JPH0330420A - Method and device for continuous formation of large area functional deposition film using microwave plasma cvd method - Google Patents

Abstract

PURPOSE:To obtain a new method of formation of a uniform functional deposition film over a wide area at high speed by a method wherein a polelike film-forming space, having a bandlike member as a side wall is formed while the band-like member is being moved continuously, and microwave plasma is grown in the film-forming space using a specific microwave applicating means. CONSTITUTION:A polelike film forming space, having a moving bandlike member 101, is formed while the bandlike member is being moved continuously in longitudinal direction. Raw gas for forming of a deposition film is introduced into the above- mentioned film forming space through the intermediary of a gas feeding means 112, and at the same time, microwave plasma is grown in the above-mentioned film forming space by emitting or transmitting microwave energy from a microwave application means 108 in such a manner that a directivity is grown in one direction vertical to the progressing direction of the microwave against the progressing direction of the microwave. As a result, the above-mentioned side wall, which is exposed to the microwave plasma, is constituted and a deposition film is formed on the surface of the bandlike member 101 which is moved continuously.

Description

Detailed Description of the Invention [Technical field to which the invention pertains] The present invention uses a novel microwave energy supply device capable of generating uniform microwave plasma over a large area, and the plasma reaction caused thereby. By decomposing and exciting the raw material gas, a large area of functional N
1 laminated film i! ! The present invention relates to a method and apparatus for continuous formation.

More specifically, it is a method and apparatus capable of dramatically increasing the utilization efficiency of the raw material gas and continuously forming a highly uniform functional deposited film over a large area at high speed. Accordingly, large-area thin film semiconductor devices such as photovoltaic elements can be mass-produced at low cost.

[Description of prior art]

In recent years, the demand for electricity has increased rapidly throughout the world, and as electricity production has become more active to meet this demand, the problem of environmental pollution has become more serious.

In addition, nuclear power generation, which is expected to be an alternative power generation method to thermal power generation and has already entered the practical stage, can cause serious radioactive contamination that can cause damage to the human body, as exemplified by the Chernobyl nuclear power plant accident. A situation has occurred that violates the natural environment, and there are concerns about the future of nuclear power generation.
In fact, some countries have even enacted laws prohibiting the construction of new nuclear power plants.

In addition, even in the case of thermal power generation, the amount of fossil fuels typified by coal and oil used continues to increase in order to meet the increasing demand for electricity, and as a result, the amount of carbon dioxide emitted increases, increasing the amount of carbon dioxide in the atmosphere. The average annual temperature of the earth is steadily rising as greenhouse gas emissions such as carbon dioxide increase, leading to global warming, and the IEA (Int
The National Energy Agency recommends reducing carbon dioxide emissions by 20% by 2005.

Against this background, it is inevitable that the population in developing countries will increase and the demand for electric power will also increase, and that electric power consumption per person will increase due to the further promotion of electronic lifestyles in developed countries. Coupled with the increase in the amount of electricity, the problem of power supply has become a necessity to be considered on a global scale.

Under these circumstances, the power generation method using solar cells that utilizes the great sunlight is not suitable for the above-mentioned radioactive contamination and +1! ! It does not cause problems such as global warming, and since sunlight falls on all parts of the earth, energy sources are less unevenly distributed, and furthermore, it does not require complex large-scale equipment and is relatively expensive. It is attracting attention as a clean power generation method that can meet future increases in power demand without causing environmental damage due to its high power generation efficiency, and various research and development efforts are being carried out to put it into practical use.

By the way, in order for the power generation method using solar cells to be able to meet the electricity demand, the solar cells used must have sufficiently high photoelectric conversion efficiency and excellent characteristic stability. Basically, it is required to be able to be mass-produced.

Incidentally, in order to provide the necessary electricity for a household that fishes by boat, it is necessary to
If a solar cell with an output of about 3 kW per meter zone is required and the photoelectric conversion efficiency of the solar cell is, for example, about 10%, then the large intestine"
The area of the X4 pond is approximately 30n1. For example, to supply the necessary electricity in a household with children, 3.0
A solar cell with an area of 00,000 n is required.

For this reason, easily available gaseous raw material gases such as silane are used and decomposed by glow discharge to deposit semiconductor thin films such as amorphous silicon onto relatively inexpensive substrates such as glass or metal sheets. Solar cells that can be manufactured using this method are attracting attention as they are highly mass-producible and have the potential to be produced at a lower cost than solar cells that are manufactured using single-crystal silicon. There is a reception room.

In a power generation system using solar cells, unit modules are connected in series or parallel to form a unit to generate the desired current,
A method of obtaining voltage is often adopted, and each module is required to be free from disconnections and short circuits. In addition, it is important that there be no variation in output voltage or output current between modules. For this reason, it is required that at least at the stage of manufacturing a unit module, the uniformity and properties of the semiconductor itself, which is the most important characteristic determining factor, must be ensured. From the viewpoint of facilitating module design and simplifying the module assembly process, providing a semiconductor deposited film with excellent uniformity of properties over a large area will increase the mass productivity of solar cells. It is required to achieve a significant reduction in production costs.

Regarding solar cells, a semiconductor layer which is an important component thereof is formed into a semiconductor junction such as a so-called pn junction or pin junction. These semiconductor junctions are formed by sequentially stacking semiconductor layers of different conductivity types, by implanting dopants of different conductivity types into semiconductor layers of conductivity types by ion implantation, or by diffusing them by thermal expansion. This is achieved by

Looking at this point with regard to solar cells using thin film semiconductors such as amorphous silicon, which are attracting attention as mentioned above, in their production, raw material gases containing dopant elements such as phosphine (PII) and diborane (BzllJ) are used. A semiconductor film having a desired conductivity type can be obtained by mixing it with silane, etc., which is the main raw material gas, and decomposing it by glow discharge. Semiconductor junctions can be easily formed by sequentially stacking these semiconductor films on a desired substrate. It is known that this can be achieved.For this reason, when producing an amorphous silicon solar cell, an independent film formation chamber is provided for forming each semiconductor layer, and each semiconductor layer is formed in the film formation chamber. A method has been proposed for forming the .

Incidentally, in the patent specification of U.S. Patent No. 4,400.409, there is a roll-to-roll (Roll, to Ra1l).
A continuous plasma CVD apparatus employing this method has been disclosed.

According to this device, a plurality of glow discharge regions are provided, and a sufficiently long flexible 7J +N of a desired width is arranged along a path through which the substrate successively passes through each of the glow discharge regions; It is said that elements having semiconductor junctions can be continuously formed by continuously transporting the substrate in its longitudinal direction while depositing a semiconductor layer of the required conductivity type in each of the glow discharge regions. ing. Note that in this specification, the dopant gas used when forming each semiconductor layer is different from other glow-emitting gases. A gas gate is used to prevent diffusion and mixing into the IJli region.

Specifically, the glow discharge regions are separated from each other by a slit-shaped dividing passage, and a means is adopted for forming a flow of a scavenging gas such as Ar, H, etc. in the M passage. ing. Because of this, this role
The two-roll method can be said to be a method suitable for mass production of semiconductor devices.

However, since the formation of each of the semiconductor layers is performed by plasma CVD using RF (radio frequency), there is a natural limit to improving the film deposition rate while maintaining the characteristics of the continuously formed film. There is. For example, even when forming a semiconductor layer having a thickness of at most 5,000 layers, it is necessary to constantly generate a predetermined plasma over a considerably long and large area, and to maintain the plasma uniformly. However, doing so requires considerable skill, and it is therefore difficult to generalize the various plasma control parameters involved. In addition, the decomposition efficiency and utilization efficiency of the film-forming raw material gas used are not high (this is also one of the factors that increases production costs).

Additionally, Japanese Patent Laid-Open No. 61-288074 discloses a deposited film forming apparatus using an improved roll-to-roll method. In this device, a holo-like slack part 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 the reaction vessel are contained in this slack part. The method is characterized in that other raw material gases are introduced as necessary and 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 slack portion in this way, the device can be made more compact. Furthermore, since active species activated in advance are used, the film forming rate can be increased compared to conventional deposited film forming apparatuses.

However, this device only utilizes a deposited film formation reaction due to chemical interaction in the presence of thermal energy, and in order to further improve the film formation rate, it is necessary to change the amount of active species introduced and the amount of thermal energy. It is necessary to increase the supply amount, but there are ways to supply heat energy uniformly in large quantities,
There are also limits to the method of generating a large amount of highly reactive active species and introducing them into the reaction space without loss.

On the other hand, a plasma process using microphone t-co waves has recently been attracting attention. Microwaves have a short frequency band, so it is possible to increase the energy density compared to conventional RF, and generate plasma efficiently.
Suitable for sustaining.

For example, U.S. Pat. No. 4,517,223 and U.S. Pat. No. 4,504,518 disclose that VS films are deposited on small area substrates in a microwave glow discharge plasma under low pressure. This method not only prevents the polymerization of active species which causes deterioration of membrane properties due to the process under low pressure, but also provides a high quality membrane. Although it is said that this method can suppress the generation of powder such as polysilane in plasma and dramatically improve the deposition rate, no specific disclosure has been made on how to form a uniform deposited film over a large area. Not yet.

On the other hand, in U.S. Patent No. 4.729.341, -
A low-pressure microwave plasma CVD method and apparatus for depositing a photoconductive semiconductor thin film on a large area cylindrical substrate by a high power process using paired radiating waveguide applicators has been disclosed. The substrate is limited to a cylindrical substrate, ie, a drum as a photoreceptor for electrophotography, and has not been applied to a large-area, long substrate.

By the way, plasma using microwaves tends to cause energy non-uniformity because the wavelength of the microwaves is short, and there are various problems that need to be solved in order to increase the area.

For example, the use of slow-wave circuits is an effective means of uniformizing microwave energy; It has a unique problem that it causes deterioration. Therefore, as a means to solve this problem, attempts have been made to make the energy density uniform near the surface of the substrate by changing the distance between the object to be processed and the slow wave circuit. ．．
No. 983 and No. 4,521,717 δ disclose such methods. In the former case, it is stated that it is necessary to tilt the slow wave circuit at a certain angle with respect to the substrate, but the efficiency of transmitting microwave energy to the plasma is not satisfactory. In the latter case, it is disclosed that two slow-wave circuits are provided non-parallelly in a plane parallel to the substrate. It is desirable to arrange the applicators so that they intersect each other in a plane parallel to the substrate and on a straight line perpendicular to the direction of movement of the substrate, and to avoid interference between the two applicators, the applicators should be placed in the waveguide. A transverse arrangement of the crossbar by half the length relative to the direction of movement of the base body is disclosed in each case.

Also, plasma uniformity (i.e. energy uniformity)
Several proposals have been made to preserve the . Those 12 proposals are published, for example, in the Journal of Vacuum Technology.
f Vacuum 5science Techn
) B-4 (January-February 1986) 29
Pages 5-298 and B-4 of the same magazine (January 1986 -
(February) Pages 126-130 found in the report written on page 126-130.

According to these reports, a microwave reactor called a microwave plasma disk source (MPDS) has been proposed. In other words, the plasma is disk-shaped or tablet-shaped, and its diameter is a function of the microwave frequency. These reports disclose the following contents: First, the plasma disk source can be varied by microwave frequency. However, 2.45
In a microwave plasma disk source designed to operate at GHz, the plasma confinement diameter is at most about 10 holes, and the plasma volume is at most about 118 Jl, so it is far from possible to achieve a large area. The report also shows that in a system designed to operate at a frequency as low as 915 MHz, the plasma diameter of approximately 40 cm and 20
It is assumed that a plasma volume of 0 - is given. The report further states that by operating at a lower frequency, for example 400 MH2, the discharge can be extended to a diameter of more than 1 m. However, the equipment required to achieve this goal is very expensive and specific.

In other words, by lowering the frequency of microwaves, it is possible to increase the area of plasma, but high-output microwave power sources in this frequency range are not available, and are difficult to obtain. Even if available, it is extremely expensive. Furthermore, it is difficult to obtain a variable frequency, high output microwave power source for Kabuto.

Similarly, as a means to efficiently generate high-density plasma using microwaves, a method is disclosed in JP-A-55-141729 in which electromagnets are placed around a cavity resonator to satisfy the ECR (electron cyclotron resonance) condition. Publication No. and Japanese Unexamined Patent Publication No. 5
7-133636, etc., and there have been many reports in academic societies that various semiconductor thin films can be formed using this high-density plasma, and this type of microwave ECR plasma CVD apparatus has already been proposed. has reached the point where it is commercially available.

However, in these methods using ECR, magnets are used to control the plasma, so in addition to the non-uniformity of the plasma due to the microwave wavelength, the non-uniformity of the magnetic field distribution is also added, resulting in large problems. It is technically difficult to form a uniform deposited film on a substrate with a large area. In addition, when increasing the size of the device to increase the area, the electromagnets used also become larger, resulting in an increase in weight and space.
In addition, various problems remain to be solved for practical use, such as heat generation countermeasures and the need for a DC stabilized power source with a large current.

Furthermore, the characteristics of the deposited film that is formed are not at the same level as those formed by conventional RF plasma CVD methods, and the deposited film is not formed in a space where ECR conditions are met. Deposited film and ECR conditions
Since the characteristics and deposition rate are significantly different from those of a deposited film formed in a so-called divergent magnetic field space, this method cannot be said to be particularly suitable for manufacturing semiconductor devices that require high quality and uniformity.

The aforementioned U.S. Pat. Nos. 4,517,223 and 4,729,341 disclose the need to maintain very low pressures in order to obtain high-density plasma. ing. That is, accelerating the deposition rate,
The company says that processes under low pressure are essential to increasing gas utilization efficiency. However, neither the slow wave circuit nor the electron cyclotron resonance method 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. It's something that doesn't exist.

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

By the way, thin film semiconductors are used not only for the solar cells mentioned above, but also for large area or large area applications such as thin film transistors (TPT) for driving pixels of liquid crystal displays, charge change elements and switching elements for contact image sensors, etc. It is also suitable for manufacturing thin film semiconductor devices that require long dimensions, and has been put into practical use as a key component for the above-mentioned image input/output devices. It is expected that by providing a new method for forming a deposited film, it will become even more widespread.

(Objective of the Invention) The present invention provides a novel method for forming functional deposits +19 uniformly and at high speed over a large area by overcoming various problems in conventional thin film semiconductor device forming methods and apparatuses as described above. The purpose of the invention is to provide a device for

Another object of the present invention is to provide a method and apparatus for continuously forming a functional deposited film on a strip member.

A further object of the present invention is to provide a method and apparatus that can dramatically increase the utilization efficiency of raw material gas for forming deposited films and realize 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 substantially uniform microwave plasma over a large area and large volume.

Still another object of the present invention is to provide a novel method and apparatus for continuously forming a photovoltaic device with good stability, high efficiency, and high photoelectric conversion efficiency on a relatively wide and long substrate. It is something to do.

(Structure and Effects of the Invention) The present inventors have conducted intensive research to solve the above-mentioned problems in conventional thin film semiconductor device forming apparatuses and to achieve the object of the present invention. A microwave-transparent member includes a microwave applicator means for radiating or transmitting waves in a direction perpendicular to the direction of propagation of the waves;
and plunge the microwave applicator means into the film forming chamber without contacting the inner circumferential wall thereof,
A raw material gas for forming a deposited film was introduced into the film forming chamber, maintained at a predetermined pressure, and microwaves were supplied from the microwave power source to the microwave applicator means. We found that it is possible to generate microwave plasma that is uniform in the longitudinal direction.

The present invention was completed as a result of further studies based on the above-mentioned knowledge, and involves continuously forming a functional deposited film with a large surface area by the microwave plasma CVD method, which has the main points as described above. Includes methods and apparatus.

The method of the present invention is as follows. That is, while continuously moving a strip member in the longitudinal direction, a columnar film forming space is formed with the moving strip member as a side wall in the middle of the movement, and a deposited film is fed into the film forming space via a gas supply means. A forming raw material gas is introduced, and at the same time, the microwave energy is radiated or transmitted with directionality in one direction perpendicular to the direction of propagation of the microwaves. generating microwave plasma in the film forming space by radiation or transmission, and forming a deposited film on the surface of the continuously moving band-shaped member forming the side wall exposed to the microwave plasma; Characteristic microwave plasma C
This is a method for continuously forming functional deposited films using the VD method.

In the method of the present invention, the moving band-shaped member uses a curved start end forming means and a curved end forming means in the middle of the moving band member, so that the moving band member is formed between the curved start end forming means and the curved end end forming means. The strip member is curved leaving a gap in the longitudinal direction of the strip member to form a side wall of the film forming space.

Microwave energy may be radiated or transmitted into the film forming space through a gap left in the longitudinal direction of the strip member between the curved start end forming means and the curved end forming means. Alternatively, the microwave applicator means is inserted into the film forming space from either end face of a columnar film forming space formed with the band member as a side wall to apply microwave energy to the film forming space. It may also be radiated or transmitted into space.

Microwave energy radiated or transmitted from the microwave applicator means is radiated or transmitted into the deposition space via a microwave transparent member provided between the deposition space and the applicator means. Make it.

The microwave applicator means is disposed close to the band-shaped member so as to be substantially parallel to the width direction of the band-shaped member without coming into contact with the microwave-transparent member, and microwave energy is applied within the columnar film-forming space. to radiate or transmit.

The microwave applicator means uniformly radiates or transmits microwave energy over a length substantially the same as the width of the strip member.

The microwave applicator means is separated from the microwave plasma generated in the deposition space via the microwave transparent member.

In the method of the present invention, the microwave energy radiated or transmitted into the columnar film-forming space is prevented from leaking out of the film-forming space.

Furthermore, the apparatus of the present invention is an apparatus for continuously forming a functional deposited film by microwave plasma CVD on a continuously moving strip-like member, the apparatus continuously forming the functional deposited film in the longitudinal direction of the strip-like member. A columnar film forming chamber is formed using the band-shaped member as a side wall and whose interior can be kept substantially in vacuum via a curved part forming means for bending the film midway while moving the film, A microwave applicator means for radiating microwave energy with directionality in one direction perpendicular to the direction of propagation of the microwave, and said microwave applicator for generating microwave plasma in a film forming chamber. Microwave energy emitted from the means in a direction perpendicular to the direction of propagation of the microwave is transmitted into the film forming chamber, and the microwave energy generated in the film forming chamber by the microwave energy is a separation means for separating the microwave applicator and the means from the wave plasma; an exhaust means for evacuating the inside of the film forming chamber; and a gas supply means for introducing a raw material gas for forming a deposited film into the film forming chamber; Temperature control n for heating and/or cooling the strip member
and means for continuously forming a deposited film on the surface of the belt-shaped member on the side exposed to the microwave plasma. .

In the device of the present invention, the curved portion forming means includes at least one set of a curved start end forming means and a curved end forming means, and the curved portion forming means includes at least one set of a curved start end forming means and a curved end end forming means. , are arranged with a gap left in the longitudinal direction of the strip member.

Note that the curved portion forming means includes at least a pair of supports and
It is composed of an IfI feeding roller and a supporting/conveying ring, and the pair of supporting/conveying rollers are arranged in parallel with a gap left in the longitudinal direction of the band-shaped member.

In the apparatus of the present invention, the separating means is disposed approximately parallel to and close to the gap left between the curved start end forming means and the curved end forming means, and outside the film forming chamber. Alternatively, the strip-shaped member may be inserted into the film-forming chamber from either end surface of a columnar film-forming chamber formed as a side wall substantially parallel to the width direction of the strip-shaped member. .

Further, the separation means may have a cylindrical shape,
Alternatively, it may be semi-cylindrical.

Meanwhile, the microwave applicator means is disposed so as to be separated from the peripheral wall of the separation means and included within 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 the 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 that is disposed inside the separating means and allows a cooling medium to flow between the cooling means and the separating means.

In the device of the invention, the microwave applicator means is a waveguide for microwave transmission, and the waveguide includes:
A substantially rectangular hole is provided in order to radiate microwave energy almost uniformly in the longitudinal direction into the film forming chamber with directionality in one direction perpendicular to the direction of propagation of the microwave.

Note that at least one rectangular hole is formed on one side of the waveguide, and the structure is such that microwaves are radiated from this hole.

Furthermore, when a plurality of the square holes are formed, these holes are arranged at intervals in the longitudinal direction of the waveguide.

Further, the square hole may be a single rectangle with a large aspect ratio, and the dimensions thereof are larger than one wavelength of the microwave and substantially the entire width in the longitudinal direction of the rectangular waveguide. approximately equal to the length.

The rectangular hole uniformly radiates microwave energy with a length of at least one wavelength of the radiated microwave in the longitudinal direction of the waveguide.

The rectangular aperture is also provided with shutter means to ensure that microwave energy is radiated from the rectangular aperture at a substantially uniform density over the entire length of the microwave applicator.

In the apparatus of the present invention, the microwave plasma is confined within a columnar film forming chamber formed by curving the band member.

Furthermore, the apparatus of the present invention is an apparatus for continuously forming a functional deposited film by a microwave plasma CVD method on a continuously moving strip member, the apparatus continuously moving the strip member in its longitudinal direction. A columnar film-forming chamber is formed using the band-shaped member as a side wall and can maintain a substantially vacuum inside the film-forming chamber, through a curved part forming means for curving the film midway through the film-forming chamber. Microwave applicator means configured to transmit evanescent microwave energy with directionality in one direction perpendicular to the direction of propagation of the microwave, and said microwave applicator for generating microwave plasma in a membrane chamber. The evanescent microwave energy transmitted from the means in a direction perpendicular to the direction of propagation of the microwave is transmitted into the film forming chamber, and the evanescent microwave energy is transmitted into the film forming chamber by the evanescent microwave energy. a separation means for separating the microwave applicator means from the microwave plasma generated in the process, an exhaust means for exhausting the inside of the film forming chamber, and a gas supply for introducing a raw material gas for forming a deposited film into the film forming chamber. and a temperature control means for heating and/or cooling the strip-shaped member, and continuously forms a deposited film on the surface of the strip-shaped member on the side exposed to the microwave plasma. This is an apparatus for continuously forming a functional deposited film, which is characterized in that:

In the apparatus of the present invention, the microwave applicator means is an elongated slow-wave circuit waveguide, and the cough slow-wave circuit waveguide applies evanescent microwave energy substantially uniformly in its longitudinal direction into the deposition chamber. It has a ladder-like structure that conveys information.

Further, the length of the ladder-like structure is made approximately equal to the length of the band-like member in the width direction.

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

The method of the present invention will be explained in more detail below.

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

In the method of the present invention, in order to uniformly generate microwave plasma in the columnar film forming space, a microwave applicator means capable of uniformly radiating or transmitting microwave energy in the width direction of the strip member is used. into the columnar film-forming space from either one of both end faces thereof, substantially parallel to the width direction of the band-shaped member, or between the curved start end forming means and the curved end forming means. It is desirable that the gap be disposed approximately parallel to and close to the gap left in the longitudinal direction. Microwave energy is radiated or transmitted from the microwave applicator means with directivity in one direction perpendicular to the direction of microwave propagation, but in either case, the columnar film forming space The microwave energy radiated or transmitted into the interior is reflected and scattered by the band-shaped member constituting the side wall, uniformly filling the deposition space, and at the same time, the raw material for deposited film formation introduced by the gas supply means Since it is efficiently absorbed by the gas, uniform microwave plasma can be formed.

However, in order to generate the microwave plasma stably and with good reproducibility, it is necessary to efficiently radiate or transmit microwave energy into the film-forming space and prevent microwave energy from leaking from within the film-forming space. Care must be taken to ensure that this does not occur.

For example, in the former case, a portion of the material remaining in the longitudinal direction of the strip member between one end surface of the applicator means that has not been plunged and the curve start end forming means and the curve end end forming means of the strip member. It is necessary to prevent microwave energy from leaking through gaps, etc., by sealing the end face and the gaps with a conductive member,
It is desirable to cover the hole with a wire mesh, punching board, etc. whose hole diameter is preferably 172 wavelength or less, more preferably 1/4 wavelength or less of the wavelength of the microwave used.

When the microwave applicator means is inserted into the film forming space, it is preferable that the microwave applicator means be disposed at a position approximately equidistant from the side wall. However, in cases where the curved shape of the side wall is asymmetric, etc. There is no particular restriction on the position where it is placed.

In the latter case, the direction in which microwave energy is directionally radiated or transmitted from the microwave applicator means remains between the curve start end forming means and the curve end end forming means of the strip member. It is necessary that it is suitable for the gap between the In order to efficiently radiate or transmit microwave energy into the columnar film forming space, the gap left between the curved start end forming means and the curved end end forming means should be directed in the longitudinal direction of the strip member. It is desirable that the minimum dimension of the aperture width is preferably 1/4 wavelength or more, more preferably 1/2 wavelength or more of the microwave wavelength.

Furthermore, if the gap and the distance between the microwave applicator means are made too large, the amount of microwave energy radiated or transmitted into the film forming space decreases, and the amount of microwave energy radiated or transmitted decreases. Confinement of microwave energy may be insufficient.

However, the radiation or transmission direction of the microwave energy, the opening width, and the distance between the gap and the microwave applicator means are important for efficiently supplying microwave energy into the columnar film forming space. They have different meanings, but they are interrelated, so it is preferable to adjust and arrange them appropriately so that the efficiency can be maximized.Please note that microwaves should not leak from both end faces of the columnar film-forming space. It is desirable to seal the hole with a conductive member or cover it with a wire mesh, punching board, etc. whose hole diameter is preferably 1/2 wavelength or less, more preferably 1/4 wavelength or less of the wavelength of the microwave used.

In the method of the present invention, the shapes of both end faces of the columnar film forming space formed by curving the moving band member using the bending start end forming means and the bending end forming means include the film forming space. It is preferable that the microwave energy radiated or transmitted into the space fills the film forming space almost uniformly, and the shape is similar to a circular, elliptical, rectangular, or polygonal shape, and is approximately A symmetrical and relatively smooth curved shape is desirable. Of course, the layer surface shape may be discontinuous in the gap portion left in the longitudinal direction of the strip member between the curve start end forming means and the curve end end forming means.

In the method of the present invention, the curving start end forming means and the curving end forming means are disposed at at least two locations in the longitudinal direction of the moving strip member, and curve the strip member, and the curved end forming means are arranged at at least two locations in the longitudinal direction of the moving strip member, and curve the curved strip member as a side wall. A columnar film formation space is formed. The curved shape is preferably kept constant in order to maintain the stability and uniformity of the microwave plasma generated therein, and the band-shaped member has the curved start end forming means and the curved end end forming means. wrinkles by forming means,
It is preferable to support the device so that sagging, lateral displacement, etc. do not occur, and in addition to the curved start end forming means and the curved end end forming means, supporting means for maintaining the curved shape may be provided. Specifically, supporting means for continuously maintaining a desired curved shape may be provided on the inside or outside of the curved band member. When the support means is provided inside the curved strip member, care is taken to minimize the portion that contacts the surface on which the deposited film is formed. For example, it is preferable that the support means be provided at both end portions of the band-shaped member.

It is preferable that the band-like member is flexible enough to continuously form the curved shape, and that smooth shapes are formed at the curve start end 1, curve end end, and intermediate curved portion. The raw material gas for salt film formation introduced into the film space by the gas supply means is efficiently exhausted to the outside of the film formation space, and the pressure inside the film formation space is maintained to such an extent that the microwave plasma is uniformly generated. There is no particular restriction on the direction in which the gas is evacuated, but there is no leakage of microwaves from the exhaust hole, and the source gas is efficiently exhausted. It is necessary to take this into account. Of course, when the raw material gas is exhausted through a plurality of exhaust holes, it is preferable to make the diffusion, flow rate, etc. of the gas almost uniform in the film forming space, and to limit the number of exhaust holes. You can do that.

In order to uniformly and stably generate and maintain microwave plasma in the columnar film-forming space, the shape and volume of the film-forming space, the type and flow rate of the source gas introduced into the film-forming space, and the Although there are optimal conditions for the pressure in the film forming space, the amount of microwave energy radiated or transmitted into the film forming space, the matching of microwaves, etc., these parameters are organically linked to each other. , - It is desirable to set preferable conditions as appropriate, rather than being generally defined.

According to the method of the present invention, a film forming space is formed with a strip member as a side wall, and the strip member constituting the side wall of the film forming space is continuously moved, and the side wall of the film forming space is By providing a microwave applicator means that radiates or transmits microwave energy uniformly in the width direction of the constituent band-shaped member, a large-area functional deposited film can be continuously formed with good uniformity. .

Objectively differentiating the method of the present invention from conventional deposited film forming methods is that the film forming space is columnar, the side walls of which move continuously, and function as a structural material; The point is that it also serves as a support for forming a deposited film.

The function of the iron as a structural material is, in particular, the function of physically and chemically EARing the atmosphere space for film formation, that is, the film formation space, and the atmosphere space not involved in film formation. Specifically, it means the function of forming atmospheres with different gas compositions and states, restricting the direction of gas flow, and furthermore, forming atmospheres with different pressure differences.

That is, in the method of the present invention, the band member is curved to form the side wall of the columnar film forming space, and the remaining wall surface, that is, the 1iFi end face and the gap left in a part of the side wall is formed. By supplying raw material gas and microwave energy for forming the salt 81 film into the film forming space from any point, and exhausting the air, microwave plasma is confined within the film forming space and the side wall is A functional deposited film is formed on the constituting band-like member, and the band-like member itself is important as a structural material for isolating the film-forming space from an external atmospheric space that is not involved in film-forming. In addition to fulfilling these functions, it can also be used as a support for forming deposited films.

Therefore, the atmosphere outside the film-forming space configured with the strip member as a side wall is quite different from the atmosphere inside the film-forming space in terms of gas composition, its state, pressure, etc.

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 formation space for forming an Nl1fl film, and is exclusively used for the formation of quasi-Mi, for example, produced in the film formation space.
It functions only as a member for depositing precursors for film formation, etc., and does not function as a structural material constituting the film forming space as in the method of the present invention.

In addition, in conventional methods such as RF plasma CVD and spackling methods, the substrate or support for forming a laminated film may also serve as an electrode for generating and maintaining discharge, but the plasma is confined. is insufficient, and isolation from external atmospheric space that is not involved in film formation is insufficient.
It is difficult to say that it functions as a structural material.

On the other hand, in the method of the present invention, a band-like member capable of functioning as a support for forming a functional deposited film is used as a side wall of the film-forming space, and the band-like member functions as the structural material, and the band-like member is It also enables continuous formation of functional deposited films.

In the method of the present invention, the band-shaped member is used to form a side wall of a columnar film-forming space, and microwave energy is uniformly radiated or transmitted in the width direction of the band-shaped member within the columnar film-forming space. By confining microwaves within the columnar film forming space, the microwave energy is efficiently consumed within the columnar film forming space, and uniform microwave plasma is generated and formed at t1! The uniformity of the deposited film also increases.

Furthermore, by constantly and continuously moving the strip member constituting the side wall exposed to the microwave plasma and discharging it out of the film forming space, uniformity can be created on the strip member in the direction of movement. It is possible to form a deposited film with a high

Of course, a fairly wide band can be accommodated as long as the amount of microwave energy radiated or transmitted from the microwave applicator means is kept uniform along its length.

In the method of the present invention, a film forming space is formed by the band-shaped member, and the gas composition and its state outside the film forming space are controlled within the film forming space so that the deposited film is formed only within the film forming space. Set the conditions differently. For example, the gas composition outside the film forming space may be a gas atmosphere that is not directly involved in the formation of a deposited film, or may be an atmosphere containing source gas discharged from the film forming space. In addition, although it goes without saying that the microwave plasma is confined within the film-forming space, it is important to prevent the microwave plasma from leaking outside the film-forming space to ensure stability and reproducibility of the plasma. It is also effective in improving properties and preventing film deposition in unnecessary areas. Specifically, it is possible to create a pressure difference between the inside and outside of the film-forming space, to create an atmosphere of so-called inert gas with a small ionization cross section, [f: gas, etc.], or to actively remove microorganisms from inside the film-forming space. It is effective to provide means to prevent wave leakage. As a means for preventing leakage of microwaves, the gap connecting the inside and outside of the film forming space may be sealed with a conductive member, or the hole diameter may preferably be 172 wavelengths or less of the wavelength of the microwave used, more preferably 1/4 wavelength. It may be covered with the following wire mesh or punching board, and the maximum dimension of the gap connecting the inside and outside of the film forming space is preferably 1/2 of the wavelength of the microwave.
It is desirable that the wavelength be less than or equal to the wavelength, more preferably less than or equal to 1/4 wavelength. Further, microwave plasma is not generated outside the film forming space by setting the pressure outside the film forming space to be very low or high compared to the pressure inside the film forming space. You can set conditions like this.

As described above, the method of the present invention is characterized by providing the band-shaped member with a function as a structural material constituting the film-forming space, which distinguishes it from conventional deposited film forming methods and brings about greater effects. .

In the method of the present invention, microwave energy is applied from the microwave applicator means at least substantially uniformly to the widthwise length of the band-like member used with directionality in one direction perpendicular to the direction of propagation of the microwaves. For radiation or transmission, either a leaky wave type or a slow wave circuit type is preferably adopted. In either method, care must be taken to ensure that the amount of microwave radiation or transmission is uniform in the direction in which the microwaves travel. Further, the microwave applicator means is separated from the microwave plasma generated in the film forming space by a microwave transparent member. By doing this, 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 if 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 at least in the longitudinal direction is maintained, and further, By providing a structure that allows the separating means to be cooled uniformly and efficiently, local non-uniformity in microwave transmission can also be avoided. Furthermore, if the separation means is sufficiently cooled, the method can be applied to considerably high-power processes.

Hereinafter, the configuration and features of the microwave plasma cvDWZ of the present invention will be described in more detail in order.

According to the apparatus of the present invention, by confining the microwave plasma region with the moving strip member, the precursor that contributes to the formation of the salt 11 film generated within the microwave plasma region is transferred onto the strip member with high yield. Furthermore, since the deposited film can be continuously formed on the strip-shaped member, the utilization efficiency of the raw material gas for forming the deposited film can be dramatically improved.

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 improved, so that the deposits formed in the width direction of the band-shaped member are improved. Not only does the film have excellent uniformity, but by continuously conveying the strip member in a direction substantially perpendicular to the longitudinal direction of the microwave ablister means, The uniformity of the deposited film formed is also excellent.

Furthermore, according to the apparatus of the present invention, discharge can be maintained continuously, stably, and with good uniformity, so that a functional deposited film with stable characteristics can be continuously deposited on a long strip-shaped member, and the interfacial properties It is possible to fabricate an excellent multilayer device.

Also, using the microwave applicator means of the present invention,
By varying the pore diameter and aperture ratio, highly uniform microwave plasma can be generated in the longitudinal direction.

In the apparatus of the present invention, when the strip member functions as a structural material, the outside of the film forming chamber may be in the atmosphere, but the functional deposited film is formed by the inflow of air into the film forming chamber. If the characteristics of the filter are affected, an appropriate means for preventing atmospheric inflow may be provided. Specifically, a mechanical sealing structure using an O-ring, a gasket, a helicopter sock, a magnetic fluid, etc., or a diluent gas atmosphere that has little effect on the characteristics of the deposited film or is effective.
Alternatively, it is desirable to provide an isolation container around the device to create an appropriate vacuum atmosphere. In the case of the mechanically sealed structure, special consideration must be taken to maintain the sealed tube while the strip member moves continuously. When the apparatus of the present invention and a plurality of other deposited film forming means are connected to successively stack deposited films on the band-shaped member,
It is desirable to connect each device using gas gate means or the like. In addition, when multiple devices of the present invention are connected, each device has an independent film forming atmosphere in the film forming chamber, so the isolation container may be a single container or may be provided in each device. good.

In the apparatus of the present invention, the pressure outside the film forming chamber may be in a reduced pressure state or a pressurized state, but if the band member is significantly deformed due to a pressure difference within the film forming chamber, an appropriate auxiliary structure may be used. The auxiliary structural material may be a wire rod made of metal, ceramics, reinforced resin, etc. and having an appropriate strength and having approximately the same shape as the side wall of the film forming chamber. , is preferably formed of a thin plate or the like, and the band-shaped member facing the side of the auxiliary structural material that is not exposed to the microwave plasma is substantially in the shadow of the auxiliary structural material. Therefore, since almost no deposited film is formed, it is desirable that the projected area of the auxiliary structural material onto the strip member be designed to be as small as possible.

Further, by bringing the auxiliary structural material into close contact with the band-shaped member and rotating or moving it in synchronization with the conveyance speed of the band-shaped member, the mesh pattern etc. applied on the auxiliary structural material can be transferred onto the band-shaped member. It can also be formed.

The material of the band-like member suitably used in the method and apparatus of the present invention is such that it deforms at the temperature required for forming the functional deposited film by the microwave plasma CVD method.
It is preferable that the material has less distortion and has the desired strength, and specifically, metal thin plates and composites thereof such as stainless steel, aluminum and its alloys, iron and its alloys, copper and its alloys, and polyimide, Heat-resistant resin sheets such as polyamide, polyethylene terephthalate, and epoxy, or composites of these with glass fibers, carbon fibers, boron fibers, metal fibers, etc., and metal thin films of different materials on the surfaces of these metal thin plates, resin sheets, etc. and/or Stow, 5i3Nn, A
Spunter method of insulating thin films such as l2zOx, Ai'N, etc.
Examples include those whose surface has been coated by a vapor deposition method, a plating method, or the like. Further, the thickness of the band-shaped member is determined to be as thin as possible in consideration of cost, storage space, etc., as long as it is within a range that exhibits strength that maintains the curved shape formed during transportation by the transportation means. is desirable. Specifically, preferably 0.01 m1 to 5 cranes, more preferably 0.02 m1 to 21 cranes, optimally 0.05 m
Although it is desirable that the width of the band-shaped member is from 1 to 1 carbon, it is easier to obtain the desired strength even if the thickness is made thinner by using a relatively thin plate of metal. As long as the microwave applicator means is used, the uniformity of the microwave plasma in the longitudinal direction is maintained, so there is no particular restriction, but it is preferable that the curved shape is maintained, and specifically, it is preferably 5cII+ to 5cII+. 200cm, more preferably 10cm to 150cm.

Further, the length of the band-shaped member is not particularly limited, and may be long enough to be wound into a roll, or a long one made longer by welding or the like. It's okay to have one.

In the apparatus of the present invention, the means for supporting and transporting the band-shaped member while continuously curving is such that the band-shaped member maintains its curved shape without sagging, wrinkles, lateral displacement, etc. during transport. It is necessary. For example, at least one pair of supporting/conveying rings having a desired curved shape is provided, and the supporting/conveying rings preferably support both ends of the band-shaped member, and the band-shaped member is curved along the shape. At least a pair of support/transport rollers as a curve start end forming means and a curve end end forming means provided in the longitudinal direction of the member narrow the member and curve it into a columnar shape.
applies a driving force to at least one of the feeding rollers to convey the strip member in its longitudinal direction while maintaining its curved shape.

The band-shaped member may be supported and conveyed by the support/transport ring by simply sliding friction, or the band-shaped member may be machined with sprocket holes, etc. As for the conveyance ring, a so-called gear-like ring having a saw blade-like protrusion around the ring may also be used.

Regarding the shape of the supporting/conveying ring, it is preferable to have a circular shape in order to form a curved shape, but even if it is an ellipse, a rectangle, or a polygon, the shape should be continuously constant. There is no particular problem as long as it has a mechanism to maintain the shape.Maintaining the conveyance speed constant is an important point in conveying the curved shape without causing sag, wrinkles, lateral displacement, etc. Therefore, it is desirable that the support/transport mechanism is provided with a detection mechanism for the conveyance speed of the belt-shaped member and a conveyance speed adjustment mechanism that provides feedback based on the detection mechanism. Furthermore, these mechanisms have a great effect on film thickness control when manufacturing semiconductor devices.

Moreover, the supporting/transporting ring is disposed within the microwave plasma region, although the degree of exposure to plasma varies depending on its purpose. Therefore, it is desirable to use a material that can withstand microwave plasma, that is, it has excellent heat resistance, corrosion resistance, etc. Also, since a deposited film will adhere to the surface of the material, it will not be suitable for long-term deposition conversion. Adhesive film peels off,
They fly off and adhere to the deposited film that is being formed, causing defects such as pinholes in the deposited film, which ultimately causes deterioration of the characteristics of the semiconductor devices being manufactured and a decrease in yield. It is preferable that the deposited film be made of a material with a low adhesion coefficient or a material and surface shape that can maintain a strong adhesion force up to a considerable thickness even if the deposited film is deposited. Specific materials include those processed using stainless steel, nickel, titanium, vanadium, tungsten, molybdenum, niobium, and their alloys, or those processed using alumina, quartz, magnesia, zirconia, silicon nitride,
Ceramic materials such as boron nitride and aluminum nitride are coated by a thermal spraying method, vapor deposition method, sputtering method, ion blating method, CVD method, etc., or materials that are formed using a single or composite material of the above ceramic materials, etc. can be mentioned. In addition, the surface shape may be mirror-finished, roughened, etc., depending on the stress of the deposited film, etc., as appropriate. translated.

It is preferable that the deposited film adhering to the supporting/conveying ring be removed before peeling, scattering, etc. occur, and dry etching in a vacuum is performed by wet etching after decomposition.
It is desirable to remove it by chemical or physical methods such as bead blasting.

The supporting/conveying roller is designed to have a larger area in contact with the strip member than the supporting/conveying ring, so that the heat exchange rate with the strip member is large. Therefore, it is desirable that the supporting/conveying roller has a mechanism for adjusting the temperature of the band member as appropriate so that the temperature of the band member does not rise or fall excessively. However, it is possible that at least one pair or more of the supporting/conveying rollers have different set temperatures. Furthermore, it is also effective for the support/conveyance roller to have a built-in conveyance tension detection atI for the belt-shaped member in order to keep the conveyance speed constant.

Furthermore, the supporting/conveying roller is provided with a crown to prevent deflection, twisting, lateral displacement, etc. of the belt-shaped member during conveyance. ! ! ! Preferably, a side is provided.

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 faces of the columnar film forming chamber formed with the strip member as a side wall may be a round shape, an ellipse shape, a square shape, a polygonal shape, etc. Deposition 1 should be approximately symmetrical with respect to
This is desirable for improving the uniformity of each layer. Furthermore, the length of the curved portion determines the volume of the microwave plasma region, and the length of the curved portion determines the volume of the microwave plasma region, and the deposit formed is substantially correlated with the time that the strip member is exposed to the microwave plasma region during transportation. IA
The utilization efficiency of the raw material gas for forming the deposited film is determined based on the ratio to the peripheral length of the separating means exposed to the microwave plasma. Therefore, it is desirable that the length of the curved portion be set to preferably within 5 times, more preferably within 4 times, the circumferential length of the separation means. In the microwave plasma region, the microwave power density (W/cm') for maintaining stable microwave plasma depends on the type and flow rate of the raw material gas used, the pressure, the microwave radiation of the microwave applicator, It depends on the transmission capacity and the absolute volume of the microwave plasma region, etc., and is difficult to define generally.

In the apparatus of the present invention, even if the strip member is not curved to form a columnar shape, it may be conveyed horizontally or in a slightly curved shape opposite to the side facing the hole means of the microwave applicator. There are no problems with plasma discharge conditions, etc.

When the band-shaped member is used as a substrate for a thick-field battery, if the band-shaped member is made of electrically conductive material such as metal, it may be used as an electrode for direct current extraction, or it may be made of electrically insulating material such as synthetic resin. In that case, ACAg, PL 11 is applied to the surface on which the laminated film is formed.

Au, Ni, Ti, Mo, W, Fe, V, Cr.

Cu, stainless steel 2 brass, nichrome, SnO,.

l nzos + Z n Or S n O! −
Plating, vapor deposition, so-called metal elements or alloys such as inzo z ([TO), and transparent conductive oxides (TCO),
It is desirable to form electrodes for current extraction by roughening and surface treatment using a method such as sputtering.

Of course, even if the strip-shaped member is made of an electrically conductive material such as a metal, it may be possible to improve the reflectance of long wavelength light on the substrate surface, or to improve the reflectance of long-wavelength light on the substrate surface, or to increase the A different metal layer or the like may be provided on the side of the substrate-H on which the deposited film is formed, for the purpose of preventing mutual diffusion of the metals or forming an interference layer for preventing short circuits. relatively transparent,
In the case of an N-configuration solar cell in which light is incident from the side of the strip member, it is desirable to deposit a conductive thin film such as the transparent conductive oxide or metal thin film in advance.

Further, the surface properties of the band-shaped member may be a so-called smooth surface or a minutely uneven surface.

In the case of a minutely uneven surface, the shape of the unevenness is spherical, conical, pyramidal, etc., and the maximum height (Rmax)
is preferably 500 to 5,000 people, whereby light reflection on the surface becomes diffused reflection, resulting in an increase in the optical path length of the reflected light on the surface.

The separation means in the apparatus of the present invention has a structure that is disposed close to or protrudes into the film formation chamber and includes a microwave applicator means for radiating or transmitting microwave energy into the film formation chamber. It exists. Therefore, the vacuum atmosphere inside the film forming chamber is separated from the outside air where the microwave applicator means is installed, and the structure is designed to withstand the pressure difference that exists between the inside and outside. Specifically, it is preferably cylindrical or semi-cylindrical, and may also have a shape with a smooth curved surface as a whole.

Further, the thickness of the peripheral wall of the separating means may vary slightly depending on the material used, but it is generally desirable that the thickness of the peripheral wall is 0.5 m to 5 m. It is preferable that the transmitted microwave energy can be transmitted into the film forming chamber with minimum loss, and that the airtightness is excellent so that the air does not flow into the film forming chamber. Examples include glasses such as quartz, alumina, silicon nitride, beryllia, magnesia, zirconia, boron nitride, and silicon carbide, and fine ceramics.

(11) When the separation means is cylindrical or semi-cylindrical, its diameter (inner diameter) is such that the microwave applicator means to be used is contained inside it and the microwave applicator means is attached to the inner circumferential wall of the separation means. It is desirable to set the dimensions to the minimum necessary so that they do not touch each other.

Further, in the separation means, it is desirable to provide a microwave confinement means or a dummy load at the end opposite to the side where the microwave applicator means is inserted, and in the former case, from the end of the band-like member. It is preferable to cover most of the protruding parts with a conductive member such as metal or wire mesh and ground them, and the latter method should be provided especially when there is a possibility of inconvenience in microwave matching at high power levels. is preferred.

Furthermore, it is safe to cover the part of the separation means that protrudes toward the side into which the microwave applicator means is inserted with a conductive member such as metal or wire mesh, and to ground the waveguide and the isolation container. It is preferable.

Further, it is preferable that the separating means is uniformly cooled to prevent thermal deterioration (cracking, destruction), etc. caused by heating by microwave energy and/or plasma energy.

Specifically, the cooling means may be an air flow flowing along the inner circumferential surface of the separating means, or may be formed concentrically inside the separating means with a substantially similar shape to 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 be passed through the conduit.

On the other hand, said separating means, such as a cylindrical shape, of the present invention may be used together with a conventional slow-wave circuit microwave applicator, in which case the microwave energy transmitted from said slow-wave circuit microwave applicator is coupled into the film forming chamber via evanescent waves. As a result, by using a separating means with a thin wall and cooling the separating means to a sufficiently low temperature, even if relatively high power microwave energy is introduced into the film forming chamber, no generation occurs. Plasma with high electron density can be generated without causing damage such as cracks to the separation means due to the heat generated.

Furthermore, in the apparatus of the present invention, film deposition occurs on at least a portion of the outer circumferential surface of the separation means that is in contact with the microwave plasma region, similar to that on the band-shaped member. Therefore, depending on the type and characteristics of the deposited +19, the microwave energy radiated or transmitted from the microwave applicator means is absorbed or reflected by the deposited film,
If the amount of radiation and transmission of microwave energy into the film forming chamber formed by the strip member decreases and the amount of change increases significantly compared to immediately after the start of discharge, it will be difficult to maintain the microwave plasma itself. In addition to this, the deposition rate of the deposited film formed may decrease or the characteristics may change. In such a case, the initial state can be restored by removing the film deposited on the separation means by dry etching, wet etching, R-mechanical method, or the like.

In particular, dry etching is preferably used as a method for removing the TFT film while maintaining a vacuum state. Further, the separating means is rotated while being kept in a vacuum, the part exposed to the microwave plasma is moved outside the microwave plasma region, the deposited film is removed in a region different from the microwave plasma region, and the deposited film is removed again. It is also possible to adopt a continuous method in which the microwave plasma region is rotated and used. Furthermore, by continuously feeding a sheet made of a material having microwave permeability substantially equivalent to that of the separating means along the outer peripheral surface of the separating means, a deposited film is attached and formed on the surface of the sheet. It is also possible to adopt a method in which the plasma is discharged outside the microwave plasma region.

The microwave applicator means in the present invention radiates microwave energy supplied from a microwave power source into the inside of the film forming chamber to turn the raw material gas for deposited film formation introduced from the gas introduction means into plasma and maintain it. It has a structure that allows it to be used. Specifically, a waveguide having an open end is preferably used.

Specific examples of the waveguide include waveguides for microwave transmission such as circular waveguides, rectangular waveguides, and elliptical waveguides. Here, by providing an open end, it is possible to prevent standing waves from forming at the end of the waveguide.

On the other hand, even if the end of the waveguide is a closed end, no particular problem will arise.

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 and mode of the microwave to be used. When designing, it is preferable to minimize transmission loss within the circular waveguide and to prevent the generation of multiple modes. Specifically, in addition to EIAJ standard circular waveguides, etc. In-house standards for 2.45 GHz include those with an inner diameter of 90 u and 100 mm.

Note that it is preferable to use a rectangular waveguide, which is relatively easy to obtain, for transmitting microwaves from a microwave power source.
In the conversion section to the circular waveguide used as a microwave applicator, it is necessary to minimize the transmission loss of microwave energy, and specifically, it is necessary to minimize the transmission loss of microwave energy. It is preferable to use

Further, in the present invention, the type of rectangular waveguide suitably used for the microwave applicator is appropriately selected depending on the frequency band and mode of the microwave used, and at least its cutoff frequency is used. It is preferable that the frequency is smaller than the frequency of *Those with a height of 27 fins can be mentioned.

In the apparatus of the present invention, as long as the applicator means of the present invention is used, the microwave energy supplied from the microwave power source is efficiently radiated and transmitted into the film forming chamber, so problems related to so-called reflected waves can be easily avoided. In microwave circuits, three stub tuners or E
-f (Although it is possible to maintain a relatively stable discharge without using a microwave matching circuit such as a tuner,
In cases where strong reflected waves are generated due to abnormal discharge or the like even before or after the start of discharge, it is desirable to provide the matching circuit to protect the microwave power source.

The waveguide is provided with at least one hole means for radiating microwave energy on one side thereof, and these hole means are opened with dimensions and intervals such that the microwave energy can be uniformly radiated. Although it is necessary for each item to be the same, it is not necessary for each item to be the same or not. Specific dimensions and the like will be disclosed in the experimental examples described later.

It is desirable that the shape of the hole formed in the waveguide is substantially rectangular, and if a plurality of holes are formed at a desired interval in the longitudinal direction from the vicinity of the end of the waveguide, By opening and closing some of them, uniform microwave plasma is generated in the width direction of the band-shaped member used. At this time, the radiated microwave energy has a length longer than at least one wavelength of the microwave radiated in the longitudinal direction of the waveguide, and is preferably radiated almost equally and uniformly in the width direction of the strip-shaped substrate. It is desirable that

Further, when only one hole is formed, the aspect ratio of the rectangle is large, and the waveguide has a dimension larger than one wavelength of the microwave in the longitudinal direction and extends over almost the entire width and length. It is preferable that the microwave energy be opened in the longitudinal direction, and to increase the uniformity of the microwave energy radiated in the longitudinal direction.
That opening degree! Shutter means is provided for adjusting the J angle. The shape of the shutter means is a short surface shape, an elongated trapezoid shape, a rectangular shape or a shape in which a part of one side of the elongated trapezoid is cut out in a half-moon shape, etc., and follows the surface shape of the waveguide. It is desirable that the material be metal or conductive treated resin. The end portion is fixed to a connecting portion provided near the corner of the hole means on the side closer to the microwave power source, and the opening degree is adjusted using this as a fulcrum. It may be fixed to improve plasma stability.

When using the hole means with a large aspect ratio, it is desirable that the length of the long side is approximately equal to the length in the width direction of the band-like member used.

Further, it is preferable that the shutter means is grounded to the waveguide only at the connecting portion, and the waveguide and the shutter means are insulated by an insulating means at a portion other than the connecting portion. preferable. Note that when 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 of microwave radiation structure.

On the other hand, in the present invention, a slow wave circuit type may be used as the microwave applicator means.

When using a slow wave circuit, most of the microwave energy is transmitted via evanescent waves.

Therefore, although microwave energy has the disadvantage that the coupling to the plasma decreases rapidly with increasing distance lateral to the microwave structure, in the present invention the microwave applicator is separated from the plasma region. This drawback can be overcome by doing this.

In the apparatus of the present invention, the film forming chamber and/or the isolation container are separated and independent of the vacuum atmosphere from a vacuum container having other film forming means, and the strip member is passed through them and continuously conveyed. In the apparatus of the present invention, it is desirable that the inside of the film forming chamber and/or isolation container be maintained at a low pressure necessary for operation near the minimum value of the modified Paschen curve. In many cases, the pressure within the film forming chamber and/or another vacuum container connected to the isolation container is at least approximately equal to or higher than that pressure. Therefore, the gas gate means must have the ability to prevent the raw material gases for forming a deposited film being used from diffusing each other due to the pressure difference generated between the containers. Therefore, although the basic concept can be adopted of the gas gate means disclosed in US Pat. No. 4,438,723, its capabilities need to be further improved. Specifically, up to 10
It is necessary to create a pressure difference of about 6 times as much as 1":f,
As the exhaust pump, an oil diffusion pump, a turbomolecular pump, a mechanical booster pump, etc. having a large exhaust capacity are preferably used. In addition, the cross-sectional shape of the gas gate is slit-like or a similar shape, and its dimensions are calculated using the -m conductance calculation formula, along with its total length and the exhaust capacity of the 1-no-1 pump used. , designed. Furthermore, it is preferable to use a gate gas in combination to increase the separation ability, for example, A r , He ,
Examples include rare gases such as NeKr, Xe, and Rn, and diluent gases for forming deposited films such as 112. Gate gas? Rff
Although i is appropriately determined depending on the conductance of the entire gas gate and the capacity of the exhaust pump used, it is sufficient to form a pressure gradient as shown in tag and fbl in FIG. 6. In Fig. 6 (ta+), there is a point at which the maximum pressure is approximately at the center of the gas gate, so the gate gas flows from the center of the gas gate to the vacuum vessel side on both sides, and in Fig. 6 (b), the point where the pressure is maximum is approximately at the center of the gas gate. Since there is a point where the pressure is minimum, the gate gas is exhausted from the center of the gas gate together with the deposited Li'i 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 reality, mass spectrometers are used to measure the amount of gas diffusing, and sediment tf
Optimum conditions are determined by conducting a composition analysis of l lta.

In the apparatus of the present invention, the gas gate means:
The deposited film forming means disposed in another vacuum container connected to the isolation container includes RF plasma CVD method, sputtering method, reactive sputtering method, ion blasting method, photo CVD method, thermal CVD method, Means for realizing a method used for forming a so-called functional deposited film can be mentioned, such as MOCVD method, MICE method, and 1-IR-CVD method. Of course, it is also possible to connect the microwave plasma CVD method of the present invention and similar microwave plasma CVD methods, and select an appropriate method for manufacturing a desired semiconductor device and connect using the gas gate means. be done.

The microwave frequency supplied from the microwave power source used in the device of the present invention is preferably 2.45 GHz, which is used for consumer use, but frequencies in other frequency bands are relatively less available. You can use whatever is easy. Further, in order to obtain stable discharge, the oscillation mode is preferably so-called continuous oscillation, and the ripple width is preferably within 30%, more preferably within 10%, in the used output range.

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 it can stabilize the properties of the deposited film formed and prevent the incorporation of impurities. It is. However, since the length of the band-like members used is finite, it is necessary to perform an operation such as welding to connect them. in particular,
Such a processing chamber may be provided close to the container (on the sending side and the winding side) in which the strip member is stored.

A specific processing method will be described below with reference to the drawings.

Figure 12 (Part 1) (i) to Figure 12 (Part 4) (x
) is a schematic diagram for explaining the outline of the band-shaped member processing chamber and the operation during film formation of the band-shaped member, etc.

In FIG. 12, 1201a is a strip-shaped member processing chamber (A) provided on the delivery side of the strip-shaped member, and 1zotb is a strip-shaped member processing chamber (B) provided on the winding side of the strip-shaped substrate. Paiton roller 1207a, 1
207b, cutting blades 1208a, 1208b, f8 fixture 1209a.

1209b is stored.

That is, FIG. 12 (Part 1)<i) shows the state during normal film formation, in which the strip member 1202 is moving in the direction of the arrow in the figure, and the roller 1207a, cutting blade 1208a, and welding jig 1209a are moving in the direction of the arrow in the figure. It is not in contact with the strip member 1202.

1210 is a connection means (
1211 is a connection means (gas gate) with a vacuum container (not shown).

FIG. 12 (Part 1) (ii) shows the first step for replacing the belt-shaped member with a new one after the film-forming process on one roll of the belt-shaped member is completed. First, the strip member 1202 is stopped, and the roller 1207a is moved in the direction of the arrow from the position indicated by the dotted line in the figure to bring it into close contact with the strip member 1202 and the wall of the strip member processing chamber 1201a. In this state, the strip member storage container and the film forming chamber are airtightly separated, and the cutting blade 12
013a is moved in the direction of the arrow in the figure to cut the strip member 1202. This cutting blade 1208a is made of one that can mechanically, electrically, or thermally cut the strip member 1202.

FIG. 12 (Part 1) (iii) shows how the cut and separated strip member 1203 is wound up toward the strip member storage container.

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

FIG. 12 (Part 2) (iv) shows a process in which a new strip member 1204 is fed and connected to the strip member 1202. The end portions of the band members 1204 and 1202 are brought into contact and welded together using a welding jig 1209a.

In FIG. 12 (part 2) (v), the inside of the strip 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 between the strip member 1202 and the strip member processing chamber. (A) shows the state in which the strip members 1202 and 1204 are rolled up away from the wall of l 201a.

Next, the operation on the winding side of the strip member will be explained.

FIG. 12 (Part 3) (vi) shows the state during normal film formation, and the jigs are arranged almost symmetrically as explained in FIG. 12 (Part 1) N).

Figure 12 (Part 3) (vi) shows that after the film-forming process for one roll of a band-like member is completed, it is taken out and replaced with an empty bobbin for winding up the band-like member that has been subjected to the next film-forming process. It shows the process to do so.

First, the strip member 1202 is stopped, and the roller 1207
Move b from the position iS indicated by the dotted line in the figure in the direction of the arrow,
The strip member 1202 is brought into close contact with the wall of the strip member processing chamber 1201b. In this state, the belt-shaped member storage container and the storage room are separated from each other. Next, the cutting blade 1208b is moved in the direction of the arrow in the figure to cut the band-shaped member 1202, and the cutting blade 1208b mechanically, electrically, and thermally operates the band-shaped substrate 1.
202 can be cut.

FIG. 12 (part 3) shows how the cut and separated strip member 1205 after the film forming process is wound up toward the strip member storage container.

The above-mentioned cutting and winding steps may be performed in the following state: 1) The interior of the member storage container is either in a vacuum state or in an atmospheric pressure leak state.

FIG. 12 (Part 4) <ix) shows a step in which a pre-winding strip member 1206 attached to a new winding bobbin is fed and connected to the strip member 1202. Preliminary winding The ends of the strip member 1206 and the strip member 1202 are brought into contact with each other, and the welding jig 1
It is welded and connected at 209b.

In FIG. 12 (part 4) (X), the inside of the strip 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 strip member 1202 and the strip member processing The state in which the band-shaped members 1202 and 1206 are rolled up away from the wall of chamber CB) 1201b is shown.

The functional deposited films that are continuously formed in the method and apparatus of the present invention include Si, Ge, and C, regardless of whether they are amorphous or crystalline.
So-called group III raw conductor thin films, 5ide, SiC, Sig
So-called group II alloy semiconductors such as n, gt191, GaAs, G
So-called m-v group compound semiconductor T'Q films such as aP, CaSb, and InPlnAs, and Zn5e, Zr1S, and ZnT.
Examples include so-called I+-■ group compound semiconductor thin films such as e, CdS, Cd5eCdTe, etc.

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

Of course, these raw material compounds can be used not only alone, but also in combination of two or more. Moreover, these raw material compounds are ITe+N e+A'+K r, X e.

Noble gases such as Rn, and Hl, l(F, 1lcj
! It may also be introduced mixed with a diluent gas such as.

Moreover, the semiconductor layers 11 that are continuously formed have valence electrons 2I
II control and bandgap control can be performed. Specifically, valence control agent or bandgap system? A raw material compound containing an element serving as a 3U agent may be introduced into the film forming chamber alone or mixed with the raw material gas for forming a self-deposited film or the diluent gas.

The raw material gas for forming a sedimentary film, etc. is supplied from a gas introduction pipe having a single or plural gas release holes at the tip thereof, which is disposed in a columnar film forming chamber formed by the strip member and the separation means. , is uniformly emitted into the columnar film forming chamber, and is turned into plasma by microwave energy to form a microwave plasma region.

In the apparatus of the present invention, part or all of the raw material gas for forming a deposited film introduced into the columnar film forming chamber from the gas introduction pipe is decomposed to generate a precursor for forming a deposited film, and the deposited film is Although formation is performed, undecomposed raw material gas or gas with a different composition due to decomposition must be promptly exhausted to the outside of the columnar film forming chamber. However, if the area of the exhaust hole is made larger than necessary, microwave energy will leak from the exhaust hole, causing instability of the plasma or having an adverse effect on other electronic equipment, the human body, etc. . Therefore, it is desirable to provide the exhaust hole using the following three methods. (i) Mesh or punching boards are provided on both sides of the supporting/conveying ring used when bending the band-shaped member, and gas exhaust from these is possible, but the microwave Prevent leaks. However, the diameter of the hole in the mesh or punching board is desirably sized to create a pressure difference between the inside and outside of the columnar film forming chamber and to prevent leakage of microwaves. Specifically 1
The maximum diameter of each hole is preferably 1/2 ID length or less of the wavelength of the microwave used, more preferably 1/4 wavelength or less, and the aperture ratio is IIT or less than 80%, more preferably 60%. Of course, in this case, the gap is formed between the curve start end and the curve end end of the strip member, or the curve start end and curve end end of the strip member, and the outer circumferential wall of the separation means. The air may be exhausted at the same time through a gap (slit), but the interval between them should be approximately T or 1/2 of the wavelength of the microwave used to prevent microwave leakage.
It is desirable that the wavelength is equal to or less than the wavelength, more preferably equal to or less than 1/4 wavelength, (ii) thin plates are provided on both sides of the supporting/conveying ring provided at the end of the ring used for curving the band-shaped member; Ensure that there is no gas exhaust or microwave leakage from here. Then, gas is exhausted only from the gap between the curve start end and the curve end end of the strip member, or the gap (slit) formed between the curve end of the strip member and the outer circumferential wall of the separation means.

However, in order to prevent leakage of microwaves, it is desirable that the interval is preferably less than L/2 wavelength of the microwave used, more preferably less than 174 wavelengths5(i
ii) On both sides of the support/conveyance ring (1) and (
One of each of the mesh or punching board and thin plate described in ii) is provided. That is, (i) and (i
A method that combines both of i) can be mentioned. It is desirable that the mesh, punching board, and thin plate are all made of the same material and subjected to the same surface treatment as the support/conveyance ring.

(Example of Apparatus) Hereinafter, the apparatus of the present invention will be explained using specific examples of the apparatus of the present invention using the drawings, but the present invention is not defined by these in any way.

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

101 is a belt-shaped member, and a supporting/conveying roller 102
403 and a supporting/transporting ring 104105, it is transported in the direction of the arrow in the figure while maintaining its cylindrical curved shape. 106.107 is the temperature for heating or cooling the strip member 101, 1 bll m 4! ! It is horizontal.

108 is a microwave applicator, and separation means 1
09 from the microwave plasma region 113. 110 is a metal tube for preventing microwave leakage, 1
11 is a wire mesh for preventing microwave leakage, and 112 is a gas introduction pipe. 114115 is a wire mesh for preventing microwave leakage, and the microwave plasma region 113 is connected to the strip member 101.
It is confined in a deposition chamber with the curved part of the sidewall as the side wall. Inside the microwave plasma region 113, a separation means 109 and a conveying roller 102403 are removed by an exhaust device (not shown).
and/or wire mesh 114 for preventing microwave leakage.
, 115.

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

The circular waveguide 202 has an end portion 203, and a plurality of holes 204 to 208 (for example, five holes in this case) arranged at intervals are opened on one side of the end portion 203, and microwaves are emitted from the arrow direction in the figure. is progressing. Here - as an example hole 2
05 shows a state where the waveguide 202 is covered with a lid made of the same material. By opening and closing several holes in this manner, the microwave energy radiated in the longitudinal direction of the waveguide 202 is made uniform.

1. This device example is an example of a device in which the device shown in device example 1 is disposed in an isolation container. FIG. 4 shows a schematic diagram thereof. 400 is an isolation container, the inside of which can be evacuated through an exhaust hole 419 using an exhaust pump (not shown). 401 and 402 are fixing flanges, which fix the separating means 109 that protrudes through both walls of the isolation container 400. Fixing flange 40
, 402 are preferably made of a suitable corrosion-resistant material such as stainless steel like the isolation container 400, and are preferably of a structure that is detachable from the isolation container 400. The fixing flange 401 is a connecting flange. 404. The connecting flange 404 is attached directly to the side wall of the isolation vessel 400 and is here provided with an opening 40 approximately coextensive with the outer circumferential surface of the cylindrical separation means 109.
5 is opened so that the separation means 109 can be inserted. Furthermore, at least two O-rings 406 and 407 are attached to the fixing flange 401 to isolate the vacuum atmosphere inside the isolation container 400 from the outside air. Here, a cooling groove 408 is provided between the O-rings 406 and 407.
are provided, through which a coolant, for example water, can be circulated to uniformly cool the O-rings 406,407. As the material for the O-ring, a material that performs its function at a temperature of 100° C. or higher, such as Python, is preferably used. Here, it is preferable that the O-ring be disposed at a location sufficiently away from the microwave plasma region, thereby preventing the O-ring from being damaged by high temperatures.

110 is a metal cylinder, and the opening end 409 is coated with gold M4.
111 is attached, and also a grounding finger 41
0 maintains electrical contact with the fixing flange 401, and these structures prevent microwave energy from leaking to the outside. Wire mesh 110 and separation means 1θ
It also has the role of allowing the cooling air of No. 9 to flow out. In addition,
A dummy load for microwave absorption may be connected to the open end 409, which is particularly effective in cases where leakage of microwave energy occurs at high power levels.

The isolation container 400 includes the fixing flange 40 described above.
A fixing flange 402 for fixing in the same way as the separation means is attached to the side wall opposite to the side wall to which the first one is attached. 411 is a connecting flange, 412 is an opening, 4
13, 414 is an O-ring, 415 is a cooling groove, 416 is a metal tube, and 417 is a grounding finger. A connecting plate 418 connects the microwave applicator means 108, the microwave power source, and the rectangular/circular conversion waveguide 403, and preferably has a structure that prevents leakage of microwave energy. For example, a choke flange can be mentioned. Furthermore, the waveguide 403 for rectangular/circular conversion has a rectangular waveguide 421 and a connecting flange 42.
Connected via 0.

FIG. 5+01 schematically shows a side sectional view of the conveying mechanism for the belt-shaped member 101 in this example of the apparatus.

The arrangement here is such that the separation means 109 has at least two adjacent points on the outer circumferential surface and is curved into a substantially cylindrical shape with respect to the side facing the hole 208 formed in the circular waveguide 202. is shown.

Supporting and conveying rollers 102 to maintain the cylindrical shape.
103 and a support/conveyance ring 104 (105) are used. Here, the supporting/conveying ring 104 (10
The width of 5) should have a ratio as small as possible to the width of the strip member used to increase the effective utilization rate of the film deposited on the substrate. In any case, the film to be deposited on the substrate is this support/transport ring 104 (10
5).

Further, on both sides of the support/transport ring 104405, there are wire meshes or thin plates 50 for confining the microwave plasma region.
, 50F (one side not shown) is preferably attached, and the mesh diameter is preferably 1/2 wavelength or less, more preferably 1/4 of the wavelength of the microwave used.
If the exhaust gas is below the wavelength and is exhausted from this surface, it is desirable that the gas is of a level that can ensure the permeation of the raw material gas.

In addition, the substrate temperature control n mechanism 106407
The substrate temperature control mechanism is for keeping the temperature constant while the substrate 1 passes through the microwave plasma region, and it is preferable that the substrate temperature control mechanism is capable of both heating and/or cooling. In order to increase the effective efficiency, it may be a structure that is in direct contact with the strip member. - During boat fishing, the temperature is likely to rise in areas exposed to microwave plasma, and the increase will depend on the type and thickness of the strip member used. Since the degree of this changes, it is necessary to control it appropriately.

Furthermore, the distances L1 and L2 at the proximate points between the outer circumferential surface of the separation means 109 and the strip member 101 are such that at least the radiation is prevented from leaking therefrom and in order to confine the microwave plasma region within the curved shape. It is preferable that the length be set to 1/2i1 of the wavelength of the microwave.

However, the distance L3 between the curve start end and the curve end end of the strip member 101 is such that the microwave energy radiated from the microwave applicator 201 is efficiently radiated into the curved region formed by the strip member 101. It is desirable to set the wavelength to be longer than 1/4 wavelength of the microwave to be emitted.

Since the microwave energy radiated from the hole 208 is directional and radiated in a direction substantially perpendicular to the side toward which the hole 208 faces, the direction of radiation is oriented at least substantially perpendicular to the distance L3. Preferably.

The gas introduction pipe 112 is provided with holes arranged and with hole diameters that allow gas to be discharged almost uniformly. Further, the position where the gas introduction pipe is installed within the curved shape is not particularly limited as long as it is within that range.

Next, there is a case in which the microwave applicator means 301 shown in FIG. 3 (al) is used in the apparatus shown in FIG. 1.

The circular waveguide 302 has an open end 303 and one elongated rectangular hole 304, through which microwaves propagate in the direction of the arrow in the figure. The hole 304 is larger than one wavelength of the microwave used, and is opened over almost the entire surface of one side of the circular waveguide 302. The open end 303 is provided to avoid standing waves, but there is no problem even if it is sealed. With this structure, microwave energy can be radiated from the entire surface of the hole 304. In particular, the concentration of microwave energy is greatest at the end of the hole near the microwave power source. Therefore, at least one shutter 306 attached to the circular waveguide 302 by means of a connection 305 can be used to adjust its concentration. Preferred shapes of the shunter 306 include a short shape, a trapezoid shape, and a shape in which one side of a rectangular shape or trapezoid is cut out into a half-moon shape or the like, as shown in FIGS.

Jl13os is composed of a groove 307 opened on the side of the shutter 306 closer to the microwave 1 source, and a fixing pin 30B. Furthermore, 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, if a contact is provided between the partial shutter 306 and the waveguide 302, this becomes an arc contact.

Apparatus considerations ↓ 1 In this apparatus example, in the apparatus examples 1 and 2, Fig. 5 (
As shown in the side cross-sectional view shown in FIG.

The arrangement here shows a case where the strip member lO1 is concentrically curved along the outer peripheral surface of the separating means 109. Here, on both sides of the supporting/conveying rings 104 and 105,
Gold 1502.5 for confinement of microwave plasma NM
02' (one side not shown) is preferably attached, and the mesh is preferably 1/2 wavelength or less, more preferably 1/4 wavelength or less of the wavelength of the microwave used, and has a mesh that allows the raw material gas to pass through. It is desirable that the

Furthermore, the surface spacing L4 of the strip member 101 between the curve start end and the curve end end of the strip member 101 is set such that at least radiation is prevented from leaking from here and to confine the microwave plasma region within the curved shape. It is necessary to set the wavelength to be shorter than the 172 wavelength of the microwave used.

Although it is preferable that the separation means 109 and the strip member 101 be relatively arranged concentrically, as long as the separation means 109 is arranged so as to be wrapped within the curved shape of the strip member 101, radiation will be emitted. Since the microwave energy is confined within the curved shape, there is no particular problem, and the direction in which the holes 208 are directed is not particularly limited.

Furthermore, it is desirable that the four-person gas pipe 112 be disposed within a region surrounded by the separation means 109 and the band-shaped member 101.

In equipment modification example 4.5, the microwave applicator 20
1 to the microwave applicator 30 used in device example 2.
An example of a similar configuration except that the number is changed to 1 can be mentioned.

Device examples 1, 2.4, and 5 have the same configuration except that a slow wave circuit type microwave applicator (not shown) is used as the microwave applicator 201.

Responsible Team 1l In this equipment example, as shown in FIG.
and 702 are connected using gas gates 721 and 722.

Reference numeral 703 indicates a bobbin for feeding out the strip-like member, and 704 indicates a bobbin for winding the strip-like member, and the strip-like member is conveyed in the direction of the arrow in the figure. Of course, this can also be carried in reverse. 706 and 707 are conveyance rollers that also serve as tension adjustment and positioning of the strip member. 712,713
is a temperature adjustment mechanism used for preheating or cooling the strip member. 707, 708, and 709 are throttle valves for adjusting the displacement, and 710, 71, and 720 are exhaust pipes, each of which is connected to an exhaust pump (not shown). 7
Reference numerals 14 and 725 are pressure gauges, 716 and 717 are gate gas introduction pipes, and 718 and 719 are gate gas exhaust pipes.
The raw material gas for film formation is exhausted. 723 is the strip member 10
This is a film forming chamber with 1 as a side wall.

In this example of the device, as shown in FIG. 8, in addition to the device shown in device example 12, two additional microwave plasma C
Isolation containers 400-a, 400 for forming deposited films by VD
-b can be connected on both sides to fabricate a stacked device.

Those labeled a and b in the figure are mechanisms that basically have the same effect as those used in isolation vessel 400.

80, 802, 803, 804 are gas gates, 80
5,806,807.808 are respectively gate gas introduction pipes,
809, 810, 81, and 812 are gate gas exhaust pipes, respectively.

"Apparatus" Microwave applicator 3 used in equipment example 3, microwave applicator 201 in earthwork earthwork equipment examples 12 and 13
The configuration may be the same except that it is changed to 01.

袈-16,1- Devices having the same configuration as those in Device Examples 12 and 13 can be mentioned except that a slow wave circuit type microwave applicator (not shown) is used as the microwave applicator 201.

As shown in Figure 9, in the device example 12, two conventional RF plasma CVs are added to the device shown in device example 12.
Connect D devices on both sides! Examples include those configured so that a fi-layer device can be manufactured.

Here, 901 and 902 are vacuum vessels, 903 and 904 are cathode electric bridges for RF application, 905 and 906 are gas introduction pipes and heaters, 907 and 908 are halogen lamps for substrate heating, 909 and 910 are anode electric fields, and 911 and 912 is the exhaust pipe.

For example, in device example 13, isolation container 4 for forming a deposited film
00,400-a, a device in which various microwave applicators described above in 400-b are combined and attached.

Further, examples include a device in which two or three of the devices shown in Device Example 13 are connected together, and a device in which the above-mentioned RF plasma CVD method for forming a deposited film is mixed and connected.

In addition, device examples 12 and 13 may include devices in which the strip member and the microwave applicator are arranged in the same manner as in device examples 4 and 5.

Advantageously by the method and apparatus of the present invention! ! ! A solar cell is an example of a manufactured semiconductor device. The 11th diagram schematically shows a typical example of the W1 configuration.
Shown in Figures (A) to (D).

The example shown in FIG. 11 (A>) includes a lower electrode 1102 on a support 1101, an n-type semiconductor layer 1
104, a photovoltaic element 1100 in which a p-type semiconductor layer 1105, a transparent electrode 1106, and a current collector type 8iill 107 are deposited in this order. Note that this photovoltaic element is based on the premise that light is incident from the transparent electrode 1106 side.

In the example shown in FIG. 11(B), a transparent electrode 1106, a p-type semiconductor layer 1105, an n-type semiconductor layer 1104, an n-type semiconductor layer 1103, and a lower electrode 11 are placed on a transparent support 1101.
A photovoltaic element 1100' in which 02 was deposited in this order,
It is. This photovoltaic element is based on the premise that light is incident from the transparent support 1101 side.

The example shown in FIG. 11(C) is a pin using two types of semiconductor layers as the i-layer, each having a band gap and/or a layer thickness.
Two junction type photovoltaic elements 1111°1112
So-called tandem photovoltaic element 11 configured in layers
It is 13. 1101 is a support body, and the lower electrode 8i11
102, n-type semiconductor layer 1103. 1-type semiconductor 11110
4, p-type semiconductor IW1105, n-type semiconductor [1108,
It is assumed that an l-type semiconductor 1i1109, a p-type semiconductor JIII101 transparent electrode 1106, and a current collector electrode 107 are laminated in this order, and that light is incident from the transparent electrode 1106 side in this photovoltaic element.

The example shown in FIG. 11(D) is a pin using three types of semiconductor layers with different band gaps and/or layer thicknesses as the i-layer.
This is a so-called triple-type photovoltaic device 1124, which is constructed by forming a three-element Mi layer of junction-type photovoltaic devices 1120° 112 and 1123.

1101 is a support body, which includes a lower electrode 8i 1102, an n-type semiconductor layer 1103, an n-type semiconductor layer 1104, a p-type semiconductor layer 1105, an n-type semiconductor layer 1114, an n-type semiconductor layer 111
5, p-type semiconductor layer 1116, n-type semiconductor layer 1117, l
It is assumed that the type semiconductor 7i1118, the p-type semiconductor IW1119, the transparent electrode 1106, and the current collector type 1f11107 are laminated in this order, and that light is incident from the transparent electrode 1106 side in this photovoltaic element.

Note that in any photovoltaic element, the n-type semiconductor layer and the p-type semiconductor layer can be used by changing the stacking order of each layer depending on the purpose.

The configurations of these photovoltaic elements will be explained below.

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 conductive or electrically insulating. Good too. Further, they may be light-transmitting or non-light-transmitting, but if light is incident from the support 1101 side, they are of course light-transmitting. It is necessary.

Specifically, the above-mentioned band-shaped member used in the present invention can be mentioned, and by using the substrate, it is possible to reduce the weight, improve the strength, and reduce the X11II space of the manufactured solar cell.

1) In the photovoltaic device of the present invention, appropriate electrodes are selected and used depending on the configuration of the device. Examples of these electrodes include a lower electrode, an upper electrode (i3 Meiden), and a current collecting electrode. (However, the lower electrode here refers to the one provided on the light incident side, and the lower electrode refers to the one provided opposite the upper electrode with the semiconductor layer in between.) The electrodes will be explained in detail below.

-〇 Uni L system; Blood The lower electrode 1102 used in the present invention is as follows:
The surface that is irradiated with light for generating photovoltaic power varies depending on whether the material of the support 1101 described above is light-permeable or not (
For example, when the support 1101 is made of a non-transparent material such as metal, the transparent electrode 1
Light for generating photovoltaic force is irradiated from the 106 side. ), the location where it is installed differs.

Specifically, in the case of layer configurations as shown in FIGS. 11(A), (C), and (D), the support 1101 and the n-type semiconductor F
il103. However, the support 110
When 1 is conductive, the support can also serve as the lower electrode. However, even if the support 1101 is conductive, if the sheet resistance value is high, it may be used as a low-resistance single pole for current extraction, or for the purpose of increasing the reflectance on the support surface and making effective use of incident light. An electrode 1102 may also be provided.

In the case of FIG. 11(B), a transparent support 1101 is used, and light is incident from the side of the support 1101, so for the purpose of extracting current and reflecting light at the electrode, A lower portion 11102 is provided facing the support 1101 with the semiconductor layer interposed therebetween.

In addition, when an electrically insulating material is used as the support 1101, the support 1101 can be used as an electrode for taking out current.
And n-type semiconductor layer! A lower electrode 1102 is provided between the lower electrode 103 and the lower electrode 1102 .

The electrode materials include Ag, Au, PL, and Ni.

Examples include metals such as Cr, Cu, Aj, Ti, Zn, Mo, and W, or alloys thereof, and IWAs of these metals are formed by vacuum evaporation, electron beam evaporation, sputtering, or the like.

In addition, care must be taken so 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 value is preferably 50Ω or less, more preferably 1
It is desirable that the resistance is 0Ω or less.

Although not shown in the figure, a diffusion prevention 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 that the electrode 1
This not only prevents the metal elements constituting 102 from diffusing into the n-type semiconductor layer, but also provides a slight resistance value between the lower electrode 1102 and the transparent electrode 1106 provided with the semiconductor layer in between. Effects include preventing syllate caused by defects such as pinholes, and confining incident light within the photovoltaic element by generating multiple interference by the thin film.

(ii) Top (') The transparent electrode 1106 used in the present invention desirably has a light transmittance of 85% or more in order to efficiently absorb light from the sun, a white fluorescent lamp, etc. into the semiconductor layer. Furthermore, electrically, it is desirable that the sheet resistance value be 100Ω or less so as not to become a resistance component with respect to the output of the photovoltaic element. Materials with such characteristics include Snow, In5Oa I ZnO+ CdO
, Cd*5nOa.

Examples include metal oxides such as ITo (InlOs +Snow), and metal thin films formed semi-transparently using metals such as Au, Affi, and Cu. ) and (D), they are laminated on the p-type semiconductor layer 1105, and in FIG. As a method for producing these, a resistance heating evaporation method, an electron beam heating evaporation method, a sputtering method, a spray method, etc. can be used, and the method is appropriately selected depending on the need.

The current collector 1tio7 used in the present invention is a transparent electrode 1106 for the purpose of reducing the surface resistance value of the transparent electrode 1106.
106. Electrode materials include Ag, Cr,
N, Al, Ag, Au.

Examples include thin films of metals such as Ti, Pt, Cu, Mo, and W, or alloys thereof. These thin films can be used in a stacked manner. Further, the shape and area of the semiconductor layer are appropriately designed so that a sufficient amount of light incident on the semiconductor layer is ensured.

For example, it is desirable that the shape spreads uniformly over the light-receiving surface of the photovoltaic element, and that its area is preferably 15% or less, more preferably 10% or less of the light-receiving area.

In addition, the sheet resistance value is preferably 50Ω or less,
More preferably, it is 10Ω or less.

Semiconductor materials constituting the t-type semiconductor layer suitably used in this photovoltaic device include A-3i:H, A-8
i:FA-3i:)l:FA-3iC:H,A-3
iC:F, A-3iC:H:F, A-3iCe:H,A
-3iGe2F.

A-3iGe:H:F, poly-3i:IIpoty
-3i:F, poly-3t:I-IF, and other so-called group 1 and group 2 alloy semiconductor materials, as well as so-called compound semiconductor materials of group 2 and low V, and the like.

The semiconductor material constituting the p-type or n-type semiconductor layer suitably used in the present photovoltaic device can be obtained by doping the semiconductor material constituting the type 1 semiconductor layer described above with a valence electron control agent. .

〔experiment〕

In order to study the conditions for generating microwave plasma and the relative positional relationship between the strip member and the separation means in order to uniformly form a functional deposited film on the strip member using the apparatus of the present invention, the following will be explained. The experiments described were conducted.

In the device having the configuration shown in Example 1 of the device for twisting twisted soil twice, the conveying ring 1
04. The ios side is an exhaust hole, connected to an exhaust pump (not shown), microwave applicators with various waveguides and hole machining dimensions shown in Table 1 are used, and the microwave plasma discharge conditions are shown in Table 2. Experiments and evaluations were conducted on plasma stability, etc. The evaluation results are shown in Table 3.
In this discharge experiment, the strip member 101 was held stationary and conveyed at a conveyance speed of 1,2 m x 7 mIn, and no particular difference was observed in the stability of the discharge between the two.

In the device having the configuration shown in Example 5 of the device for the construction of a landowner, the band-shaped member and the microwave applicator are arranged as shown in FIG. 5(b). Using a microwave applicator with waveguide and hole machining dimensions,
Experiments and evaluations of plasma stability, etc. were conducted under the microwave plasma discharge conditions shown in Table 4.

The evaluation results are shown in Table 5. In addition, in this discharge experiment, when the strip member 101 was stationary and when 1, jm/si
The experiment was conducted with the case of conveying at a conveyance speed of n, and no particular difference was observed in the stability of discharge between the two.

In the device having the configuration shown in Example 3 of the two-main construction device, the conveyor ring 1
The side of 04405 is used as an exhaust hole, connected to an exhaust pump (not shown), using various waveguides, holes, and shutter processing dimensions shown in Table 6, and under the microwave plasma discharge conditions shown in Table 2. Experiments and evaluations were conducted on plasma stability, etc. The evaluation results are shown in Table 7. In this discharge experiment, the strip member 101 was held stationary and was conveyed at a conveyance speed of jm/min. No particular difference was observed.

In the device having the configuration shown in Device Example 7, microwave applicators with various waveguides, holes, and shutter processing dimensions shown in Table 6 were used, and microwave plasmas shown in Table 4 were used. Experiments and evaluations were conducted on plasma stability, etc. under discharge conditions.

The evaluation results are shown in Table 8. In this discharge experiment, when the strip member was stationary and when the band member was stationary,
The experiment was conducted with the case of conveying at a conveyance speed of n and no particular difference was observed in the stability of discharge between the two.

In Experimental Examples 2, 7.21 and 25, only the pressure was varied as shown in Table 9 without changing the other conditions among the microwave plasma discharge conditions shown in Table 2. The state of the plasma at that time was evaluated from the viewpoints of stability, uniformity, etc. Regarding the evaluation, the case where the most stable condition is obtained is ◎
, O1 stability is slightly lacking in stability and uniformity but does not pose a practical problem, △ is a case in which lack of uniformity is a problem in practical use, and full (no discharge or abnormal discharge, etc.) Cases that are not true are ranked as ×, and the 9th
The evaluation results are shown in R.

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

Note that no particular change was observed in these results even when the strip member was stationary or when it was being transported at a transport speed of 5 m/sin.

North 1m2L Experimental example 2. , 21 and 25, among the microwave plasma discharge conditions shown in Table 2, only the microwave power was varied as shown in Table 10 without changing the other conditions, and the plasma state at that time was stabilized. Evaluate from the viewpoint of stability, uniformity, etc., and if the most stable condition is obtained, ◎,
01 is a case where there is a slight lack of stability or uniformity but there is no practical problem, Δ is a case where a lack of uniformity is a practical problem, and it is not practical due to no discharge or abnormal discharge, etc. The cases were ranked as X, and the evaluation results are shown in Table 10.

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

Note that no particular change was observed in these results even when the strip member was stationary or when it was being transported at a transport speed of 5 m/sin.

9-12 In Experimental Examples 2.7.21 and 25, among the microwave plasma discharge conditions shown in Table 2, only L+ and Li were varied as shown in Table 11 without changing the other conditions. Evaluate the state of the plasma at that time from the viewpoints of stability, uniformity, etc., and mark the case where the most stable state is obtained as ◎, and the case where there is a slight lack of stability and uniformity but no practical problems as O.
1. Lack of stability and uniformity is ranked as Δ if there is a practical problem, and × is ranked if there is no discharge at all or abnormal discharge, etc., and these evaluations are shown in Table 11. The results were shown.

As can be seen from these, if L+ and Lx are small (if either one is larger than 1/4 of the microwave wavelength, the microwave plasma will flicker and the microwave leakage will increase, but both It can be seen that stable and uniform microwave plasma is formed when the wavelength is below /4 wavelength.

Note that no particular change was observed in these results even when the strip member was stationary or when it was being transported at a transport speed of 5 m/sin.

13-16 In Experimental Examples 2, 7, 21 and 25, among the microwave plasma discharge conditions shown in Table 2, the other conditions were kept unchanged as shown in Table 12, and only the conditions were varied, The state of the plasma at that time was evaluated from the viewpoint of stability, uniformity, etc., and the most stable state was ◎, moderately stable,
○ indicates that there is a lack of uniformity but there is no practical problem; Δ indicates that lack of stability or uniformity causes a practical problem; × indicates that there is no discharge at all or there is abnormal discharge, etc., which is impractical The evaluation results are shown in Table 12.

As can be seen from these, L is 1 of the microwave wavelength.
It can be seen that the discharge becomes unstable at a wavelength of 1/2 or less, but stable and uniform microwave plasma is formed at a wavelength of 1/2 or more.

However, if L+ and Lx are larger than 1/4 wavelength and L
If , is too large, the microwave leakage will be large;
The discharge was also unstable.

Note that no particular change was observed in these results even when the strip member was stationary or when it was being transported at a transport speed of 5 m/sin.

17-20 In Experimental Examples 2, 7, 21 and 25, among the microwave plasma discharge conditions shown in Table 2, only the inner diameter of the curved shape was varied as shown in Table 13 without changing the other conditions. Then, evaluate the state of the plasma at that time from the viewpoint of stability, uniformity, etc., and if the most stable state is obtained, ◎,
O1 stability is a case where there is a slight lack of stability or uniformity but no practical problem, △ is a case where a lack of uniformity is a practical problem, and it is not practical due to no discharge or abnormal discharge, etc. Cases were ranked as ×, and the evaluation results are shown in Table 13.

As can be seen from these figures, it can be seen that stable and uniform microwave plasma can be formed up to a relatively large inner diameter.

Note that no particular change was observed in these results even when the strip member was stationary or when it was being transported at a transport speed of 5 m/sin.

21-24 In Experimental Examples 11, 18, 30 and 37, among the microwave plasma discharge conditions shown in Table 4, only the pressure was varied as shown in Table 14 without changing the other conditions,
Evaluate the state of the plasma at that time from the viewpoints of stability, uniformity, etc., and choose ◎ when the most stable state is obtained, and O2 when there is a slight lack of stability and uniformity but no practical problems.
If there is a lack of stability or uniformity, it is ranked as Δ if there is a practical problem, and if there is no discharge at all or there is abnormal discharge, etc., which is impractical, it is ranked as ×.Table 14 shows the evaluation results. showed that.

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

Note that no particular change was observed in these results even when the strip member was stationary or when it was being transported at a transport speed of 5 m/sin.

25-28 In Experimental Examples 11, 18, 30 and 37, among the microwave plasma discharge conditions shown in Table 4, only the microwave power was varied as shown in Table 15 without changing the other conditions. 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 ◎
, O2 stability is a case where there is a slight lack of stability or uniformity but no practical problem, Δ is a case where a lack of uniformity is a practical problem, and Δ is a case where there is no discharge at all or abnormal discharge, etc., which is not practical. Cases where this was not the case were ranked as ×, and the evaluation results are shown in Table 15.

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

Note that no particular change was observed in these results even when the strip member was stationary or when it was being transported at a transport speed of 5 m/sin.

8-29 to 32 In Experimental Examples 1, 18, 30 and 37, among the microwave plasma discharge conditions shown in Table 4, only L4 was varied as shown in Table 16 without changing the other conditions. , evaluate the state of the plasma at that time from the viewpoints of stability, uniformity, etc., and indicate the case where the most stable state is obtained as ◎, and the case where there is a slight lack of stability and uniformity but no practical problem is O1 stable. If there is a lack of quality or uniformity, it is ranked as Δ if there is a practical problem, and if there is no discharge at all or if there is abnormal discharge, etc., which is impractical, it is ranked as ×. Table 16 shows the evaluation results. Indicated.

As can be seen from these figures, it can be seen that stable and uniform microwave plasma is formed in the range where L4 is approximately 1/2 wavelength or less of the wavelength of the microwave.

Note that no particular change was observed in these results even when the strip member was stationary or when it was being transported at a transport speed of 5 m/sin.

33-36 In Experimental Examples 1, 18, 30 and 37, among the microwave plasma discharge conditions shown in Table 4, only the inner diameter of the curved shape was varied as shown in Table 17 without changing the other conditions. 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 ◎
, O1 stability is a case where there is a slight lack of stability or uniformity but no practical problem, △ is a case where a lack of uniformity is a practical problem, and there is no discharge at all or abnormal discharge, etc., which is not practical. Cases where this was not the case were ranked as ×, and the evaluation results are shown in Table 17.

As can be seen from these figures, it can be seen that stable and uniform microwave plasma is formed within a range where the inner diameter is approximately five times the diameter of the separation means.

Note that no particular change was observed in these results even when the strip member was stationary or when it was being transported at a transport speed of 5 m/m111.

6 37-40 In Experimental Examples 1 and 37, except for changing the punching board for confining the microwave region to a thin plate made of 5US316L with alumina sprayed on the surface, other discharge conditions were not changed, and the plasma was stabilized. When similar Q evaluations were conducted regarding gender, etc., no particular differences were observed.

Amount of unborn children! In the method and apparatus of the present invention, the stability, uniformity, etc. of the microwave plasma are determined by, for example, the type and shape of the microwave applicator, the pressure inside the film forming chamber during film formation, the microwave power, and the confinement of the microwave plasma. Various parameters such as degree, volume and shape of discharge space? 3 [Since the parameters are maintained in a crudely intertwined manner, it is difficult to determine the optimal conditions using only a single parameter, but from the results of this experiment, the following trends and condition ranges were found.

Regarding the pressure, preferably 1 to 3 mTorr to 20
0-500mTorr, more preferably 3-10mT
It was found to be between 100 and 200 mTorr. Regarding microwave power, preferably 300 to 7
00W to 3000-5000W, more preferably 30
It was found that the power was from 0 to 700W to 1500 to 3000W. Furthermore, the inner diameter of the curved shape is approximately stabilized by setting the condition to a range of preferably about 5 times, more preferably about 4 times, the length of the outer circumferential wall of the separation means exposed to the microwave plasma region. It was found that a uniform microwave plasma was maintained.

Furthermore, it has been found that if the amount of microwave energy leaking from the microwave plasma region increases, the plasma becomes unstable. It has been found that it is desirable to set the wavelength to 1/2 wavelength or less, more preferably 1/4 wavelength or less.

From now on, we decided to conduct manufacturing experiments with reference to these condition ranges.

[Production Examples] Hereinafter, specific production examples using the microwave plasma CVD apparatus of the present invention will be shown, but the present invention is not limited to these production examples in any way.

Continuous deposition of amorphous silicon films was carried out using the continuous microwave plasma CVD apparatus shown in Example 12 of the apparatus. Note that the microwave applicator used was of the Arashi 13 type.

First, a strip-shaped substrate made of SLISA 30BA (width 601 x length 100 m x thickness 0.2 mm) that has been thoroughly degreased and cleaned is placed in a vacuum container 701 that has a substrate delivery mechanism.
The bobbin 703 wound with M M
Pass through vacuum field 2% 702 with iS removal mechanism,
The tension was adjusted to the extent that there was no slack. Table 18 shows the conditions such as the curved shape of the strip member.

Therefore, each vacuum container 701, 702 and isolation container 400
Roughly pump it with a rotary pump (not shown), then start a mechanical booster pump (not shown) to increase the pressure to 10" Torr.
After evacuation to the vicinity, temperature control mechanism 10640
5 using an oil diffusion pump (not shown) (Parian H3-32) while maintaining the substrate surface temperature at 250°C.
The vacuum was evacuated to below XlO-'Torr.

When sufficient degassing has been performed, 5iIn 600sec and 5iFa 10sccm are introduced from the gas introduction pipe 112.

50 sccva of Ha was introduced, and the pressure inside the film forming chamber 723 was maintained at 9 mTorr by adjusting the opening degree of the throttle valve attached to the oil diffusion pump. At this time, the pressure inside the isolation container 400 was 1,5 m Torr. When the pressure was stabilized, a microwave power source (not shown) radiated microwaves with an effective power of 8 kW from the applicator 301. Immediately, the introduced raw material gas turns into plasma and forms a microwave plasma region, which is formed by wire meshes 501, 501' (wire diameter lU, interval 5- There was no leakage from 1) to the vacuum container side, and no microwave leakage was detected.

Therefore, the supporting/conveying rollers 102, 103 and the supporting/conveying rings 104, 105 (drive mechanisms not shown in both cases) are started, and the conveying speed of the strip member 102 is controlled to be 5 m/l1in. did.

In addition, H8 gas is supplied as a gate gas for 50 seconds from the gate gas introduction pipes 716 and 717 to the gas gauges 721 and 722.
EC-flushing was carried out, and the gas was evacuated from exhaust holes 718 and 718 using an oil diffusion pump (not shown), and the internal pressure of the gas gate was controlled to be 1 mTorr.

The deposited film was formed continuously for 30 minutes after the start of transportation. Note that since a long strip-shaped member is used, after the completion of this production example, another deposited film was formed, and after all the depositions were completed, the strip-shaped member was cooled and taken out.
MiI12 on the strip member formed in this production example
When the film thickness distribution was measured in the width direction and longitudinal direction, it was within 5%, and the average deposition rate was 110 A.
/sec. Also, cut out a part of it and FT-
When the infrared absorption spectrum was measured by the reflection method using IR (Perkin Elmer 1720X), it was found that 200
Absorption was observed at 0 cm-' and 630 es-' a-3
The absorption pattern was unique to i:H:FW4.

Furthermore, when the crystallinity of the film was evaluated using RHEED (JEM-100SX, manufactured by JEOL Ltd.), it was found that it was amorphous with a halo. In addition, a metal hydrogen analyzer (E
The amount of hydrogen in the film was determined using MGA-1100 (manufactured by Horiba, Ltd.) and was found to be 22±2aLosic%.

11 Group 1 Following the deposited film formation process carried out in the manufacturing example,
After stopping the introduction of the raw material gas used and evacuating the internal pressure of the isolation container 400 to 5 X I Q-'' Torr or less,
From the gas introduction pipe 112, SiH, 1509CCII,
G e Ha 120sccs~ Si
An amorphous silicon germanium film was formed under the same deposited film formation conditions except that Fa 5 sccm and H kick 30 sc+m were introduced, the internal pressure of the film forming chamber 723 was maintained at 15 mTorr, the microwave applicator was set to &11, and the microwave power was set to OKW. Continuous deposition was performed.

After this manufacturing example and other manufacturing processes were completed, the strip member was cooled and taken out, and the film thickness distribution of the deposited film formed in this manufacturing example was measured in the width direction and longitudinal direction, and it was found that it was within 5%. , the average deposition rate was 48 persons/sec.

In addition, when a part of it was cut out and the infrared absorption spectrum was measured by the reflection method using FT-iR (Perkin Elmer 1720X), the results were 2000c11-', 18
Absorption was observed at 80ea-' and 630cm-'.
The absorption pattern was unique to 5iGe:f(:FM).

Furthermore, when the crystallinity of the film was evaluated by RHIEED (JEi: M-100SX, JEOL Ltd.), it was found that it was amorphous with a halo. Further, the amount of hydrogen in the film was quantified using a metal water analyzer (EMCA-ttoo, manufactured by Horiba, Ltd.) and found to be 16±2 atomic%.

Following the deposited film forming step carried out in Production Example 1,
After stopping the introduction of the raw material gas used and evacuating the internal pressure of the isolation container 400 to 5 X I Q-'Torr or less,
From gas introduction pipe 105, 5tH4280ICCII%
CHa 40sccmSSiFn 5sccm, H*
50 sccm was introduced, and the internal pressure of the film forming chamber 723 was set to 25 mT.
An amorphous silicon carbide film was continuously deposited under the same deposited film formation conditions except that the film was kept at orr.

After this manufacturing example and other manufacturing steps were completed, the strip member was cooled and taken out, and the film thickness distribution of the deposited film formed in this manufacturing example was measured in the width direction and longitudinal direction, and it was found that it was within 5%. , the average deposition rate was 54 persons/sec. In addition, when a part of it was cut out and the infrared absorption spectrum was measured by the reflection method using FT-IR (1720X manufactured by Perkin-Elmer), it was found to be 2080 cm-' , 12
50cm-', 960cm-', 77 Telm-'
Absorption was observed at 660e11-' and a-S i,
The absorption pattern was unique to C:II:FIIQ.

Furthermore, when the crystallinity of the film was evaluated using RHIEED (JEM-100SX, manufactured by 8 Electronics), it was found that there was a halo.
It was found to be amorphous. In addition, a water-in-metal analyzer (
The amount of hydrogen in the film was determined using EMC (A-1100, manufactured by Horiba, Ltd.) and was found to be 12±2 atomic%.

Production spots ↓ Following the deposited film formation process carried out in Production Example 1,
After stopping the introduction of the raw material gas used and evacuating the internal pressure of the isolation container 400 to 5 X 10-'Torr or less, Si, H4250scc, m-,
B F3 (3000ppm) [diluted] 50scca
, S i Fa 45 sec, Hz 50 sec, the internal pressure of the film forming chamber 723 was maintained at 20 mTorr, the microwave applicator was set to 3, and the microwave power was set to 3. P-type Wl and crystalline silicon films were successively deposited under the same deposition film formation conditions except that OK W was used.

After this manufacturing example and other manufacturing steps were completed, the strip member was cooled and taken out, and the film thickness distribution of the deposited film formed in this manufacturing example was measured in the width direction and longitudinal direction, and it was found that it was within 5%. , the average deposition rate was 42 persons/sec.

In addition, when a part of it was cut out and the infrared absorption spectrum was measured by the reflection method using FTIR (Perkin Elmer 1720X), the 2100 value °1 and 630C
Absorption was observed at 1l-', which was an absorption pattern specific to the μc-si:ti:F film. Furthermore, R1(EED (
JEM-100SX.

When the crystallinity of the film was evaluated by JEOL Ltd., it was found to be ring-shaped and non-oriented polycrystalline. Also,
The amount of hydrogen in the film was determined using a metal water analyzer (EMGA-1100, manufactured by Horiba, Ltd.) and was found to be 5 ± 1 atoms.
c%.

Ko 1 Mi 11 Following the deposited film forming step carried out in Production Example 1,
After stopping the introduction of the raw material gas used and evacuating the internal pressure of the isolation container 400 to 5×10-'Torr or less, SiH4360sSiH4360 was introduced from the gas introduction pipe 105.
sc%H2 dilution) 303CCII% 5iFn5SC
CN,, )l ≧20 sec was introduced into the film forming chamber 72.
Continuous deposition of an n-type amorphous silicon film was performed under the same deposited film forming conditions except that the internal pressure of No. 3 was maintained at 12 mTorr and the microwave power was set at 2 kW.

After this manufacturing example and other manufacturing steps were completed, the strip member was cooled and taken out, and the film thickness distribution of the deposited film formed in this manufacturing example was measured in the width direction and longitudinal direction, and it was found that it was within 5%. , the average deposition rate was 65 people/see.

In addition, when a part of it was cut out and the infrared absorption spectrum was measured by the reflection method using FT-IR (272QX manufactured by Perkin Elmer), the infrared absorption spectrum was found to be 2000 cm-' and 63 cm-'.
Absorption was observed at 0 cm-', which was an absorption pattern specific to the a-3t:H:F film.
When the crystallinity of the film was evaluated using M-1003X (JEOL Ltd.), it was found to be halo and amorphous. In addition, the amount of hydrogen in the film was determined using a metal hydrogen analyzer (EMGA-1100, manufactured by Horiba, Ltd.) and was found to be 20±2.
The product was 1Lo ic%.

■ In production example 1, instead of the 5t JS430BA strip substrate, PUT (polyethylene terephthalate)) was used! ! Band-shaped member 101 (width 5Qcm x length 100m x J ¥0.
Continuous deposition of amorphous silicon films was carried out in exactly the same manner except that the substrate surface temperature was 220°C.

The strip member was taken out after cooling, and the film thickness distribution was measured in the width direction and longitudinal direction, and the film thickness distribution was within 5%, and the average deposition rate was 105λ/see. In addition, when a part of it was cut out and the infrared absorption spectrum was measured by the reference transmission method using FT-IR (1720X manufactured by Perkin Elmer), absorption was observed at 2000 cm-' and 630 cm-', and a- 3i:H:F
The absorption pattern was unique to the film. Also, 2000co
The amount of hydrogen in the film was determined from the absorption attributed to 5i-1 (around +-') and was found to be 24±2 atomic%.

Furthermore, when the crystallinity of the film was evaluated using RIIEED (JEM-100SX, manufactured by JEOL Ltd.), it was found that there was a halo.
It was found to be amorphous.

In addition, other 20 parts were randomly cut out, and each part was made of AIl < L-shaped gear tooth electrode (width 250 μm).
AM-1
Photocurrent value under light (100 mw/a) irradiation, and II
The dark current value in Q was measured using 1lP4140B,
Bright conductivity σp (S/cm) and dark conductivity σd (S/c
＠), respectively (6,0±0.5)X
10"SS/(J and (2,0±0.5)×10"'1
It was within the range of S/cIl.

In this manufacturing example, a Schottky junction diode having the layer structure shown in the horizontal cross-sectional view of FIG. 10 was manufactured using the apparatus shown in FIG.

Here, 1001 is a substrate, 1002 is a lower electrode, 100
3 is an n-type semiconductor layer, 1004 is a non-doped semiconductor layer, 1005 is a metal stone, and 1006 and 1007 are current extraction terminals.

First, a 5US430BA strip member 101 similar to that used in Production Example 1 was set in a continuous sputtering device, and Cr(
99,98%) using the electrode as a target, 150
A Cr thin film was deposited to form a lower electrode 1002.

Subsequently, the strip member 101 is transferred to the seventh device shown in device example 12.
It is set in the delivery bobbin 703 in the vacuum container 701 of the series 1 sulfur deposited film forming apparatus shown in the figure, and is placed in the vacuum container 702 through the isolation container 400 with the surface on which the Cr thin film is deposited facing downward. The end portion was wound around a winding bobbin 704, and the tension was adjusted to prevent slack.

Note that the conditions such as the curved shape of the substrate in this manufacturing example are as follows.
The same procedure as shown in Table 3 was used, and the microwave applicator was the same type 11h13 as in Production Example 1.

Thereafter, rough evacuation and high vacuum evacuation operations similar to those in Production Example 1 were performed using an evacuation pump (not shown) via the evacuation pipes 709, 710, and 711 of each vacuum container.

At this time, the temperature control mechanism 106407 controlled the substrate surface temperature to 250°C.

When sufficient degassing has been performed, from the gas introduction pipe 112, 5iHa 350mmcm, 5iFn 5sc
cvAsP II 3/l (z (4%l■, diluted) 60scc+a, lit 303CCN1 was introduced, the opening degree of the throttle valve 709 was adjusted to maintain the internal pressure of the film forming chamber 723 at 12 mTorr, and the pressure was stabilized. By the way, 2.
Microwaves of 0 kW were emitted from the applicator 301. As soon as plasma was generated, transport started, and 55
A deposition operation was performed for 5 minutes while transporting from the left side to the right side in the figure at a transport speed of cm/win. This results in n
・Semiconductor [n 4 type a-3i as 1003: l
-1: A F film is formed on the lower electrode 1002.

During this time, H2 was passed through the gas gates 72, 722 as a gate gas for 50 seconds, and was exhausted from the exhaust hole 718 by an exhaust pump (not shown), so that the internal pressure of the gas gate was 2 mT+.
) rr.

After stopping the supply of microwaves and introducing the raw material gas, and stopping the conveyance of the strip member 101, the internal pressure of the isolation container 400 was evacuated to 5 X 10-6 Torr or less, and then
From the gas introduction pipe again, 5iHn350SCCIW% 5
Introducing tF410sccm, Hz 50sccm,
Adjust the opening degree of the throttle valve 709 to open the film forming chamber 72.
The internal pressure of 3 was maintained at $ m 'l'' orr, and when the pressure became stable, the microwave power source (not shown) was immediately turned on.
An 8 kW microwave was emitted from the applicator 301. Transport started at the same time as plasma was generated, and 6
The deposition operation was performed for 5.5 minutes while being transported in reverse from the right side to the left side in the figure at a transport speed of 0 m/+min. As a result, n゛ type a3! : An a-3i:H:F film serving as a non-doped semiconductor 711004 is stacked on the H:F film.

After all the deposition operations were completed, the supply of microwaves and raw material gas was stopped, the conveyance of the strip member 101 was stopped, the residual gas in the isolation container 400 was sufficiently exhausted, and the strip member was cooled and then taken out.

φ5 crane permalloy masks are randomly attached to 10 locations of the band-shaped member, and A u as metal layer 1005 is applied.
The i'ji film was deposited by 80 people using the electron beam evaporation method. Next, use a wire bonder to connect the current extraction terminal 1006.
．． 1007 was bonded and diode characteristics were evaluated using HP 414013.

As a result, the diode factor n = ,1±0.05,±
It showed good diode characteristics with a rectification ratio of about 6 orders of magnitude at IV.

In the cup production example, a pin-type photovoltaic device having the layer structure shown in the schematic cross-sectional view of FIG. 11(A) was manufactured using the apparatus shown in FIG.

The photovoltaic element has a lower electrode 1102 on a substrate 1101.
, n-type semiconductor layer l103, i-type semiconductor layer 1104, p-type semiconductor layer 1105, transparent electrode 1106, and current collection bridge 11
This is a photovoltaic element 1100 in which 07 is deposited in this order. Note that this photovoltaic element is based on the premise that light is incident from the transparent electrode 1106 side.

First, a PET strip member 101 similar to that used in Production Example 6 was set in a continuous sputtering apparatus, and Ag (99,99
A lower electrode 1102 was formed by sputter-depositing a 1000 Ag thin film using the ZnO (99,999%) electrode as a target, and then a 1 μm ZnO3 film using the Zn0 (99,999%) electrode as a target.

Subsequently, the strip member 1 on which the lower electrode 1002 is formed
Manufacturing Example 7 was added to the continuous deposited film forming apparatus shown in FIG.
I made cents in the same way as I did with . Table 19 shows the conditions such as the curved shape of the substrate in the isolation container 400 at this time.

In addition, in the isolation containers 400-a and 400-b, the n-type a-3i:I+:F
A p″ type pc-3i:H:F film was formed.

First, microwave plasma is generated in a vacuum container, and when the discharge etc. are stabilized, the strip member 101 is conveyed at a speed of 5.
4 (^1n) from the left side to the right side in the figure, and n-, i-, and p-type semiconductor layers were successively stacked.

After semiconductor layers were laminated over the entire length of the strip member 101, the strip member 101 was cooled and then taken out, and solar cell modules of 40 am+×80 cm were continuously manufactured using a continuous module forming apparatus.

Regarding the produced solar cell module, AMl,5 (
When characteristics were evaluated under light irradiation (100 mW/c+J), a photoelectric conversion efficiency of 8.5% or more was obtained, and the variation in characteristics between modules was within 5%.

Also, AM, 5 (100 mW/cd) light of 500
When the rate of change in photoelectric conversion efficiency with respect to the initial ruI value after continuous irradiation was measured, it was within 10%.

By connecting these modules, we were able to create a 3kW power supply system.

In this manufacturing example, an a-3iGe:H:F film is used instead of an a-Si:H:F film as an i-type semiconductor layer in the pin-type photovoltaic device manufactured in Manufacturing Example 8. Here is an example.

The formation of the a-3iGe:H:F film requires a transport speed of 40 (7
)/min, the same operations and methods as in Production Example 2 were carried out, and the other semiconductor layers and the module formation process were carried out in the same operations and methods as in Production Example 8, to produce a solar cell module. .

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

Also, 500 of AMl, 5 (100 mW/cj) light
When the rate of change in photoelectric conversion efficiency with respect to the initial value after continuous irradiation was measured, it was within 10%.

By connecting these modules, we were able to create a 3kW power supply system.

In this production example, in the pin-type photovoltaic device produced in production example 8, a-3i as an l-type semiconductor layer: 11
: An example using a-3iC:H:FJli instead of F film is shown.

Except for the formation of the a-S: C: H: F film, the transport speed was 42 cm/min! l! ! a The same operations and methods as in Example 3 were carried out, and the other semiconductor layers and the modularization process were carried out in the same operations and methods as in Production Example 8.
A solar cell module was created.

Regarding the produced solar cell module, A Ml, 5
(100mW/CIJ) Nite characteristic evaluation under light irradiation 1a
As a result, a photoelectric conversion efficiency of 6.5% or more was obtained, and the variation in characteristics between modules was within 5%.

Also, AM, 5 (100m"iV/aJ) 50 of light
When the rate of change in photoelectric conversion efficiency with respect to the initial M value after continuous irradiation for 0 hours was measured, it was within 10%.

By connecting these modules, we were able to create a 3kW power supply system.

In this manufacturing example, a photovoltaic device having the layer structure shown in FIG. 11 <C> was manufactured. In manufacturing, an isolation container 400-a is used in the apparatus shown in FIG.

400. Isolation container 400a' of similar configuration to 400-b
, 400', and 400-b' were further connected in this order via a gas gate (not shown).

Note that the lower element 1111 is Manufacturing Example 9, and the upper element 111
Sample No. 2 had the same layer structure as that produced on the manufacturing example day, and the conditions for producing the deposited film of each semiconductor layer are shown in Table 21. The modierization step was performed using the same operations and methods as in Production Example 8 to produce a solar cell module.

Regarding the produced solar cell module, AMl, 5
When the characteristics were evaluated under light irradiation (100 mW/cd), a photoelectric conversion efficiency of 10.2% or more was obtained, and the variation in characteristics between modules was within 5%.

Also, AMl, 5 (l OOmW/cd) 500 of light
When the rate of change in photoelectric conversion efficiency with respect to the initial value after continuous irradiation was measured, it was within 9%.

By connecting these modules, we were able to create a 3kW power supply system.

Part 1 In this production example, a photovoltaic element having the layer structure shown in FIG. 11(C) was produced. In manufacturing, an isolation container 400-a is used in the apparatus shown in FIG.

400.40 (400
-a', 400', and 400-b' were further connected in this order via a gas gate (not shown).

Note that the lower element 1111 is Manufacturing Example 8, and the upper element 111
Sample No. 2 had the same layer structure as that produced in Production Example 10, and the conditions for producing the deposited film of each semiconductor layer are shown in Table 22. The modularization process was performed using the same operations and methods as in Production Example 8 to produce a solar cell module.

Regarding the produced solar cell module, AMl, 5
When the characteristics were evaluated under light irradiation (100 mW/cffl), a photoelectric conversion efficiency of 10.3% or more was obtained, and the variation in characteristics between modules was within 5%.

Further, when the rate of change in photoelectric conversion efficiency with respect to the initial value after 500 hours of continuous irradiation with AM,5 (100 mW/cj) light was measured, it was within 9%.

By connecting these modules, we were able to create a 3kW power supply system.

Enuresis 1 In this production example, a photovoltaic element having the layer structure shown in FIG. 11(D) was produced. In manufacturing, an isolation container 400-a is used in the apparatus shown in FIG.

400. Isolation container 400-a of similar configuration to 400-b
', 400', 400-b', 400-a"40
0' and 400-b'' were further connected in this order via a gas gate (not shown).

Note that the lower element 1120 has a manufacturing example of 9°, and the intermediate element 11
21 is Manufacturing Example 8, the upper element 1123 has the same layer structure as that produced in Manufacturing Example 0, and the deposited film manufacturing conditions of each semiconductor layer are shown in Table 23. The modularization process was performed using the same operations and methods as on the manufacturing example day to produce a solar cell module.

Regarding the produced solar cell module, AM1, 5 (
When characteristics were evaluated under light irradiation (LOOmW/c4), a photoelectric conversion efficiency of 10.5% or more was obtained, and the variation in characteristics between modules was within 5%.

Also, the first photoelectric conversion efficiency after 500 hours of continuous irradiation with AM, 5 (100 mW/ci) light! When the rate of change with respect to the III value was measured, it was within 8.5%.

By connecting these modules, we were able to create a 3kW power supply system.

Table 3 Table 3 Table 7 Table 12 No discharge, 11m1 discharge flicker Table 3! ) Flickering of electrical discharge 5th Omote Pass Flickering of electrical discharge O) Abnormal electrical discharge 16th Table 1 vessel Flickering of electrical discharge, microwave leakage -) Significant microwave leakage 9th Table 7 Table B Table A Table *) Place the board cover for fine adjustment of film thickness inside the curved shape.
4.1 Summary of Effects of the Invention] According to the method of the present invention, the strip-like member constituting the side wall of the film-forming space is continuously moved, and the strip-like member constituting the side wall of the film-forming space is moved in the width direction. , by comprising a microwave applicator means that radiates or transmits microwave energy uniformly with directivity in one direction perpendicular to the direction of propagation of the microwave, and by confining the microwave plasma in the film forming space. , a large-area functional deposited film can be continuously formed with good uniformity.

By confining the microwave plasma within the film forming space, the method and apparatus of the present invention improve the stability and reproducibility of the microwave plasma, and dramatically increase the utilization efficiency of the raw material gas for forming the deposited film. I can do it. Furthermore, by continuously conveying the band-shaped member, the shape of the curve, the length, and the conveyance speed can be variously changed to uniformly deposit a deposited film of any thickness over a large area (continuously). Deposits can be formed.

According to the method and apparatus of the present invention, it is possible to form a functional deposited film continuously and with good uniformity on the surface of a relatively wide and long strip member.
It can be suitably used.

Further, since a deposited film can be continuously formed without stopping the discharge, good interface characteristics can be obtained when manufacturing a stacked device or the like.

In addition, it is possible to form a deposited N1 film under low pressure, suppressing the generation of polysilane powder, and suppressing polymerization of active species, reducing defects, improving film properties, and improving film properties. Stability can be improved.

Therefore, the operating rate and yield can be improved, and it becomes possible to mass-produce inexpensive and highly efficient solar cells.

Furthermore, the solar cell produced by the method and apparatus of the present invention has a high conversion efficiency of light 1 and has little characteristic deterioration over a long period of time.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of a microwave plasma CVD apparatus of the present invention. Figures 2 and 3 (a) to (di
1 is a schematic diagram of the microwave applicator means of the present invention; FIG. FIG. 4 shows the microwave plasma CVD of the present invention.
FIG. 2 is a schematic cross-sectional view of the device; Figure 5 fa+,
(b) is a diagram schematically showing a lateral cross-sectional view of the belt-shaped member in the transport la of the present invention. FIG. 6 is a diagram schematically showing the pressure gradient of the gas gate means in the present invention. 7 to 9 are overall schematic diagrams of an example of a continuous microwave plasma CVD apparatus of the present invention. FIG. 10 is a schematic cross-sectional view of a square key junction diode manufactured in the present invention. 1st
1 (A) to (C1) are schematic cross-sectional views of pin-type photovoltaic elements (single, tandem, triple) produced in the present invention. FIGS. 12(i) to (X) are
It is a figure for explaining the processing method of a strip|belt-shaped member. Regarding FIGS. 1 to 12, 101... Band-shaped member, 102.103... Support/conveyance roller 104.1
05...Support/conveyance ring, 106.107...
Temperature control mechanism, 108...Microwave applicator 109...Separation means, 110.416...Metal tube, 111...Wire mesh, 112...Gas introduction pipe, 113...
... Microwave plasma region, 114.115 ... Wire mesh for preventing microwave leakage, 20, 301 ... Microwave applicator 202.302 ... Circular waveguide, 2
03... End part, 204.205, 206.207,
208.304==・hole, 303...opening end, 305
...Connection part, 306...Shutter, 307...
Groove, 308... Fixing bottle, 309... Insulator, 4
00...Isolation container, 40, 402...Fixing flange, 403...Square, circular conversion waveguide, 404.411
...Connection flange, 405.412...Opening, 406.407,413.4L4・0 ring, 408
゜4!5...Cooling groove, 409...Open end, 11
0,417... Earthing finger 418... Connection plate, 419... Exhaust hole, 420... Connection flange,
421...square roaring wave tube, 50, 501', 502,5
02'...wire mesh, 70, 702, 901, 902-
...Vacuum container, 703...Bobbin for sending out, 704...Bobbin for winding, 705, 706=-R feeding 0-R-707, 708
,709... Throttle valve, 710.711,7
18,719.720...Exhaust hole, 712.713.
...Temperature adjustment mechanism, 714.715...Pressure gauge, 716.717,805,806.807,808...
・Gate gas introduction pipe, 72, 722, 80, 11102.803.804-・
・Gas gate, 723... Film formation chamber, 809.810, 811, 812... Gate gas exhaust pipe, 903.904... Cathode electrode, 90, 906... Gas introduction pipe, 907.908...・Halogen lamp, 909.910
... Anode electrode, 91, 912 ... Exhaust pipe, 100, 1101 ... Support body, 1002.1102 ... Lower electric bridge, 1003.1103. , 108.1114.1, 17.
... n-type semiconductor layer, 1004.1104, 1109, 1115.1118.
. . . i-type semiconductor layer, 1005 . . . metal layer, 1006.
1007... Current extraction terminal, 1100.110
0', 1111, 1112° 1120.1121,, 1
23-apin junction photovoltaic element, 1105.1110.1116.1119...p-type semiconductor layer, 1106...upper bridge, ! 107... Current collecting electrode, 1113... Tandem type photovoltaic element, 1124... Triple type photovoltaic element,
1201a...Band-shaped member processing chamber (A), 1201b...
...Band-shaped member processing room (B),! 202.1203,12
04,1205.1206...Strip member, 1207 for, 1207b...Roller 1208a. 1 208 b - Cutting blade, 1209a 1209b Welding jig, 1210 21 1212.1213 Connection means. Figure 2 χ2 Figure (a) Figure 3 (b) Figure (C) Figure (d) Prisoner (a) 501 (501') Figure 5 (b) 502 (502') 1'/ j (a) Elevation Figure 6 (b) River Figure 10 1006 Figure 11 CA) Figure i1 (D) Figure 11 (B) Figure 11 (C) 107 Second Cause (Part 1) Figure 12 (Part 2) Figure 12 (Part 3)

Claims (43)

[Claims] (1) While continuously moving the strip member in the longitudinal direction, a columnar film forming space is formed with the moving strip member as a side wall in the middle of the movement, and the film is deposited in the film forming space via a gas supply means. A microwave applicator means that introduces a raw material gas for film formation and simultaneously radiates or transmits microwave energy with directionality in one direction perpendicular to the direction of propagation of the microwave.
radiating or transmitting the microwave energy to generate microwave plasma in the film forming space, and depositing a film on the surface of the continuously moving band-shaped member forming the side wall exposed to the microwave plasma. 1. A method for continuously forming a large area functional deposited film by a microwave plasma CVD method, which is characterized by forming a functional deposited film over a large area. (2) In the middle of the moving band-like member, a curved start end forming means and a curved end forming means are used to create a space between the curved start end forming means and the curved end forming means, so that the longitudinal direction of the band-like member is 2. The method for continuously forming a large area functional deposited film according to claim 1, wherein the side wall of the film forming space is formed by curving the strip member leaving a gap in the direction. (3) According to claim 2, wherein microwave energy is radiated or transmitted into the film forming space through a gap left in the longitudinal direction of the strip member between the curved start end forming means and the curved end end forming means. A method of continuously forming the described large-area functional deposited film. (4) The microwave applicator means is inserted into the film-forming space from either end face of the columnar film-forming space formed using the band-shaped member as a side wall to apply microwave energy to the film-forming space. 3. The method of continuously forming a large area functional deposited film according to claim 2, wherein the functional deposited film is radiated or transmitted into the interior. (5) Radiating or transmitting microwave energy from the microwave applicator means into the film forming space via a microwave transparent member provided between the film forming space and the applicator means; 2. A method for continuously forming a large area functional deposited film according to claim 1. (6) The microwave applicator means is arranged close to the band-shaped member so as to be substantially parallel to the width direction of the band-shaped member without coming into contact with the microwave-transparent member, and the microwave applicator means is placed in the columnar film-forming space. 6. The method of continuously forming a large area functional deposited film according to claim 5, wherein microwave energy is radiated or transmitted. (7) The microwave applicator means radiates or transmits uniform microwave energy in a length substantially the same as the width direction of the band-shaped member. How to form. (8) The large-area functional deposited film according to claim 7 is continuously formed by separating the microwave applicator means from the microwave plasma generated in the film forming space through the microwave transparent member. How to form. (9) Continuously forming a large-area functional deposited film according to claim 1, in which microwave energy radiated or transmitted into the columnar film-forming space is prevented from leaking out of the film-forming space. how to. (10) An apparatus for continuously forming a large-area functional deposited film by microwave plasma CVD on a continuously moving strip-shaped member, the device comprising: continuously moving the strip-shaped member in its longitudinal direction; , having a columnar film forming chamber formed with the strip member as a side wall through a curved part forming means for curving the film midway therein, and capable of maintaining the inside thereof in a substantially vacuum state; microwave applicator means configured to radiate microwave energy with directionality in one direction perpendicular to the direction of propagation of the microwaves for generating microwave plasma; and from the microwave applicator means; Microwave energy that is directionally radiated in one direction perpendicular to the direction of propagation of the microwave is transmitted into the film forming chamber, and the microwave plasma generated in the film forming chamber by the microwave energy is removed. separation means for separating the microwave applicator and the means; exhaust means for evacuating the inside of the film forming chamber; means for introducing raw material gas for forming a deposited film into the film forming chamber; and heating the strip member. and/or temperature control means for cooling, and a deposited film is continuously formed on the surface of the strip member on the side exposed to the microwave plasma. Continuous formation device for functional deposited films. (11) The curved portion forming means is constituted by at least one set of curved start end forming means and curved end forming means, and the curved start end forming means and the curved end forming means are arranged in the strip shape. 11. The continuous formation device for a functional deposited film according to claim 10, wherein the device is disposed with a gap left in the longitudinal direction of the member. (12) The curved portion forming means is composed of at least a pair of supporting/conveying rollers and a supporting/conveying ring,
12. The apparatus for continuously forming a functional deposited film according to claim 11, wherein the pair of supporting/conveying rollers are arranged in parallel with a gap left in the longitudinal direction of the strip member. (13) The separating means is disposed approximately parallel to and close to the gap left between the curved start end forming means and the curved end forming means, and outside the film forming chamber. 12. The apparatus for continuously forming a functional deposited film according to item 11. (14) The separating means is protruded into the film forming chamber from either end surface of a columnar film forming chamber having the band member as a side wall, substantially parallel to the width direction of the band member. 12. The apparatus for continuously forming a functional deposited film according to item 11. (15) The apparatus for continuously forming a functional deposited film according to claim 10, wherein the separating means has a substantially cylindrical shape. (16) Claim 10, wherein the separating means has a substantially semi-cylindrical shape.
An apparatus for continuously forming a functional deposited film as described in . (17) The apparatus for continuously forming a functional deposited film according to claim 10, wherein the microwave applicator means is arranged so as to be separated from the peripheral wall of the separation means and included within the separation means. (18) The apparatus for continuously forming a functional deposited film according to claim 10, wherein the separating means is provided with a cooling means. (19) The apparatus for continuously forming a functional deposited film according to claim 18, wherein the cooling means is an air flow flowing along the inner peripheral surface of the separating means. (20) The cooling means is configured concentrically with the separation means so as to have a conduit structure that is disposed inside the separation means and allows a cooling medium to flow between the separation means and the separation means. An apparatus for continuously forming a functional deposited film as described in . (21) The microwave applicator means is a waveguide for microwave transmission, and the waveguide is configured to apply microwave energy substantially uniformly in the longitudinal direction of the waveguide in one direction perpendicular to the direction of propagation of the microwave. 11. The apparatus for continuously forming a functional deposited film according to claim 10, wherein substantially rectangular holes are formed for directional radiation. (22) Continuous formation of a functional deposited film according to claim 21, wherein at least one rectangular hole is opened on one side of the waveguide, and microwaves are radiated from the hole. Device. (23) The apparatus for continuously forming a functional deposited film according to claim 22, wherein when a plurality of the rectangular holes are formed, these holes are arranged at intervals in the longitudinal direction of the waveguide. (24) The apparatus for continuously forming a functional deposited film according to claim 22, wherein the rectangular hole is a single substantially rectangular hole with a large aspect ratio. (25) The functional deposited film according to claim 24, wherein the dimensions of the rectangular hole are larger than one wavelength of microwaves and are substantially equal to substantially the entire width and length of the waveguide in the longitudinal direction. Continuous forming equipment. (26) According to claim 22, the rectangular hole is configured to uniformly radiate microwave energy with a length of at least one wavelength in the longitudinal direction of the waveguide. An apparatus for continuously forming the functional deposited film described above. (27) A series of functional deposited films according to claim 24, wherein the square hole is provided with a shutter means so that microwave energy of substantially uniform density is reliably radiated from the square hole over the entire length. Forming device. (28) The apparatus for continuously forming a functional deposited film according to claim 10, wherein the microwave plasma is confined in a columnar film forming chamber formed by curving the band member. (29) An apparatus for continuously forming a large-area functional deposited film on a continuously moving strip-shaped member by microwave plasma CVD, the apparatus comprising: continuously moving the strip-shaped member in its longitudinal direction; , having a columnar film forming chamber formed with the strip member as a side wall through a curved part forming means for curving the film midway therein, and capable of maintaining the inside thereof in a substantially vacuum state; microwave applicator means configured to transmit evanescent microwave energy with directionality in one direction perpendicular to the direction of propagation of the microwaves, for generating microwave plasma; and from the microwave applicator means. , transmitting evanescent microwave energy directed in one direction perpendicular to the direction of propagation of the microwaves into the film forming chamber, and causing microwaves generated in the film forming chamber by the evanescent microwave energy. separation means for separating the microwave applicator means from plasma; exhaust means for exhausting the inside of the film forming chamber; means for introducing source gas for forming a deposited film into the film forming chamber; and the strip member. temperature control means for heating and/or cooling, and a deposited film is continuously formed on the surface of the strip member on the side exposed to the microwave plasma. A device for continuously forming functional deposited films. (30) The curved portion forming means is constituted by at least one set of curved start end forming means and curved end forming means, and the curved start end forming means and the curved end forming means are arranged in the strip shape. 30. The apparatus for continuously forming a functional deposited film according to claim 29, wherein the apparatus is disposed with a gap left in the longitudinal direction of the member. (31) The curved portion forming means is composed of at least a pair of supporting/conveying rollers and a supporting/conveying ring,
31. The apparatus for continuously forming a functional deposited film according to claim 30, wherein the pair of supporting/conveying rollers are arranged in parallel with a gap left in the longitudinal direction of the strip member. (32) The separating means is disposed approximately parallel to and close to the gap left between the curved start end forming means and the curved end forming means, and outside the film forming chamber. 31. The apparatus for continuously forming a functional deposited film according to item 30. (33) The separating means is protruded into the film forming chamber from either end surface of a columnar film forming chamber having the band member as a side wall, substantially parallel to the width direction of the band member. 31. The apparatus for continuously forming a functional deposited film according to item 30. (34) The apparatus for continuously forming a functional deposited film according to claim 29, wherein the separating means has a substantially cylindrical shape. (35) Claim 29 wherein said separating means is substantially semi-cylindrical.
An apparatus for continuously forming a functional deposited film as described in . (36) The apparatus for continuously forming a functional deposited film according to claim 29, wherein the microwave applicator means is arranged so as to be separated from the peripheral wall of the separation means and included within the separation means. (37) The apparatus for continuously forming a functional deposited film according to claim 29, wherein the separating means is provided with a cooling means. (38) The apparatus for continuously forming a functional deposited film according to claim 37, wherein the cooling means is an air flow flowing along the inner peripheral surface of the separating means. (39) The cooling means is configured concentrically with the separation means so as to have a conduit structure that is disposed inside the separation means and allows a cooling medium to flow between the separation means and the separation means. An apparatus for continuously forming a functional deposited film as described in . (40) The microwave applicator means is an elongated slow-wave circuit waveguide, and the slow-wave circuit waveguide transmits evanescent microwave energy substantially uniformly in its longitudinal direction into the deposition space. The apparatus for continuously forming a functional deposited film according to claim 29, having a ladder-like structure. (41) The apparatus for continuously forming a functional deposited film according to claim 40, wherein the length of the ladder-like structure is approximately equal to the widthwise length of the band-like member. (42) The series of functional deposited films according to claim 40, wherein the ladder-like structure has a structure that uniformly transmits evanescent microwave energy over a length at least equal to or longer than the wavelength of the transmitted microwave in its longitudinal direction. Forming device. (43) The apparatus for continuously forming a functional deposited film according to claim 29, wherein the microwave plasma is confined in a columnar film forming chamber formed by curving the band member.