the film forming chamber.

The present invention has been completed as a result of further studies based on the above-described findings, and continuously forms a large-area functional deposited film by a microwave plasma CVD method having the following points. Methods and apparatus.

The method of the present invention is as follows. That is, while continuously moving the band-shaped member in the longitudinal direction, a column-shaped film-forming space having the moving band-shaped member as a side wall is formed in the middle thereof, and the deposited film is formed in the film-forming space via a gas supply means. The raw material gas for formation is introduced, and at the same time, the microwave energy is applied from the microwave applicator means which emits or transmits the microwave energy in one direction perpendicular to the traveling direction of the microwave. Irradiating or transmitting microwave plasma in the film forming space to form a deposited film on the surface of the continuously moving strip-shaped member constituting the side wall exposed to the microwave plasma. Characteristic microwave plasma
This is a method for continuously forming a functional deposited film by a CVD method.

In the method of the present invention, the moving strip-shaped member
On the way, using the curved start end forming means and the curved end end forming means, the band-shaped member is left with a gap in the longitudinal direction of the band-shaped member between the curved start end forming means and the curved end end forming means. The member is curved to form a side wall of the film forming space.

Then, microwave energy may be radiated or transmitted into the film forming space from a gap left in the longitudinal direction of the band-shaped member between the bending start end forming unit and the bending end end forming unit. Alternatively, the microwave energy is applied to the film forming space by projecting the microwave applicator means into the film forming space from one of both end surfaces of a columnar film forming space formed with the band-shaped member as a side wall. You may make it radiate | transmit or transmit in space.

The microwave energy radiated or transmitted from the microwave applicator means is radiated or transmitted into the film deposition space via a microwave permeable member provided between the film deposition space and the applicator means. To

In a range not to contact the microwave permeable member,
The microwave applicator means is disposed close to and substantially parallel to the width direction of the band-shaped member so as to radiate or transmit microwave energy into the columnar deposition space.

The microwave applicator radiates or transmits microwave energy uniformly to a length substantially equal to the width direction of the band-shaped member.

The microwave applicator means is separated from the microwave plasma generated in the film forming space via the microwave permeable member.

In the method of the present invention, the microwave energy radiated or transmitted into the columnar deposition space is prevented from leaking outside the deposition space.

Further, the apparatus of the present invention is an apparatus for continuously forming a functional deposition film on a continuously moving band member by a microwave plasma CVD method, wherein the band member is continuously formed in a longitudinal direction thereof. While moving, via a curved portion forming means for bending in the middle, the band-shaped member is formed as a side wall, and has a columnar film-forming chamber capable of holding the inside thereof substantially in a vacuum, Microwave applicator means for emitting microwave energy with directivity in one direction perpendicular to the traveling direction of microwaves, for generating microwave plasma in the film forming chamber, and the microwave applicator Means for transmitting microwave energy radiated in one direction perpendicular to the direction in which the microwave travels into the film formation chamber, and A separating means for separating the microwave applicator means from microwave plasma occurred in the film forming chamber by wave energy,
Exhaust means for exhausting the film formation chamber, gas supply means for introducing a source gas for forming a deposited film into the film formation chamber,
Temperature control means for heating and / or cooling the strip-shaped member, and a deposited film is formed continuously on the surface of the strip-shaped member on the side exposed to the microwave plasma. This is a functional deposition film continuous forming apparatus characterized by the following.

In the apparatus of the present invention, the bending portion forming means includes at least one or more sets of a bending start end forming means and a bending end end forming means, wherein the bending start end forming means and the bending end end forming means are provided. The belt-shaped member is disposed with a gap left in the longitudinal direction.

The curved portion forming means is constituted by at least a pair of support / transport rollers and a support / transport ring,
The pair of support / transport rollers are disposed in parallel with a gap left in the longitudinal direction of the belt-shaped member.

In the apparatus according to the aspect of the invention, the separation unit may be disposed substantially parallel to a gap left between the bending start end forming unit and the bending end end forming unit, and may be disposed outside the film forming chamber. Alternatively, the band-shaped member may be made to protrude into the film forming chamber substantially in parallel with the width direction of the band-shaped member from one of both end faces of the columnar film-forming chamber formed with the band-shaped member as a side. good.

The separating means may be substantially cylindrical or substantially semi-cylindrical.

On the other hand, the microwave applicator means is disposed so as to be separated from the peripheral wall of the separation means and included in the inside of the separation means.

In the apparatus of the present invention, the separating means is provided with a cooling means, and the cooling means is an air flow flowing along an inner peripheral surface of the separating means.

Further, the cooling means may be configured concentrically with the separating means so as to have a conduit structure provided inside the separating means and capable of flowing a cooling medium between the separating means.

In the apparatus of the present invention, the microwave applicator means is a microwave transmission waveguide, and the microwave energy is applied to the film forming chamber substantially uniformly in a longitudinal direction of the microwave application direction. A substantially rectangular hole is provided for directing radiation in one direction perpendicular to.

In addition, at least one or more rectangular holes are formed on one surface of the waveguide, and microwaves are radiated from the holes.

When a plurality of rectangular holes are formed, these holes are arranged at intervals in the longitudinal direction of the waveguide.

In addition, the rectangular hole may be a single rectangular having a large aspect ratio, the size of which is greater than one wavelength of microwave and substantially the entire width and the longitudinal direction of the rectangular waveguide. Approximately equal in length.

Then, microwave energy is uniformly radiated from the rectangular hole in a length direction of at least one wavelength of the radiated microwave in the longitudinal direction of the waveguide.

Also, the square hole is provided with shutter means to ensure that microwave energy is emitted from the square hole at substantially uniform density over the entire length of the microwave applicator.

In the apparatus of the present invention, the microwave plasma is confined in a column-shaped film forming chamber formed by bending the band-shaped member.

Further, the apparatus of the present invention is an apparatus for continuously forming a functional deposition film on a continuously moving strip member by a microwave plasma CVD method, wherein the strip member is continuously moved in a longitudinal direction thereof. And a column-shaped film-forming chamber formed with the band-shaped member as a side wall and capable of holding the inside of the member substantially at a vacuum, through a curved portion forming means for bending in the middle thereof. Microwave applicator means for transmitting evanescent microwave energy with directivity in one direction perpendicular to the traveling direction of microwaves for generating microwave plasma in the film chamber; and the microwave applicator. Means for transmitting evanescent microwave energy transmitted with directivity in one direction perpendicular to the traveling direction of microwaves into the film forming chamber. Separating means for separating the microwave applicator means from microwave plasma generated in the film forming chamber by the evanescent microwave energy, and exhaust means for evacuating the film forming chamber; A gas supply unit for introducing a source gas for forming a deposited film into the chamber; and a temperature control unit for heating and / or cooling the band-shaped member, wherein the band-shaped member is exposed to the microwave plasma. A continuous apparatus for forming a functional deposited film, characterized in that a deposited film is continuously formed on the surface on the other side.

In the apparatus of the present invention, the microwave applicator means is an elongated slow-wave circuit waveguide, and the slow-wave circuit waveguide substantially uniformly emits evanescent microwave energy in the longitudinal direction into the film forming chamber. It has a ladder-like structure for transmitting.

The length of the ladder-like structure is substantially equal to the length of the band-shaped member in the width direction.

The ladder-like structure has a structure in which evanescent microwave energy is transmitted uniformly over at least one wavelength of the microwave transmitted in the longitudinal direction.

 Hereinafter, the method of the present invention will be described in more detail.

In the method of the present invention, most of the side wall of the columnar film-forming space formed by bending the band-shaped member using the bending start end forming unit and the bending end end forming unit in the middle of the moving band-shaped member. Is formed of the moving strip-shaped member, and a gap is left between the bending start end forming means and the bending end end forming means in the longitudinal direction of the strip-shaped member.

In the method of the present invention, in order to uniformly generate microwave plasma in the columnar deposition space, microwave applicator means capable of uniformly radiating or transmitting microwave energy in the width direction of the band-shaped member. From either one of both end surfaces in the columnar film-forming space, in a direction substantially parallel to the width direction of the band-shaped member, or between the bending start end forming means and the bending end end forming means. It is desirable to dispose in close proximity almost parallel to the gap left in the longitudinal direction. From the microwave applicator means, microwave energy is radiated or transmitted with directivity in one direction perpendicular to the traveling direction of the microwave, but in any case, the columnar film forming space The microwave energy radiated or transmitted into the inside is reflected and scattered by the band-like member constituting the side wall, uniformly fills the film forming space, and is simultaneously introduced by the gas supply means. Since the gas is efficiently absorbed, uniform microwave plasma can be formed.

However, in order to stably generate the microwave plasma with good reproducibility, the microwave energy is efficiently radiated or transmitted into the film formation space, and the microwave energy leaks from the film formation space. Care must be taken to prevent the occurrence of

For example, in the former case, a gap left in the longitudinal direction of the band-shaped member between one end face of the applicator unit that is not protruded and the curved start end forming unit and the curved end end forming unit of the band-shaped member. It is necessary to prevent leakage of microwave energy from the like, and the end face and the gap are sealed with a conductive member, or the hole diameter is preferably 1/2 wavelength or less of the wavelength of microwave used. It is more desirable to cover with a wire mesh of less than 1/4 wavelength, a punching board or the like.

When projecting the microwave applicator means into the film forming space, it is desirable that the microwave applicator means be disposed at a position substantially equidistant from the side wall, but when the curved shape of the side wall is asymmetric, etc. Is not particularly limited.

In the latter case, the direction in which the microwave energy is radiated or transmitted from the microwave applicator means with directivity is left between the bending start end forming means and the bending end end forming means of the band-shaped member. It must be suitable for the gap. Then, in order to efficiently radiate or transmit the microwave energy into the columnar deposition space, the longitudinal direction of the band-shaped member in the gap left between the curved start end forming means and the curved end end forming means The minimum dimension of the opening width is preferably 1/4 wavelength or more, more preferably 1/2 wavelength or more of the microwave wavelength.

If the gap and the interval between the microwave applicator means are too large, the amount of microwave energy radiated or transmitted into the film formation space decreases, and the radiated or transmitted microwave energy is reduced. There is a case where the confinement of wave energy becomes insufficient.

However, the radiation or transmission direction of the microwave energy and the opening width, and the interval between the gap and the microwave applicator are important in efficiently supplying the microwave energy into the columnar deposition space. Although it has a meaning but is mutually related, it is preferable to appropriately adjust and arrange so as to maximize the efficiency.

In addition, from both end surfaces of the columnar film-forming space, it is sealed with a conductive member so that microwaves do not leak, or the hole diameter is preferably 1/2 wavelength or less of the wavelength of microwave used, more preferably 1 or less. It is desirable to cover with a wire mesh of / 4 wavelength or less, a punching board or the like.

In the method of the present invention, both ends of a columnar film-forming space formed by curving the moving belt-shaped member using the curving start end forming means and the curving end forming means may be the film forming It is preferable that the microwave energy radiated or transmitted into the space is substantially uniformly filled in the film forming space, and the shape is similar to a circular shape, an elliptical shape, a square shape, a polygonal shape, and It is desirable to have a symmetrical and relatively smooth curved shape. Of course, in the gap portion left in the longitudinal direction of the band-shaped member between the bending start end forming means and the bending end end forming means, the end face shape may be discontinuous.

In the method of the present invention, the bending start end forming means and the bending end end forming means are disposed at least two places in the longitudinal direction of the moving band-shaped member, the band-shaped member is curved, and the curved band-shaped member is A columnar film-forming space is formed. It is preferable that the curved shape is always kept constant in order to maintain the stability and uniformity of the microwave plasma generated therein, and the band-shaped member is formed by the bending start end forming means and the bending end end. It is desirable that the forming means be supported so as not to cause wrinkles, sagging, lateral displacement and the like. Further, in addition to the bending start end forming means and the bending end end forming means, a support means for holding a curved shape may be provided. Specifically, a support means for continuously holding a desired curved shape may be provided inside or outside the curved band-shaped member. In the case where the support means is provided inside the curved band-shaped member, care should be taken to minimize the portion in contact with the surface on which the deposited film is formed. For example, it is preferable to provide the support means at both ends of the band-shaped member.

It is desirable to use a flexible member capable of continuously forming the curved shape as the band-shaped member, and to form a smooth shape at the curved start end, the curved end end, and the middle curved portion.

The source gas for forming a deposited film introduced into the film forming space by the gas supply means is efficiently exhausted to the outside of the film forming space, and the pressure in the film forming space is such that the microwave plasma is uniformly generated. , But there is no particular limitation on the direction in which the gas is exhausted. However, in the exhaust hole, it is necessary to take care that the microwave does not leak from the location and the source gas is efficiently exhausted. Of course, when the source gas is exhausted from the plurality of exhaust holes, it is preferable to make the gas diffusion, flow type, and the like in the film forming space substantially uniform. It may be restricted.

In order to uniformly and stably generate and maintain the microwave plasma in the columnar deposition space, the shape and volume of the deposition space, the type and flow rate of the source gas introduced into the deposition space, Although there are optimal conditions for the pressure in the film formation space, the amount of microwave energy radiated or transmitted into the film formation space, and the matching of microwaves, these parameters are organically connected to each other. It is not necessarily defined unconditionally, and it is desirable to set preferable conditions as appropriate.

According to the method of the present invention, a film-forming space having a band-shaped member as a side wall is formed, and the band-shaped member constituting the side wall of the film-forming space is continuously moved, and the side wall of the film-forming space is formed. By providing microwave applicator means for radiating or transmitting microwave energy uniformly in the width direction of the belt-shaped member to be formed, a large-area functional deposition film can be continuously formed with good uniformity. Can be.

The point that the method of the present invention is objectively distinguished from the conventional method of forming a deposited film is that the deposition space is formed in a columnar shape, the sidewall thereof continuously moves, and functions as a structural material. The point is that it also serves as a support for formation.

Here, the function as a structural material is a function of physically and chemically isolating an atmosphere space for film formation, that is, a film formation space and an atmosphere space not involved in film formation. This means, for example, a function of forming atmospheres with different gas compositions and states, restricting the flow direction of gas, and forming atmospheres with different pressure differences.

That is, in the method of the present invention, the band-shaped member is curved to form the side wall of the columnar film-forming space, and the other remaining wall surfaces, that is, both of the end surfaces and the gap left on a part of the side wall are formed. A source gas for forming a deposited film and microwave energy are supplied into the film formation space from any location, and the gas is exhausted, thereby confining the microwave plasma in the film formation space and forming the side wall. A functional deposition film is formed on a strip-shaped member to be formed, and the strip-shaped member itself plays an important function as a structural material for isolating a film-forming space from an external atmosphere space not involved in film-forming. Also, it can be used as a support for forming a deposited film.

Therefore, the atmosphere outside the film formation space configured with the strip-shaped member as a side wall is in a state considerably different from the inside of the film formation space in the gas composition, its state, pressure, and the like.

On the other hand, in the conventional method for forming a deposited film, a support for forming a deposited film is disposed in a film forming space for forming a deposited film, and is exclusively formed in the film forming space. It functions only as a member on which the precursor of the above is deposited, and does not function as a structural material constituting the film forming space as in the method of the present invention.

Further, in the conventional method such as RF plasma CVD, sputtering, etc., the substrate or the support for forming the deposited film may also serve as an electrode for generating and maintaining discharge, but the plasma confinement is insufficient. In addition, isolation from an external atmosphere space that is not involved in film formation is insufficient, and it cannot be said that the material functions as a structural material.

On the other hand, the method of the present invention uses a band-shaped member that can function as a support for forming a functional deposited film as a side wall of the film formation space, and exhibits a function as the structural material.
It is also possible to continuously form a functional deposition film on the belt-like member.

In the method of the present invention, a side wall of a columnar film-forming space is formed using the band-shaped member, and microwave energy is uniformly radiated or transmitted in the width direction of the band-shaped member into the column-shaped film-forming space, By confining microwaves in the columnar deposition space, microwave energy is efficiently consumed in the columnar deposition space, uniform microwave plasma is generated, and uniformity of the deposited film formed Also increase. Further, the belt-like member constituting the side wall exposed to the microwave plasma is continuously moved and discharged out of the film forming space, so that the band-like member has uniformity in the moving direction. High deposited film can be formed.

Of course, even if the band-shaped member is considerably wide, it can cope as long as the radiation or transmission of microwave energy from the microwave applicator means is kept uniform in the longitudinal direction.

In the method of the present invention, the gas composition and the state outside the film formation space are set in the film formation space so that a film formation space is formed by the strip-shaped member and a deposited film is formed only in the film formation space. Condition is set to be different from For example,
The gas composition outside the film formation space may be a gas atmosphere not directly involved in the formation of a deposited film, or may be an atmosphere containing a source gas discharged from the film formation space. Further, it is needless to say that the microwave plasma is confined in the film formation space, but it is necessary to prevent the microwave plasma from leaking out of the film formation space. This is also effective in improving the performance and preventing film deposition on unnecessary portions. Specifically, a pressure difference is applied between the inside and outside of the film formation space, an atmosphere of a so-called inert gas having a small ionization cross-sectional area, an atmosphere of H ₂ gas, or the like, or a microwave is actively generated from the inside of the film formation space. It is effective to provide a means that does not cause leakage. As means for preventing microwave leakage, a gap portion connecting the inside and outside of the film forming space is sealed with a conductive member, or the hole diameter is preferably 波長 wavelength or less of the wavelength of microwave used,
More preferably 1/4 wavelength or less wire mesh, may be covered with a punching board, and the maximum dimension of the gap connecting the inside and outside of the film forming space is preferably 1/2 wavelength or less of the microwave wavelength, more preferably It is desirable to set the wavelength to 1/4 wavelength or less.
Also, by setting the pressure outside the film formation space to be very low compared to the pressure in the film formation space, or by setting the pressure to a very high value, microwave plasma does not occur outside the film formation space. Such conditions can be set.

As described above, the method of the present invention is characterized in that the band-shaped member has a function as a structural material constituting a film-forming space, and is distinguished from the conventional method of forming a deposited film, and has a great effect. .

In the method of the present invention, the microwave energy is applied by giving a directivity in one direction perpendicular to the traveling direction of the microwave at least substantially uniformly with respect to the length in the width direction of the band-shaped member used from the microwave applicator means. Either a leaky wave type or a slow wave type is preferably applied for radiation or transmission. Regardless of the method, care is taken so that the amount of microwave radiation or transmission is uniform in the direction in which the microwave travels. Further, the microwave applicator means separates from microwave plasma generated in the film forming space by a microwave permeable member. By doing so, the microwave energy radiated or transmitted from the microwave applicator means is kept uniform in its longitudinal direction irrespective of changes in the external environment. For example, even in a case where a deposited film is deposited on the outer peripheral wall of the separation means and the absolute amount of microwave transmission changes, the uniformity of the microwave plasma in at least the longitudinal direction is maintained, and By employing a structure in which the separation means can be uniformly and efficiently cooled, it is also possible to avoid local nonuniformity of microwave transmission. Also,
If the cooling of the separating means is sufficiently performed, the method can cope with a considerably high power process.

Hereinafter, the configuration and features of the microwave plasma CVD apparatus of the present invention will be described in further detail in order.

According to the apparatus of the present invention, by confining the microwave plasma region with the moving band-shaped member, the precursor contributing to the formation of the deposited film generated in the microwave plasma region is formed on the band-shaped member with high yield. Since the capture and further the deposition film can be continuously formed on the belt-like member, the utilization efficiency of the source gas for forming the deposition film can be drastically increased.

Furthermore, by using the microwave applicator means of the present invention, the uniformity of the microwave plasma generated in the longitudinal direction of the microwave applicator means is enhanced, and thus the deposition formed in the width direction of the band-shaped member is improved. Of course, the uniformity of the film is excellent, and the belt-like member is formed in the longitudinal direction of the belt-like substrate by continuously transporting the belt-like member in a direction substantially perpendicular to the longitudinal direction of the microwave applicator means. The uniformity of the deposited film is also excellent.

In addition, according to the apparatus of the present invention, since the discharge can be maintained stably and uniformly, a functional deposition film having stable characteristics can be continuously formed on the long belt-shaped member, and the interface characteristics can be formed. , It is possible to manufacture a laminated device having excellent characteristics.

In addition, by using the microwave applicator means of the present invention and changing its pore diameter and aperture ratio variously, it is possible to generate microwave plasma with high uniformity in the longitudinal direction.

In the apparatus of the present invention, when the band-shaped member functions as a structural material, the outside of the film formation chamber may be air, but a functional deposition film formed by the inflow of air into the film formation chamber. In this case, an appropriate air inflow prevention means may be provided. Specifically, an O-ring, a gasket, a helicflex, a mechanically sealed structure using a magnetic fluid, or the like, or a diluted gas atmosphere that has little or no effect on the characteristics of the deposited film to be formed, or It is desirable to dispose an isolation container for forming an appropriate vacuum atmosphere around the container. In the case of the mechanical sealing structure, special care needs to be taken so that the sealing state can be maintained while the belt-shaped member moves continuously.
When connecting the apparatus of the present invention to a plurality of other deposited film forming means and continuously depositing deposited films on the belt-like member, it is desirable to connect the respective apparatuses using gas gate means or the like. In the case where only a plurality of the apparatuses of the present invention are connected, the film forming chamber is an independent film forming atmosphere in each apparatus. Therefore, the isolation container may be single or may be provided in each apparatus. good.

In the apparatus of the present invention, the pressure outside the film forming chamber may be in a depressurized state or a pressurized state. However, when the band-shaped member is greatly deformed by a pressure difference from the film forming chamber, an appropriate auxiliary structure is used. A material may be provided in the film forming chamber.
As the auxiliary structure material, it is desirable that the shape substantially the same as the side wall of the film forming chamber is formed by a wire, a thin plate, or the like made of metal, ceramics, reinforced resin, or the like having appropriate strength. In addition, since the auxiliary film is hardly formed on the belt-like member facing the surface of the auxiliary structure that is not exposed to the microwave plasma, the auxiliary structure is substantially shaded by the auxiliary structure. It is desirable that the projection area of the material on the strip is designed to be as small as possible.

Further, by bringing the auxiliary structure material into close contact with the band-shaped member, and rotating or moving the auxiliary structure material in synchronization with the conveyance speed of the band-shaped member, a mesh pattern or the like applied to the auxiliary structure material is formed on the band-shaped member. It can also be formed.

As the material of the belt-shaped member suitably used in the method and the apparatus of the present invention, deformation at a temperature required at the time of forming a functional deposited film by a microwave plasma CVD method,
It is preferable that the material has a small distortion and a desired strength.Specifically, stainless steel, aluminum and its alloys, iron and its alloys, metal thin plates such as copper and its alloys and composites thereof, and polyimide, Heat-resistant resin sheets such as polyamide, polyethylene terephthalate and epoxy or composites of these with glass fiber, carbon fiber, boron fiber, metal fiber, etc., and metals of different materials on the surface of thin sheets of these metals, resin sheets, etc. Examples thereof include those obtained by subjecting a thin film and / or an insulating thin film such as SiO ₂ , Si ₃ N ₄ , Al ₂ O ₃ , or AlN to a surface coating treatment by a sputtering method, a vapor deposition method, a plating method, or the like. Also,
As long as the thickness of the band-shaped member is within a range that exhibits a strength that maintains a curved shape formed at the time of conveyance by the conveyance means, it is preferable that the thickness be as thin as possible in consideration of cost, storage space, and the like. . Specifically, preferably 0.01
mm to 5 mm, more preferably 0.02 mm to 2 mm, optimally 0.
It is desirable that the thickness is from 05 mm to 1 mm, but it is easier to obtain a desired strength by using a relatively thin plate of metal or the like even if the thickness is reduced. The width dimension of the band-shaped member is not particularly limited because the uniformity of the microwave plasma in the longitudinal direction is maintained as long as the microwave applicator means of the present invention is used, but it is to the extent that the curved shape is maintained. Preferably, specifically, preferably 5cm to 200cm,
More preferably, it is desirable to be 10 cm to 150 cm.

Furthermore, the length of the belt-shaped member is not particularly limited, and may be a length that can be wound up in a roll shape, and a longer one is made longer by welding or the like. There may be.

In the apparatus of the present invention, as the means for supporting and transporting the belt-like member while continuously bending the belt-like member, the belt-like member does not sag during transportation, wrinkles, lateral displacement, etc.
It is necessary to keep its curved shape constant. For example, at least one pair of support / transport rings having a desired curved shape is provided, and preferably both ends of the band-shaped member are supported by the support / transport rings, and further curved along the shape, and At least one pair of support / transport rollers provided in the longitudinal direction of the belt-shaped member as a bending start end forming means and a bending end end forming means are squeezed, curved substantially in a columnar shape, and further, the support / transport ring and the support / transport ring.
A driving force is applied to at least one of the transport rollers, and the belt-shaped member is transported in its longitudinal direction while maintaining a curved shape. In addition, as a method of supporting and transporting the belt-shaped member by the support / transport ring, only sliding friction may be used, or a process such as a sprocket hole may be performed on the belt-shaped member, and the support / transport ring may be used. Also, a so-called gear-shaped one having a saw-tooth-shaped projection provided around it may be used.

Regarding the shape of the support / transport ring, it is preferable to form a curved shape, preferably a circular shape, but an elliptical shape, a square shape, and a polygonal shape. There is no particular problem as long as it has a holding mechanism. Maintaining a constant transport speed is an important point in transporting the curved shape without causing slack, wrinkles, lateral displacement and the like. Therefore, the support
It is preferable that the transport mechanism is provided with a mechanism for detecting the transport speed of the belt-like member and a transport speed adjusting mechanism to which feedback is applied. These mechanisms also have a great effect on controlling the film thickness in manufacturing a semiconductor device.

In addition, the supporting / transporting ring is disposed in the microwave plasma region, although the degree of the exposure is varied depending on the purpose. Therefore, a material that can withstand microwave plasma, that is, a material having excellent heat resistance, corrosion resistance, etc., is desirable. In addition, a deposited film adheres to the surface thereof, and the deposited film adheres during a long-time deposition operation. The film is peeled off and scattered, and adheres to the deposited film being formed, causing defects such as pinholes in the deposited film, and consequently the characteristics of the manufactured semiconductor device and the yield are reduced. Therefore, it is desirable that the deposited film be made of a material having a low adhesion coefficient or a material and surface shape capable of maintaining a strong adhesive force up to a considerable film thickness even if adhered. Specific materials include those processed using stainless steel, nickel, titanium, vanadium, tungsten, molybdenum, niobium and alloys thereof, or alumina, quartz, magnesia, zirconia, silicon nitride, boron nitride, nitrided on the surface thereof. Examples thereof include a material obtained by coating a ceramic material such as aluminum by a thermal spraying method, a vapor deposition method, a sputtering method, an ion plating method, a CVD method, or the like, or a material obtained by molding a single or composite ceramic material. The surface shape is appropriately selected in consideration of the stress of the film to be deposited, such as mirror finishing and unevenness processing.

The deposited film attached to the support / transport ring is preferably removed before peeling, scattering, etc. occur, and after dry etching or decomposition in a vacuum, wet etching, chemical chemistry such as bead blasting, etc. It is desirable that it be removed by a technique.

The support / transport roller is designed to have a larger area in contact with the belt-shaped member than the support / transport ring, and thus has a higher heat exchange rate with the belt-shaped member. Therefore, it is desirable to have a mechanism for appropriately adjusting the temperature so that the temperature of the belt-shaped member is not extremely increased or decreased by the supporting / transporting roller. However, the set temperatures of at least one pair of supporting / transporting rollers may be different. Furthermore,
The incorporation of a transport tension detecting mechanism for the belt-like member in the support / transport roller is also effective in keeping the transport speed constant.

Further, it is preferable that a crown mechanism is provided on the support / transport roller in order to prevent the belt-shaped member from bending, twisting, laterally displacing, and the like at the time of transport.

The curved shape formed in the present invention is formed in a columnar shape so as to be close to the separating means or to include the separating means.

The shape of both end surfaces of the columnar deposition chamber formed with the strip-shaped member as a side wall is substantially circular, elliptical, square,
It is desirable to have a polygonal shape or the like and to be substantially symmetrical with respect to the central axis of the microwave applicator means in order to enhance the uniformity of the deposited film. Further, the length of the curved portion determines the volume of the microwave plasma region, and substantially the length of the deposited film formed in correlation with the time during which the band-shaped member is exposed to the microwave plasma region during transportation. The utilization efficiency of the source gas for forming a deposited film is determined based on the ratio of the thickness to the peripheral length of the separation means exposed to the microwave plasma. Therefore, it is desirable that the length of the curved portion is set to preferably not more than five times, more preferably not more than four times the peripheral length of the separating means. In the microwave plasma region, the microwave power density (W / cm ³ ) for maintaining stable microwave plasma depends on the type and flow rate of the raw material gas used, the pressure, microwave radiation of the microwave applicator, It is determined by the correlation between the transmission capacity and the absolute volume of the microwave plasma region, and it is difficult to unambiguously define it.

In the apparatus of the present invention, even if the band-shaped member is not curved and forms a columnar shape, even if it is conveyed in a horizontal or slightly curved shape opposite to the side facing the hole means of the microwave applicator, particularly the microwave is applied. There is no hindrance to the plasma discharge conditions and the like.

When the band-shaped member is used as a substrate for a solar cell, when the band-shaped member is electrically conductive such as a metal, the band-shaped member may be directly used as an electrode for extracting current, or is electrically insulating such as a synthetic resin. In this case, Al, Ag, Pt, Au, Ni, Ti, Mo, W, Fe, V, Cr, Cu, stainless steel, brass, nichrome, SnO ₂ , In ₂ O ₃ , ZnO, SnO ₂ -In ₂ O ₃ (ITO)
It is desirable to form a current extraction electrode by performing a surface treatment in advance by a method such as plating, vapor deposition, or sputtering on a so-called metal simple substance or alloy or a transparent conductive oxide (TCO).

Of course, even if the strip-shaped member is made of an electrically conductive material such as metal, it is possible to improve the reflectance of long-wavelength light on the substrate surface or to interdiffuse constituent elements between the substrate material and the deposited film. A different kind of metal layer or the like may be provided on the side of the substrate on which the deposited film is formed, for the purpose of preventing the occurrence of a short circuit or forming an interference layer for preventing a short circuit. When the band-shaped member is relatively transparent and a solar cell having a layer configuration in which light is incident from the side of the band-shaped member, a conductive thin film such as the transparent conductive oxide or a metal thin film is previously deposited. It is desirable to form it.

Further, the surface property of the belt-shaped member may be a so-called smooth surface or a fine uneven surface. In the case of a fine uneven surface, the uneven shape is spherical, conical, pyramidal, or the like, and its maximum height (Rmax) is preferably 50.
By setting the angle between 0 ° and 5000 °, light reflection on the surface becomes irregular reflection, and the optical path length of light reflected on the surface is increased.

In the apparatus of the present invention, the separation means is disposed in the vicinity of or protrudes into the film formation chamber, and includes therein a microwave applicator means for radiating or transmitting microwave energy into the film formation chamber. It has. Therefore, the structure is designed to separate the vacuum atmosphere in the film forming chamber from the outside air in which the microwave applicator means is installed, and to withstand the pressure difference existing between the inside and the outside. Specifically, it is preferably a cylindrical shape or a semi-cylindrical shape, and may be a shape having a smooth curved surface as a whole.

In addition, the thickness of the peripheral wall of the separation means is slightly different depending on the material used, but is preferably about 0.5 mm to 5 mm.
mm is desirable. As a material thereof, microwave energy radiated or transmitted from the microwave applicator means can be transmitted into the film formation chamber with a minimum loss, and airtightness which does not cause air to flow into the film formation chamber is generated. Preferred are those having excellent properties, specifically, quartz,
Glass or fine ceramics such as alumina, silicon nitride, beryllia, magnesia, zirconia, boron nitride, and silicon carbide are included.

If the separating means is cylindrical or semi-cylindrical, its diameter (inner diameter) is such that the microwave applicator means used is contained inside it and the microwave applicator means contacts the inner peripheral wall of the separating means. It is desirable that the dimensions be set to the minimum required.

Further, in the separating means, it is desirable to provide a microwave confinement means or a dummy load at an end opposite to a side where the microwave applicator means is inserted. In the former case, it is preferable to cover most of the portion protruding from the end of the band-like member with a conductive member such as a metal or a wire mesh, and to ground the same. Particularly, at a high power level, inconvenient microwave matching may occur. If there is a possibility, it is preferable to provide the latter means.

Further, in the separating means, it is safe to cover a part protruding on the side where the microwave applicator means is inserted with a conductive member such as a metal or a wire mesh, and to ground the waveguide and the isolation container. Above.

In addition, it is preferable that the separation unit is uniformly cooled in order to prevent heat deterioration (crack, destruction) or the like due to heating by microwave energy and / or plasma energy.

Specifically, the cooling means may be an air flow flowing along the inner peripheral surface of the separating means, or a shape substantially similar to the separating means and formed concentrically inside the separating means. A conduit may be formed between the enclosure and the separating means, and a cooling fluid such as water, oil, or freon may flow through the conduit.

On the other hand, the separating means such as the cylindrical shape of the present invention may be used together with a usual slow-wave type microwave applicator, in which case the microwave energy transmitted from the slow-wave type microwave applicator is used. Are coupled into the film forming chamber via an evanescent wave. Thus, by utilizing the separation means having a small thickness and cooling the separation means to a sufficiently low temperature, even when microwave energy of relatively high power is introduced into the film forming chamber, the heat generated Thus, high-electron-density plasma can be generated without causing breakage such as cracks in the separation means.

Further, in the apparatus according to the present invention, film deposition occurs on at least a portion of the outer peripheral surface of the separation means that is in contact with the microwave plasma region, as on the strip-shaped member. Therefore, although depending on the type and characteristics of the film to be deposited, microwave energy radiated and transmitted from the microwave applicator means is absorbed or reflected by the deposited film, and enters the film forming chamber formed by the belt-shaped member. If the amount of radiation and transmission of microwave energy decreases and the amount of change increases significantly compared to immediately after the start of discharge, not only is maintenance of the microwave plasma itself difficult, but also
In some cases, the deposition rate of the deposited film to be formed is reduced, and the characteristics and the like are changed. In such a case, the initial state can be restored by removing the film deposited on the separation means by dry etching, wet etching, a mechanical method, or the like. In particular, dry etching is preferably used as a method for removing the deposited film while maintaining a vacuum state. Further, the separation means is rotated while maintaining the vacuum, the portion exposed to the microwave plasma is moved out of the microwave plasma region, and the deposited film is removed in a region different from the microwave plasma region. It is also possible to adopt a continuous method of rotating the microwave plasma region. Further, by continuously feeding a sheet made of a material having a microwave permeability substantially equivalent to that of the separation means along the outer peripheral surface of the separation means,
It is also possible to employ a method of depositing and forming a deposited film on the surface of the sheet and discharging the film outside the microwave plasma region.

The microwave applicator means in the present invention radiates microwave energy supplied from a microwave power supply into the inside of the film forming chamber to convert the deposited film forming raw material gas introduced from the gas introduction means into a plasma and maintain it. It has a structure that can be used. Specifically, a waveguide having an open end at the end is preferably used. Specific examples of the waveguide include a waveguide for microwave transmission such as a circular waveguide, a square waveguide, and an elliptical waveguide. Here, it is possible to prevent the standing wave from hitting at the end of the waveguide by setting the opening end. On the other hand, even if the end of the waveguide is a closed end, there is no particular problem.

In the device of the present invention, the dimensions of the circular waveguide suitably used for the microwave applicator are appropriately designed depending on the frequency band (band) and mode of the microwave used. In designing, it is preferable that transmission loss in the circular waveguide is small, and that consideration is given so that multiple modes do not occur as much as possible.Specifically, other than EIAJ standard circular waveguide, etc., 2.45 GHz In-house standards for use include those having an inner diameter of 90 mm and 100 mm.

Note that transmission of microwaves from a microwave power supply is relatively easy to use, and it is preferable to use a rectangular waveguide. However, in the conversion unit to the circular waveguide used as a microwave applicator, microwave energy is transmitted. It is necessary to minimize the transmission loss, and specifically, it is preferable to use an electromagnetic horn type waveguide for rectangular or circular conversion.

In the present invention, the type of the rectangular waveguide suitably used for the microwave applicator is appropriately selected depending on the frequency band (band) and mode of the microwave used, and at least the cutoff frequency is used. It is preferable that the frequency is lower than the standard frequency, specifically, standard products such as JIS, EIAJ, IEC, JAN, and 2.
In-house standard for 45GHz, 96mm width with square cross-section inner diameter
X 27 mm height etc. can be mentioned.

In the apparatus of the present invention, as long as the applicator means of the present invention is used, microwave energy supplied from a microwave power supply is efficiently radiated and transmitted into the film forming chamber, so that a problem related to a so-called reflected wave is easily avoided,
In microwave circuits, three-stub tuners or E
-A relatively stable discharge can be maintained without using a microwave matching circuit such as an -H tuner, but in the case where a strong reflected wave is generated due to an abnormal discharge or the like before or after the start of the discharge. It is desirable to provide the matching circuit for protecting the microwave power supply.

The waveguide has at least one hole means for radiating microwave energy on one side thereof, and these hole means are sized and spaced so as to uniformly radiate microwave energy. It is necessary that they are complete, but they may or may not be complete. Specific dimensions and the like will be disclosed in an experimental example described later.

The shape of the hole means formed in the waveguide is desirably substantially rectangular, and when a plurality of holes are formed at desired intervals in the longitudinal direction from near the end of the waveguide,
By opening or closing some of them, uniform microwave plasma is generated in the width direction of the band-shaped member to be used. At this time, the radiated microwave energy has a length of at least one wavelength or more of the radiated microwave in the longitudinal direction of the waveguide, and is preferably radiated almost equally in the width direction of the band-shaped substrate. Is desirable.

When only one hole means is formed, the aspect ratio of the square is large, and the dimension is larger than one wavelength of microwave in the longitudinal direction of the waveguide, and covers almost the entire width and length. It is desirable to be able to open it. In order to enhance the uniformity of the microwave energy radiated in the longitudinal direction, a shutter means for adjusting the aperture is provided. The shape of the shutter means is a strip shape, an elongated trapezoidal shape, or a shape in which a part of one side of the strip or the elongated trapezoid is cut off in a half-moon shape, etc., and is along the surface shape of the waveguide. Preferably, the material is a metal or a resin subjected to a conductive treatment. Then, the end is fixed to a connecting portion provided near the corner of the hole means on the side near the microwave power source, and the opening degree is adjusted using the connecting portion as a fulcrum. It may be fixed for improving the stability of plasma.

When the hole means having a large aspect ratio is used, it is preferable that the length of the long side is substantially equal to the length in the width direction of the band-shaped member to be used.

Further, it is desirable that the shutter means be grounded to the waveguide only at the connection part, and that the waveguide and the shutter means be insulated by insulation means at a place other than the connection part. preferable. If a contact is additionally provided between the shutter means and the rectangular waveguide, this becomes an arc contact.

The microwave applicator means using the hole means described above is a so-called "leakage wave" type microwave radiating structure.

On the other hand, in the present invention, the microwave applicator may be of a slow wave circuit type. When a slow wave circuit is used, most of the microwave energy is transmitted via an evanescent wave. Therefore, microwave energy has the disadvantage that the amount coupled to the plasma decreases sharply with increasing lateral distance to the microwave structure, but in the present invention the microwave applicator is separated from the plasma region. This can solve this drawback.

In the apparatus of the present invention, the film formation chamber and / or the isolation container are separated from a vacuum container having another film formation means and a vacuum atmosphere, and the belt-shaped member is continuously conveyed through the inside thereof. The gas gate means is suitably used for the above. In the apparatus of the present invention, it is desirable that the inside of the film forming chamber and / or the isolation vessel is maintained at a low pressure necessary for operation near the minimum value of the modified Paschen curve. In many cases, the pressure in another vacuum vessel to be connected is at least substantially equal to or higher than the pressure. Therefore, it is necessary for the gas gate means to have a capability of preventing the mutually used deposition film forming source gases from diffusing due to a pressure difference generated between the containers. Thus, the basic concept can employ the gas gating means disclosed in U.S. Pat. No. 4,438,723, but its capabilities need to be further improved. Specifically, it is necessary to withstand the pressure differential up to 10 ⁶ times, as an exhaust pump large oil diffusion pump exhaust capability, turbo molecular pump, such as a mechanical booster pump is preferably used. In addition, the cross-sectional shape of the gas gate is a slit shape or a shape similar thereto, and the dimensions thereof are calculated and designed using a general conductance calculation formula together with the overall length and the exhaust capacity of the exhaust pump to be used. . Further, it is preferable to use a gate gas in combination to enhance the separation ability, for example, a rare gas such as Ar, He, Ne, Kr, Xe, or Rn or H
_{And a second} dilution gas for forming a deposited film. The flow rate of the gate gas is appropriately determined depending on the conductance of the entire gas gate, the capacity of the exhaust pump to be used, and the like. However, a pressure gradient generally shown in FIGS. 6 (a) and 6 (b) may be formed. In FIG. 6 (a), since there is a point where the pressure becomes maximum substantially at the center of the gas gate, the gate gas flows from the center of the gas gate to the vacuum vessel side on both sides, and in FIG. Since there is a point where the pressure becomes minimum at the center, the gate gas is also exhausted from the center of the gas gate together with the deposited film forming raw material gas flowing from the containers on both sides. Therefore, in both cases, mutual gas diffusion between the containers on both sides can be minimized. In practice, the optimum conditions are determined by measuring the amount of gas diffused using a mass spectrometer or by analyzing the composition of the deposited film.

In the apparatus of the present invention, the deposition film forming means disposed in another vacuum vessel connected to the isolation vessel by the gas gate means includes RF plasma CVD, sputtering and reactive sputtering, and ion plating. Means for realizing a method used for forming a so-called functional deposited film, such as a plating method, a photo CVD method, a thermal CVD method, a MOCVD method, an MBE method, and an HR-CVD method. And, of course, it is also possible to connect the means of the microwave plasma CVD method of the present invention and similar microwave plasma CVD method, select an appropriate means for manufacturing a desired semiconductor device, and connect using the gas gate means. Is done.

The microwave frequency supplied from the microwave power supply used in the device of the present invention is preferably 2.45 GHz, which is preferably used for consumer use, but is relatively easily available even in other frequency bands. Anything can be used. In addition, in order to obtain a stable discharge, the oscillation mode is preferably a so-called continuous oscillation, and the ripple width thereof is preferably within 30%, more preferably within 10% in a used output region.

In the apparatus of the present invention, it is effective to continuously form a deposited film without exposing the film forming chamber and / or the isolation container to the atmosphere because the deposited film can be prevented from being mixed with impurities in terms of stable characteristics. It is. However, since the length of the band-shaped member used is limited, it is necessary to perform an operation of connecting the band-shaped member by processing such as welding. Specifically, such a processing chamber may be provided in the vicinity of the container (the sending side and the winding side) in which the band-shaped member is stored.

Hereinafter, a specific processing method will be described with reference to the drawings.

FIG. 12 (part 1) (i) to FIG. 12 (part 4) (x)
The figure shows a schematic view for explaining the outline of the band-shaped member processing chamber and the operation at the time of film formation of the band-shaped member and the like.

In FIG. 12, reference numeral 1201a denotes a band-shaped member processing chamber (A) provided on the feeding side of the band-shaped member, and 1201b denotes a band-shaped member processing chamber (B) provided on the winding side of the band-shaped substrate. Viton rollers 1207a, 1207b, cutting blade 1208
a, 1208b and welding jigs 1209a, 1209b are stored.

That is, FIG. 12 (No. 1) (i) shows the state at the time of normal film formation, the belt-like member 1202 is moving in the direction of the arrow in the figure, and the roller 1207a, the cutting blade 1208a, and the welding jig 1209a are in the belt-like state. Not in contact with member 1202. Reference numeral 1210 denotes a connection means (gas gate) with a belt-shaped member storage container (not shown), and reference numeral 1211 denotes a connection means (gas gate) with a vacuum container (not shown).

FIG. 12 (part 1) and (ii) show a first step for exchanging a new band-shaped member after the film-forming step on one band of the band-shaped member is completed. First, stop the belt-shaped member 1202,
The roller 1207a is moved in the direction of the arrow from the position shown by the dotted line in the figure to be brought into close contact with the band member 1202 and the wall of the band member processing chamber 1201a. In this state, the band-shaped member storage container and the film forming chamber are air-tightly separated. Next, the cutting blade 1208a is operated in the direction of the arrow in the figure to cut the band-shaped member 1202. The cutting blade 1208a is made of any of those capable of mechanically, electrically, and thermally cutting the band-shaped member 1202.

FIG. 12 (part 1) (iii) shows a state in which the strip-shaped member 1203 cut and separated is wound up to the strip-shaped member storage container side.

The above-described cutting and winding steps may be performed in either a vacuum state or an atmospheric pressure leak state in the belt-shaped member storage container.

FIG. 12 (part 2) (iv) shows a process in which a new band-shaped member 1204 is fed in and connected to the band-shaped member 1202. The ends of the belt-shaped members 1204 and 1202 are brought into contact with each other and are welded and connected by a welding jig 1209a.

In FIG. 12 (part 2) and (v), the inside of the band-shaped member storage container (not shown) is evacuated, and after the pressure difference with the film forming chamber is sufficiently reduced, the roller 1207a is moved to the band-shaped member 1202 and the band-shaped member processing chamber. (A) shows a state in which the belt-like members 1202 and 1204 have been wound apart from the wall of 1201a.

 Next, the operation on the winding side of the belt-shaped member will be described.

FIG. 12 (part 3) (vi) shows a state at the time of normal film formation, but each jig is arranged substantially symmetrically as described in FIG. 12 (part 1) (i).

FIG. 12 (part 3) (vii) shows that after the film forming step on one roll of the band-shaped member is completed, this is taken out and replaced with an empty bobbin for winding the band-shaped member subjected to the next film forming process. The steps for performing the steps are shown.

First, the belt-shaped member 1202 is stopped, and the roller 1207b is moved in the direction of the arrow from the position indicated by the dotted line in the drawing, so that the belt-shaped member
1202 and the wall of the strip-shaped member processing chamber 1201b. In this state, the band-shaped member storage container and the film forming chamber are air-tightly separated.
Next, the cutting blade 1208b is operated in the direction of the arrow in the figure to cut the band-shaped member 1202. The cutting blade 1208b is made of any of those capable of mechanically, electrically, and thermally cutting the strip-shaped base 1202.

FIG. 12 (part 3) (viii) shows a state in which the strip-shaped member 1205 after the cut and separated film formation step is wound up toward the strip-shaped member storage container.

The above-described cutting and winding steps may be performed in either a vacuum state or an atmospheric pressure leak state in the belt-shaped member storage container.

FIG. 12 (part 4) (ix) shows a step in which the preliminary winding band member 1206 attached to the new winding bobbin is fed in and connected to the band member 1202. The end portions of the prewinding belt-like member 1206 and the belt-like member 1202 are brought into contact with each other, and are connected by welding with a welding jig 1209b.

In FIG. 12 (part 4) (X), the inside of the band-shaped member storage container (not shown) is evacuated, and after the pressure difference with the film forming chamber is sufficiently reduced, the roller 1207b is moved to the band-shaped member 1202 and the band-shaped member processing. This shows a state in which the belt-shaped members 1202 and 1206 have been wound away from the wall of the chamber (B) 1201b.

As the functional deposited film continuously formed in the method and the apparatus of the present invention, a so-called group IV semiconductor thin film such as Si, Ge, C, or a so-called group IV alloy semiconductor such as SiGe, SiC, SiSn Thin film, GaAs, GaP, GaSb, InP, InAs, etc., so-called II
Group IV compound semiconductor thin film, and ZnSe, ZnS, ZnTe, CdS, CdSe,
A so-called II-VI group compound semiconductor thin film such as CdTe can be used.

As the material gas for forming a functional deposited film used in the method and the apparatus of the present invention, hydrides, halides, organometallic compounds, etc. of the constituent elements of the above-mentioned various semiconductor thin films are preferably introduced into the film formation chamber in a gaseous state. Those that can be introduced in are selected and used.

Of course, these starting compounds can be used alone or in combination of two or more. Further, these raw material compounds may be introduced as a mixture with a rare gas such as He, Ne, Ar, Kr, Xe, and Rn, and a diluent gas such as H ₂ , HF, and HCl.

Further, the semiconductor thin film formed continuously can perform valence electron control and forbidden band width control. Specifically, a raw material compound containing an element serving as a valence electron controlling agent or a forbidden band width controlling agent may be used alone or mixed with the deposited film forming raw material gas or the diluent gas and introduced into the film formation chamber. .

The deposited film forming raw material gas and the like are formed from a gas introduction pipe having a single or a plurality of gas discharge holes at a tip end thereof disposed in a columnar film formation chamber formed by the strip-shaped member and the separation unit. The plasma is uniformly discharged into the columnar deposition chamber and is converted into plasma by microwave energy to form a microwave plasma region.

In the apparatus of the present invention, the deposited film forming source gas introduced into the columnar film forming chamber from the gas introduction pipe is partially or entirely decomposed to generate a deposited film forming precursor,
Although a deposited film is formed, an undecomposed raw material gas or a gas having a different composition due to decomposition needs to be quickly exhausted to the outside of the columnar film forming chamber. However, if the area of the exhaust hole is made unnecessarily large, microwave energy leaks from the exhaust hole, causing instability of plasma or adversely affecting other electronic devices, the human body, and the like. . Therefore, it is desirable to provide exhaust holes by the following three methods. (I) A mesh or a punching board is provided on both sides of a ring provided at the end of the support / transport ring used for bending the belt-shaped member, and gas can be exhausted therefrom. Prevent leaks. However, it is preferable that the hole diameter of the mesh or the punching board is a size that causes a pressure difference between the inside and outside of the columnar film formation chamber and prevents microwave leakage. Specifically, the maximum diameter of each hole is preferably not more than 1/2 wavelength of the microwave used, more preferably not more than 1/4 wavelength, and the aperture ratio is preferably not more than 80%, more preferably. Is 60%
It is desirable that: Of course, at this time, air is simultaneously exhausted from a gap between the bending start end and the bending end end of the band-shaped member or a gap (slit) formed between the bending start end and the bending end end of the band-shaped member and the outer peripheral wall of the separating means. However, in order to prevent microwave leakage, the interval is preferably not more than 1/2 wavelength, more preferably not more than / 4 wavelength of the wavelength of microwave used. (Ii) Thin plates are provided on both sides of the support / transport ring used for bending the belt-shaped member, which is provided at the end, so that gas exhaust and microwave leakage therefrom do not occur. Then, gas is exhausted only from a gap between the bending start end and the bending end end of the band-shaped member or a gap (slit) formed between the curved end of the band-shaped member and the outer peripheral wall of the separating means. However, in order to prevent microwave leakage, the interval is preferably not more than 1/2 wavelength of the microwave used, more preferably not more than 1/4 wavelength. (Iii) (i) on both sides of the support / transport ring
And any one of the mesh or punching board and the thin plate described in (ii). That is, a method combining both (i) and (ii) can be mentioned. It is desirable that both the mesh, the punching board, and the thin plate have been subjected to the same material and surface treatment as the support / transport ring.

(Example of device)

Hereinafter, the device of the present invention will be described with reference to the drawings, using a specific device example of the present invention, but the present invention is not limited thereto.

Apparatus Example 1 FIG. 1 shows a schematic diagram of a microwave plasma CVD apparatus of the present invention.

Reference numeral 101 denotes a belt-shaped member, and rollers 102 and 103 for supporting and transporting.
The sheet is conveyed in the direction of the arrow in the figure while maintaining a cylindrically curved shape by the supporting and conveying rings 104 and 105. Ten
Reference numeral 6107 denotes a temperature control mechanism for heating or cooling the belt-shaped member 101.

Reference numeral 108 denotes a microwave applicator,
Is separated from the microwave plasma region 113. 110 is a metal tube for preventing microwave leakage, 111 is a wire mesh for preventing microwave leakage, and 112 is a gas inlet tube. 114,115
Is a wire mesh for preventing microwave leakage. The microwave plasma region 113 is confined in a film forming chamber having a curved portion of the belt-shaped member 101 as a side wall. Microwave plasma region 11
The inside of 3 is evacuated by an exhaust device (not shown) through a gap between the separating means 109 and the transport rollers 102 and 103 and / or the wire meshes 114 and 115 for preventing microwave leakage.

FIG. 2 shows a specific schematic diagram of the microwave applicator means 201 used as the microwave applicator 108.

The circular waveguide 202 has a distal end 203 on one side of which a plurality of (here, for example, five) spaced holes 20 are provided.
4 to 208 are opened, and microwaves or traveling from the direction of the arrow in the figure. Here, as an example, the hole 205 is the waveguide 2
It shows a state where the lid is closed with a lid made of the same material as 02. By opening and closing several holes in this manner, the microwave energy radiated in the longitudinal direction of the waveguide 202 is made uniform.

Apparatus Example 2 In this apparatus example, an apparatus example in which the apparatus shown in Apparatus Example 1 is disposed in an isolated container can be given. FIG. 4 shows a schematic diagram thereof. Reference numeral 400 denotes an isolation container, the inside of which can be evacuated through an exhaust hole 419 using an exhaust pump (not shown). Reference numerals 401 and 402 denote fixing flanges, which are separating means 1 protruding through both walls of the isolation container 400.
09 is fixed. Fixing flanges 401 and 402 are isolated containers 4
It is preferably made of a suitable corrosion-resistant material such as stainless steel as in the case of 00, and is preferably detachable from the isolation container 400. The fixing flange 401 is attached to the connection flange 404. Connecting flange 404
Is attached directly to the side wall of the isolation container 400. Here, an opening 405 which is substantially coextensive with the outer peripheral surface of the cylindrical separating means 109 is opened so that the separating means 109 can be inserted. At least two O-rings 406 and 407 are attached to the fixing flange 401 to separate the vacuum atmosphere in the isolation container 400 from the outside air. Here, a cooling groove 408 is provided between the O-rings 406 and 407, through which a coolant such as water is circulated,
The rings 406 and 407 can be cooled uniformly. As the material for the O-ring, for example, a material that performs its function at a temperature of 100 ° C. or more, such as viton, is preferably used. Here, it is preferable that the O-ring is provided at a position sufficiently distant from the microwave plasma region, so that the O-ring can be prevented from being damaged at a high temperature.

Reference numeral 110 denotes a metal cylinder. A wire mesh 111 is attached to an open end 409 of the metal cylinder. The ground finger 410 keeps electrical contact with the fixing flange 401. Leakage is prevented. The wire mesh 111 also has a role of allowing the cooling air of the separating means 109 to flow out. Note that a dummy load for microwave absorption may be connected to the opening end 409. This is particularly useful where leakage of microwave energy occurs at high power levels.

The isolation container 400 is provided with a fixing flange 402 for fixing similarly to the separating means on a side wall opposite to the side wall on which the fixing flange 401 described above is mounted. 411 is a connection flange, 412 is an opening, 413 and 414 are O-rings, 415 is a cooling groove, 416 is a metal cylinder, and 417 is a ground finger. 418 is a connection plate, which connects the microwave applicator means 108 with the microwave power supply and the rectangular, circular conversion waveguide 403, and preferably has a structure without leakage of microwave energy here, For example, a chalk flange can be used.
Further, the square / circular conversion waveguide 403 is connected to the square waveguide 421 via a connection flange 420.

FIG. 5 (a) schematically shows a cross-sectional side view of a transport mechanism of the belt-shaped member 101 in the present example of the apparatus.

The arrangement here has at least two proximity points on the outer peripheral surface of the separating means 109, and a hole 2 formed in the circular waveguide 202.
The figure shows a case where it is curved in a substantially cylindrical shape with respect to the side facing 08. Support / transport rollers 102 and 103 and support / transport rings 104 (105) are used to maintain the cylindrical shape. Here, the support / transport ring 104 (105)
When the width of the film is as small as possible with respect to the width of the belt-like member to be used, the effective utilization rate of the film deposited on the substrate is increased. This is because a film to be deposited on the substrate is deposited on the support / transport ring 104 (105).

In addition, wire meshes or thin plates 501, 50 for confining the microwave plasma region are provided on both sides of the support / transport rings 104, 105.
1 'is preferably attached (one side not shown), and the mesh diameter is preferably less than 1/2 wavelength, more preferably less than 1/4 wavelength of the wavelength of the microwave used, and this surface In the case where the exhaust gas is exhausted from the air, it is desirable that the exhaust gas is of such an extent that the permeation of the source gas can be ensured.

Further, the substrate temperature control mechanisms 106 and 107 are for maintaining the temperature of the belt-shaped member 101 constant while passing through the microwave plasma region, and are desirably a means that can perform both heating and / or cooling. Further, the substrate temperature control mechanism may have a structure directly in contact with the belt-shaped member in order to increase heat exchange efficiency. In general, the temperature of a part exposed to microwave plasma tends to rise, and the degree of the rise varies depending on the type and thickness of the belt-shaped member to be used.

Further, the gaps L1 and L2 at the close point between the outer peripheral surface of the separating means 109 and the strip-shaped member 101 are radiated at least in order to prevent leakage of microwave energy therefrom and to confine the microwave plasma region in a curved shape. It is preferably set to be shorter than half the wavelength of the microwave. However, the interval L3 between the bending start end and the bending end end of the band-shaped member 101 is because microwave energy radiated from the microwave applicator 201 is efficiently radiated into the curved region formed by the band-shaped member 101. In addition, it is desirable that the wavelength is set to be longer than 1/4 wavelength of the emitted microwave.

Since the microwave energy radiated from the hole 208 is radiated with directivity in a direction substantially perpendicular to the side facing the hole 208, the radiation direction is directed substantially perpendicular to at least the distance L3. Is preferred.

The gas introduction pipe 112 is provided with a hole having an arrangement and a hole diameter at which gas is almost uniformly discharged. The position where the gas introduction pipe is installed in the curved shape is not particularly limited as long as it is within the range.

Apparatus Example 3 Next, there can be mentioned a case where the microwave applicator means 301 shown in FIG. 3A is used in the apparatus shown in FIG.

An open end 303 and one elongated rectangular hole 304 are formed in the circular waveguide 302, and microwaves travel from the direction of the arrow in the figure. The hole 304 is larger than one wavelength of the microwave to be used, and is formed substantially over one entire surface of the circular waveguide 302. The open end 303 is provided to prevent standing waves from hitting, but there is no particular problem even if it is sealed. With this structure, microwave energy can be radiated from the entire surface of the hole 304, but the concentration of the microwave energy is maximized particularly at the end of the hole closer to the microwave power supply. Therefore, the connecting portion 305
By using at least one shutter 306 attached to the circular waveguide 302, the degree of concentration can be adjusted. Preferred shapes of the shutter 306 include a strip shape, a trapezoid shape, and a shape in which one side of the strip or trapezoid is cut out in a half-moon shape or the like as shown in FIGS. 3 (b) to 3 (d).

The connecting portion 305 includes a groove 307 opened on the side of the shutter 306 near the microwave power supply, and a fixing pin 308. An insulator 309 made of glass, Teflon, or the like is provided around the hole 304. This is because the shutter 306 is brought into contact with the waveguide 302 only at the connecting portion 305. Here, when a contact is provided between the shutter 306 and the waveguide 302, this becomes an arc contact.

Apparatus Examples 4 and 5 In this apparatus example, as shown in the side sectional view of FIG. 5 (b) in the apparatus examples 1 and 2, a case where the strip-shaped member 101 and the separating means 109 are arranged can be mentioned. .

This arrangement shows a case where the belt-shaped member 101 is concentrically curved along the outer peripheral surface of the separating means 109. Here, it is preferable that wire meshes 502, 502 '(not shown on one side) for confining the microwave plasma region are attached to both side surfaces of the support / transport rings 104, 105, and the mesh has a wavelength of the microwave used. It is preferable that the wavelength is not more than 1/2 wavelength, more preferably not more than 1/4 wavelength, and of such a degree that the permeation of the source gas can be ensured.

Furthermore, the surface interval L4 of the band-shaped member 101 at the bending start end and the bending end end of the band-shaped member 101 prevents at least radiation of microwave energy therefrom and confine the microwave plasma region within the curved shape. It is necessary to set the wavelength to be shorter than half the wavelength of the microwave to be used.

The relative arrangement of the separating means 109 and the belt-shaped member 101 is preferably concentric,
As long as 9 is wrapped in the curved shape of the band-shaped member 101, the emitted microwave energy is not particularly hindered because it is confined within the curved shape, and the direction in which the hole 208 is directed is not particularly limited. .

Further, it is desirable that the gas introduction pipe 112 is disposed in a region surrounded by the separating means 109 and the band-shaped member 101.

Apparatus Examples 6 and 7 In Apparatus Examples 4 and 5, the microwave applicator 201 was used.
Was changed to the microwave applicator 301 used in the device example 2, and the same configuration can be mentioned.

Apparatus Examples 8 to 11 In Apparatus Examples 1, 2, 4 and 5, the same configuration can be mentioned except that the microwave applicator 201 is a slow wave circuit type microwave applicator (not shown).

Apparatus Example 12 In this apparatus example, as shown in FIG. 7, vacuum containers 701 and 70 for feeding and winding the strip-like member 101 to the microwave plasma CVD apparatus for forming a deposited film shown in Apparatus Example 2 are used.
2 can be mentioned using gas gates 721 and 722.

Reference numeral 703 denotes a feeding bobbin for the belt-like member, and reference numeral 704 denotes a bobbin for winding the belt-like member. The belt-like member is conveyed in the direction of the arrow in the drawing. Of course, this can be reversed and transported. Reference numerals 706 and 707 denote conveying rollers that also serve to adjust the tension and position the belt-shaped member. Reference numerals 712 and 713 denote temperature adjusting mechanisms used for preheating or cooling the belt-like member. 707,
708,709 are throttle valves for adjusting the displacement, 710,711,7
Reference numeral 20 denotes an exhaust pipe, each of which is connected to an exhaust pump (not shown). 714 and 715 are pressure gauges, 716 and 717 are gate gas introduction pipes, and 718 and 719 are gate gas exhaust pipes, and a gate gas and / or a source gas for forming a deposited film are exhausted by an exhaust pump (not shown). Reference numeral 723 denotes a film forming chamber having the strip-shaped member 101 as a side wall.

Device Example 13 In this device example, as shown in FIG. 8, two more microwave plasma CVs of the present invention were added to the device shown in Device Example 12.
An example in which isolation containers 400-a and 400-b for forming a deposited film by D are connected to both sides so that a stacked device can be manufactured.

In the drawing, those denoted by reference numerals a and b are mechanisms having basically the same effects as those used in the isolation container 400.

801,802,803,804 are gas gates, 805,806,807,808
, 809, 810, 811, 812 are gate gas exhaust pipes, respectively.

Apparatus Examples 14 and 15 In Apparatus Examples 12 and 13, the microwave applicator 20 was used.
One having the same configuration except that 1 is changed to the microwave applicator 301 used in the apparatus example 3 can be mentioned.

Apparatus Examples 16 and 17 In Apparatus Examples 12 and 13, the microwave applicator 20 was used.
A similar configuration can be mentioned except that a slow-wave circuit type microwave applicator (not shown) is used.

Apparatus Example 18 In this apparatus example, as shown in FIG. 9, two conventional RF plasma CVD apparatuses are connected to both sides of the apparatus shown in Apparatus Example 12 so that a stacked device can be manufactured. Can be cited.

Here, 901 and 902 are vacuum vessels, 903 and 904 are cathode electrodes for RF application, 905 and 906 are gas introduction tubes and heaters, 907 and 908 are halogen lamps for heating the substrate, 909 and 910 are anode electrodes, and 9
11,912 is an exhaust pipe.

Other Apparatus Examples For example, in Apparatus Example 13, an isolation container 40 for forming a deposited film is used.
A device equipped with a combination of the various microwave applicators described above for 0,400-a, 400-b.

Further, there may be mentioned an apparatus in which the apparatus shown in the apparatus example 13 is connected in two or three stations, an apparatus in which a deposition film forming means by the RF plasma CVD method is mixed and connected.

Further, there may be mentioned, for example, devices in which the arrangement of the band-shaped member and the microwave applicator in the device examples 12 and 13 is the same as that described in the device examples 4 and 5.

An example of a semiconductor device suitably manufactured by the method and apparatus of the present invention is a solar cell. FIGS. 11A to 11D schematically show typical examples of the layer structure.

In the example shown in FIG. 11A, the lower electrode 11 is placed on a support 1101.
02, a photovoltaic element 1100 in which an n-type semiconductor layer 1103, an i-type semiconductor layer 1104, a p-type semiconductor layer 1105, a transparent electrode 1106, and a collecting electrode 1107 are formed in this order. In this photovoltaic element, it is assumed that light enters from the transparent electrode 1106 side.

In the example shown in FIG. 11B, a transparent electrode 1106, a p-type semiconductor layer 1105, an i-type semiconductor layer 1104, and an n-type
This is a photovoltaic element 1100 'in which a mold semiconductor layer 1103 and a lower electrode 1102 are formed in this order. In this photovoltaic element, it is assumed that light enters from the light-transmitting support 1101 side.

The example shown in FIG. 11 (C) is formed by laminating two pin junction type photovoltaic elements 1111 and 1112 using two kinds of semiconductor layers having different band gaps and / or layer thicknesses as i-layers. This is a so-called tandem photovoltaic element 1113. Reference numeral 1101 denotes a support, and the lower electrode 1102, the n-type semiconductor layer 1103, the i-type semiconductor layer 1104, the p-type semiconductor layer 1105, the n-type semiconductor layer 1108,
An i-type semiconductor layer 1109, a p-type semiconductor layer 1110, a transparent electrode 1106, and a current collecting electrode 1107 are stacked in this order, and it is assumed that light is incident from the transparent electrode 1106 side in the present photovoltaic element. .

The example shown in FIG. 11 (D) is configured by stacking three pin junction type photovoltaic elements 1120, 1121, and 1123 using three types of semiconductor layers having different band gaps and / or layer thicknesses as i-layers. This is a so-called triple type photovoltaic element 1124.
Reference numeral 1101 denotes a support, and the lower electrode 1102, the n-type semiconductor layer 110
3, i-type semiconductor layer 1104, p-type semiconductor layer 1105, n-type semiconductor layer 1114, i-type semiconductor layer 1115, p-type semiconductor layer 1116, n-type semiconductor layer 1117, i-type semiconductor layer 1118, p-type semiconductor layer 1119, A transparent electrode 1106 and a current collecting electrode 1107 are laminated and formed in this order,
In this photovoltaic element, it is assumed that light is incident from the transparent electrode 1106 side.

In any of the photovoltaic elements, the n-type semiconductor layer and the p-type semiconductor layer can be used in a different order of lamination according to the purpose.

Hereinafter, the configurations of these photovoltaic elements will be described.

Support The support 1101 used in the present invention is preferably made of a material that is flexible and capable of forming a curved shape, and may be either conductive or electrically insulating. Good. Further, they may be light-transmitting or non-light-transmitting, but are light-transmitting when light is incident from the support 1101 side. It is necessary.

Specifically, the belt-like member used in the present invention can be mentioned, and by using the substrate, a solar cell to be manufactured can be reduced in weight, improved in strength, reduced in transportation space, and the like.

Electrode In the photovoltaic element of the present invention, an appropriate electrode is selected and used depending on the configuration of the element. Examples of these electrodes include a lower electrode, an upper electrode (transparent electrode), and a collecting electrode. (However, the upper electrode referred to here indicates the electrode provided on the light incident side, and the lower electrode indicates the electrode provided opposite to the upper electrode with the semiconductor layer interposed therebetween.) The electrodes are described in detail below.

(I) Lower Electrode As the lower electrode 1102 used in the present invention, the surface to which the light for photovoltaic generation is irradiated differs depending on whether or not the material of the support 1101 is translucent (for example, When the support 1101 is made of a non-translucent material such as a metal, light for photovoltaic generation is irradiated from the transparent electrode 1106 side as shown in FIG. 11A.) Location is different.

Specifically, in the case of a layer configuration as shown in FIGS. 11A, 11C and 11D, it is provided between the support 1101 and the n-type semiconductor layer 1103. However, when the support 1101 is conductive, the support can also serve as the lower electrode. However, if the sheet resistance is high even if the support 1101 is conductive, the electrode may be used as a low-resistance electrode for extracting current, or for the purpose of increasing the reflectivity on the support surface and making effective use of incident light. 1102 may be installed.

In the case of FIG. 11B, a light-transmitting support 1101 is used, and light is incident from the support 1101 side. Therefore, for the purpose of current extraction and light reflection at the electrode, A lower electrode 1102 is provided to face the support 1101 with the semiconductor layer interposed therebetween.

When an electrically insulating material is used as the support 1101, a lower electrode 1102 is provided between the support 1101 and the n-type semiconductor layer 1103 as an electrode for extracting current.

As electrode materials, Ag, Au, Pt, Ni, Cr, Cu, Al, Ti, Zn, Mo,
Metals such as W or alloys thereof are mentioned, and thin films of these metals are formed by vacuum evaporation, electron beam evaporation, sputtering, or the like. Further, care must be taken that the formed metal thin film does not become a resistance component with respect to the output of the photovoltaic element, and the sheet resistance is preferably 50Ω or less, more preferably 10Ω or less.

Although not shown in the drawing, a diffusion preventing layer such as conductive zinc oxide may be provided between the lower electrode 1102 and the n-type semiconductor layer 1103. The effect of the diffusion prevention layer is not only to prevent the metal element constituting the electrode 1102 from diffusing into the n-type semiconductor layer, but also to provide a slight resistance value so that the lower electrode provided with the semiconductor layer interposed therebetween. The effect of preventing short-circuiting caused by a defect such as a pinhole between the 1102 and the transparent electrode 1106, and the effect of generating multiple interference by the thin film and confining the incident light within the photovoltaic element are mentioned. it can.

(Ii) Upper electrode (transparent electrode) The transparent electrode 1106 used in the present invention has a light transmittance of 85% or more in order to efficiently absorb light from the sun or a white fluorescent lamp into the semiconductor layer. The sheet resistance is desirably 100Ω or less so that the output of the photovoltaic element does not become a resistance component. As a material having such properties, Sn
Metal oxides such as O ₂ , In ₂ O ₃ , ZnO, CdO, Cd ₂ SnO ₄ , ITO (In ₂ O ₃ + SnO ₂ ), and metals such as Au, Al, Cu etc. Metal thin film and the like. The transparent electrode is laminated on the p-type semiconductor layer 1105 in FIGS. 11 (A), (C) and (D), and is laminated on the substrate 1101 in FIG. 11 (B). Therefore, it is necessary to select ones having good adhesion to each other. These fabrication methods include:
A resistance heating evaporation method, an electron beam heating evaporation method, a sputtering method, a spray method, or the like can be used, and is appropriately selected as desired.

(Iii) Current collecting electrode The current collecting electrode 1107 used in the present invention is a transparent electrode.
It is provided on the transparent electrode 1106 for the purpose of reducing the surface resistance of the 1106. Ag, Cr, Ni, Al, Ag, Au, Ti, P
Examples include thin films of metals such as t, Cu, Mo, W, and the like, or alloys thereof. These thin films can be stacked and used.
The shape and area of the semiconductor layer are appropriately designed so that the amount of light incident on the semiconductor layer is sufficiently ensured.

For example, it is desirable that the shape is uniformly spread over the light receiving surface of the photovoltaic element, and the area is preferably 15% or less, more preferably 10% or less, with respect to the light receiving area.

Further, as a sheet resistance value, preferably 50Ω or less,
More preferably, it is desirably 10Ω or less.

i-type semiconductor layer The semiconductor material constituting the i-type semiconductor layer suitably used in the present photovoltaic element includes A-Si: H, A-Si: F, AS
i: H: F, A-SiC: H, A-SiC: F, A-SiC: H: F, A-SiGe: H, A-SiGe: F,
A-SiGe: H: F, poly-Si: H, poly-Si: F, poly-Si: H: F and the like so-called group IV and group IV alloy semiconductor materials, II-VI and III
-V group compound semiconductor materials.

P-type semiconductor layer and n-type semiconductor layer P-type or n-type preferably used in the present photovoltaic device
As the semiconductor material constituting the semiconductor layer, the above-mentioned i
It can be obtained by doping a valence electron controlling agent into a semiconductor material constituting the type semiconductor layer.

[Experiment]

Using the apparatus of the present invention, in order to examine the generation conditions of microwave plasma and the relative positional relationship between the strip-shaped member and the separating means for uniformly forming a functional deposition film on the strip-shaped member, The experiments described were performed.

Experimental Examples 1 to 9 In the apparatus having the configuration shown in the apparatus example 1, the transfer ring was used.
The 104 and 105 sides are exhaust holes, connected to an exhaust pump (not shown), using various waveguides and microwave applicators having hole processing dimensions shown in Table 1, and microwave plasma discharge conditions shown in Table 2. Experiments and evaluations were conducted on plasma stability and the like. Table 3 shows the evaluation results. In addition, in this discharge experiment, when the belt-shaped member 101 was stopped and when the belt-shaped member 101 was transported at a transport speed of 1.2 m / min, there was no particular difference in discharge stability between the two.

Experimental Examples 10 to 18 In the apparatus having the structure shown in the apparatus example 5, the arrangement of the band-shaped member and the microwave applicator was arranged as shown in FIG. 5 (b), and the various waveguides shown in Table 1 were used. Experiments and evaluations were performed on the stability of plasma and the like using a microwave applicator having a tube and hole processing dimensions and under microwave plasma discharge conditions shown in Table 4.

Table 5 shows the evaluation results. In addition, in this discharge experiment, when the belt-shaped member 101 was stopped and when the belt-shaped member 101 was transported at a transport speed of 1.2 m / min, there was no particular difference in discharge stability between the two.

Experimental Examples 19 to 28 In the apparatus having the configuration shown in the apparatus example 3, the transfer ring was used.
The 104, 105 side is an exhaust hole, connected to an exhaust pump (not shown), various waveguides and holes shown in Table 6 and shutter processing dimensions were used, and microwave plasma discharge conditions shown in Table 2 were used. Experiments on plasma stability, etc.
An evaluation was performed. Table 7 shows the evaluation results. In this discharge experiment, the case where the band-shaped member 101 was stationary and the case where
It was carried out with the case of transporting at a transport speed of m / min,
There was no particular difference in discharge stability between the two.

EXPERIMENTAL EXAMPLES 29-38 In the apparatus having the configuration shown in Apparatus Example 7, the microwave applicator having various waveguides, holes, and shutter processing dimensions shown in Table 6 was used, and the microwave plasma shown in Table 4 was used. Experiments and evaluations were performed on plasma stability and the like under discharge conditions. Table 8 shows the evaluation results. In addition,
In this discharge experiment, a test was performed when the belt-shaped member was stationary and when the belt was transported at a transport speed of 1.2 m / min, but no particular difference was observed in the discharge stability between the two.

Comparative Experimental Examples 1 to 4 In Experimental Examples 2, 7, 21 and 25, among the microwave plasma discharge conditions shown in Table 2, other conditions were not changed and only the pressure was variously changed as shown in Table 9. Then, the state of the plasma at that time was evaluated from the viewpoint of stability, uniformity, and the like. Regarding the evaluation, ◎ indicates the case where the most stable state was obtained, や indicates that there was no practical problem although the stability was somewhat poor, and △ indicates that there was a practical problem due to lack of stability and uniformity.
In the case where no discharge was performed or abnormal discharge or the like was present and it was not practical, the results were ranked as x, and the evaluation results are shown in Table 9.

As can be seen from these, it is understood that stable and uniform microwave plasma is formed in a relatively wide pressure range.

It should be noted that there was no particular change in these results even when the belt-shaped member was stationary or when the belt-shaped member was transported at a transport speed of 1.5 m / min.

Comparative Experimental Examples 5 to 8 In Experimental Examples 2, 7, 21 and 25, among the microwave plasma discharge conditions shown in Table 2, the other conditions were not changed and only the microwave power was varied as shown in Table 10. The plasma state at that time was evaluated from the viewpoints of stability, uniformity, etc., and the case where the most stable state was obtained was evaluated as ◎, and the case where the stability was somewhat lacking but there was no practical problem ○,
Stability and lack of uniformity and a problem in practical use are rated as △, and no discharge or abnormal discharge etc. are impractical and are ranked as × .The evaluation results are shown in Table 10. Indicated.

As can be seen from these, it is understood that stable and uniform microwave plasma is formed in a relatively wide microwave power range.

It should be noted that there was no particular change in these results even when the belt-shaped member was stationary or when the belt-shaped member was transported at a transport speed of 1.5 m / min.

Comparative Experimental Examples 9 to 12 In Experimental Examples 2, 7, 21 and 25, among the microwave plasma discharge conditions shown in Table 2, other conditions were not changed and only L ₁ and L ₂ were used as shown in Table 11. Is changed in various ways, and the state of the plasma at that time is evaluated from the viewpoint of stability, uniformity, etc., and the case where the most stable state is obtained is ◎, slightly unstable, although there is no practical problem although it lacks uniformity. The case was rated as 、, the stability and uniformity were not practical due to lack of uniformity, and the case where there was no discharge or abnormal discharge, etc. was impractical and ranked as ×. The results of the evaluation are shown.

As can be seen from these, when at least one of L ₁ and L ₂ is larger than 1/4 wavelength of the microwave, microwave plasma flickers or microwave leakage increases, It can be seen that when the wavelength is four wavelengths or less, a stable and uniform microwave plasma is formed.

It should be noted that there was no particular change in these results even when the belt-shaped member was stationary or when the belt-shaped member was transported at a transport speed of 1.5 m / min.

In Comparative Experiment Example 13-16 Experimental Examples 2,7,21 and 25, of the microwave plasma discharge conditions shown in Table 2, various changes only L ₃ as shown in Table 12 without changing the other conditions Then, the state of the plasma at that time was evaluated from the viewpoints of stability, uniformity, etc., and the case where the most stable state was obtained was ◎, and the case where the stability was slightly lacking but there was no practical problem was ○.場合, when there is a practical problem due to lack of stability and uniformity, and when it is not practical due to no discharge or abnormal discharge, etc., are ranked as ×, and the evaluation results are shown in Table 12. showed that.

As can be seen, L ₃ is 1/1 of the wavelength of the microwave.
It can be seen that the discharge becomes unstable at two wavelengths or less, but that stable and uniform microwave plasma is formed at half wavelength or more.

However, when L ₁ and L ₂ were larger than / 4 wavelength and L ₃ was too large, microwave leakage was large and discharge was unstable.

It should be noted that there was no particular change in these results even when the belt-shaped member was stationary or when the belt-shaped member was transported at a transport speed of 1.5 m / min.

Comparative Experimental Examples 17 to 20 In Experimental Examples 2, 7, 21 and 25, of the microwave plasma discharge conditions shown in Table 2, other conditions were not changed and only the inner diameter of the curved shape was changed as shown in Table 13. By variously changing
The state of the plasma at that time was evaluated from the viewpoints of stability, uniformity, etc., ◎ when the most stable state was obtained, ○ when the stability was somewhat lacking, but there was no practical problem,
Stability, lack of uniformity and a problem in practical use are rated as △, and no discharge, or abnormal discharge, etc., and it is impractical are ranked as ×, and the evaluation results are shown in Table 13. Indicated.

As can be seen from these, it is understood that uniform microwave plasma is formed stably up to a relatively large inner diameter.

It should be noted that there was no particular change in these results even when the belt-shaped member was stationary or when the belt-shaped member was transported at a transport speed of 1.5 m / min.

Comparative Experimental Examples 21 to 24 In Experimental Examples 11, 18, 30, and 37, among the microwave plasma discharge conditions shown in Table 4, the other conditions were the same.
As shown in the table, only the pressure was variously changed, and the state of the plasma at that time was evaluated from the viewpoint of stability, uniformity, etc., and the case where the most stable state was obtained was evaluated as ◎, somewhat stable, uniformity Rank a case where there is no practical problem with lacking, 、, a case where there is a practical problem with lack of stability and uniformity, and a case where it is impractical due to no discharge or abnormal discharge etc. Table 14 shows the evaluation results.

As can be seen from these, it is understood that stable and uniform microwave plasma is formed in a relatively wide pressure range.

It should be noted that there was no particular change in these results even when the belt-shaped member was stationary or when the belt-shaped member was transported at a transport speed of 1.5 m / min.

Comparative Experimental Examples 25 to 28 In Experimental Examples 11, 18, 30, and 37, among the microwave plasma discharge conditions shown in Table 4, the other conditions were the same.
By changing only the microwave power as shown in the table,
The state of the plasma at that time was evaluated from the viewpoints of stability, uniformity, etc., ◎ when the most stable state was obtained, ○ when the stability was somewhat lacking, but there was no practical problem,
Stability and lack of uniformity and a problem in practical use are ranked as △, and cases where no discharge is performed or abnormal discharge etc. are not practical are ranked as ×, and the evaluation results are shown in Table 15. Indicated.

As can be seen from these, it is understood that stable and uniform microwave plasma is formed in a relatively wide microwave power range.

It should be noted that there was no particular change in these results even when the belt-shaped member was stationary or when the belt-shaped member was transported at a transport speed of 1.5 m / min.

Comparative Experimental Examples 29 to 32 In Experimental Examples 11, 18, 30, and 37, among the microwave plasma discharge conditions shown in Table 4, the other conditions were not changed.
As shown in the table, only L ₄ was changed variously, and the state of the plasma at that time was evaluated from the viewpoints of stability, uniformity, etc., and the case where the most stable state was obtained was ◎, slightly stable, uniformity If there is no practical problem but lacks, rank ○ if there is a practical problem due to lack of stability and uniformity, and × if it is not practical due to no discharge or abnormal discharge etc. Table 16 shows the evaluation results.

As can be seen from these, L ₄ is stable in almost half wavelength or less in the range of wavelength of the microwave, it can be seen that uniform microwave plasma is formed.

It should be noted that there was no particular change in these results even when the belt-shaped member was stationary or when the belt-shaped member was transported at a transport speed of 1.5 m / min.

Comparative Experimental Examples 33 to 36 In Experimental Examples 11, 18, 30, and 37, among the microwave plasma discharge conditions shown in Table 4, other conditions were not changed.
As shown in the table, only the inner diameter of the curved shape was changed variously, and the state of the plasma at that time was evaluated from the viewpoint of stability, uniformity, etc.を, when there is no practical problem with lack of uniformity, △, when there is a practical problem with lack of stability and uniformity,
Cases in which no discharge was performed or abnormal discharge or the like was impractical due to abnormal discharge were ranked as x, and the evaluation results are shown in Table 17.

As can be seen from these, it is understood that a stable and uniform microwave plasma is formed in a range where the inner diameter is up to about five times the diameter of the separation means.

It should be noted that there was no particular change in these results even when the belt-shaped member was stationary or when the belt-shaped member was transported at a transport speed of 1.5 m / min.

Comparative Experimental Examples 37 to 40 In Experimental Examples 1 and 37, except that the punching board for confining the microwave region was changed to one obtained by spraying alumina on the surface of a SUS316L thin plate, the other discharge conditions were not changed, and the plasma was not changed. When the same evaluation was performed for the stability and the like, no particular difference was found in any case.

Outline of Experimental Results In the method and apparatus of the present invention, the stability and uniformity of the microwave plasma are determined by, for example, the type and shape of the microwave applicator, the pressure in the deposition chamber during deposition, the microwave power, and the microwave plasma. Since various parameters such as the degree of confinement, the volume and the shape of the discharge space are intricately entangled, it is difficult to find the optimum conditions with only a single parameter.
The following trends and condition ranges were found.

Regarding the pressure, preferably 1-3 mTorr to 200-50
0 mTorr, more preferably 3-10 mTorr to 100-200 mT
orr. Regarding microwave power,
Preferably 300-700W to 3000-5000W, more preferably
It was found to be 300-700W to 1500-3000W. Furthermore,
With respect to the inner diameter of the curved shape, the length is preferably set to about 5 times, more preferably about 4 times, the length of the outer peripheral wall of the separating means exposed to the microwave plasma region, so that it is almost stable. It was found that uniform microwave plasma was maintained.

Also, it has been found that when the amount of microwave energy leaking from the microwave plasma region increases, the stability of the plasma is lacking, and the gap formed by either the curved end of the belt-shaped member or the separating means is preferably 1 μm of the microwave. It has been found that it is desirable to set the wavelength to not more than / 2 wavelength, more preferably not more than 1/4 wavelength.

Thereafter, a production experiment was performed with reference to these condition ranges.

(Production example)

Hereinafter, specific production examples using the microwave plasma CVD apparatus of the present invention will be described, but the present invention is not limited to these production examples.

Production Example 1 The continuous microwave plasma CVD apparatus shown in Apparatus Example 12 was used to continuously deposit an amorphous silicon film.
The microwave applicator used was No. 13 type.

First, a sufficiently degreased and cleaned SUS430BA strip-shaped substrate (width 60 cm ×
A wound bobbin 703 having a length of 100 m and a thickness of 0.2 mm) is set, and the band-shaped member 101 is attached to the gas gate 721 and the isolation container 40.
The tension was adjusted to a level without sag through the transfer mechanism in FIG. 7 and further through the gas gate 722 to the vacuum vessel 702 having the substrate take-up mechanism. Table 18 shows conditions such as the curved shape of the belt-shaped member.

Therefore, each of the vacuum vessels 701 and 702 and the isolation vessel 400 is roughly evacuated by a rotary pump (not shown), and then a mechanical booster pump (not shown) is activated to evacuate the pressure to about 10 ^-3 Torr, and then the temperature control mechanisms 106 and 107 are used. While maintaining the substrate surface temperature at 250 ° C., the pressure was evacuated to 5 × 10 ⁻⁶ Torr or less using an oil diffusion pump (not shown) (Varian HS-32).

At the time when sufficient degassing was performed, SiH ₄ 600 sccm, SiF _{4 10} sccm, and H ₂ 50 sccm were introduced from the gas introduction tube 112,
The pressure in the film forming chamber 723 was maintained at 9 mTorr by adjusting the opening of a throttle valve attached to the oil diffusion pump. At this time, the pressure inside the isolation container 400 was 1.5 mTorr. When the pressure is stable, microwave power of 1.8 kW in effective power is applied from a microwave power supply (not shown) to applicator 3.
Emitted from 01. Immediately, the introduced raw material gas is turned into plasma to form a microwave plasma region. The microwave plasma region is connected to the vacuum vessel side from wire nets 501, 501 '(wire diameter 1 mm, interval 5 mm) attached to the side surfaces of the transfer rings 104, 105. No leakage was detected, and no microwave leakage was detected.

Therefore, the supporting / transporting rollers 102, 103 and the supporting / transporting rings 104, 105 (both drive mechanisms are not shown) were activated, and the transport speed of the belt-shaped member 102 was controlled to be 1.5 m / min.

The gas gates 721, 722 have gate gas inlet pipes 716, 7
Flow 50sccm H ₂ gas as the gate gas from 17, the exhaust hole 71
The gas was exhausted from an oil diffusion pump (not shown) from 8,718, and the inside pressure of the gas gate was controlled to be 1 mTorr.

A deposited film was formed continuously for 30 minutes after the start of transport. In addition, since a long strip-shaped member is used, after the end of this manufacturing example, another deposition film is continuously formed, and after all the depositions are completed, the strip-shaped member is cooled and taken out.
The thickness distribution of the deposited film on the belt-shaped member formed in this production example was measured within 5% in the width direction and the longitudinal direction, and was found to be within 5%. The deposition rate was 110 ° / sec on average. Also, cut out a part, it was measured infrared absorption spectrum by a reflection method using FT-IR (Perkin Elmer 1720X), observed absorption at 2000 cm ^-1 and 630cm ^-1 a-Si: H : Absorption pattern peculiar to the F film. Furthermore, when the crystallinity of the film was evaluated by RHEED (JEM-100SX, manufactured by JEOL Ltd.), it was found that the film was halo and amorphous. The hydrogen content in the film was determined using a hydrogen-in-metal analyzer (EMGA-1100, manufactured by HORIBA, Ltd.) and found to be 22 ± 2 atomic%.

Production Example 2 Following the deposition film forming process performed in Production Example 1, the introduction of the used raw material gas was stopped, and the internal pressure of the isolation container 400 was evacuated to 5 × 10 ⁻⁶ Torr or less.
Than _{12, SiH 4 150sccm, GeH 4} 120sccm, SiF 4 5sccm, H 2
Introducing 30 sccm, maintaining the internal pressure of the deposition chamber 723 at 15 mTorr, setting the microwave applicator to No. 11, and setting the microwave power to 1.0 kW, the continuous deposition of the amorphous silicon germanium film was performed under the same deposition film forming conditions. Deposition was performed.

After completion of this production example and other production examples, the belt-shaped member was cooled and taken out, and the film thickness distribution of the deposited film formed in this production example was measured in the width direction and the longitudinal direction. The average deposition rate was 48Å / sec.

Also, cut out a part, it was measured infrared absorption spectrum by a reflection method using FT-IR (Perkin Elmer 1720X), 2000cm ^-1, 1880cm ^-1 and 630 cm ^-1
The absorption pattern was unique to the a-SiGe: H: F film. Furthermore, when the crystallinity of the film was evaluated by RHEED (JEM-100SX, manufactured by JEOL Ltd.), it was found that the film was halo and amorphous. In addition, hydrogen analyzer in metal (EMGA-1100,
The amount of hydrogen in the film was determined using HORIBA, Ltd. 16 ± 2a
tomic%.

Production Example 3 Following the deposition film forming process performed in Production Example 1, the introduction of the used source gas was stopped, and the internal pressure of the isolation container 400 was evacuated to 5 × 10 ⁻⁶ Torr or less.
Than _{05, SiH 4 280sccm, CH 4} 40sccm, SiF 4 5sccm, H 2 5
The amorphous silicon carbide film was continuously deposited under the same deposition film forming conditions except that 0 sccm was introduced and the internal pressure of the film formation chamber 723 was maintained at 25 mTorr.

After completion of this production example and other production examples, the belt-shaped member was cooled and taken out, and the film thickness distribution of the deposited film formed in this production example was measured in the width direction and the longitudinal direction. The average deposition rate was 54 ° / sec.

Further, a part thereof was cut out, and an infrared absorption spectrum was measured by a reflection method using FT-IR (1720X manufactured by Perkin-Elmer Co., Ltd.) to find that it was 2080 cm ⁻¹ , 1250 cm ⁻¹ , 960 c
m ^-1, a-SiC observed absorption at 777cm ^-1 and 660 cm ^-1: H: was absorbing pattern specific to F film. In addition, RHEED (JEM-100
SX, manufactured by JEOL) and evaluated the crystallinity of the film.
It was found to be halo and amorphous. In addition, when the amount of hydrogen in the film was determined using a hydrogen-in-metal analyzer (EMGA-1100, manufactured by HORIBA, Ltd.), it was 12 ± 2 atomic%.

Production Example 4 Following the deposition film forming process performed in Production Example 1, the introduction of the used raw material gas was stopped, and the internal pressure of the isolation container 400 was evacuated to 5 × 10 ⁻⁶ Torr or less.
Than _{05, SiH 4 250sccm, BF 3} (3000ppm H 2 dilution) 50Scc
m, SiF ₄ 45 sccm, H ₂ 50 sccm were introduced, the internal pressure of the film formation chamber 723 was maintained at 20 mTorr, and the microwave applicator was No. 3
The p-type microcrystalline silicon film was continuously deposited under the same deposition film forming conditions except that the microwave power was set to 3.0 kW.

After completion of this production example and other production examples, the belt-shaped member was cooled and taken out, and the film thickness distribution of the deposited film formed in this production example was measured in the width direction and the longitudinal direction. The average deposition rate was 42Å / sec.

Also, cut out a part, it was measured infrared absorption spectrum by a reflection method using FT-IR (Perkin Elmer 1720X), observed absorption at 2100 cm ^-1 and 630cm ^-1 μC-Si: H : Absorption pattern peculiar to the F film. Further, when the crystallinity of the film was evaluated by RHEED (JEM-100SX, manufactured by JEOL Ltd.), it was found to be ring-shaped and non-oriented polycrystalline. In addition, hydrogen analyzer in metal (EMGA-110
0, manufactured by Horiba, Ltd.)
± 1 atomic%.

Production Example 5 Following the deposition film forming step performed in Production Example 1, the introduction of the used raw material gas was stopped, and the internal pressure of the isolation container 400 was evacuated to 5 × 10 ⁻⁶ Torr or less.
From 05, SiH ₄ 360sccm, PF ₃ (1% H ₂ dilution) 30sccm, SiF
₄ 5 sccm, introducing H ₂ 20 sccm, a pressure of the film forming chamber 723 12m T
Continuous deposition of an n-type amorphous silicon film was performed under the same deposition film forming conditions except that the power was maintained at orr and the microwave power was set to 1.2 kW.

After completion of this production example and other production examples, the belt-shaped member was cooled and taken out, and the film thickness distribution of the deposited film formed in this production example was measured in the width direction and the longitudinal direction. The average deposition rate was 65 ° / sec.

Further, a portion cut out, was measured infrared absorption spectrum by a reflection method using FT-IR (Perkin Elmer 1720X), absorption was observed at 2000 cm ^-1 and 630cm ^-1, a-Si: The absorption pattern was specific to the H: F film. Furthermore, when the crystallinity of the film was evaluated by RHEED (JEM-100SX, manufactured by JEOL Ltd.), it was found that the film was halo and amorphous. When the amount of hydrogen in the film was determined using a hydrogen-in-metal analyzer (EMGA-1100, manufactured by HORIBA, Ltd.), the result was 20 ± 2 atomic.
%Met.

Production Example 6 In Production Example 1, instead of the SUS430BA band-shaped substrate,
PET (polyethylene terephthalate) strip 101 (width
(50cm x length 100m x thickness 0.8mm)
A continuous deposition of an amorphous silicon film was performed in exactly the same manner except that the temperature was set to 20 ° C.

The belt-shaped member was taken out after cooling, and the film thickness distribution was measured within the width direction and the longitudinal direction and found to be within 5%, and the deposition rate was 105 ° / sec on average. In addition, a part of it is cut out and FT-IR (1720X manufactured by Perkin-Elmer)
The use, by measurement of infrared absorption spectrum by the reference transmission method, observed absorption at 2000 cm ^-1 and ^{630cm -1, a-Si: H} : was absorbing pattern specific to F film. The amount of hydrogen in the film was determined from the absorption attributable to Si-H near 2000 cm ⁻¹ , and was found to be 24 ± 2 atomic%.

Furthermore, when the crystallinity of the film was evaluated by RHEED (JEM-100SX, manufactured by JEOL Ltd.), it was found that the film was halo and amorphous.

In addition, the other 20 parts were cut out at random, and for each of them, a comb-shaped gap electrode made of Al (width 250 μm, length 5 mm) was deposited by a resistance heating evaporation method, and AM-1 light (100 mw / c
m ² ) The photocurrent value under irradiation and the dark current value in the dark
The measurement was performed using 40B, and the light conductivity σp (S / cm) and the dark conductivity σd (S / cm) were determined.
5) It was within the range of × 10 ^-5 S / cm and (2.0 ± 0.5) × 10 ^-11 S / cm.

Production Example 7 In this production example, a Schottky junction diode having the layer configuration shown in the schematic sectional view of FIG. 10 was produced using the apparatus shown in FIG.

Here, 1001 is a substrate, 1002 is a lower electrode, 1003 is an n ⁺ type semiconductor layer, 1004 is a non-doped semiconductor layer, 1005 is a metal layer,
1006 and 1007 are current extracting terminals.

First, a strip member 101 made of SUS430BA similar to that used in Production Example 1 was set in a continuous sputtering apparatus, and a Cr thin film of 1500Å was deposited using a Cr (99.98%) electrode as a target to form a lower electrode 1002. did.

Subsequently, the strip-shaped member 101 was set on the delivery bobbin 703 in the vacuum vessel 701 of the continuous deposition film forming apparatus of FIG. 7 shown in the apparatus example 12, and the surface on which the Cr thin film was deposited faced downward. In this state, the end was wound around the winding bobbin 704 in the vacuum container 702 via the isolation container 400, and the tension was adjusted so that there was no slack.

Note that the conditions such as the curved shape of the substrate in this manufacturing example
The microwave applicator was the same as that shown in Table 13 and the No. 13 type microwave applicator used in Production Example 1 was used.

Thereafter, roughing and high vacuuming operations similar to those of Production Example 1 were performed by an exhaust pump (not shown) through the exhaust pipes 709, 710, and 711 of the respective vacuum vessels. At this time, the substrate surface temperature is 250 ° C
Are controlled by the temperature control mechanisms 106 and 107 so that

When the degassing is sufficiently performed, 350 sccm of SiH ₄ , 5 sccm of SiF _4, 60 sccm of PH ₃ / H ₂ (diluted with 1% H ₂ ), and 30 sccm of H ₂ are introduced from the gas inlet tube 112, and the throttle valve 709 is introduced.
The internal pressure of the film forming chamber 723 was maintained at 12 mTorr by adjusting the opening degree, and when the pressure was stabilized, a microwave of 2.0 kW was immediately emitted from the microwave power supply (not shown) from the applicator 301. The transfer was started at the same time as the plasma was generated, and a deposition operation was performed for 5 minutes while transferring from the left side to the right side in the figure at a transfer speed of 65 cm / min. This gives n ⁺
An n ⁺ type a-Si: H: F film as the semiconductor layer 1003 is formed on the lower electrode 1002.

During this time, H2 was flowed through the gas gates 721 and 722 as gate gas at a flow rate of 50 sccm, and the gas was exhausted from an exhaust hole 718 by an exhaust pump (not shown), and the internal pressure of the gas gate was controlled to ₂ mTorr.

Stop supplying microwaves and introducing raw material gas,
After the conveyance of the band-shaped member 101 is stopped, the internal pressure of the isolation container 400 is reduced to 5
After evacuation to × 10 ^-6 Torr or less, SiH ₄ 350 sccm, SiF _{4 10} sccm, H ₂ 50 sccm were again introduced from the gas introduction tube,
The opening degree of the throttle valve 709 was adjusted to maintain the internal pressure of the film formation chamber 723 at 8 mTorr, and when the pressure was stabilized, a microwave of 1.8 kW was immediately emitted from the microwave power supply (not shown) from the applicator 301. . The transfer was started at the same time when the plasma was generated, and the deposition operation was performed for 5.5 minutes while the transfer was performed reversely from the right to the left in the drawing at a transfer speed of 60 cm / min. Thus, an a-Si: H: F film as a non-doped semiconductor layer 1004 is formed on the n ⁺ -type a-Si: H: F film.

After completion of all the deposition operations, the supply of the microwave and the supply of the raw material gas were stopped, the conveyance of the belt-like member 101 was stopped, the residual gas in the isolation container 400 was sufficiently exhausted, and the belt-like member was taken out after cooling.

A permalloy mask having a diameter of 5 mm was randomly adhered to ten portions of the strip-shaped member, and an Au thin film as the metal layer 1005 was vapor-deposited at 80 ° by an electron beam vapor deposition method. Subsequently, the current extraction terminals 1006 and 1007 were bonded using a wire bonder, and diode characteristics were evaluated using HP4140B.

As a result, good diode characteristics were obtained with a rectification ratio of about 6 digits at a diode factor n = 1.1 ± 0.05 and ± 1V.

Production Example 8 In this production example, a pin-type photovoltaic element having a layer configuration shown in the schematic sectional view of FIG. 11A was produced using the apparatus shown in FIG.

The photovoltaic element has a lower electrode 1102, an n-type semiconductor layer 1103, an i-type semiconductor layer 1104, a p-type semiconductor layer 1105,
This is a photovoltaic element 1100 in which a transparent electrode 1106 and a current collecting electrode 1107 are formed in this order. In this photovoltaic element, it is assumed that light enters from the transparent electrode 1106 side.

First, the same PET band-shaped member 101 as used in Production Example 6 was used.
Is set in a continuous sputtering apparatus, and a 1000 μg Ag thin film is used as a target using an Ag (99.99%) electrode as a target.
A ZnO thin film having a thickness of m was sputter deposited to form a lower electrode 1102.

Subsequently, the band-shaped member 101 on which the lower electrode 1002 is formed
Was set in the continuous deposition film forming apparatus shown in FIG. 8 in the same manner as in Production Example 7. Isolation container 40 at this time
Table 19 shows conditions such as the curved shape of the substrate within 0.

In the isolation containers 400-a and 400-b, the n-type a-Si: H: F film and the p ⁺ -type μc-Si: H: F
A film was formed.

First, microwave plasma is generated in a vacuum vessel, and when the discharge or the like is stabilized, the belt-shaped member 101 is transferred at a transport speed of 54 c.
transported from left to right at m / min
An n, i, p-type semiconductor layer was formed by lamination.

After laminating and forming a semiconductor layer over the entire length of the belt-shaped member 101, take out after cooling, and further, with a continuous modularization device
A solar cell module of 40 cm × 80 cm was continuously produced.

For the fabricated solar cell module, AM1.5 (100mW
/ cm ²⁾ was subjected to characteristic evaluation under optical irradiation, obtained over 8.5% in photoelectric conversion efficiency had more variation in the characteristics among the modules accommodated within 5%.

In addition, the rate of change of the photoelectric conversion efficiency from the initial value after 500 hours of continuous irradiation with AM1.5 (100 mW / cm ² ) light was measured.
Within 10%.

By connecting these modules, a 3 kW power supply system was made.

Production Example 9 In this production example, an a-SiGe: H: F film was used instead of the a-Si: H: F film as the i-type semiconductor layer in the pin-type photovoltaic device produced in Production Example 8. Here is an example.

The formation of the a-SiGe: H: F film is performed by the same operation and method as in Production Example 2, except that the transfer speed is set to 40 cm / min.
The other semiconductor layer module forming process was performed by the same operation and method as in Production Example 8 to produce a solar cell module.

For the fabricated solar cell module, AM1.5 (100mW
/ cm ² ) When the characteristics were evaluated under light irradiation, a photoelectric conversion efficiency of 7.5% or more was obtained, and the variation in characteristics between modules was within 5%.

In addition, the rate of change of the photoelectric conversion efficiency from the initial value after 500 hours of continuous irradiation with AM1.5 (100 mW / cm ² ) light was measured.
Within 10%.

By connecting these modules, a 3 kW power supply system was made.

Production Example 10 In this production example, an a-SiC: H: F film was used instead of the a-Si: H: F film as the i-type semiconductor layer in the pin-type photovoltaic device produced in Production Example 8. Here is an example.

The formation of the a-SiC: H: F film is performed by the same operation and method as in Production Example 3, except that the transfer speed is set to 42 cm / min.
The other semiconductor layers and the module forming process were performed by the same operation and method as in Production Example 8 to produce a solar cell module.

For the fabricated solar cell module, AM1.5 (100mW
/ cm ² ) When the characteristics were evaluated under light irradiation, a photoelectric conversion efficiency of 6.5% or more was obtained, and the variation in characteristics between modules was within 5%.

In addition, the rate of change of the photoelectric conversion efficiency from the initial value after 500 hours of continuous irradiation with AM1.5 (100 mW / cm ² ) light was measured.
Within 10%.

By connecting these modules, a 3 kW power supply system was made.

Production Example 11 In this production example, a photovoltaic element having a layer configuration shown in FIG. 11 (C) was produced. At the time of fabrication, in the apparatus shown in FIG. 8, isolation containers 400-a ', 400', 400-b 'having the same configuration as the isolation containers 400-a, 400, 400-b are further connected in this order via a gas gate. (Not shown).

The lower element 1111 has the same layer structure as that of the production example 9 and the upper element 1112 has the same layer constitution as that of the production example 8, and the conditions for producing the deposited films of the respective semiconductor layers are shown in Table 21. The modularization process was performed by the same operation and method as in Production Example 8 to produce a solar cell module.

For the fabricated solar cell module, AM1.5 (100mW
/ cm ²⁾ was subjected to characteristic evaluation under optical irradiation, obtained over 10.2% in the photoelectric conversion efficiency had more variation in the characteristics among the modules accommodated within 5%.

Further, the rate of change of the photoelectric conversion efficiency with respect to the initial value after continuous irradiation of AM1.5 (100 mW / cm ² ) light for 500 hours was within 9%.

By connecting these modules, a 3 kW power supply system was made.

Production Example 12 In this production example, a photovoltaic device having a layer configuration shown in FIG. 11 (C) was produced. At the time of fabrication, in the apparatus shown in FIG. 8, the isolation containers having the same configuration as the isolation containers 400-a, 400, 400-b are further connected to the isolation containers 400-a ', 400', 400-b 'in this order via a gas gate. A device (not shown) was used.

The lower element 1111 was manufactured in Production Example 8, and the upper element 1112 was formed in the same layer structure as manufactured in Manufacturing Example 10. The conditions for forming the deposited films of the respective semiconductor layers are shown in Table 22. The modularization process was performed by the same operation and method as in Production Example 8 to produce a solar cell module.

For the fabricated solar cell module, AM1.5 (100mW
/ cm ²⁾ was subjected to characteristic evaluation under optical irradiation, obtained over 10.3% in the photoelectric conversion efficiency had more variation in the characteristics among the modules accommodated within 5%.

Further, the rate of change of the photoelectric conversion efficiency with respect to the initial value after continuous irradiation of AM1.5 (100 mW / cm ² ) light for 500 hours was within 9%.

By connecting these modules, a 3 kW power supply system was made.

Production Example 13 In this production example, a photovoltaic element having a layer configuration shown in FIG. 11D was produced. At the time of fabrication, an isolation container having the same configuration as that of the isolation container 400-a, 400, 400-b in the apparatus shown in FIG. 8 was used for 400-a ', 400', 400-b ', 400-a ", 400", 400 -b ″
Were connected in this order via a gas gate (not shown).

The lower element 1120 is the same as that of the ninth example, the intermediate element 1121 is the same as that of the eighth example, and the upper element 1123 is of the same layer structure as that of the tenth example. Indicated. The modularization process was performed by the same operation and method as in Production Example 8 to produce a solar cell module.

For the fabricated solar cell module, AM1.5 (100mW
/ cm ²⁾ was subjected to characteristic evaluation under optical irradiation, obtained over 10.5% in the photoelectric conversion efficiency had more variation in the characteristics among the modules accommodated within 5%.

In addition, the rate of change of the photoelectric conversion efficiency from the initial value after 500 hours of continuous irradiation with AM1.5 (100 mW / cm ² ) light was measured.
Within 8.5%.

By connecting these modules, a 3 kW power supply system was made.

[Summary of Effects of the Invention] According to the method of the present invention, a belt-like member constituting a side wall of a film forming space is continuously moved, and a micro member is formed in a width direction of the band-like member constituting a side wall of the film forming space. Microwave applicator means for radiating or transmitting microwave energy uniformly with directivity in one direction perpendicular to the traveling direction of the wave is provided, and by confining the microwave plasma in the film forming space, It is possible to form a functional deposited film having a large area continuously and with good uniformity.

By confining the microwave plasma in the film forming space by the method and apparatus of the present invention, the stability and reproducibility of the microwave plasma are improved, and the utilization efficiency of the source gas for forming the deposited film is dramatically increased. Can be. Further, by continuously transporting the band-shaped member,
By changing the shape, length, and transfer speed of the curve in various ways, a deposited film having an arbitrary film thickness can be continuously deposited with good uniformity over a large area.

ADVANTAGE OF THE INVENTION According to the method and apparatus of this invention, a functional deposition film can be formed continuously and with good uniformity on the surface of a comparatively wide and long strip-shaped member. Therefore, it can be suitably used especially as a mass production machine for large area solar cells.

In addition, since a deposited film can be formed continuously without stopping discharge, good interface characteristics can be obtained when a stacked device or the like is manufactured.

In addition, it is possible to form a deposited film under low pressure, suppress generation of borosilane powder, and suppress polymerization of active species, so that defects are reduced, film characteristics are improved, and film characteristics are stable. Improvement can be achieved.

Therefore, it is possible to improve the operation rate and the yield, and mass-produce inexpensive and highly efficient solar cells.

Further, the solar cell manufactured by the method and the apparatus of the present invention has high photoelectric conversion efficiency and has less characteristic deterioration over a long period of time.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a microwave plasma CVD apparatus of the present invention. 2 and 3 (a) to (d)
FIG. 2 is a schematic view of the microwave applicator means of the present invention. FIG. 4 is a schematic cross-sectional view of the microwave plasma CVD apparatus of the present invention. FIG. 5 (a), (b)
FIG. 3 is a diagram schematically showing a side cross-sectional view of a belt-shaped member transport mechanism according to the present invention. FIG. 6 is a diagram schematically showing a pressure gradient of the gas gate means in the present invention. 7 to 9 show the continuous microwave plasma CVD of the present invention.
It is the whole schematic of an example of an apparatus. FIG. 10 is a schematic cross-sectional view of a Schottky junction diode manufactured in the present invention. FIGS. 11A to 11D are schematic cross-sectional views of a pin-type photovoltaic device (single, tandem, triple) manufactured in the present invention. FIGS. 12 (i) to (X) are views for explaining a method of processing a band-shaped member. 1 to 12, 101... Belt-shaped members, 102, 103.
104, 105: Support / transport rings, 106, 107: Temperature control mechanism, 108: Microwave applicator, 109: Separation means, 110, 416: Metal cylinder, 111: Wire mesh, 112: Gas introduction pipe, 113 ... Microwave plasma region, 114,115 ……
Wire mesh for preventing microwave leakage, 201,301 ... Microwave applicator, 202,302 ... Circular waveguide, 203 ... End, 204,205,206,207,208,304 ... Hole, 303 ... Open end,
305 ... Connecting part, 306 ... Shutter, 307 ... Groove, 308 ...
… Fixing pin, 309 …… Insulator, 400 …… Isolated container, 401,
402: fixing flange, 403: square, circular conversion waveguide, 404, 411: connecting flange, 405, 412: opening, 40
6,407,413,414 …… O-ring, 408,415 …… Cooling groove, 40
9 ... Open end, 410, 417 ... Ground finger, 418
…… Connection plate, 419… Exhaust hole, 420 …… Connection flange, 42
1… Square waveguide, 501,501 ′, 502,502 ′… Wire mesh, 701,
702,901,902 …… Vacuum container, 703 …… Bobbin for sending out,
704: Winding bobbin, 705, 706: Transport roller, 707, 708, 709: Throttle valve, 710, 711, 718, 7
19,720 …… Exhaust hole, 712,713 …… Temperature control mechanism, 714,715
…… Pressure gauge, 716,717,805,806,807,808 …… Gate gas inlet pipe, 721,722,801,802,803,804 …… Gas gate, 723
…… Deposition chamber, 809,810,811,812 …… Gate gas exhaust pipe, 9
03,904 …… Cathode, 905,906 …… Gas inlet tube, 90
7,908 …… halogen lamp, 909,910 …… Anode electrode,
911,912 …… Exhaust pipe, 1001,1101 …… Support, 1002,1102
... lower electrode, 1003, 1103, 1108, 1114, 1117 ... n-type semiconductor layer, 1004, 1104, 1109, 1115, 1118 ... i-type semiconductor layer, 10
05: Metal layer, 1006, 1007: Current extraction terminal, 110
0,1100 ', 1111,1112,1120,1121,1123 ... pin junction type photovoltaic element, 1105,1110,1116,1119 ... p-type semiconductor layer, 110
6 Upper electrode, 1107 Collector electrode, 1113 Tandem photovoltaic element, 1124 Triple photovoltaic element, 12
01a: Strip member processing chamber (A), 1201b ... Strip member processing chamber (B), 1202, 1203, 1204, 1205, 1206 ... Strip member, 12
07a, 1207b …… Roller, 1208a, 1208b …… Cutting blade, 1209
a, 1209b: welding jig, 1210, 1211, 1212, 1213 ... connecting means.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshimitsu Kariya 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yasushi Fujioka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Tetsuya Takei 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Hiroshi Echizen 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. ( 56) References JP-A-61-288074 (JP, A) JP-A-62-294181 (JP, A) JP-A-59-100516 (JP, A) JP-A-59-68925 (JP, A) Sho 61-263120 (JP, A) JP-A Sho 63-114973 (JP, A)

Claims (43)

(57) [Claims] 1. A column-shaped film-forming space having a side wall formed by the moving band-like member is formed in the middle of the belt-like member while moving the band-like member continuously in the longitudinal direction. A microwave applicator means for introducing a source gas for forming a deposited film and simultaneously radiating or transmitting the microwave energy with directivity in one direction perpendicular to the traveling direction of the microwave.
The microwave energy is radiated or transmitted to generate microwave plasma in the film-forming space, and the deposited film is formed on the surface of the strip-shaped member that constitutes the side wall exposed to the microwave plasma and moves continuously. A method for continuously forming a large-area functional deposition film by a microwave plasma CVD method, characterized by forming a film. 2. In the middle of the moving band-shaped member, the band-shaped member is interposed between the curved start-end forming unit and the curved end-end forming unit using a curved start end forming unit and a curved end end forming unit. The method for continuously forming a large-area functional deposition film according to claim 1, wherein the band-shaped member is curved so as to form a side wall of the film-forming space while leaving a gap in a longitudinal direction of the film. 3. A microwave energy is radiated or transmitted into the film forming space from a gap left in a longitudinal direction of the band-shaped member between the bending start end forming means and the bending end end forming means. 3. The method for continuously forming a large-area functional deposition film according to 2. 4. The microwave applicator means is inserted into one of the two end surfaces of a columnar film-forming space formed with the band-shaped member as a side wall, and the microwave energy is applied to the film-forming space. 3. The method for continuously forming a large-area functional deposition film according to claim 2, wherein the functional deposition film is radiated or transmitted into the film space. 5. A microwave energy radiated or transmitted from said microwave applicator means is introduced into said film formation space via a microwave permeable member provided between said film formation space and said applicator means. The method for continuously forming a large-area functional deposition film according to claim 1, which emits or transmits. 6. The column-shaped film-forming space, wherein the microwave applicator means is disposed so as to be substantially parallel to the width direction of the band-shaped member so as not to come into contact with the microwave-permeable member. The method for continuously forming a large-area functional deposition film according to claim 5, wherein microwave energy is radiated or transmitted into the inside. 7. A large-area functional deposition film according to claim 6, wherein uniform microwave energy is radiated or transmitted from said microwave applicator means to a length substantially equal to the width direction of said strip-shaped member. Method to form the target. 8. A large-area functional deposition film according to claim 7, wherein said microwave applicator means is separated from microwave plasma generated in said film formation space via said microwave transmission member. A method of forming continuously. 9. A large area functional deposition film according to claim 1, wherein microwave energy radiated or transmitted into said columnar deposition space is prevented from leaking out of said deposition space. How to form. 10. An apparatus for continuously forming a large-area functional deposition film on a continuously moving strip member by a microwave plasma CVD method, wherein the strip member is continuously moved in its longitudinal direction. And a column-shaped film-forming chamber formed with the band-shaped member as a side wall and capable of holding the inside thereof substantially at a vacuum, through a curved portion forming means for bending in the middle thereof. Microwave applicator means for generating microwave plasma in the membrane chamber, and radiating microwave energy with directivity in one direction perpendicular to the traveling direction of the microwave; and the microwave applicator means To transmit microwave energy radiated in one direction perpendicular to the direction in which the microwave travels into the film forming chamber, and Separation means for separating the microwave applicator and the means from microwave plasma generated in the film formation chamber by wave energy; exhaust means for exhausting the film formation chamber; raw material for forming a deposited film in the film formation chamber A means for introducing gas; and a temperature control means for heating and / or cooling the strip-shaped member, wherein a continuous surface is provided on a surface of the strip-shaped member that is exposed to the microwave plasma. An apparatus for continuously forming a functionally-deposited film, wherein the deposited film is formed by forming the film. 11. The bending portion forming means comprises at least one set of a bending start end forming means and a bending end end forming means, wherein the bending start end forming means and the bending end end forming means are 11. The apparatus for continuously forming a functional deposited film according to claim 10, wherein the apparatus is disposed with a gap left in the longitudinal direction of the band-shaped member. 12. The curved portion forming means comprises at least a pair of support / transport rollers and a support / transport ring, wherein the pair of support / transport rollers leave a gap in the longitudinal direction of the band-shaped member. Claims that are arranged in parallel
12. The apparatus for continuously forming a functional deposition film according to item 11. 13. The separating means is disposed substantially parallel to a gap left between the curved start end forming means and the curved end end forming means, and is disposed outside the film forming chamber. 12. The continuous apparatus for forming a functional deposition film according to claim 11. 14. The separating means protrudes into the film-forming chamber from one of both end faces of a columnar film-forming chamber having the band-shaped member as a side wall, substantially in parallel with the width direction of the band-shaped member. 12. The continuous apparatus for forming a functional deposition film according to claim 11. 15. The apparatus of claim 15, wherein said separating means is substantially cylindrical.
11. The continuous functional film forming apparatus according to 10. 16. An apparatus for continuously forming a functional deposition film according to claim 10, wherein said separation means is substantially semi-cylindrical. 17. The microwave applicator means comprising:
11. The apparatus for continuously forming a functional deposition film according to claim 10, wherein the apparatus is arranged so as to be separated from a peripheral wall of the separating unit and included in the separating unit. 18. The apparatus for continuously forming a functional deposited film according to claim 10, wherein said separating means is provided with a cooling means. 19. The apparatus according to claim 18, wherein the cooling means is an airflow flowing along an inner peripheral surface of the separating means. 20. The cooling means is concentric with the separating means so as to have a conduit structure disposed inside the separating means and through which a cooling medium can flow between the separating means. Item 19. A continuous apparatus for forming a functional deposition film according to Item 18. 21. The microwave applicator means is a microwave transmission waveguide. The microwave applicator means applies microwave energy substantially uniformly in the longitudinal direction to the microwave applicator means in a direction perpendicular to the microwave traveling direction. A substantially rectangular hole is provided for directing radiation in a direction.
11. The continuous functional film forming apparatus according to 10. 22. The functional deposition film according to claim 21, wherein at least one of the rectangular holes is formed on one side of the waveguide, and microwaves are radiated from the holes. Continuous forming device. 23. An apparatus for continuously forming a functional deposition film according to claim 22, wherein when a plurality of said rectangular holes are formed, these holes are arranged at intervals in a longitudinal direction of said waveguide. 24. An apparatus for continuously forming a functional deposition film according to claim 22, wherein said rectangular hole is a single, substantially rectangular having a large aspect ratio. 25. The size of the rectangular hole is set to one of microwaves.
25. The continuous apparatus for forming a functional deposited film according to claim 24, wherein the dimension is larger than the wavelength and is substantially equal to substantially the entire width and length in the longitudinal direction of the waveguide. 26. A structure in which microwave energy is uniformly radiated from the rectangular hole in the longitudinal direction of the waveguide at a length of at least one wavelength or more of microwaves radiated. 23. The apparatus for continuously forming a functional deposited film according to 22. 27. The functional deposition film according to claim 24, wherein said rectangular hole is provided with shutter means so as to reliably radiate microwave energy of substantially uniform density from said rectangular hole over its entire length. Continuous forming equipment. 28. The continuous functional deposition film forming apparatus according to claim 10, wherein the microwave plasma is confined in a columnar film forming chamber formed by bending the band-shaped member. 29. An apparatus for continuously forming a large-area functional deposition film on a continuously moving strip member by a microwave plasma CVD method, wherein the strip member is continuously moved in its longitudinal direction. And a column-shaped film-forming chamber formed with the band-shaped member as a side wall and capable of holding the inside thereof substantially at a vacuum, via a curved portion forming means for bending in the middle thereof. Microwave applicator means for transmitting evanescent microwave energy with directivity in one direction perpendicular to the traveling direction of microwaves, for generating microwave plasma in the film chamber; and the microwave applicator. Means for transmitting evanescent microwave energy transmitted with a directivity in one direction perpendicular to the direction in which the microwave travels, Separating means for separating the microwave applicator means from microwave plasma generated in the film forming chamber by the evanescent microwave energy and allowing the light to pass therethrough; exhaust means for exhausting the film forming chamber; and the film forming chamber And a temperature control unit for heating and / or cooling the belt-like member, and a side of the belt-like member exposed to the microwave plasma. An apparatus for continuously forming a functional deposited film, wherein a deposited film is continuously formed on a surface. 30. The bending portion forming means comprises at least one set of a bending start end forming means and a bending end end forming means, wherein the bending start end forming means and the bending end end forming means comprise: 30. The apparatus for continuously forming a functional deposition film according to claim 29, wherein the apparatus is disposed with a gap left in the longitudinal direction of the band-shaped member. 31. The curved portion forming means comprises at least a pair of supporting / transporting rollers and a supporting / transporting ring, wherein the pair of supporting / transporting rollers leave a gap in the longitudinal direction of the band-shaped member. Claims that are arranged in parallel
31. The continuous functional film deposition apparatus according to 30. 32. The separating means is disposed substantially parallel to a gap left between the bending start end forming means and the bending end end forming means, and is disposed outside the film forming chamber. 31. The apparatus for continuously forming a functional deposition film according to claim 30. 33. The separating means protrudes into the film forming chamber substantially in parallel with the width direction of the band-shaped member from one of both end surfaces of a columnar film-forming chamber having the band-shaped member as a side wall. 31. The apparatus for continuously forming a functional deposition film according to claim 30. 34. The separation means is substantially cylindrical.
30. The continuous functional deposition film forming apparatus according to 29. 35. An apparatus for continuously forming a functional deposition film according to claim 29, wherein said separation means is substantially semi-cylindrical. 36. The microwave applicator means comprising:
30. The apparatus for continuously forming a functional deposition film according to claim 29, wherein the apparatus is disposed so as to be separated from a peripheral wall of the separation unit and included in the separation unit. 37. The apparatus for continuously forming a functional deposited film according to claim 29, wherein said separating means is provided with a cooling means. 38. An apparatus for continuously forming a functional deposition film according to claim 37, wherein said cooling means is an air flow flowing along an inner peripheral surface of said separating means. 39. The cooling means is concentric with the separating means so as to have a conduit structure which is disposed inside the separating means and through which a cooling medium can flow between the separating means. Item 41. The continuous formation device for a functional deposited film according to Item 37. 40. The microwave applicator means is an elongated slow-wave circuit waveguide, wherein the slow-wave circuit waveguide transmits evanescent microwave energy into the deposition space substantially uniformly in the longitudinal direction. 30. The continuous functional deposition film forming apparatus according to claim 29, which has such a ladder-like structure. 41. The continuous functional deposition film forming apparatus according to claim 40, wherein the length of the ladder-like structure is made substantially equal to the length of the band-shaped member in the width direction. 42. The functional deposition film according to claim 40, wherein the evanescent microwave energy is transmitted more uniformly than the ladder-like structure at least in the longitudinal direction at a wavelength longer than the wavelength of the microwave transmitted. Continuous forming equipment. 43. The continuous functional deposition film forming apparatus according to claim 29, wherein the microwave plasma is confined in a columnar film forming chamber formed by bending the band-shaped member.