JPH06216039A - Microwave plasma cvd device - Google Patents

Abstract

PURPOSE:To prevent a film from being formed on a microwave inlet window and to keep gas plasma stable for a long time by a method wherein a multi- pillared structure, which is formed of microwave transmitting member and whose symmetrical axis is vertical to the surface of a microwave inlet window exposed to plasma, is provided to the surface of a microwave inlet window exposed to plasma. CONSTITUTION:A microwave inlet window 102 formed of microwave transmitting member is provided to the end of a circular waveguide 101. Gas diffusion restraining pipes 103 of a large number of hollow ceramic pipes are provided throughout the side of the microwave inlet window 102 exposed to plasma. A large number of ceramic pipes which are bundled and brought into close contact with the microwave inlet window 102 can be used as the gas diffusion restraining pipes 103, the ceramic pipes are vertically provided throughout the side of the microwave inlet window 102, and it is preferable that the ceramic pipes are arranged most in density. By this setup, material gas is restrained from diffusing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma CVD method using microwaves, and more particularly, to a roll roll for stably maintaining plasma for a long time by suppressing formation of a deposited film on a microwave introduction window. The present invention relates to a two roll type microwave plasma CVD apparatus.

[0002]

2. Description of the Related Art In a plasma CVD apparatus, it has been required to stably control plasma and form a film at a high speed because of recent demands for high performance and low cost of devices.

By the way, a technique which has recently received attention in response to the demand for high-speed film formation is plasma processing using microwaves. Since the microwave has a high frequency, the electron density can be increased as compared with the case of using the conventional RF, and it is suitable for efficiently generating and sustaining plasma.

In the microwave plasma CVD method, a low pressure (10 ⁻⁴ Torr) is used as compared with the conventional RF method.
It is possible to generate plasma at a temperature of up to a table, prevent the polymerization of active species that causes deterioration of film characteristics, and not only obtain a high quality deposited film, but also generate powder such as polysilane in plasma. It is possible to suppress the above, and to perform high-speed film formation.

A conventional microwave plasma processing apparatus is disclosed in Japanese Patent Publication No. 54-03343 and Japanese Patent Publication No. 54-033.
As described in Japanese Patent Laid-Open No. 44-44, it is generally constituted by a magnetron, a waveguide, a source gas introduction tube, a discharge tube or a film forming chamber, a vacuum pump and the like. In order to operate the plasma processing apparatus having such a configuration, a predetermined amount of raw material gas supplied from the gas introduction tube is introduced into the discharge tube, and a vacuum pump is used to pull the gas while keeping the discharge tube internal pressure constant. ,
Microwave power can be supplied to the source gas from outside the discharge tube via the waveguide and the discharge tube to generate plasma. Here, there are cases where plasma contacts the wall of the discharge tube where the microwave power is maximum, and the discharge tube is damaged.

As another example of the conventional microwave plasma processing apparatus, the so-called EC described in Japanese Patent Publication No. 63-67332 and Japanese Patent Publication No. 62-43335.
R device can be mentioned. In this ECR device, electromagnets are concentrically arranged around a cylindrical cavity resonator having a microwave introduction window, and high-speed plasma processing is performed by using electron cyclotron resonance (= ECR) at a pressure of a few millitorr. To do. When this device was operated to form a semiconductor film, it was observed that the microwave power was absorbed by the semiconductor film adhering to the microwave introduction window and the discharge was cut off or became unstable. It is considered that the above-mentioned problems can be solved by preventing the film formation on the microwave introduction window (hereinafter referred to as "anti-adhesion"). An apparatus provided with an adhesion-preventing component therefor is disclosed in JP-A-3-110798 and JP-A-3-12.
No. 2273 is proposed. In each case, those proposals are based on [Technical idea 1] described below.

[Technical idea 1] "A microwave or electric field is vertically divided by a metal or a microwave reflecting member to make it difficult to generate plasma in the divided portion. The distance from the wave introduction window is increased to obtain a protective effect. 49 and FIG. 50 are views showing the deposition-inhibitory structure proposed in the above-mentioned Japanese Patent Laid-Open No. 3-110798, and are views of the same structure seen from different directions. In these figures, the deposition-inhibitory structure is composed of a large number of spindle-shaped division plates 4902 for vertically dividing a microwave electric field 5001 injected in a circular H ₁₁ mode through a circular waveguide 4901 on the plasma side of a microwave introduction window. It is composed of.

On the other hand, FIG. 51 and FIG.
It is a figure which shows the adhesion prevention structure proposed by the -122273 publication, and is a front view and a top view of the same structure. In these figures, the deposition-inhibitory structure is composed of a large number of concentric circular division plates 5101 for vertically dividing the microwave electric field input in the circular E ₀₁ mode. In particular, the dividing plate 518
The structure of 1 is as follows: (1) The dividing plate is attached in a direction perpendicular to the microwave electric field. (2) The dividing plate has a portion perpendicular to the microwave electric field and a portion inclined at a predetermined angle at the same time. (3) The partition plate serves as a slot antenna and a cavity resonator end face plate, and has the functions of both the antenna and the cavity resonator. And are proposed respectively, and have the same protective effect.

Another method for preventing deposition is disclosed in Japanese Patent Laid-Open No. 62-62.
There is also a method of ejecting a non-depositing gas onto the surface of the microwave introduction window as disclosed in Japanese Patent No. 80275.

By the way, in the plasma CVD apparatus,
In order to promote mass production, in addition to the high-speed film formation described above, technological development for large-area film formation is also required.

For example, US Pat. No. 4,400,409 discloses a roll-to-roll method.
A continuous RF plasma CVD apparatus adopting the Roll method is disclosed. According to this device, a flexible substrate having a desired width and having a sufficiently long length has a plurality of RF glow discharge regions arranged along a path that sequentially penetrates the RF glow discharge regions, and is required in each RF glow discharge region. It is said that an element having a semiconductor junction can be continuously formed by continuously transporting the substrate in the longitudinal direction while depositing and forming a conductive type semiconductor layer. In this specification, a gas gate is used to prevent the dopant gas used when forming each semiconductor layer from diffusing and mixing into other RF glow discharge regions. Specifically, the RF glow discharge regions are separated from each other by a slit-shaped separation passage, and a flow of a separation gas such as Ar or H ₂ is formed in the separation passage. From this, it can be said that the roll-to-roll method is suitable for mass production of semiconductor devices.

Further, as an apparatus for large area film formation by microwave plasma CVD, it is necessary to form a uniform plasma corresponding to a large area member. The method of introduction is important.

FIG. 53 shows a conventional microwave introduction method compatible with large-area film formation. In this conventional example, a microwave 530 is used in the film formation chamber 5302 by using a horn-shaped waveguide 5301.
This is a method of introducing 3.

US Pat. No. 4,729,341 discloses a microwave plasma CVD method and apparatus for depositing and forming a photoconductive semiconductor thin film on a cylindrical substrate using a pair of microwave power input means. However, the substrate is limited to a cylindrical shape, that is, a drum as an electrophotographic photoreceptor, and is not applied to a large-area and long substrate.

By the way, since plasma using microwaves has a short wavelength of microwaves, non-uniformity of power distribution is likely to occur, and various problems remain to be solved for increasing the area.

For example, a leaky wave circuit is used as an effective means for increasing the area. In the leaky wave circuit, however, the microwave power to be injected into the plasma rapidly increases as the length of the microwave in the transmission direction increases. It has a unique problem of deterioration. Therefore, as a means for solving this problem, a method of making the power distribution near the surface of the substrate uniform by changing the distance between the substrate and the leaky wave circuit has been attempted. For example, U.S. Pat. Nos. 3,814,983 and 4,521,717 disclose such a method. And in the former, it is described that it is necessary to incline the leaky wave circuit at an angle with respect to the substrate. In the latter case, it is desirable that the two inclined leaky-wave circuits are arranged in parallel with respect to the moving substrate with the opposite inclinations so as to cancel the respective power distributions and make them uniform. In order to avoid microwave interference between the leaky wave circuits, it is disclosed that the leaky wave circuits are arranged so as to be displaced in the moving direction of the substrate by half the length of the waveguide crossbar.

Further, some proposals have been made for maintaining the uniformity of plasma (ie, the uniformity of microwave power distribution). These suggestions can be found, for example, in journals
Of Vacuum Science Technology (Jo
urinal of Vacuum Science T
technology) B-4 (January-February 1986)
295-298 and B-4 of the same magazine (1986, 1
Mon-Feb) See pages 126-130. According to these reports, a microwave reactor called a microwave plasma disk source (MPDS) has been proposed. That is, the plasma has a disk shape or a tablet shape, and its diameter is a function of the microwave frequency. And those reports disclose that the diameter of MPDS can be changed with frequency. For example, the MPDS operating at 2.45 GHz has a diameter of about 10 cm and a plasma volume of about 0.2 liters, which cannot be said to be a large area. Also reported is MPD operating at 915MHz
S is supposed to provide a plasma diameter of about 40 cm and a plasma volume of 2 liters. The report further
It is said that the MPDS can be expanded to a diameter exceeding 1 m by operating at a lower frequency, for example, 400 MHz.

[0018]

First, in the conventional roll-to-roll apparatus using the RF method, since the RF is used, the film forming rate is several Å / sec, which is not suitable for high-speed film forming. Therefore, in order to mass-produce, there is no choice but to lengthen the device, and the time required for each process such as heating, cooling, and vacuum exhaust increases, the ratio of film forming process time decreases, and the manufacturing cost increases. There is.

Next, the conventional microwave plasma CVD apparatus has the following problems. For example, FIGS. 49 to 5
The amorphous silicon film (hereinafter,
When a functional deposited film such as a-Si: H film) is formed, a part of the deposition-inhibitory component is sputtered by discharge and mixed into the functional-deposited film on the substrate because the shape of the deposition-inhibitory component is complicated. There is a problem that electrical characteristics are deteriorated.

Further, in the case where the non-depositing gas is sprayed on the surface of the microwave introduction window, a large amount of gas is sprayed, so that it is necessary to upsize the vacuum pump, which causes a problem of increase in manufacturing cost.

Further, the apparatus of FIG. 53 has a problem that the transmission mode is not fixed and the discharge becomes unstable.

Further, in the case of increasing the area,
There is a problem that it is difficult to make the power density uniform and it is difficult to create a photovoltaic element with high photoelectric conversion efficiency. Due to the non-uniformity of the power density, unevenness in the layer thickness and characteristics of the formed deposited film is likely to occur, and as a result, the yield of the photovoltaic element, the thin film transistor, the electrophotographic light-receiving member, etc. is reduced. There's a problem.

Furthermore, in an apparatus in which a leaky wave circuit is installed at an inclination, there is a problem that adjustment is delicate and it is difficult to manufacture semiconductor devices with good reproducibility and high yield. A device using MPDS has a problem that the device becomes extremely expensive and special.

The present invention has been made in view of the problems of the above-described conventional techniques, and prevents film formation on a microwave introduction window in a film forming apparatus using microwaves, It is an object of the present invention to provide a film forming apparatus capable of stably maintaining plasma for a long time and capable of mass production.

Another object of the present invention is to overcome the above-mentioned problems and to easily obtain discharge generation and stable discharge, and
To produce a microwave plasma CVD apparatus capable of obtaining a high-quality and uniform deposited film over a large area, and to reduce the required apparatus cost.

Another object of the present invention is to solve the above-mentioned problems in the microwave plasma CVD apparatus, to stabilize the discharge, and to make the exhaust apparatus larger than necessary.
Microwave plasma C capable of continuously forming a p-type or n-type semiconductor thin film doped with impurities for a long time
It is to provide a VD device.

Another object of the present invention is to overcome the problems in the conventional apparatus and to provide a functional deposition in which the chemical composition continuously changes in the thickness direction of a film formed on a continuously moving strip substrate. An object is to provide a device for forming a film.

Another object of the present invention is to provide an apparatus for forming a photovoltaic element having a high photoelectric conversion efficiency with a high stability in a continuous manner on a relatively wide and long substrate. is there. Another object of the present invention is to provide an apparatus capable of uniformly forming a deposited film having excellent electrical characteristics, especially interface characteristics, under a high deposition rate. In addition, the layer thickness of the deposited film and the unevenness of characteristics are reduced, and as a result, the device characteristics and yield of photovoltaic elements, thin film transistors, sensors, electrophotographic light-receiving members, etc. are improved, and these electronic devices are manufactured. An object is to provide a device that reduces costs.

[0029]

A microwave plasma CVD apparatus with a deposition-prevention structure of the present invention is a microwave plasma CVD apparatus provided with a microwave power input means, a source gas supply means, an exhaust means, and a film forming chamber. On the surface of the microwave introduction window exposed to the plasma, a multi-columnar structure composed of a microwave transparent member is arranged, and the axis of symmetry of each columnar structure is perpendicular to the surface exposed to the plasma. Is characterized in that.

In this case, each columnar structure may be a plurality of ceramic thin tubes which are in parallel with and in close contact with each other.

The microwave plasma CVD apparatus of the present invention is provided with a microwave power CVD means, a source gas supply means, an exhaust means, and a film forming chamber.
In the device, a multi-layered structure composed of a microwave transparent member is disposed on the surface of the microwave introduction window exposed to the plasma, and each layer is parallel to the surface exposed to the plasma. And

In this case, each layer has a large number of through holes,
The layers may be arranged parallel to each other and at intervals.

The microwave plasma CVD apparatus of the present invention is a microwave plasma CVD apparatus for forming a p-type or n-type semiconductor thin film doped with an impurity element by applying microwave power to the film formation chamber through a microwave introduction window. ,
It is characterized in that a source gas containing a main component element of the semiconductor thin film and containing no impurity element is blown to the microwave power introduction window.

Further, in the microwave plasma CVD apparatus provided with a plurality of microwave power input means arranged in parallel, the electric field directions of the microwaves of the adjacent microwave power input means are made orthogonal to each other before the discharge and made parallel after the discharge. It is characterized by

In this case, the microwave radiation direction of the microwave power input means may be one direction parallel to the strip-shaped substrate.

The microwave plasma CVD apparatus according to the present invention is a roll-to-roll type microwave plasma CVD apparatus having a belt-shaped substrate, wherein the moving belt-shaped substrate is used as one wall surface of a quadratic prism-shaped film forming chamber. The microwave power input means is arranged in the film chamber in parallel with the moving direction of the strip substrate.

In this case, the gas supply means may be arranged parallel to the width direction of the strip-shaped substrate so that the source gas is discharged in one direction toward the adjacent strip-shaped substrate.

The microwave plasma CVD apparatus of the present invention is a microwave plasma CVD apparatus for continuously forming a deposited film on a belt-shaped substrate, and a vacuum chamber and a discharge chamber provided in the vacuum chamber and penetrated by the belt-shaped substrate. In the discharge chamber, the wall surface of the discharge chamber is disposed so as to face the belt-shaped substrate in at least one of the carrying-in portion and the unloading portion of the belt-shaped substrate, and the length of the wall surface of the microwave chamber extends in the moving direction of the belt-shaped substrate. The wavelength is ½ or more of the wavelength, and the distance from the strip substrate is ½ or less of the wavelength of the microwave.

[0039]

Operation: Microwave plasma CVD with deposition-proof structure of the present invention
The apparatus includes microwave power input means, raw material gas supply means,
Microwave plasma C provided with exhaust means and film forming chamber
In a VD device, a multi-columnar structure composed of a microwave transparent member is disposed on a surface of a microwave introduction window exposed to plasma, and a symmetry axis of each columnar structure is a surface exposed to plasma. It is characterized by being perpendicular to. In addition, each columnar structure is a plurality of ceramic thin tubes that are parallel to and closely attached to each other.

The technical idea of the present invention is that "the multi-columnar structure functions as a gas selection element. As a result, a large amount of gas with high discharge start power is generated in the vicinity of the microwave introduction window, making it difficult to generate plasma in this portion, thereby increasing the distance between the plasma in the film formation and the microwave introduction window. And get a protective effect. [Technical Thought 2] This [Technical Thought 2] is clearly different from [Technical Thought 1] of the conventional example.

In embodying this [Technical idea 2], the following two properties are utilized. Under the same pressure, the mean free path varies depending on the gas species. (Nikkan Kogyo Publishing "Basics of Plasma and Film Formation" p18
(Refer to (2.18)) Hydrogen gas has larger discharge start power than hydrogen compound gas such as silane.

For simplification, for example, a case where the microwave plasma CVD method is performed under the conditions shown in the table below will be described.

[0043]

[Table 1] Under the conditions in Table 1 above, SiH ₄ gas is almost 1
The inventors of the present invention have found that it is decomposed by 00% into H ₂ gas and Si. Therefore, SiH ₄ is present in the vapor phase.
H ₂ gas which is a decomposition product of gas and newly introduced S
It is considered that iH ₄ gas is mixed. H ₂ gas is S
It has the property that the mean free path is several times longer at the same pressure than the iH ₄ gas. Therefore, if disposed of gas selected element on the microwave introducing window, since the easily diffused toward the H ₂ gas from the SiH ₄ gas, in the vicinity of the microwave introducing window H ₂
The gas is present in a higher concentration than the SiH ₄ gas. As a result, discharge becomes difficult inside the gas selection element, and discharge becomes possible in the film forming chamber. Therefore, the microwave introduction window is separated from the plasma by a distance corresponding to the length of the gas selection element, and is also separated from the silane-based radicals at the same time, so that the deposition effect is exhibited.

[0044]

【Example】

[Embodiment 1-1] Next, an embodiment of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic cross-sectional view of the vicinity of a microwave introduction window, which is the main part of one embodiment according to the first structure of the present invention,
FIG. 2 is a schematic side view (partially omitted).

In FIG. 1, 100 is a film forming chamber, 101 is a circular waveguide, 102 is a microwave introduction window, 103 is a gas diffusion suppressing tube, 104 is a gas pipe / bias electrode, and 1 is a gas pipe.
Reference numeral 05 is a gas nozzle, 106 is a gas ejection direction, 107 is a belt-shaped substrate, and 108 is a gas exhaust direction.

In FIG. 1, a circular waveguide 101 is provided at its end with a microwave introduction window 102 made of a microwave transparent member. As the microwave permeable member, a member having a high thermal conductivity such as alumina ceramics (Al ₂ O ₂ ), beryllia (BeO), or boron nitride (BN) is desirable, and in this embodiment, the maximum outer diameter φ110.
mm alumina / ceramics is used. A gas diffusion suppressing tube 1 composed of a large number of hollow ceramic tubes over the entire surface of the microwave introduction window 102 in contact with the plasma.
03 is provided. As with the microwave introduction window 102, it is desirable that the ceramic material forming the gas diffusion suppressing tube 103 has good thermal conductivity and a large thermal shock fracture coefficient. In this embodiment, alumina ceramics is used. . The gas diffusion suppressing tube 103 is the microwave introduction window 1
No. 02 may be integrally sintered and molded, or a large number of ceramic tubes may be bundled in close contact with the microwave introduction window 102. In any case, as shown in FIG. 2, the arrangement is such that the ceramic tube forming the gas diffusion suppressing tube 103 is vertically arranged over the entire surface of the microwave introduction window.
It is desirable for adjacent ceramic tubes to be closely packed.

A gas pipe 10 also serving as a bias electrode is provided near the ceramic pipe forming the gas diffusion suppressing pipe 103.
4 are provided. The gas pipe 104 is attached so that its central axis and the central axis of the microwave introduction window 102 are substantially aligned with each other, and the gas nozzle 10 is so designed that the raw material gas is ejected to the gas pipe 104 in a direction perpendicular to the central axis.
Many 5 are provided. Therefore, the ejection direction 106 of the source gas and the surface of the microwave introduction window 102 are substantially parallel to each other. In particular, in this embodiment, the nozzles are provided in rows in three directions so as to equally divide the gas pipe 104 by 120 degrees, and eight nozzles are provided at equal intervals in the longitudinal direction of the gas pipe 104 per row. There is. Here, the gas pipe 104 has a double-tube structure, and one thin tube is built in the gas pipe 104. The gas pipe used in this example has an outer diameter of φ1 / 2 inch and a length of 327 mm.

Next, the belt-like substrate 107 is curved around the central axis of the microwave introduction window 102 in an Ω shape and conveyed.
A space surrounded by the strip substrate 107 is a film forming chamber 100.

The source gas introduced into the film forming chamber 100 through the gas nozzle 105 is exhausted in the exhaust direction 108 by a vacuum pump (not shown). The exhaust direction 108 is substantially parallel to the surface of the microwave introduction window 102.

The present inventors have found that, in addition to the anti-adhesion effect of the gas selective element, the flow direction of the raw material gas also has a great influence on the anti-adhesion effect. That is, when the raw material gas is jetted in the direction parallel to the surface of the microwave introduction window, the deposition effect is more remarkable than when it is jetted in the vertical direction. There are various confirmation methods, but the simplest method can also be determined by visually comparing the film thickness deposited on the microwave introduction window. The results are shown in Table 2.

[0052]

[Table 2] FIG. 3 is a schematic perspective view of a microwave plasma CVD apparatus with an attachment-preventing structure according to the first configuration of the present invention.

In FIG. 3, the microwave introduction window 102b and the circular waveguide 101 are shown so that the inside of the device can be easily understood.
"b" is drawn with a shift from the actual position.

In FIG. 3, reference numeral 300 is a microwave plasma CVD apparatus with a deposition-preventing structure, 301 is a belt-shaped substrate, and 302 is a substrate.
a and 302b are supporting and conveying rollers, 303 is a film forming chamber, 3
Reference numerals 04a and 304b denote supporting and conveying discs, 305 denotes a bias electrode also serving as a gas pipe, 306 denotes a gap, 307 and 308 denote rectangular waveguides, 101a and 101b denote circular waveguides, and 102.
a and 102b are microwave introduction windows, and 103a and 103b.
Is a ceramic tube.

In the microwave plasma CVD apparatus 300 with the deposition-proof structure shown in FIG. 3, means for continuously transporting the strip substrate 301 in the longitudinal direction and a film forming chamber 303 for forming a deposited film on the strip substrate 301 are provided. And a means for supplying a source gas into the film forming chamber 303, an evacuation means, and a means for applying microwave power for dissociating the source gas supplied into the film forming chamber 303.

Hereinafter, a microwave plasma CV with a deposition-prevention structure
Each component of the D device 300 will be described in detail. (1) Conveying Means The conveying means is a delivery bobbin (not shown) and a film forming chamber 303.
A first supporting / conveying roller 302a for folding back the belt-shaped substrate 301 provided therein, and first and second supporting / conveying discs 304 around which two side ends of the belt-shaped substrate 301 are respectively wound.
a, 304b and the second supporting and conveying roller 302b that repeats the belt-shaped substrate 301 again, and a winding bobbin (not shown)
Consists of. Here, the first and second supporting and conveying rollers 3
02a and 302b are provided in parallel and close to each other so as to contact the lower sides of the first and second supporting and conveying discs 304a and 304b in the drawing. The lengths of the first and second supporting and conveying rollers are slightly longer than the width of the belt-shaped substrate 301. In addition, the first and second supporting and conveying discs 304a, 3a
04b are arranged to face each other with an interval slightly narrower than the width of the strip substrate 301. The common center line of the first and second support / conveyance disks is arranged so as to be substantially parallel to the center lines of the first and second support / conveyance rollers 302a, 302b. (2) Film Forming Chamber In the film forming chamber 303, the belt-shaped substrate 301 is folded back by the first supporting and conveying rollers 302a, and both side ends thereof are wound around the first and second supporting and conveying discs 304a and 304b, respectively. , The columnar space formed by being folded back again by the second supporting and conveying roller 302b. (3) Raw Material Gas Supply Means The raw material gas supply means is a gas cylinder (not shown) for the raw material gas and a gas introduction for supplying the raw material gas from the gas cylinder into the film forming chamber 303 via a gas supply valve (not shown). And a tube 305. Here, the gas introduction pipe 305 is the first
From the gap between the second supporting and conveying roller 302a and the second supporting and conveying roller 302a.
It is inserted into the film forming chamber 303 in parallel with 2a and 302b. In the bias electrode 305 also serving as a gas pipe, a large number of nozzles serving as gas ejection ports are formed as shown in FIG. (4) Exhaust Means The exhaust means is composed of a vacuum exhaust system including an auxiliary pump (not shown) and a main pump (not shown) and an exhaust pipe (not shown). The first and second supporting and conveying rollers 302a, 302
02b through a gap 306 provided below the figure.
The film forming gas, air, reaction product gas, etc. are exhausted in the direction of arrow 306. The auxiliary pump is a rotary pump and a mechanical booster pump, and the main pump is an oil diffusion pump. (5) Microwave Power Input Means The microwave power input means is provided with the deposition-preventive structure which is a feature of the present invention. The microwave power input means includes a microwave power source (not shown) and an isolator (not shown).
, Directional coupler (not shown), and tuner (not shown)
And rectangular waveguides 307 and 308 for connecting them appropriately
And circular waveguides 101a and 101b and microwave introduction window 1
02a, 102b Ceramic tube 103 having a deposition-proof structure
a and 103b are included.

Here, the rectangular waveguides 307 and 308 are installed so as to face each other such that their central axes are substantially aligned with the central axis of the film forming chamber 303. Further, the rectangular waveguide 30
The long sides of 7, 308 form an angle of approximately 90 ° with each other, and at the same time, the long sides of the long sides are approximately 45 with respect to the direction in which the space 306 is connected to a vacuum pump (not shown) (the direction of the thick arrow in FIGS. It is arranged to make an angle of °. With such an arrangement, the rectangular waveguides 307 facing each other,
The crosstalk between 308 is suppressed, and at the same time, the gap 306
The microwave leakage in the direction can be minimized.

The dimensions of the rectangular waveguides 307 and 308 are
It is appropriately designed depending on the microwave frequency band and mode used. In designing, it is preferable to consider that the transmission loss in the rectangular waveguides 307 and 308 is small and that the transmission is performed in a single mode. Specifically, other than the EIAJ standard rectangular waveguide and the like. ,
Internal size of 96 mm x 2 as in-house standard for 2.45 GHz
It can be 7 mm.

Circular waveguides 101a and 101b are fastened to the rectangular waveguides 307 and 308, respectively, and the end portions of the circular waveguides 101a and 101b are microwave-transmissive members. Wave introduction windows 102a, 102b
Is provided. This microwave introduction window 102a, 1
02b has a function of introducing the microwave transmitted through the above-described waveguide into the film forming chamber 303 and a function of maintaining the airtightness of the film forming chamber 303. This microwave introduction window 102a,
The circumference of 102b is directly water-cooled, and at the same time, circular waveguides 101a, 1 are formed by a vortex cooler (registered trademark).
It is forcedly cooled from the 01b side with a pressure of 8 kg / cm ² . The microwave introduction window 10 is made of two ceramic plates.
2a and 102b are formed, and a thin and uniform silicone grease is applied between them. Microwave introduction window 1
The ceramic tubes 103a and 103b, which are the deposition-proof structures provided on the 02a and 102b, have already been described.

Next, the operation of the microwave plasma CVD apparatus 300 with the deposition preventive structure shown in FIG. 3 will be described. The operation of the microwave plasma CVD apparatus 300 with the deposition preventive structure is as follows.
The process is generally performed according to the following steps. (Step 1) Attaching the band-shaped substrate that has undergone predetermined cleaning (Step 2) Transfer of the band-shaped substrate in the atmosphere, confirmation of transfer and stop of transfer (Step 3) Installation of a vacuum chamber (not shown) incorporating the band-shaped substrate and transfer means Exhaust (Step 4) Introduction of Source Gas into Film Forming Chamber (Step 5) Temperature Control of Strip-shaped Substrate (Step 6) Discharge by Microwave (Film Forming Step 1) (Step 7) Transfer of Strip-shaped Substrate (Film Forming Step) Part 2) (Step 8) Cooling of the strip-shaped substrate and stop of transport (Step 9) Stop of introduction of source gas (Step 10) Nitrogen leak in vacuum chamber (Step 11) Removal of strip-shaped substrate Hereinafter, the above (Step 1) to (Step) 11) will be described in detail. (Step 1) Attachment of Strip-Shaped Substrate after Predetermined Cleaning Strip-shaped Substrate 301 Wound on Feeding Bobbin (not shown)
Is attached to a predetermined position, and the band-shaped substrate 301 is fed by a bobbin.
The first and second supporting / conveying discs 304a, 304b while being fed back by the first supporting / conveying roller 302a.
After being wound around and wound about one round, it is folded again by the second supporting and conveying roller 302b to form the film forming chamber 303. Further, the end portion of the strip-shaped substrate 301 is fixed to a winding bobbin (not shown) so that the strip-shaped substrate can be wound by the winding bobbin. (Step 2) Transfer of the band-shaped substrate in the air, transfer confirmation, and stop of transfer When the mounting of the band-shaped substrate 301 is completed, in the air, a winding bobbin rotating mechanism (not shown), a supporting transfer roller driving mechanism (not shown), etc. Whether or not the belt-shaped substrate 301 is continuously conveyed by the belt-shaped substrate driving means is checked. Here, it is preferable that the belt-shaped substrate driving means has both a forward movement function and a backward movement function, and it is preferable that the belt-shaped substrate drive means be provided with an indicator of the amount of feeding of the belt-shaped substrate.

After confirming that the belt-shaped substrate 301 can be transported without any trouble, the belt-shaped substrate 301 is returned to the initial setting position while monitoring the indicator of the amount of feeding the belt-shaped substrate.
Stop at that position. (Step 3) Evacuation of the vacuum chamber containing the belt-shaped substrate and the transfer means The lid of the vacuum chamber containing the belt-shaped substrate 301 and the transfer means is closed, and the gas exhausting means exhausts the vacuum chamber. That is, the pressure in the film forming chamber 303 surrounded by the belt-shaped substrate 301 inside the vacuum chamber is set to 2 × 10 ⁻⁵ Torr by a procedure in which the rotary pump and the mechanical booster pump perform rough evacuation and then the oil diffusion pump performs main evacuation. Evacuate continuously until reaching. (Step 4) Introduction of Raw Material Gas into Film Forming Chamber Gas is supplied from a gas cylinder (not shown) to a mixing panel (not shown) that performs precise control of gas mixing and gas flow rate through a stainless pipe (not shown). A source gas, which is guided and controlled to a predetermined flow rate by a mass flow controller (not shown) in the mixing panel, is introduced into the film forming chamber 303 through the gas introduction pipe 305. At this time, the film forming chamber 303
The exhaust capacity of the vacuum pump and the exhaust conductance of the exhaust pipe are selected in advance so that the internal pressure becomes a predetermined value. (Step 5) Temperature Control of Strip Substrate While the source gas is flowing, the temperature control mechanism (not shown) brings the strip substrate 301 to a predetermined temperature. Here, in the microwave plasma CVD apparatus, the electron density and the electron temperature are both higher than those in the plasma CVD apparatus using RF (radio frequency), and therefore the temperature of the strip substrate 301 is likely to rise due to the heat from the plasma. Further, when the temperature control mechanism is not operated, the equilibrium temperature of the strip substrate 301 is determined according to the microwave power to be input. For example, strip substrate 301: material SUS430BA (bright anneal), width 430 mm deposition chamber 303: φ160 mm × 390 mm deposition conditions: SiH ₄ 270 sccm (5 × 10 ⁻³ Tor)
r) The equilibrium temperature of the strip substrate 301 when the bias voltage is 60 V and the bias current is about 5 A is as shown in Table 3.

[0062]

[Table 3] When the desired temperature is different from the equilibrium temperature shown in Table 3, the temperature control mechanism can be operated to control the temperature to a predetermined value.

Therefore, the material of the strip substrate 301, the surface treatment, the size of the film forming chamber 303, the gas flow rate, the gas mixture ratio,
Even when the conditions such as the pressure, bias voltage, and microwave power of the film forming chamber 303 are different, if the equilibrium temperature is similarly measured and the performance of the temperature control mechanism is optimized, the desired strip substrate 30 can be obtained.
The film forming temperature may be 1. (Process 6) Discharge by Microwave (Film Forming Process 1) Microwave is oscillated by a microwave oscillator to generate an isolator, a directional coupler (power meter), a tuner, and a waveguide 30.
7,308,101a, 102b, microwave introduction window 1
02a, 102b and the microwave introduction window 102a,
Ceramic tube 103a, 10 integrally formed with 102b
After passing through 3b, microwave power is applied to the inside of the film forming chamber 303. At this time, the first and second supporting and conveying discs 304 that form the disc-shaped bottom surface of the cylindrical film forming chamber 303.
If microwave leakage occurs from a and 304b, the film forming chamber 3
The discharge inside 03 may become unstable or may not occur. Therefore, the first and second supporting and conveying discs 304
a and 304b, take care so that there are no scratches or irregularities on the outer circumference, and at the same time, at the same time, the first and second supporting and conveying discs 304
It is desirable to provide a microwave shield plate also at the end portions of a and 304b.

After making the above arrangements,
Microwave power is applied to the film forming chamber 303 to move the film forming chamber 30.
3 is generated, and the pressure inside the film formation chamber 303 after discharge is set to 5 × 10 ⁻³ Torr. The resulting radicals are used to form most of the inner side wall of the film formation chamber 303. A uniform deposited film is formed on the surface of the substrate 301. In the case of the present invention, plasma could be stably maintained for 6 hours from the start of discharge. (Step 7) Conveyance of Strip Substrate (Film Forming Step 2) After the film formation is started by the above-mentioned “discharge by microwaves” and the plasma emission generated by the discharge reaches a stable state, on the surface of the strip substrate 301. The belt-shaped substrate 301 is conveyed to form a deposited film over a wide area. The transport speed is determined by the film thickness of the deposited film, the deposition speed, and the inner circumference of the film forming chamber 303. That is, when the thickness of the deposited film is 2000 and the Å deposition rate is 100 Å / sec, the residence time in the film forming chamber 303 may be 2000 ÷ 100 = 20 sec. Therefore, in the case of the film forming chamber 303 having a diameter of 160 mm, the inner peripheral length is about 480 mm, and therefore the inner periphery of the film forming chamber 303 is 2 mm.
In order to transport the strip substrate 301 in 0 sec, the transport speed may be set to 480 mm / 20 sec = 24 mm / sec = 144 cm / min.

However, in practice, the circumferences of the first and second supporting and conveying rollers 302a and 302b are damaged, and the effective length of the film forming chamber 303 is shortened. Only the belt-shaped substrate 301 should be transported slowly. That is, since the transport speed, the film thickness of the deposited film, the deposition speed, and the effective length of the film forming chamber 303 are correlated with each other,
These values may be matched appropriately.

By continuously transporting the strip substrate 301 at the transport speed determined by the above procedure, the strip substrate 3
It is possible to form a deposited film having a wide desired thickness on the surface of No. 01. (Step 8) Cooling of the strip-shaped substrate and stop of transporting the strip-shaped substrate 301 while transporting the strip-shaped substrate 301 to continuously form a deposited film and wind the strip-shaped substrate 3 around the feeding bobbin
When the remaining amount of 01 is almost exhausted, the conveyance of the strip substrate 301, the microwave discharge and the temperature control are stopped. Here, as the remaining amount detecting means of the strip-shaped substrate 301 wound around the delivery bobbin, the above-described delivery length indicator of the strip-shaped substrate 301, outer diameter detection of the delivery bobbin, or the like may be used.
Further, in order to take out the band-shaped substrate 301 on which the film formation is completed into the atmosphere, the band-shaped substrate 301 must be cooled in advance. In order to prevent the peeling of the deposited film due to this cooling,
It is desirable to slowly cool, and the raw material gas is allowed to flow for a while even after the microwave discharge is stopped. (Step 9) Stopping Introduction of Raw Material Gas After the raw material gas is flowed for about 5 minutes, the introduction of the raw material gas is stopped and an inert (He) gas is flown at a flow rate of about 200 sccm. When the surface temperature of the strip substrate 301 reaches about 70 ° C., the introduction of the inert gas is stopped, the residual gas is exhausted, and the exhaust is continued until the pressure in the film forming chamber reaches 2 × 10 ⁻⁵ Torr. (Step 10) Nitrogen Leakage in Vacuum Chamber In order to return the pressure in the film forming chamber 303 from 2 × 10 ⁻⁵ Torr to atmospheric pressure, dry nitrogen was introduced into the film forming chamber 303.
After confirming that the pressure in the film forming chamber 303 has reached atmospheric pressure with a Bourdon tube pressure gauge (not shown), the lid of the vacuum chamber is opened, and the strip-shaped substrate 301 on which film formation has been completed is taken out from the vacuum chamber. (Step 11) Extraction of Strip Substrate The strip substrate 301 can be extracted by the following two methods.

(A) The roll-shaped substrate 301 for one roll is completely wound on the winding bobbin, the feeding bobbin is emptied, and then the winding bobbin and the feeding bobbin are taken out.

(B) When the feeding bobbin still remains, the belt-shaped substrate 301 is cut, and the feeding bobbin is replaced with another feeding bobbin on which another belt-shaped substrate 301 is wound.
The end portion of the new strip-shaped substrate and the cut portion of the cut strip-shaped substrate 301 are joined. Then, after transporting the new strip-shaped substrate until the joining line comes close to the winding bobbin, the strip-shaped substrate is cut again by this joining line. After cutting, the winding bobbin on which the film-shaped substrate 301 after film formation is wound is taken out, and another winding bobbin is attached.

Which of the two taking-out methods is preferable depends on the length of the apparatus and the number of the cylindrical film forming chambers 303, and therefore it is preferable to appropriately select it.

Next, specific production examples by the microwave plasma CVD apparatus with an attachment-preventing structure of the present invention will be shown, but the present invention is not limited to these production examples. [Manufacturing Example 1] Using a microwave plasma CVD apparatus 300 with a deposition-prevention structure shown in FIG. 3, degreasing and cleaning were sufficiently performed without using a transfer means, and a- was formed on a Corning 7059 glass and Si wafer. The Si film was continuously deposited to examine whether or not the deposition preventive structure adversely affects the film quality. here,
The size of the film forming chamber 303 was set to: film forming chamber: φ180 [mm] × 600 [mm] (about 15 liters).

The inside of the film forming chamber 303 is a rotary pump,
5 × by mechanical booster pump and oil diffusion pump
A vacuum was drawn up to 10 ⁻⁶ Torr. In this state, the belt-shaped substrate 301 was heated by a heater (not shown) to degas. When degassing was sufficiently performed, SiH ₄ gas was introduced at a flow rate of 600 sccm and He gas was introduced at a flow rate of 200 sccm through the gas introduction pipe 305. The pressure in the film forming chamber 303 was maintained at 5 mTorr by the pressure control valve.

After that, the waveguide 30 is fed from the microwave power source.
7, 308, 101a, 101b, microwave introduction windows 102a, 102b, and ceramic tubes 103a, 1
Microwave power with an effective value of 3.0 kW was applied to the inside of the film forming chamber 303 via 03b to cause discharge. The effective value of the microwave power supplied to the inside of the film forming chamber 303 while maintaining the discharge is reduced to 1.0 kW, and the state is maintained for a while, and the fluctuation of the plasma emission intensity due to the discharge is measured by an emission monitor. did. The output of the emission monitor is connected to the recorder, and the plasma emission intensity is ± 5.
It was confirmed to be within%.

As described above, 7059 glass and Si
As a result of measuring the film thickness distribution of the deposited film formed on the wafer at 10 mm intervals in the width direction and the longitudinal direction, the film thickness distribution was 5%. The average deposition rate at this time is 75Å
/ Sec. In addition, a part of it is cut out and the reflection type F
T-IR device (Perkin Elmer, 1720X)
As a result of measuring the infrared absorption spectrum using
absorption was observed in cm ^-1 and 630cm ^-1, a-Si
The absorption pattern was peculiar to the film.

In the above-mentioned embodiments, the deposition-preventing structure is the ceramic tube 103, which has a circular cross section and is hollow. Here, the sectional shape of the ceramic tube 103 is not limited to a circular shape, and may be a quadrangle or a triangle as long as it can be in close contact with the microwave introduction window 102 and shield the entire surface thereof.

Further, as shown in FIGS. 4 and 5, the ceramic taper portions 401 and 5 are provided inside the ceramic tube 103.
01 may be provided. This ceramic taper 40
1, 501 is filled in the inside of the ceramic tube 103 on the side close to the microwave introduction window 102, and the filling rate is gradually reduced toward the opposite side. As a manufacturing method, a semitransparent microwave permeable semi-solid (for example, Aaron Ceramic [registered trademark] or Shin-Etsu Chemical manufactured by Toagosei Kagaku Co. Silicone [registered trademark])
The method of filling is mentioned. From the viewpoint of heat conduction, the integral sintering molding method is desirable. The ceramic taper portion 40
Alumina-ceramics are preferable as the material of 1,501 in consideration of the ease of integral molding. The shape of the ceramic taper portions 401 and 501 may be symmetrical or asymmetrical as long as the filling rate gradually decreases as described above. By devising the structure in this way, it has been found that the impedance can be matched even for gases other than SiH ₄ described above or various mixed gases.

Furthermore, the shape of the ceramic tube 103 is not limited to a cylinder, a triangular prism, and a quadrangular prism, and the ceramic tube 103 itself may have a tapered hollow structure. In this case, the tapered shape defining the outer diameter of the ceramic tube 103 may be thicker on the microwave introduction window 102 side and thinner on the opposite side, or vice versa. Further, as described above, the ceramic tube 103 may not have a hollow structure and the filling rate of the ceramic may gradually decrease. [Embodiment 1-2] Next, the second embodiment of the present invention will be described.
An example will be described.

FIG. 6 is a schematic sectional view in the vicinity of the microwave introduction window, which is the main part of the second embodiment according to the first structure of the present invention, and FIG. 7 is a perspective explanatory view seen from the side.

In this embodiment, the microwave introducing window 102 and the gas diffusion suppressing plate 103 of the embodiment shown in FIG. 1 are used as a microwave introducing window 602 and a gas diffusion suppressing plate 601, which are constructed as follows. A membrane gas supply pipe 701 is provided. Since the other structure is similar to that of the embodiment shown in FIGS. 1 and 2, the same reference numerals are given and the description thereof is omitted.

As shown in FIG. 6, a microwave introduction window 602 made of a microwave transparent member is provided at the end of the circular waveguide 101. As the microwave permeable member, one having good thermal conductivity such as alumina ceramics (Al ₂ O ₃ ), beryllia (BeO), boron nitride (BN) is desirable, and in the present embodiment, alumina having a maximum outer diameter φ110 mm is used. Uses ceramics.

The gas diffusion suppressing plate 601 is also made of a microwave permeable member and is provided with a large number of holes. Then, a plurality of ceramic plates forming the gas diffusion suppressing plate 601 are stacked in parallel so as to shift the multiple holes.

Reference numeral 701 is a non-film forming gas supply pipe. The non-film forming gas supply pipe 701 passes through the peripheral portion of the gas diffusion suppressing plate 601 and reaches near the central portion of the microwave introduction window 602. Then, for example, hydrogen gas can be introduced into the central portion of the microwave introduction window 602 from the outside of the film formation chamber 100 via the non-film formation gas supply pipe 701. Therefore, the hydrogen gas concentration near the microwave introduction window 602 can be controlled. Other than hydrogen gas, a rare gas such as helium gas or argon gas, or a mixed gas of hydrogen gas and a rare gas can be used.

The raw material gas introduced into the film forming chamber 100 through the nozzle is exhausted in the exhaust direction 108 by a vacuum pump not directed. This exhaust direction 108 is the microwave introduction window 1
It is almost parallel to the plane of 02.

Also in the case of this embodiment having the above-described structure, the diffusion of the source gas can be controlled similarly to the embodiment shown in FIGS. 1 and 2, and the plasma can be stably maintained. It became a thing. When the same deposition operation as that of the embodiment shown in FIGS. 1 and 2 was performed, similarly good results could be obtained.

Next, a second embodiment of the present invention will be described.

In the microwave plasma CVD apparatus according to the second structure of the present invention, microwave power is applied to the film formation chamber through the microwave introduction window to form a p-type or n-type semiconductor thin film doped with an impurity element. Wave plasma CVD
The apparatus is characterized in that a source gas containing a main component element of the semiconductor thin film and containing no impurity element is blown to the microwave power introduction window.

According to the second structure of the present invention, by increasing the resistance of the film adhering to the microwave introduction window, the plasma discharge is interrupted even if the film doped with impurities adheres to the microwave introduction window. It is difficult to do.

A semiconductor thin film is formed on the surface of the microwave introducing window by blowing a source gas containing the main element of the semiconductor thin film formed on the substrate to the microwave introducing window. The concentration of the gas containing the impurity element decreases near the surface of the.

The concentration of the source gas containing the main element of the semiconductor thin film increases. Then, the doping rate and the crystallinity of the semiconductor film attached to the surface of the microwave introduction window decrease.

As a result, the resistance of the semiconductor film attached to the microwave introduction window is greatly increased, and even if the film is attached, the transmittance of microwaves is less likely to decrease.

For example, when a non-single-crystal silicon semiconductor is formed, if the concentration of the gas containing the impurity element is reduced by one digit except for the excessive impurity doping region, the dark resistance of the film increases by about two digits.

When the crystallinity of the film changes from amorphous to polycrystal, the dark resistance increases by about 3 digits.

Due to such a large increase in resistance, although the amount of the film adhering to the microwave introduction window is somewhat increased in the present invention, the microwave transmittance is kept high and the discharge is less likely to be interrupted.

The semiconductor thin film formed by the device of the second structure of the present invention includes Si, Ge, C, SiGe,
So-called IV such as SiC, GeC, SiSn, GeSn, SnC
Group semiconductor thin film, GaAs, GaP, GaSb, InP,
So-called III-V group compound semiconductor thin films such as InAs, ZnSe, Z
nS, ZnTe, CdS, CdSe, CdTe, etc., so-called II
-Group VI compound semiconductor thin film, CuAlS ₂ , CuAlS
e ₂ , CaAlTe ₂ , CuInS ₂ , CuInSe ₂ , C
uInTe ₂ , CuGaS ₂ , CuGaSe ₂ , CuGa
Te, AgInSe ₂ , AgInTe ₂ , etc., so-called I-III-VI group compound semiconductor thin films, ZnSiP ₂ , ZnGeAs ₂ , Cd
SiAs _2, CdSnP ₂ Hitoshishoi II-IV-V double compound semiconductor thin _{film, Cu 2 O, TiO 2,} In 2 O 3, SnO 2, ZnO,
Examples thereof include so-called oxide semiconductor thin films such as CdO, Bi ₂ O ₃ , and CdSnO ₄ , which contain an impurity element for controlling valence electrons.

In accordance with the second aspect of the present invention IV
Suitable for forming Group IV semiconductors or Group IV alloy semiconductor thin films
Used appropriately. Raw materials containing Group IV elements of the periodic table
As the atom, Si atom, Ge atom, C atom, Sn atom,
A compound containing a Pb atom, specifically SiH_Four，
Si₂H₆, Si₃H₈, Si₃H₆, Si_FourH₈, Si_FiveH_Ten
Silane compounds such as SiF_Four, (SiF₂)_Five, (Si
F₂)₆, (SiF₂)_Four, Si₂F₆, Si₃F₈, SiHF
₃, SiH₂F₂, Si₂H₂F_Four, Si₂H₃F₃, SiC
l_Four, (SiCl₂)_Five, SiBr_Four, (SiBr₂)_Five, S
i₂Cl₆, Si₂Br₆, SiHCl₃, SiHBr₃, S
iHI₃, Si₂Cl₃F₃Halogenated silane compounds such as
GeH_Four, Ge₂H₆Germane compounds such as GeF_Four, (G
eF₂)_Five, (GeF₂)₆, (GeF₂)_Four, Ge₂F₆, G
e₃F₈, GeHF₃, GeH₂F₂, Ge₂H₂F_Four, Ge₂
H₃F₃, GeCl_Four, (GeCl₂)_Five, GeBr_Four, (G
eBr₂)_Five, Ge₂Cl₆, Ge₂Br₆, GeHCl₃，
GeHBr₃, GeHI₃, Ge₂Cl₃F₃Halogen etc.
Germanium compound, CH_Four, C₂H₆, C₃H₈Etc.
Tandem hydrocarbon gas, C₂H_Four, C₃H₆Ethylene column charcoal
Hydrogen gas, C₆H₆Cyclic hydrocarbon gas such as CF_Four，
(CF₂)_Five, (CF₂)₆, (CF₂)_Four, C₂F₆, C
₃F₈, CHF₃, CH₂F₂, CCl_Four, (CCl₂)_Five, C
Br_Four, (CBr₂)_Five, C ₂Cl₆, C₂Br₆, CHC
l₃, CHI₃, C₂Cl₃F₃Halogenated carbon compounds such as
Thing, SnH_Four, Sn (CH₃)_FourTin compounds such as Pb
(CH₃)_Four, Pb (C₂H_Five)₆Lead compounds such as
be able to. Even if these compounds are used in one kind, two or more kinds are used.
You may mix and use above.

The valence electron control agent used for controlling the valence electrons of the group IV semiconductor or the group IV alloy semiconductor formed in the present invention is, as a p-type impurity, a compound of the periodic table.
Group III elements such as B, Al, Ga, In, and Tl are preferred, and n-type impurities include elements of Group V of the periodic table such as N, P, As, Sb, and Bi.
And the like, but especially B, Ga,
P, Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined according to desired electrical and optical characteristics.

As the source gas containing such an impurity element, a gas which is in a gas state at room temperature and atmospheric pressure or which can be easily gasified under at least the film forming conditions is adopted. As the starting material for introducing such impurities, specifically, n
PH ₃ , P ₂ H ₄ , PF ₃ , PF ₅ ,
PCl ₃ , ASH ₃ , AsF ₃ , AsF ₅ , AsCl ₃ , S
bH _3, SbF _5, the BiH _3, etc., are for p-type impurity introduction _{BF 3, BCl 3, BBr 3} , B 2 H 6, B 4 H 10, B 5 H 9,
_{B 5 H 11, B 6 H} 10, B 6 H 12, AlCl 3 and the like. The compounds containing the above impurity elements may be used alone or in combination of two or more.

According to the second structure of the present invention,
Periods used to form II-VI compound semiconductors
Specific examples of the compound containing a Group II element of the table include Zn
(CH₃)₂, Zn (C₂H_Five)₂, Zn (OCH₃)₂, Z
n (OC₂H_Five)₂, Cd (CH ₃)₂, Cd (C₂H_Five)₂，
Cd (C₃H₇)₂, Cd (C_FourH₉)₂, Hg (CH₃)₂，
Hg (C₂H_Five)₂, Hg (C₆H_Five)₂, Hg [C = (C₆
H_Five)]₂Etc. It also contains Group VI elements of the periodic table.
As the compound, specifically, NO, N₂O, CO₂, C
O, H₂S, SCl₂, S₂Cl₂, SOCl₂, SeH₂，
SeCl₂, Se₂Br₂, Se (CH₃)₂, Se (C₂H
_Five)₂, TeH₂, Te (CH₃)₂, Te (C₂H_Five)₂Etc.
Can be mentioned.

Of course, these raw material gases may be used alone or in combination of two or more.

According to the second structure of the present invention,
The valence electron control agent used for controlling the valence electrons of the formed II-VI group compound semiconductor includes the periodic tables I and II.
Compounds containing group I, IV, and V elements can be cited as effective ones.

Specifically, as the compound containing a group I element, LiC ₃ H ₇ , Li (sec-C ₄ H ₉ ), Li ₂ S,
Li ₃ N etc. can be mentioned as a suitable thing.

Further, as a compound containing a group III element,
_{BX 3, B 2 H 6,} B 4 H 10, B 5 H 9, B 5 H 11, B 6 H 10,
_{B (CH 3) 3, B} (C 2 H 5) 3, B 6 H 12, AlX 3, A
l (CH ₃ ) ₂ Cl, Al (CH ₃ ) ₃ , Al (OC
_{H 3) 3, Al (CH} 3) Cl 2, Al (C 2 H 5) 3, Al
(OC ₂ H ₅ ) ₃ , Al (CH ₃ ) Cl ₃ , Al (i-C ₄ H
_{9) 3, Al (i-} C 3 H 7) 3, Al (C 3 H 7) 3, Al
(OC ₄ H ₉ ) ₃ , GaX ₃ , Ga (OCH ₃ ) ₃ , Ga (O
_{C 2 H 5) 3, Ga} (Oc 3 H 7) 3, Ga (OC 4 H 9) 3,
_{Ga (CH 3) 3, Ga} 2 H 6, GaH (C 2 H 5) 2, Ga
(OC ₂ H ₅ ) (C ₂ H ₅ ) ₂ , In (CH ₃ ) ₃ , In (C _{3
H 7) 3, In (C} 4 H 9) 3, as the compound containing a V group element _{NH 3, HN 3, N 2} H 5 N 3, N 2 H 4, NH 4 N 3, P
_{X 3, P (OCH 3)} 3, P (OC 2 H 5) 3, P (C 3 H 7)
₃ , P (OC ₄ H ₉ ) ₃ , P (CH ₃ ) ₃ , P (C ₂ H ₅ ) ₃ ,
P (C ₃ H ₇ ) ₃ , P (C ₄ H ₉ ) ₃ , P (OCH ₃ ) ₃ , P
(OC ₂ H ₅ ) ₃ , P (OC ₃ H ₇ ) ₃ , P (OC ₄ H ₉ ) _3, P
(SCN) ₃ , P ₂ H ₄ , PH ₃ , AsH ₃ , AsX ₃ , As
(OCH ₃ ) ₃ , As (OC ₂ H ₅ ) ₃ , As (OC
₃ H ₇ ) ₃ , As (OC ₄ H ₉ ) ₃ , As (CH ₃ ) ₃ , As
_{(CH 3) 3, As (} C 2 H 5) 3, As (C 6 H 5) 3, Sb
X ₃ , Sb (OCH ₃ ) ₃ , Sb (OC ₂ H ₅ ) ₃ , Sb (O
_{C 3 H 7) 3, Sb} (OC 4 H 9) 3, Sb (CH 3) 3, Sb
_{(C 3 H 7) 3,} Sb (C 4 H 9) 3 and the like.

In the above, X is halogen (F, Cl,
Br, I) is shown.

Of course, these source gases may be used alone or in combination of two or more.

Further, as the compound containing the group IV element, the above-mentioned compounds can be used.

In the second aspect of the present invention, II
Period used to form I-V compound semiconductors
Specific examples of the compound containing a Group III element of the table include B
X₃(However, X represents a halogen atom.), B₂H₆, B_Four
H_Ten, B_FiveH₉, B_FiveH₁₁, B₆H_Ten, B₆H₁₂, AlX
₃(However, X represents a halogen atom.), Al (CH₃)
₂Cl, Al (CH₃)₃, Al (OCH₃)₃, Al (C
H₃) Cl₂, Al (C₂H_Five)₃, Al (OC₂H_Five)₃, A
l (CH₃)₃Cl₃, Al (i-C_FourH₉)₃, Al (i-
C₃H₇)₃, Al (C₃H₇)₃, Al (OC_FourH₉)₃, G
aX₃(However, X represents a halogen atom.), Ga (O
CH₃)₃, Ga (OC₂H_Five)₃, Ga (OC₃H ₇)₃, G
a (OC_FourH₉)₃, Ga (CH₃)₃, Ga₂H₆, GaH
(C₂H_Five)₂, Ga (OC₂H_Five) (C₂H_Five)₂, In (C
H₃)₃, In (C₃H₇)₃, In (C_FourH₉)₃Etc.
Be done. Further, as a compound containing a Group V element of the periodic table,
Specifically NH₃, HN₃, N₂H_FiveN₃, N₂H_Four, NH_FourN
₃, PX₃(However, X represents a halogen atom.), P (O
CH₃)₃, P (OC₂H_Five)₃, P (C₃H₇)₃, P (OC
_FourH₉)₃, P (CH₃)₃, P (C₂H_Five)₃, P (C₃H₇)
₃, P (C_FourH₉)₃, P (OCH₃)₃, P (OC
₂H_Five)₃, P (OC₃H₇)₃, P (OC_FourH₉)₃, P (S
CN)₃, P₂H_Four, PH₃, AsX₃(However, X is a halogen
Represents a hydrogen atom. ), AsH₃, As (OCH₃)₃, As
(OC₂H_Five)₃, As (OC₃H₇)₃, As (OC_FourH₉)
₃, As (CH₃)₃, As (CH₃)₃, As (C
₂H_Five)₃, As (C₆H_Five)₃, SbX₃(However, X is halo
Indicates a gen atom. ), Sb (OCH₃)₃, Sb (OC₂
H_Five)₃, Sb (OC₃H₇)₃, Sb (OC_FourH₉)₃, Sb
(CH₃)₃, Sb (C₃H₇)₃, Sb (C_FourH₉)₃Etc.
You can [However, X is a halogen atom, specifically F,
At least one selected from Cl, Br, I
You ] Of course, these raw materials are one kind or two or more kinds.
It can be mixed and used.

According to the second structure of the present invention,
As the valence electron control agent used for controlling the valence electrons of the formed III-V compound semiconductor, the periodic table II, IV,
Compounds containing Group VI elements can be cited as effective ones.

Specifically, as a source gas containing a group II element,
For Zn (CH₃)₂, Zn (C₂H_Five)₂, Zn (OC
H₃)₂, Zn (OC₂H_Five)₂, Cd (CH₃)₂, Cd
(C₂H _Five)₂, Cd (C₃H₇)₂, Cd (C_FourH₉)₂, H
g (CH₃)₂, Hg (C₂H_Five)₂, Hg (C₆H_Five)₂, H
g [C≡ (C₆H_Five)]₂The VI group
The compounds containing element are NO, N₂O, CO₂, CO,
H₂S, SCl₂, S₂Xl₂, SOCl₂, SeH₂, Se
Cl₂, Se₂Br₂, Se (CH₃)₂, Se (C
₂H _Five)₂, TeH₂, Te (CH₃)₂, Te (C₂H_Five)₂
Etc. can be mentioned.

Of course, these source gases may be used alone or in combination of two or more.

Further, as the compound containing the group IV element, the above-mentioned compounds can be mentioned.

According to the second structure of the present invention,
The source gases mentioned above are He, Ne, Ar, Kr, Xe, R.
It may be introduced by mixing with a rare gas such as n and a diluting gas such as H ₂ , HF and HCl.

The material of the substrate preferably used in the apparatus of the second structure of the present invention is microwave plasma C
It is preferable that the VD apparatus has a small amount of deformation and distortion at a temperature required for forming a semiconductor thin film and has a desired strength, specifically, stainless steel,
Thin plates of metal such as aluminum and its alloys, iron and its alloys, copper and its alloys, and their composites, and metal thin films of different materials and / or Si on their surfaces
An insulating thin film of O ₂ , Si ₃ N ₄ , Al ₂ O ₃ , AlN, etc., which has been surface-coated by a sputtering method, a vapor deposition method, a plating method, or the like. Further, polyimide, polyamide, polyethylene terephthalate, heat-resistant resinous sheet of epoxy or the like or a composite of these with glass fiber, carbon fiber, boron fiber, metal fiber or the like and a simple metal or alloy on its surface, and transparent conductive oxidation The thing (TCO) etc. which carried out electroconductivity processing by methods, such as plating, vapor deposition, sputtering, and application, are mentioned.

According to the second structure of the present invention,
The microwave introduction window is provided at the tip of the microwave power input means to separate the vacuum atmosphere in the deposition chamber from the outside air in which the microwave power input means is installed, and to have a structure that can withstand the pressure difference. Designed. Specifically, it is desirable that the cross-sectional shape with respect to the traveling direction of the microwave is preferably circular, rectangular, elliptical flat plate, bell jar shape, doublet shape, or conical shape.

Further, it is desirable that the thickness of the microwave introduction window with respect to the traveling direction of the microwave is designed in consideration of the dielectric constant of the material used so that the reflection of the microwave here can be suppressed to the minimum. . For example, in the case of a flat plate shape, it is preferable that it is approximately equal to 1/2 wavelength of the microwave wavelength. Further, as the material, it is preferable that the microwave power can be transmitted into the film forming chamber with a minimum loss, and that the airtightness is excellent so that the air does not flow into the film forming chamber. Examples thereof include glass such as quartz, alumina, silicon nitride, beryllia, magnesia, zirconia, boron nitride and silicon carbide, or fine ceramics.

Further, it is preferable that the microwave introduction window is uniformly cooled in order to prevent thermal deterioration (cracking, destruction) due to microwave power or plasma.

As a concrete cooling means, a cooling air flow may be blown toward the surface of the microwave introduction window on the atmosphere side, or the microwave power input means itself may be cooled air.
The microwave introduction window may be indirectly cooled by heat conduction through a portion in contact with the microwave power input means by cooling with a coolant such as water, oil or freon. By cooling the microwave introduction window to a sufficiently low temperature, even if a relatively high microwave power is introduced into the film formation chamber, the microwave introduction window will not be damaged by heat and will not be damaged. An electron density plasma can be generated.

As an example of the apparatus having the second structure of the present invention, the apparatus having the structure shown in FIG. 8 can be mentioned.

In FIG. 8, reference numeral 801 is a film forming chamber, 802 is a microwave introduction window, 803 is a microwave waveguide, and 804.
Is a microwave power source, 805 is an exhaust pipe for exhausting the film forming chamber by an exhaust device (not shown), 806 is a source gas supply pipe for supplying a source gas containing an impurity element from a source gas supply system (not shown), and 807 is a substrate Reference numeral 808 is a heater for heating the substrate, 809 is a source gas supply pipe for blowing a source gas containing a main component element of the semiconductor thin film formed on the substrate to the microwave introduction window, and 810 is leakage of the microwave to the exhaust pipe. It is a metal mesh for preventing.

The semiconductor thin film is formed by such an apparatus as follows.

First, the film forming chamber 801 is sufficiently evacuated by the exhaust pipe 805. Next, for example, when a B-doped film of amorphous silicon is formed on the substrate, a source gas containing an impurity element such as a mixed gas of SiH ₄ gas and B ₂ H ₆ gas is supplied from the source gas supply pipe 806. Film forming chamber 80
Supply within 1.

Further, microwave power is introduced into the film forming chamber 801 from the microwave introduction window 802, the source gas supplied from the source gas supply pipe 806 is excited to generate plasma, and the heater 808 is used to generate a desired plasma. An impurity-doped semiconductor thin film is formed on the substrate 807 heated to the temperature.

At this time, on the surface of the microwave introduction window 802 on the film formation chamber side, from the source gas supply pipe 809, for example, when a B-doped film of amorphous silicon is formed on the substrate, the main component of the semiconductor film is formed. Contains the element Si element,
A source gas such as SiH ₄ gas containing no B element as an impurity element is sprayed.

[Embodiment 2-1] The microwave plasma CV of the present invention is carried out as follows by using the apparatus shown in FIG.
P doped with boron as an impurity on the substrate by the D method
A type amorphous silicon thin film was formed.

First, the film forming chamber 801 is sufficiently exhausted through the exhaust pipe 805, and then the source gas supply pipe 806 is continuously exhausted.
From SiH ₄ gas and B ₂ as source gases containing impurity elements
A mixed gas of H ₆ gas is introduced in the vicinity of the surface of the substrate 807, and SiH ₄ gas is introduced as a raw material gas containing the main element Si of the semiconductor thin film and not containing the impurity element boron from the raw material gas supply pipe 809 into the microwave introduction window 802. Sprayed towards the surface.

10 cm square by heater 808, thickness 1
A SUS304 stainless steel substrate 807 (mm) is heated from the back surface to a predetermined temperature, and microwave power of 2.45 GHz is introduced from a microwave power source 804 through a microwave waveguide 803 and a ceramic microwave introduction window 802 to form a film. A discharge was generated in the chamber to form a boron-doped p-type amorphous silicon film on the substrate.

Before the semiconductor film was formed, no film was attached to the surface of the microwave introducing window, and the semiconductor film forming conditions were as shown in Table 4.

[0126]

[Table 4] The discharge was continued for 119 minutes, and the p-type amorphous silicon thin film doped with boron could be continuously formed for a long time.

[Comparative Example 2-1] Doping boron on the substrate by the microwave plasma CVD apparatus under the conditions shown in Table 1 in the same manner as in Example 1 except that the raw material gas was not blown to the microwave introduction window. Although the p-type amorphous silicon thin film was formed, the discharge was interrupted in 3 minutes and the semiconductor thin film could not be formed continuously for a long time.

[Comparative Example 2-2] The same procedure as in Example 2-1 was repeated except that the raw material gas was not blown to the microwave introduction window and the amount of the raw material gas introduced near the substrate was increased accordingly. A p-type amorphous silicon thin film doped with boron was formed on the substrate by the microwave plasma CVD apparatus under the conditions shown in the table, but the discharge was interrupted for 5 minutes, and the semiconductor thin film could not be formed continuously for a long time. It was

[Comparative Example 2-3] Microwave plasma was performed under the conditions shown in Table 4 in the same manner as in Example 2-1 except that the gas blown to the microwave introduction window was changed to H ₂ and the flow rate was increased 10 times. A p-type amorphous silicon thin film doped with boron was formed on the substrate by a CVD device, and the discharge was 5
It was not possible to form a semiconductor thin film continuously for a long time, interrupted by a minute.

Further, in order to maintain the pressure inside the film forming chamber at the same pressure as in Example 2-1, the exhaust capacity of the exhaust device had to be increased about twice.

[Comparative Example 2-4] The same procedure as in Example 1 was carried out except that the raw material gas blown to the microwave introduction window was made to contain the impurity element. Although a p-type amorphous silicon thin film doped with boron was formed, the discharge was interrupted for 10 minutes, and it was not possible to form a semiconductor thin film continuously for a long time.

[Example 2-2] The microwave of the present invention was carried out in the same manner as in Example 1 except that the raw material gas introduced in the vicinity of the substrate and the raw material gas blown to the microwave introduction window were changed as shown in Table 5. An n-type amorphous silicon carbide thin film doped with phosphorus as an impurity was formed on the substrate by a plasma CVD apparatus.

Before the semiconductor film was formed, no film was attached to the surface of the microwave introducing window, and the semiconductor film forming conditions were as shown in Table 5.

The discharge was continued for 151 minutes, and an n-type amorphous silicon carbide thin film doped with phosphorus could be continuously formed for a long time.

[0135]

[Table 5] [Comparative Example 2-5] The substrate was doped with phosphorus by a microwave plasma CVD apparatus under the conditions shown in Table 5 in the same manner as in Example 2-2 except that the gas blown to the microwave introduction window was changed to Ar. Although the n-type amorphous silicon carbide thin film was formed, the discharge was interrupted for 15 minutes, and the semiconductor thin film could not be formed continuously for a long time.

[Example 2-3] The present invention was carried out in the same manner as in Example 2-1 except that the raw material gas introduced in the vicinity of the substrate and the raw material gas blown to the microwave introduction window were changed as shown in Table 6. A p-type amorphous silicon thin film doped with boron was formed on the substrate by the microwave plasma CVD apparatus having the second configuration.

Before the formation of the semiconductor film, the film was not attached to the surface of the microwave introducing window, and the semiconductor film forming condition was the sixth condition.
It was as shown in the table.

The discharge was continued for 72 minutes, and the boron-doped p-type amorphous silicon germanium thin film could be continuously formed for a long time.

[0139]

[Table 6] [Comparative Example 2-6] Boron was doped on the substrate by a microwave plasma CVD apparatus under the conditions shown in Table 6 in the same manner as in Example 2-3 except that the gas blown to the microwave introduction window was changed to He. Although a p-type amorphous silicon germanium thin film was formed, the discharge was interrupted for 4 minutes, and the semiconductor thin film could not be formed continuously for a long time.

Next, an embodiment according to the third structure of the present invention will be described.

The third structure of the present invention is a microwave plasma C having a plurality of microwave power input means arranged in parallel.
The VD device is characterized in that the electric field direction of the microwaves in the adjacent microwave power input means is changed before and after the electric discharge to form a film.

In the above-mentioned device, before the electric discharge is generated, the microwave electric power is applied by making the electric field directions orthogonal to each other so that the microwave introduced by the microwave electric power applying means is not received by the adjacent microwave electric power applying means. Place means.

Further, there is provided means for making the electric field directions of the microwaves introduced into the film forming chamber parallel after the discharge.

Further, the means for changing the electric field direction of the introduced microwave utilizes the Faraday effect.

The microwave plasma CVD apparatus used in this embodiment has a film forming chamber for forming a deposited film on the substrate. The film forming chamber is formed of a conductive wall surface with the substrate as a part thereof. The base body may be a belt-shaped substrate having at least one surface subjected to a conductive treatment, or may be a plurality of Si wafers fixed to a holder, glass, or stainless pieces. A plurality of applicators are arranged in the film forming chamber, and microwave power can be supplied from a microwave power source outside the apparatus by a waveguide connected to the applicators. At the tip of the applicator, a microwave transparent member that transmits microwave power to the film forming space and introduces the microwave power is disposed.

The applicator is arranged parallel to the substrate, and microwaves are introduced from the applicator parallel to the substrate.

The film forming chamber has means for introducing a source gas from the outside of the apparatus and means for exhausting the gas, and the film forming chamber can be maintained at a reduced pressure. The belt-shaped substrate is continuously moved and supplied to the film forming chamber to form a deposited film.

The following is a detailed description of the experiments conducted by the inventors to complete the third structure of the present invention.

[Experimental Procedure 3-1] Various experiments were conducted on plasma generation conditions and discharge stability by a plurality of applicators, and will be described below.

This experiment was conducted using the apparatus shown in FIG.

The film forming chamber 910 has a size of the strip substrate 911.
Has a length of 1500 mm in the transport direction and a depth of 200 m
m, the height is 150 mm. Applicator 904 ~
906 is 3 at variable intervals of 200 to 300 mm in the transport direction.
The pedestal and the microwave are arranged on one side surface so that the microwaves are introduced in parallel to the strip substrate. Applicator has inner diameter φ
A cylindrical waveguide having a length of 100 mm and a length of 150 mm is provided with a microwave permeable member at its tip to perform vacuum isolation from the film forming chamber (decompression on the film forming chamber side, atmospheric pressure in the applicator).
Microwaves are propagated and supplied from each of three microwave oscillators to each applicator in a circular H ₁₁ mode, and introduced into the film forming chamber 910 from the microwave permeable member at the tip. Film forming chamber 91
The electric field direction of the microwaves introduced into 0 (that is, the plane of polarization) can be adjusted by the attachment angles of the rectangular waveguides 901 to 903 connected to the applicators 904 to 906, respectively. The angles θ ₁ , θ ₂ , and θ ₃ were set as illustrated in order to explain the relative angles of the electric field directions 907 to 909 of the microwaves introduced from the applicators.

The microwave oscillator used in the experiment had a frequency of 2.45 GHz and low ripple continuous oscillation output of maximum output of 3 kW and 1.5 kW.

A source gas is supplied to the film forming chamber 910 by a gas supply means (not shown) so that the source gas is evenly distributed in the film forming chamber. Further, the gas in the film forming chamber 910 is exhausted toward the exhaust pump (not shown) through the exhaust board 912 having a large number of small openings of φ5 mm.

The pressure in the film forming chamber can be adjusted by changing the aperture ratio of the conductance valve installed between the film forming chamber and the exhaust pump.

[Experimental Example 3-1] As shown in Tables 7 and 8, various amounts of gas introduced into the film forming chamber, gas species, and pressure were set, and the direction of electric field of the introduced microwaves was changed. Various relative angles were set to investigate the discharge electromotive force, the discharge stability, and the minimum power (discharge sustaining power) with which the discharge can be maintained for all three applicators.

[0156]

[Table 7]

[0157]

[Table 8] As shown in Tables 7 and 8, the amount of gas introduced into the film formation space,
Various kinds of gas and pressure are set, and the relative angle of the electric field direction of the radiated microwave is also set variously, and the discharge electromotive force, the discharge stability, and the minimum power that can maintain the discharge of all three applicators (discharge maintenance) Power).

(Results) As shown in Tables 7 and 8, the discharge electromotive force was measured under the condition that the electric field directions of the microwaves introduced from the adjacent applicators were parallel (1, 7, 9, 10,
12, 14, 24), the discharge electromotive force was high and the discharge did not occur in some cases. It was found that the discharge electromotive force was low under the condition that the electric field directions were alternately vertical (4,5, 8, 11, 13, 13, 15 to 23). The discharge stability and the discharge sustaining power after the occurrence of discharge were good regardless of whether the electric field directions were parallel or perpendicular to each other.

After the electric discharge was generated, the microwave was not received by other applicators regardless of the electric field direction of the microwave.

[Experimental example 3-2] Some of the experimental conditions were extracted, an amorphous silicon film was deposited, and the film thickness distribution and film quality distribution in the large area film formation were investigated.

The film forming area is 800 (mm) in the direction in which the applicators are arranged (center distribution) and 200 (mm) in the direction of microwave introduction, that is, 80 (cm) × 20 (c).
m) = 1600 (cm ² ). A 1-inch square quartz glass and a φ1-inch silicon wafer were used as substrates and fixed and arranged in a holder.

The film thickness distribution was measured using a stylus pressure gauge.

The film thickness distribution depends on the dark conductivity, ημτ product (η quantum efficiency, μ electron mobility, τ electron lifetime) and activation energy, and the hydrogen concentration calculated from the Si—H peak of the infrared absorption spectrum. evaluated.

(Results) Table 9 shows the results.

[0165]

[Table 9] It was found that when the electric fields of the microwaves introduced into the film forming chamber were parallel to each other, a uniform deposited film was obtained over the entire film forming area.

From Experimental Examples 3-1 and 3-2, it is desirable that the microwave electric field directions are alternately perpendicular to each other when a discharge occurs and that the microwave electric field directions are preferably parallel to each other during film formation. I understood.

The means for changing the electric field direction of the microwave used in this embodiment (polarization plane rotating mechanism) is a mechanism for rotating the plane of polarization (that is, the electric field direction) by using the Faraday effect (hereinafter referred to as a polarization plane rotator). Is.

In this embodiment, as a structure for producing the Faraday effect, a phenomenon that a plane of polarization of an electromagnetic wave propagating in the ferrite is rotated when a ferrite is used as a magnetic material and a DC magnetic field is applied to the ferrite. I am using.

FIG. 10 is an explanatory view showing the inside of the polarization rotator 1003 used in the third embodiment of the present invention. The configuration and operation will be described below.

For the cylindrical waveguide 1002 (φ100 mm),
Rectangular wave guide 100 for microwave of frequency 2.45 GHz
1 (WJA-2: JIS standard). The microwave propagates after being converted from the rectangular H ₀₁ mode to the circular H ₁₁ mode through the rectangular waveguide 1001 and the cylindrical waveguide 1002. The polarization rotator 1003 is installed along the central axis of the cylindrical waveguide 1002, and along the central axis of the cylindrical waveguide 1002, a ferrite cylinder 1004 fixed to its inner wall and a cylindrical waveguide 1004. It is constituted by a coil 1006 covering the outer circumference of the wave tube 1002. When the coil 1006 is energized, a DC magnetic field is induced in the cylindrical waveguide 1002 from the front to the back of the drawing. Both the microwaves traveling from the rectangular waveguide 1001 to the cylindrical waveguide 1002 (waves traveling in the Z-axis positive direction) and the microwaves traveling in the opposite direction (waves traveling in the Z-axis negative direction) are ferritic cylinders. After passing through 1004, the plane of polarization rotates clockwise toward the direction of the DC magnetic field by the same rotation angle.

The rotation angle θ is θ≈−1 / 2 · (εμ) ^1/2 · μ ₀ γ _e M ₀ l ε: Permittivity of ferrite μ: Permeability of ferrite μ ₀ : Permeability of vacuum γ _e : Rotational magnetic ratio M ₀ : Saturation magnetization due to DC magnetic field in ferrite l: Length of ferrite

When the polarization plane rotator is designed so that the rotation angle θ becomes 45 °, microwaves propagating in the positive Z-axis direction with the electric field direction parallel to the x-axis rotate the polarization plane by 45 ° and form a cylindrical waveguide. Go through the tube. The microwaves traveling from the cylindrical waveguide in the negative Z-axis direction with the electric field direction parallel to the x-axis also rotate the plane of polarization by 45 °, but the electric field direction becomes perpendicular to the wide direction of the rectangular waveguide. The cut-off frequency is lower than the cut-off frequency, and the microwave cannot propagate in the rectangular waveguide toward the microwave oscillator (not shown).

[Example 3-1] An amorphous silicon film was formed using the microwave plasma CVD apparatus having the third structure of the present invention shown in FIG.

Reference numeral 1101 denotes an outer peripheral wall forming the film forming chamber 1121, 1102 a strip substrate (having a width of 15 cm), 11
Reference numeral 03 denotes a transport direction L, 1104 denotes a gas discharge port for discharging the source gas 1106 by the gas supply means 1105, and 110
Reference numeral 7 denotes a gas exhaust port, and 1108 denotes an exhaust direction. The dimensions of the film forming chamber 1121 are 45 cm in the belt-shaped substrate transfer direction, 16 cm in the belt-shaped substrate width direction, and 14 cm above and below. 1111
a and 1111b are center distances of 25c in the strip substrate transfer direction.
m is an applicator, 1112 is a microwave transparent member (φ 106 mm), 1113 is ferrite,
1114 is a coil, 1115 is a microwave introduction direction, 1
Reference numerals 116 and 1117 denote microwave electric field directions at the time of being supplied to the applicator, and reference numerals 1118 and 1119 denote electric field directions of microwaves introduced into the film forming chamber by the applicator 1111a.

The formation of the amorphous silicon deposited film is as follows.
The procedure was performed. SiH in the film forming chamber _Four400 sccm,
H₂400 sccm was introduced, and the pressure was 6 mTorr.
It was Leave the strip substrate stationary, then two microwaves
From the oscillator (not shown) to the applicators 1111a, 1111
Microwave power was applied to each of 11b. At this time,
Energize the coil of the applicator 1111a
The plane of polarization of the microwave propagating in the CAT 1111a
Rotate 45 degrees to rotate applicator 1111a and app
Microwave introduced into the film formation chamber from the caterer 1111b
The angle formed by the direction of the electric field was 90 °. Then microwave
Increase the microwave power output from the power supply
It caused an electric power. Discharge microwave power of 450W
It happened in.

After the occurrence of discharge, the coil of the applicator 1111a is energized in the opposite direction, and the applicator 1111a is rotated.
The electric field direction of the microwave introduced into the film formation chamber from the device is rotated by 90 ° in the direction opposite to the above, and the applicator 1111b is rotated.
Was parallel to the direction of radiation from the to the film formation space. The movement of the strip substrate was started, the microwave power was adjusted to 400 W each, and continuous film formation was started. The discharge during film formation was stable. The characteristics of the amorphous silicon film deposited on the strip substrate are as follows: dark conductivity 1 to 2 × 10 ^-10 (Ω ^-1 cm ^-1 ),
A film having a thickness of ^{6 to} 8 × 10 ⁻⁶ (Ω ⁻¹ cm ⁻¹ ) and a film thickness of 1.4 μm was obtained.

[Embodiment 3-2] In the embodiment shown in FIG. 12, three or more (four) applicators for introducing microwaves are provided in the film forming chamber 1205.

In this embodiment, the applicators 1201 and 1203 provided with the polarization plane rotator and the normal applicators 1202 and 120 not provided with the polarization plane rotator.
Every other 4 is attached. Since the other structure is almost the same as that of the embodiment shown in FIG. 11, the description thereof will be omitted.

In this embodiment, the electric field directions of the microwaves of the applicators 1201 and 1203 are controlled at the time of occurrence of electric discharge, so that the electric field directions of the microwaves of the adjacent applicators are orthogonal to each other. As a result, it was possible to generate a discharge while minimizing the microwave interference. After the discharge is generated, the polarization planes of the applicators 1201 and 1203 are rotated so that the applicators 1201 and 1203 move from the film forming chamber 1205
By aligning the direction of the electric field introduced into the device, stable discharge and uniform film formation could be performed over a large area.
[Embodiment 3-3] In the embodiment shown in FIG. 13, eight applicators for introducing microwaves are provided in the film forming chamber 1301.

Of the eight applicators described above, applicators 1302 to 1305 provided with a polarization plane rotating machine are used.
For 09, a normal one without a polarization plane rotating machine is used. The applicators 1302 to 1305 and the applicators 1306 to 1309 are respectively formed in the film forming chamber 130.
1 are provided so as to face each other and are parallel to each other. In addition, the applicators provided with the polarization plane rotating machines are arranged side by side every other row. Deposition chamber 1301
A bias electrode 1310, which also serves as a gas pipe, for applying a DC bias or a high frequency bias is provided between the facing applicators. Since the other structure is almost the same as that of the embodiment shown in FIG. 11, the description thereof will be omitted.

In this embodiment, when electric discharge is generated, the electric field directions of the microwaves introduced from the opposing applicators intersect at a right angle (90 °), and the electric fields of the microwaves introduced from the adjacent applicators are arranged side by side. By making the directions perpendicular to each other, the microwave interference was minimized and the discharge could be generated. After the electric discharge was generated, the film formation was performed by controlling the electric field direction of the microwave with a polarization plane rotating machine so that a high-quality film quality could be obtained over a large area.

Also in this example, it was possible to generate a discharge by minimizing the interference of microwaves, and to perform stable discharge and uniform film formation over a large area. Next, an example according to the fourth configuration of the present invention will be described.

In the fourth structure of the present invention, a rectangular columnar film forming chamber is formed with the belt-like substrate as one wall surface of the film forming chamber, and the belt-like substrate is conveyed in the direction (abbreviated as direction L) and the traveling direction of microwaves. A microwave power input means (hereinafter abbreviated as an applicator) is arranged so that and are parallel to each other, and further, a source gas is introduced into the film forming chamber and the pressure in the film forming chamber is kept under a predetermined reduced pressure. When more microwave power is input,
It was found that plasma having a desired density distribution in the direction L can be generated in the film forming chamber.

The fourth structure of the present invention has been completed as a result of further studies based on the above-mentioned findings, and is a roll-to-roll type microwave plasma CVD whose main points are as described below. It is a device.

The device of the present invention is as follows. That is, while continuously moving the strip-shaped substrate in the longitudinal direction, a quadratic prism-shaped film forming chamber having the moving strip-shaped substrate as one wall surface is formed, and at least two kinds of source gases having different compositions are supplied to the film forming chamber. Separately introduced, and at the same time, microwave power is applied from the applicator to generate plasma in the film forming chamber, and a roll-to-film forming a composition-controlled deposited film is formed on the surface of the strip-shaped substrate exposed to the plasma. It is a roll type microwave plasma CVD apparatus.

In the above-mentioned apparatus of the present invention, the strip-shaped substrate forms one wall surface of the film forming chamber formed in the shape of a quadrangular prism. The wall surfaces of the film forming chamber other than the strip substrate are made of a conductive material (for example, aluminum or stainless steel).

Of course, the shape of the film forming chamber is not limited as long as it has a columnar shape that satisfies the requirement that the applicator is installed and the strip-shaped substrate is one wall surface.

Microwave power is applied to the film forming chamber through at least one or more applicators which are arranged so as to penetrate from one side or both sides of both end faces having a normal line to the direction L of the film forming chamber. To do.

Further, the microwave power is supplied to the film forming chamber through a microwave transparent member provided between the film forming chamber and the applicator.

A film having a rectangular prism shape is formed by arranging the applicator so as to be substantially parallel to the direction L (that is, substantially at a right angle to the width direction of the strip substrate) within a range in which the applicator is not in contact with the microwave transparent member. Apply microwave power to the room.

Microwave power is applied from the applicator over the length of the film forming chamber in the direction L with a desired power density distribution.

Microwave power is applied from the applicator over the length of the film forming chamber in the direction L with a desired power density distribution in order to have a composition distribution.

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

In the above apparatus of the present invention, the microwave power supplied to the film forming chamber having a rectangular column shape is prevented from leaking out of the film forming chamber.

In the apparatus of the present invention, the gas introduced into the film forming chamber is exhausted through the opening provided in the wall surface of the film forming chamber facing the strip substrate.

In the above apparatus of the present invention, when the deposited film forming raw material gas is introduced into the film forming chamber, the deposited film forming raw material gas discharged from the gas supply means is uniformly distributed in the width direction of the strip substrate. Further, it is desirable that the gas is discharged in one direction toward the strip-shaped substrate in the vicinity of the gas supply means. And
The gas supply means are arranged parallel to the strip-shaped substrates. It is desirable that the gas supply means is arranged so as to be included in the film forming chamber having a rectangular column shape so that the raw material gas for forming the deposited film is surely excited and decomposed. Further, in order to give the deposited film a desired composition distribution, it is desirable to appropriately adjust the arrangement of the gas supply means.

The functional deposited film formed by the above apparatus of the present invention includes SiGe, SiC, GeC and Si.
So-called IV group semiconductor thin films such as Sn, GeSn, SnC, GaA
s, GaP, GaSb, InP, InAs, etc., so-called III-
Group V compound semiconductor thin film, ZnSe, ZnS, ZnTe,
So-called II-VI group compound semiconductor thin films such as CdS, CdSe, CdTe, CuAlS ₂ , CuAlSe ₂ , CuAlT
e ₂ , CuInS ₂ , CuInSe ₂ , CuInTe ₂ , C
uGaS ₂ , CuGaSe ₂ , CuGaTe ₂ , AgIn
Se _2, AgInTe ₂ Hitoshishoi I-III-VI compound semiconductor thin film, ZnSiP _2, ZnGeAs _2, CdSiA
s _2, CdSnP ₂ Hitoshishoi II-IV-V group compound semiconductor thin _{film, Cu 2 O, TiO 2,} In 2 O 3, SnO 2, ZnO,
Examples include so-called oxide semiconductor thin films such as CdO, Bi ₂ O ₃ , and CdSnO ₄ , and those containing a valence electron control element for valence electron control of these semiconductors. Further, a so-called group IV semiconductor thin film such as Si, Ge, C containing a valence electron control element can be mentioned. Of course a-
In an amorphous semiconductor such as Si: H, a-Si: H: F,
The hydrogen and / or fluorine content may be changed.

By controlling the composition of the above-mentioned semiconductor thin film, forbidden band width control, valence electron control, refractive index control,
Crystal control and the like are performed. By controlling the composition in the vertical direction or the horizontal direction on the band-shaped substrate, a large area thin film semiconductor device having excellent electrical, optical and mechanical characteristics can be manufactured.

That is, the forbidden band width and / or the valence electron density are changed in the vertical direction of the semiconductor layer to improve the carrier traveling property, or the recombination of carriers at the semiconductor interface is prevented to improve the electrical characteristics. .

Further, the light transmittance into the semiconductor layer can be improved by continuously changing the refractive index to form an optically non-reflective surface. Furthermore, stress is relieved by changing the hydrogen content and the like to give a structural change, and a deposited film having high adhesion to the substrate can be formed.

By forming semiconductor layers having different crystallinity in the lateral direction, for example, a photoelectric conversion element formed of an amorphous semiconductor and a switching element formed of a crystalline semiconductor can be continuously formed on the same substrate at the same time. Can be formed.

By the way, when the band gap control is applied to the p-i-n type photovoltaic element, a-SiGe: H, a-SiG
e: F, a-SiGe: H: F, a-SiC: H, a-
When a so-called group IV alloy-based semiconductor such as Si: F, a-SiC: H: F is used for the i-type semiconductor layer, the forbidden band width (bandgap: Eg ^opt ) from the light incident side is appropriately changed. Open circuit voltage (Voc) and fill factor (FF: Fi
ll Factor) is proposed to be significantly improved.
(20th IEEE PVSC, 1988 A NOVEL DESIGN FORAMORPHOUS
SILICON SOLAR CELLS, S. GuhaJ. Yang et al.).

14 (a) to 14 (d) show specific examples of bandgap profiles. The → mark in each figure represents the incident side of light.

The bandgap profile shown in FIG. 14 (a) has a constant bandgap from the light incident side. The bandgap profile shown in FIG. 14B is of a type in which the bandgap on the light incident side is narrow and the bandgap gradually widens, and is effective in improving FF. The bandgap profile shown in FIG. 14C is of a type in which the bandgap on the light incident side is wide and the bandgap is gradually narrowed, and is effective in improving Voc. The bandgap profile shown in FIG. 14D is a type in which the bandgap on the light incident side is wide, the bandgap narrows relatively steeply, and then widens again. The effect of both can be obtained simultaneously by combining with c).

With the above apparatus of the present invention, for example, a-
Si: H and (Eg ^opt = 1.72 eV) and a-SiG
FIG. 14 using e: H (Eg ^opt = 1.45 eV)
An i-type semiconductor layer having the bandgap profile shown in (d) can be produced. In addition, a-SiC: H
(Eg ^opt = 2.05 eV) and a-Si: H (Eg ^opt =
1.72 eV), an i-type semiconductor layer having a bandgap profile shown in FIG. 14C can be manufactured.

The applicator in the above device of the present invention will be described in detail below.

The applicator in the above-mentioned apparatus of the present invention has a structure capable of supplying microwave power supplied from a microwave power source to the film forming chamber, ionizing the raw material gas for forming the deposited film, and maintaining discharge. I have. Specifically, a waveguide having an open end is preferably used. Specific examples of the waveguide include a waveguide for microwave transmission such as a circular waveguide, a rectangular waveguide, and an elliptical waveguide. Here, the open end can prevent standing waves from fluttering at the end of the waveguide. On the other hand, even if the end portion of the waveguide is a closed end, if microwave power is consumed before the microwave reaches the end portion, there is no particular problem.

In the above-mentioned device of the present invention, the size of the circular waveguide used is appropriately designed according to the microwave frequency band (band) and mode used. In designing, it is preferable to consider transmission loss in the circular waveguide so that multiple modes are not generated as much as possible. Specifically, other than EIAJ standard circular waveguide, etc., it is 2.45 GHz. As our own standard for
Examples thereof include those having inner diameters of 90 mm and 100 mm.

For the transmission of microwaves from the microwave power source, it is preferable to use a rectangular waveguide, which is relatively easy to obtain. However, the transmission loss of microwave power is minimized in the conversion portion into a circular waveguide. It is necessary to suppress it to the limit, and specifically, it is preferable to use an electromagnetic horn type rectangular or circular conversion waveguide.

Further, in the above-mentioned device of the present invention, the type of the rectangular waveguide used is appropriately selected depending on the frequency band (band) and mode of the microwave used, and at least its cutoff frequency is used. It is preferable that the frequency is lower than the specified frequency. Specifically, in addition to standard products such as JIS, EIAJ, IEC, and JAN,
As an in-house standard for 2.45 GHz, a rectangular cross-section having an inner diameter of 96 mm width × 27 mm height can be mentioned.

In the apparatus of the present invention, as long as the applicator of the present invention is used, the microwave power supplied from the microwave power source is efficiently input to the film forming chamber, so that the problem of so-called reflected waves can be easily avoided. In a wave circuit, it is possible to maintain a relatively stable discharge without using a microwave matching circuit such as a stub tuner or an E-H tuner, but it is stronger due to abnormal discharge before or after the start of discharge. When a reflected wave is generated, it is desirable to provide a matching circuit to effectively use the microwave power.

At least one or more holes for radiating microwaves are formed in the waveguide on one side thereof, and these holes are sized and spaced so that microwave power can be input with a desired density distribution. It needs to be open.

A typical circular waveguide hole used in the above device of the present invention is shown in FIGS. The holes of the rectangular waveguide are shown in FIGS. 17 and 18.

Waveguides 1501, 1 shown in the above figures
Holes 1502 formed in 601, 1701, 1801
It is desirable that the shapes of 1602, 1702, and 1802 are substantially rectangular, and as shown in FIGS. 15 and 16, when a plurality of waveguides 1602, 1702, and 1802 are opened in the longitudinal direction from the vicinity of the end of the waveguide at desired intervals. Are some of the holes 15
By opening or closing 02, 1702, plasma having a desired density distribution is generated in the moving direction of the strip-shaped substrate to be used.

When only one hole is formed as shown in FIGS. 16 and 18, the aspect ratio of the square is large, and the dimension is larger than one wavelength of the microwave in the longitudinal direction of the waveguide. It is desirable to be able to open over almost the entire width and length. Then, in order to adjust the distribution of the microwave power density radiated in the longitudinal direction, a shutter whose opening degree can be controlled is provided.

Typical shapes of the shutter as described above are shown in FIGS. 19 (a) to 19 (c) and 20 (a) to 20 (d).

Shutters 1901 to 1903 shown in FIGS. 19A to 19C are used in the circular waveguide shown in FIGS. 15 and 16, respectively.
Each of the shutters 2001 to 2004 shown in (d) is used in the rectangular waveguide shown in FIGS. 17 and 18.

The shape of each of the above shutters is a strip shape, a slender trapezoidal shape, and a shape in which a part of one side of the strip or slender trapezoidal shape is cut out in a half-moon shape, which follows the surface shape of the waveguide. Is preferable, and the material thereof is preferably a metal or a conductive-treated resin. And
The end of the hole is fixed to a connecting part provided near the corner of the hole close to the microwave power source, and the opening degree is adjusted with this as a fulcrum, but after the desired conditions are set, the stability of the plasma is improved. Therefore, it may be fixed.

When a hole having a large aspect ratio is used, it is desirable that the long side be substantially equal to the dimension in the moving direction L of the film forming chamber.

Further, it is preferable that the shutter electrically contacts the waveguide only at the connecting portion, and it is preferable that the waveguide and the shutter are electrically insulated at a place other than the connecting portion. If a contact is additionally provided between the shutter and the rectangular waveguide, this becomes an arc contact.

By the way, as shown in FIG.
When microwave power is applied from both ends of the film forming chamber 2104 in parallel to the moving direction of 01 by the applicators 2102, larger microwave power can be supplied to the film forming chamber, and the plasma density can be further increased. In the above case, the microwave permeable member has two applicators 21 arranged separately from both ends of the film forming chamber.
It may be composed of one for each 02, but to prevent the interference between microwaves, the applicator 210
A partition plate 2103 made of a conductive material is provided near the end of
It is desirable to provide (for example, wire mesh, metal plate, punching board).

Further, as shown in FIG. 22, a strip substrate 220 is provided.
1 in the width direction of the applicator 2202 parallel to the strip-shaped substrate 2201 and parallel to each other in two or more rows.
By arranging, it becomes possible to deal with a wider strip substrate. That is, uniform microwave power can be input in the width direction of the wide strip substrate. Also, as shown in FIG.
A T-shaped electrode 2203 that also serves as a gas pipe is arranged in the width direction of the strip-shaped substrate, and a bias voltage is applied.

The applicator using the holes described above is a so-called "leaky wave" type microwave radiation structure.

On the other hand, in the fourth structure of the present invention, a slow wave circuit type applicator may be used. When a slow wave circuit is used, most of microwave power is transmitted as surface waves. Therefore, the microwave power has a drawback that the amount of coupling to the plasma sharply decreases as the distance increases in the lateral direction with respect to the microwave structure, but in the fourth configuration of the present invention, the applicator is removed from the plasma region. Separation can solve this drawback.

In the present invention, a desired microwave power density distribution can be created in the direction L by controlling the opening shape of the holes with the shutter of the applicator. It is also possible to make them uniform. It is possible to form a deposited film whose composition is controlled from two or more kinds of source gases by utilizing the dissociation rate of the source gas according to the microwave power density distribution. Further, if the microwave power supplied to the film forming chamber is uniform in the direction L, a uniform deposited film can be formed over a large area by adjusting the means for introducing the raw material gas for forming the deposited film, and the composition-controlled deposited film can be formed. Can be formed.

In the apparatus of the present invention having the above-mentioned structure, the stability and distribution of plasma are determined by, for example, the type and shape of the applicator, the pressure in the film forming chamber during film formation, the microwave power, the degree of plasma confinement, Since various parameters such as the volume and shape of the film forming chamber are intricately entangled and maintained, it is difficult to find the optimum conditions with only a single parameter, but with the following trends and condition ranges: is there.

The pressure is preferably 3 to 10 mTorr to 100 to 200 mTorr. For microwave power, 300-700W to 1500-3000
W is preferred.

Further, it was found that when the amount of microwave power leaked from the plasma region was large, the stability of the plasma was lost, and microwaves were blocked in the gap between the strip-shaped substrate and the wall of the film forming chamber 1/10. It is desirable that the wavelength is set to the wavelength or less.

FIG. 23 is a schematic diagram showing a schematic structure of a typical microwave plasma CVD apparatus used in the method of forming the a-Si: H film.

Reference numeral 2301 is a belt-shaped substrate, 2302 is a side wall of the film forming chamber, 2303 is an end surface wall of the film forming chamber, 2304 is a side wall, which is an exhaust port provided with a microwave leakage prevention measure.
Reference numeral 305 is a gas pipe / bias electrode, 2306 is an applicator, 2307 is a separating means, and 2308 is a wire mesh. The microwave CVD apparatus described later basically has the configuration shown in FIG.

[Experimental Example 4-1] FIG. 24 shows the fourth example of the present invention.
It is a figure which shows the structure of the microwave plasma CVD apparatus of a roll-to-roll system by the structure of FIG.

First, a vacuum container 2401 having a substrate delivery mechanism was thoroughly degreased and washed to obtain SUS430B.
A strip-shaped substrate (width 60 cm x length 100 m x thickness 0.2
(mm) bobbin 2403 is set, and the belt-shaped substrate 2404 is attached to the gas gate 2405 and the vacuum container 24.
Via the transport mechanism in 06 and the gas gate 2407,
Passing up to a vacuum container 2402 having a substrate winding mechanism,
The tension was adjusted so that slack would not occur.

Therefore, each of the vacuum vessels 2401 and 4022 and the vacuum vessel 2406 is roughly evacuated by a rotary pump (not shown), and then a mechanical booster pump (not shown) is activated to evacuate to a pressure of around 10 ^-3 Torr and then temperature control is further performed. The mechanism 2408 is used to increase the substrate surface temperature to 28
While maintaining the temperature at 0 ° C., an oil diffusion pump (HS-32 manufactured by Varian) (not shown) was evacuated to 5 × 10 ⁻⁶ Torr or less.

At the time of sufficient degassing, the raw material gas was introduced through the respective gas introduction pipes under the conditions shown in FIG.
The pressure inside the film formation chamber 2409 was maintained at 12 mTorr by adjusting the opening of the throttle valve attached to the oil diffusion pump. At this time, the pressure inside the vacuum container 2406 is 4 mT.
It was orr. Effective pressure (= input power-reflected power) from a microwave oscillation mechanism (not shown) when the pressure is stable.
Then, a microwave of 1.2 kW was input through the applicator 2410. The introduced raw material gas is immediately ionized,
A plasma region was formed. The formed plasma regulates the area of the wire mesh 2411 (wire diameter 1 mm, interval 5 mm).
No leak to the vacuum container side, and no microwave leak was detected.

Then, the supporting / conveying roller and the supporting / conveying ring (both of which have drive mechanisms not shown) are activated, and the conveying speed of the belt-shaped substrate 2404 is 1.2 m / mi.
It was controlled to be n.

H ₂ gas of 50 sccm as a gate gas is made to flow through the gas gates 2405 and 2407 through the gate gas introduction pipes 2412 and 2413, and the exhaust ports 2414 and 2
It was exhausted from an oil diffusion pump (not shown) from 415, and the pressure inside the gas gate was controlled to be 1 mTorr.

[0237] The deposited film was continuously formed for 30 minutes after the conveyance was started. Since a long strip-shaped substrate is used, another deposited film is continuously formed after the end of this experimental example, and after all deposition is completed, the strip-shaped substrate is cooled and taken out to form in this experimental example. The film thickness distribution of the deposited film on the strip-shaped substrate measured in the width direction and the longitudinal direction was within 5%, and the deposition rate was 44 Å / average.
It was sec. A portion of the substrate on which the deposited film is formed is arbitrarily cut out at six places, and SIMS (ims manufactured by CAMECA)
-3f) was used to analyze the composition of the deposited film in the depth direction, the depth profiles shown in FIG. 26 were obtained, respectively, and it was found that the band gap profile shown in FIG. 14B was formed. . In addition, the total hydrogen content in the film was quantified using a hydrogen analyzer in metal (EMGA-1100, manufactured by Horiba Ltd.) and found to be 18 ± 2 atomic%.

[Experimental Example 4-2] Following the deposition film forming step carried out in Experimental Example 4-1, the introduction of the raw material gas used was stopped and the internal pressure of the vacuum container 2406 was set to 5 × 10 ⁻⁶ Torr.
After evacuation to r or less, the raw material gas is introduced through the respective gas introduction pipes under the conditions shown in FIG. 27, and the internal pressure is 10 mTorr.
The deposited film was continuously formed under the same conditions except that the temperature was maintained at r and the microwave power was set to 1.1 kW.

After the completion of this experimental example and other experimental examples, the substrate was cooled and taken out, and the film thickness distribution of the deposited film formed in this experimental example was measured in the width direction and the longitudinal direction, and it was within 5%. And the average deposition rate is 51Å
/ Sec.

[0240] A part of the substrate on which the deposited film is formed is optionally 6
Cut out at a place, SIMS (ims-3 manufactured by CAMECA)
When f) was used to analyze the composition of the deposited film in the depth direction, the depth profiles shown in FIG. 28 were obtained, respectively.
It was found that the band gap profile shown in FIG. 4 (d) was formed. In addition, hydrogen analyzer in metal (EMG
A-1100, manufactured by Horiba Ltd.) was used to quantify the total amount of hydrogen in the film, which was 17 ± 2 atomic%.

[Experimental Example 4-3] Following the deposited film forming step carried out in Experimental Example 4-1, the introduction of the raw material gas used was stopped and the internal pressure of the vacuum chamber 2406 was set to 5 × 10 ⁻⁶ Torr.
After evacuating to r or less, the raw material gas is introduced from each gas introduction pipe under the conditions shown in FIG. 29, and the internal pressure is set to 19 mTorr.
The deposited film was continuously formed under the same conditions except that the temperature was maintained at r and the microwave power was set to 1.8 kW.

After the completion of this experiment example and other experiment examples, the substrate was cooled and taken out, and the film thickness distribution of the deposited film formed in this experiment example was measured in the width direction and the longitudinal direction, and it was within 5%. And the average deposition rate is 55Å
/ Sec.

A part of the substrate on which the deposited film is formed is optionally 6
Cut out at a place, SIMS (ims-3 manufactured by CAMECA)
When f) was used to analyze the composition of the deposited film in the depth direction, the depth profiles shown in FIG. 30 were obtained, respectively.
It was found that the bandgap profile shown in 4 (c) was formed. In addition, hydrogen analyzer in metal (EMG
A-1100, manufactured by Horiba Ltd.) was used to quantify the total amount of hydrogen in the film, and it was 14 ± 2 atomic%.

[Experimental Example 4-4] The internal pressure of the vacuum chamber was set to 5 ×, similarly to the deposited film forming step performed in Experimental Example 4-1.
After evacuating to 10 ^-6 Torr or less, raw material gas was introduced from each gas introduction pipe under the conditions shown in FIG. 31, the internal pressure was kept at 6 mTorr, and the microwave power was set to 1.9 kW under the same conditions. The deposited film was continuously formed by.

After the completion of this experimental example and other experimental examples, the substrate was cooled and taken out, and the film thickness distribution of the deposited film formed in this experimental example was measured in the width direction and the longitudinal direction. The average deposition rate was 112Å. / Sec.

A part of the substrate on which the deposited film is formed is optionally 6
Cut out at a place, SIMS (ims-3 manufactured by CAMECA)
When the composition analysis in the depth direction of the deposited film was performed using f), the depth profiles shown in FIG.
It was found that the doping profile shown in FIG. 4 (d) was formed. In addition, a hydrogen analyzer in metal (EMGA-
1100, manufactured by Horiba Ltd.), the total amount of hydrogen in the film was determined to be 17 ± 2 atomic%.

[Summary of Experimental Examples] The above-mentioned Experimental Examples 4-1 to 4
-4 revealed that a large area functionally deposited film whose composition was controlled by the above method of the present invention could be continuously formed. In Experimental Examples 4-1 to 4-3, a uniform microwave power density distribution was utilized to control the composition by selecting the gas supply method.

In Experimental Example 4-4, the difference in the microwave power dependence of the gas dissociation rate depending on the gas species was superimposed on the microwave power density distribution inclined in the moving direction (direction L) of the strip substrate in the film forming chamber. Then, the composition was controlled.

[Example 4-1] Using the fourth structure of the present invention, a pin type photovoltaic element having a layer structure shown in the schematic sectional view of FIG. 33 was produced by the apparatus shown in FIG.

The electromotive force element comprises a lower electrode 3302, an n-type semiconductor layer 3303, and an i-type semiconductor layer 3 having a bandgap profile shown in FIG. 14D on a substrate 3301.
A photovoltaic element 3300 is formed by depositing 304, a p-type semiconductor layer 3305, a transparent electrode 3306, and a collector electrode 3307 in this order. In this photovoltaic element, it is premised that light is incident from the transparent electrode 3306 side.

First, a strip substrate made of SUS430BA was set in a continuous sputtering apparatus, an Ag (99.99%) electrode was used as a target to form a 1000 Å Ag thin film, and a ZnO (99.999%) electrode was continuously targeted. Used as a sputter-deposited ZnO thin film of 1.2 μm,
The lower electrode 3302 was formed.

Subsequently, the strip substrate on which the lower electrode 3302 was formed was set in the continuous deposited film forming apparatus shown in FIG.

The apparatus shown in FIG. 34 has two vacuum vessels 3401 and 34 having the same structure as the vacuum vessel 2406 shown in FIG.
03 and a vacuum chamber 3402 provided with applicators at both ends of a film forming chamber having the same structure as in FIG. 21 are provided in the gas gate. The other structure is similar to that of the apparatus shown in FIG. 24, and therefore its explanation is omitted. Further, FIG. 35 shows the conditions for forming a deposited film in the vacuum container 3401 at the time of actual production.

In the vacuum vessels 3401 and 3403, n-type a-Si: was formed under the deposition film forming conditions shown in Table 10.
An H: F film and a p-type μc-Si: H: F film were formed.

[0255]

[Table 10] First, plasma is generated in each film forming chamber, and when the discharge is stabilized, the belt-like substrate is transported at a speed of 48 cm / mi.
It was conveyed from the left side to the right side in FIG. 34 by n, and the n, i, and p-type semiconductor layers were continuously laminated.

After the semiconductor layers were laminated and formed over the entire length of the strip-shaped substrate, they were cooled and taken out, and further, a solar cell module having a size of 35 cm × 70 cm was continuously produced by a continuous modularizing device.

Regarding the manufactured solar cell module, A
When the characteristics were evaluated under irradiation with M1.5 (100 mW / cm) light, a photoelectric conversion efficiency of 7.5% or more was obtained.
Furthermore, the variation in characteristics between modules was within 5%.

The rate of change of the photoelectric conversion efficiency with respect to the initial value after continuous irradiation of AM1.5 (100 mW / cm) light for 500 hours was measured and found to be within 9.5%.

A power supply system of 5 kW could be produced by connecting these modules.

[Example 4-2] In this example, a photovoltaic element having the layer structure shown in FIG. 36 was produced.

A triple photovoltaic element 36 shown in FIG.
24 has a structure in which the photovoltaic elements shown in FIG. 33 are stacked in three stages. Between the lower electrode 3602 on the substrate 3601 and the transparent electrode 3606, an n-type semiconductor layer 3603, i
P including a p-type semiconductor layer 3604 and a p-type semiconductor layer 3605
In-junction photovoltaic element 3620 and n-type semiconductor layer 36
14, a pin-junction photovoltaic element 3621 including an i-type semiconductor layer 3615 and a p-type semiconductor layer 3616, an n-type semiconductor layer 3617, an i-type semiconductor layer 3618, and a p-type semiconductor layer 3
A pin junction type photovoltaic element 3623 made of 619 is laminated, and a collector electrode 3607 is provided on the transparent electrode 3606.

The device shown in FIG. 34 was used to manufacture the photovoltaic device having the above-mentioned structure. In actual manufacture, three sets of vacuum vessels 3401 to 3403 were connected in series in this order via the gas gate. A further connected device (not shown) was used.

In manufacturing the photovoltaic device having the layer structure shown in FIG. 36, the photovoltaic device 3620 serving as the lower cell is the leftmost one of the three sets of vacuum containers, and the photovoltaic device 3621 serving as the intermediate cell is vacuum. The photovoltaic element 3623, which is the center of the three sets of containers and serves as the upper cell, was formed by the rightmost one of the three sets of the vacuum containers.

The conditions for forming the deposited film in the vacuum chamber 3402 at this time are shown in FIG. 37 and Table 11.

[0265]

[Table 11] Regarding the created solar cell module, A. M1.5
When the characteristics were evaluated under irradiation with light of (100 mW / cm ² ), the photoelectric conversion efficiency was 10.8% or more, and the characteristic variation between the modules was within 5%.

In addition, A. M1.5 (100mW / c
The rate of change of the photoelectric conversion efficiency with respect to the initial value after continuous irradiation with m ² ) light for 500 hours was measured and found to be within 8.5%. It was possible to fabricate a 5 kW power supply system by continuously using these modules. [Example 4-3]
A container equipped with a microwave plasma CVD type film forming chamber using the apparatus of the present invention has a high frequency (for example, 13.56M).
H ₂ ) A multilayer film continuous film forming system having an apparatus configuration as shown in FIG. 38, which is connected to a vacuum container having a plasma CVD film forming chamber through a gas gate, is possible.

Three vacuum vessels 3801 shown in FIG.
To 3803, the vacuum container 3801 and the vacuum container 3
In 803, a deposited film is formed by a high frequency plasma CVD method, and in a vacuum container 3802 arranged in the center, a deposited film is formed by a microwave plasma CVD method according to the present invention.

In this example, a pin type photovoltaic element having the same layer structure as the photovoltaic element shown in FIG. 33 was produced by the apparatus of the multilayer film continuous film forming method shown in FIG. The electromotive force element will be described with reference to FIG.

The photovoltaic element 3300 is a strip substrate 330.
1 on the lower electrode 3302 n-type semiconductor layer 3303, FIG.
The i-type semiconductor layer 3304, the p-type semiconductor layer 3305, and the transparent electrode 3 having the band gap profile shown in (d).
A photovoltaic element 3300 is formed by sequentially depositing and forming 306 and a collecting electrode 3307. In the photovoltaic element of this example, light is incident from the transparent electrode 3306 side.

The conditions for producing the lower electrode, the transparent electrode and the current collecting electrode are the same as in Example 4-1.

In the vacuum vessels 3801 and 3803,
The deposited film is formed by the high frequency plasma CVD method, and the microwave plasma CVD according to the present invention is performed in the vacuum container 3802.
The deposited film is formed by the method. Vacuum vessels 3801 and 3
The plasma in 803 is generated by the high frequency supplied to the counter plate electrode in parallel with the strip substrate moving through the container.

The electrode area is 35 cm wide and 1 m long.

Conditions for forming a deposited film in the vacuum vessels 3801 and 3803 are shown in FIG. 39 and Table 12.

[0274]

[Table 12] Regarding the manufactured solar cell module, A. M1.5
When the characteristics were evaluated under irradiation with light of (100 mW / cm ² ), a photoelectric conversion efficiency of 11.0% or more was obtained, and the characteristic variation between modules was within 5%.

AM1.5 (100 mW / cm ² )
The rate of change of the photoelectric conversion efficiency with respect to the initial value after continuous irradiation with light for 500 hours was measured and found to be within 8.5%.

A power supply system of 5 kW could be produced by connecting these modules.

Next, a fifth embodiment of the present invention will be described.

The fifth structure of the present invention is, in a microwave plasma CVD apparatus for continuously forming a deposited film on a belt-shaped substrate, a vacuum chamber, a discharge chamber provided in the vacuum chamber, and penetrated by the belt-shaped substrate. , A microwave power input means in the discharge chamber, the length of the wall surface of the discharge chamber is at least one of the wavelength of the microwave in the moving direction of the strip substrate in at least one of the loading / unloading part of the strip substrate of the discharge chamber. It is characterized in that it is 1/2 or more and the distance from the strip substrate is 1/2 or less of the wavelength of the microwave. Then, the action is to form a weak plasma at the interface of the deposited film to reduce the ion bombardment to the surface of the belt-like substrate, and to form the deposited film at a relatively slow deposition rate in the environment where the ion bombardment is reduced. In addition, it is possible to improve the characteristics due to the physical properties of the interface and mass-produce photovoltaic elements with few defects.

Then, by using the microwave plasma CVD apparatus of the present embodiment described above to form a deposited film, the above-mentioned problems are solved and the above-mentioned requirements are satisfied, and a continuously moving strip-shaped substrate. A high-quality deposited film with few defects can be formed thereon.

The microwave plasma CVD apparatus having the fifth structure of the present invention will be described in detail below.

FIG. 40 is a schematic view showing the structure of the main part of the fifth structure of the present invention, and FIG. 41 is a view showing the microwave plasma CVD apparatus shown in FIG. It is a schematic sectional drawing of an apparatus.

A discharge chamber 4001 is provided in a vacuum container 4000.
The first, second, and third film forming chambers 4002, 4003, and 4004 formed by the strip-shaped substrate 4019 and the substrate 4019. The vacuum container and the discharge chamber 4001 are metallic and electrically connected to each other. The belt-shaped substrate 4019 is introduced into the discharge chamber 4001 through the gas gate (see FIG. 41) attached to the left side of the vacuum container in the drawing, that is, the side wall on the carry-in side, and the first, second, and third film forming chambers 4002 are provided. , 400
3,4004, respectively, on the right side of the vacuum vessel in the figure,
That is, the gas is discharged to the outside of the vacuum container through the gas gate attached to the side wall on the carry-out side.

Here, on the wall surface of the discharge chamber 4001, the carry-in section 4017 and the carry-out section 40 through which the strip substrate 4019 penetrates.
18, in the moving direction of the strip substrate 4019,
The structure is close to the deposition film formation surface of the belt-shaped substrate 4019 (lower side in FIG. 40) over the length L1 up to the distance L2. The distances L1 and L2 satisfy the relationship of L1 ≧ λ / 2 L2 ≦ λ / 2 with respect to the wavelength λ of the microwave introduced into the discharge chamber 4001.

In each of the film forming chambers 4002, 4003 and 4004, the first, second and third applicators 4005 and 4400 are provided.
006 and 4007 are arranged in parallel along the moving direction of the belt-shaped substrate 4019. Applicator 4005 to 4007
Are for introducing microwave power into the film forming chambers 4002 to 4004, respectively, and are waveguides 4124, 4125, 412 whose one ends are connected to a microwave power source (not shown).
6 (see FIG. 41) are connected to each other. Further, the connecting portions between the applicators 4005, 4006 and 4007 and the respective film forming chambers are formed by microwave transmitting members 4008, 4009 and 4010, respectively.

Further, first, second, and third gas introducing means 4011 to 4013 for releasing the raw material gas are attached to the bottom surfaces of the film forming containers 4001 to 4003, respectively. The gas introducing units 4011 to 4013 are strip substrates 401.
A large number of gas discharge holes are arranged on the surface facing the plate 9.
These gas releasing means 4011 to 4013 are connected to a gas supply facility (not shown). Further, exhaust punching boards 4014 to 4016 are attached to the opposite side of the applicators 4005 to 4007, that is, the side wall on the front side in the drawing, and the microwave power is confined in the film forming chamber and the exhaust pipes 4115 and 4116 (see FIG. 41). The exhaust throttle valves 4111 and 4112 (see FIG. 41) connected to the exhaust gas are connected to exhaust means (not shown) such as a vacuum pump. The device shown in FIG. 41 has a strip substrate 4019.
For feeding and winding vacuum containers 4101 and 4102, and a vacuum container 4000 for producing the first conductivity type layer
This is an apparatus in which a vacuum container 4000 for producing n-type and i-type layers and a vacuum container 4000p for producing second conductivity type layers are connected via gas gates.

Vacuum container 4000 for preparing first conductivity type layer
n and a vacuum container for producing the second conductivity type layer 4000p
In the vacuum container 4000 for the i-type layer production described above, a single applicator is used for the structure inside the vacuum container 4000.
In n and 4000p, film-forming chambers are formed by the discharge chambers 4001n and 4001p and the belt-shaped substrate 4019 each having a substantially rectangular parallelepiped shape. The vacuum containers 4000n and 4000p and the film forming chambers 4001n and 4001p are metallic and are electrically connected to each other.

Reference numeral 4103 is a bobbin for sending out the strip substrate 4019, and 4104 is a bobbin for winding the strip substrate 4019, and the strip substrate 4019 is conveyed in the direction of the arrow in the figure. Of course, this can also be reversed and conveyed.
In addition, in the vacuum containers 4101 and 4102, the strip-shaped substrate 40
The interleaving paper winding and feeding means used for surface protection of 19 may be provided. As the material of the interleaving paper,
Heat-resistant resins such as polyimide, Teflon and glass wool are preferably used. Numerals 4105 and 4106 are transport rollers for adjusting tension and positioning the belt-shaped substrate. 4109 and 4110 are pressure gauges. 4111
n, 4111, 4112, 4112p, 4107, 41
08 is a throttle valve for adjusting conductance, 41
15n, 4115, 4116, 4116p, 4113,
Reference numeral 4114 denotes an exhaust pipe, which is connected to an exhaust pump (not shown).

4138, 4139, 4117, 4118
Is a gas gate, 4119, 4120, 4121,
Reference numeral 4122 is a gate gas introduction pipe, which is connected to a gas supply facility (not shown). 4005n, 4005, 4
006, 4007, 4005p are applicators for introducing microwaves. Microwave transparent member is attached to the tip of the applicator,
Waveguide 4123, 4124, 4125, 4126, 41
Through 27, it is connected to a microwave power source (not shown).

Each film forming container 4001n, 4001, 400
A large number of infrared lamp heaters 4128, 412 are provided on the opposite side of the film forming chamber with the 1p band-shaped substrate 4019 interposed therebetween.
9, 4130 and lamp houses 4131, 4132, 4133 for efficiently concentrating the radiant heat from these infrared lamp heaters on the belt-shaped substrate 4019, respectively. Further, thermocouples 4134 to 4137 for monitoring the temperature of the strip substrate 4019 at four places are connected so as to be in contact with the strip substrate 4019.

(Wall Shape of Discharge Chamber) In the fifth configuration of the present invention, the wall surface of the discharge chamber has a shape close to the strip-shaped substrate over a predetermined length in at least one of the loading / unloading portion of the strip-shaped substrate. There is.

In general, in order to efficiently introduce microwave power into the discharge chamber and generate a strong plasma, the wall of the discharge chamber should be placed away from the belt-shaped substrate by about the wavelength of the introduced microwave. Is preferable, and for example, when the microwave is 2.45 GHz, the microwaves are separated by about 12 cm. On the contrary, in order to generate a weak plasma, the wall surface of the discharge chamber is not longer than ½ of the wavelength of the microwave in the moving direction of the strip substrate, preferably over the length of the wavelength. It is desirable that they are arranged close to each other up to a distance of ½ or less of the wavelength, preferably ¼ or less of the wavelength.

In the loading / unloading part of the strip-shaped substrate, a portion where the distance from the strip-shaped substrate to the wall surface of the discharge chamber is 1/2 or less of the wavelength of microwave is 1/1 of the wavelength of microwave.
If the length is 2 or more, the distance from the strip substrate to the wall surface of the discharge chamber may change with respect to the moving direction of the strip substrate. For example, it may be changed such that it gradually becomes longer, gradually becomes shorter, or changes stepwise in the moving direction of the strip substrate.

Further, as disclosed in Japanese Patent Laid-Open No. 3-30419, when the moving strip-shaped substrate forms almost the entire wall surface of the discharge chamber, the strip-shaped substrate surrounding the plasma is used as the discharge chamber. Considering this as a wall, this wall surface is made to be close to the strip-shaped substrate at least at one of the loading / unloading part of the strip-shaped substrate to / from the film formation space.

(Applicator) As the applicator in the fifth structure of the present invention, the one having the structure shown in FIG. 42 is preferably used.

In FIG. 42, reference numerals 4201 and 4202 denote microwave permeable members, which are fixed to the inner cylinder 4204 and the outer cylinder 4205 by using a metal seal 4212 and a fixing ring 4206 and are vacuum-sealed. There is. In addition, the refrigerant 4 is placed between the inner cylinder 4204 and the outer cylinder 4205.
209 is made to flow and is sealed at one end with an O-ring 4210.
It is designed to uniformly cool the whole. Refrigerant 4209
As such, water, freon, oil, cooling air, etc. are preferably used. Microwave matching disks 4203 and 4208 are fixed to the microwave transparent member 4201. A choke flange 4207 having a groove 4211 formed therein is connected to the outer cylinder 4205. Also, 4213,
Reference numeral 4214 is an inlet and an outlet for cooling air, which are used to cool the inside of the applicator.

(Strip-shaped substrate) As a material of the strip-shaped substrate which is preferably used in the fifth structure of the present invention, there is little deformation and distortion at the temperature required for manufacturing a semiconductor film,
It is preferable to have desired strength and conductivity, specifically, a thin metal plate such as stainless steel, aluminum and its alloys, iron and its alloys, copper and its alloys, and a composite thereof. , And thin metal films of different materials and / or SiO _{2 on} their surfaces,
An insulating thin film such as Si ₃ N ₄ , Al ₂ O ₃ or AlN which has been surface-coated by a sputtering method, a vapor deposition method, a plating method or the like. Further, polyimide, polyamide, polyethylene terephthalate, a sheet made of heat-resistant resin such as epoxy or these and glass fiber, carbon fiber,
Examples include those obtained by subjecting the surface of a composite with boron fibers, metal fibers, etc., to a surface of a metal alone or an alloy, and conducting conductive treatment by a method such as plating, vapor deposition, sputtering or coating with a transparent conductive oxide (TCO) or the like. .

Further, the thickness of the belt-shaped substrate is as thin as possible in consideration of cost, storage space and the like as long as it is within a range in which the curved shape produced during the transportation by the transportation means can be maintained. Is preferable. Specifically, 0.
It is desirable that the thickness is from 05 mm to 1 mm, but when a thin plate made of metal or the like is used, the desired strength can be easily obtained even if the thickness is relatively thin.

The width of the belt-like substrate is not particularly limited, and is determined by the size of the semiconductor film forming means, its container or the like.

The length of the strip substrate is not particularly limited, and may be such a length that it can be wound into a roll, and a long one is further lengthened by welding or the like. It may be.

When the belt-shaped substrate is electrically conductive such as metal, it may be used as an electrode for direct current extraction, and when it is electrically insulating such as synthetic resin, it may be formed on the surface of the side where the semiconductor film is formed. Al, Ag, Pt, Au, Ni, Ti, M
o, W, Fe, V, Cr, Cu, stainless steel, brass, nichrome, SnO ₂ , In ₂ O ₃ , ZnO, SnO ₂ −
So-called simple metal or alloy such as In ₂ O ₃ (ITO),
Further, it is desirable that the transparent conductive oxide (TCO) is surface-treated in advance by a method such as plating, vapor deposition, and sputtering to prepare an electrode for current extraction.

When the strip-shaped substrate is a non-translucent one such as metal, it is necessary to form a reflective conductive film on the strip-shaped substrate for improving the reflectance of long wavelength light on the substrate surface. Is preferred. Examples of materials preferably used as the material of the reflective conductive film include Ag, Al, and Cr.

Further, a metal layer or the like is used as a reflective conductive film for the purpose of preventing mutual diffusion of constituent elements between the substrate material and the semiconductor film, or serving as a buffer layer for preventing short circuit, and the semiconductor on the substrate is It is preferably provided on the side where the film is prepared. ZnO is mentioned as a material suitably used for the buffer layer.

In the case where the band-shaped substrate is relatively transparent and the solar cell has a layer structure in which light is incident from the side of the band-shaped substrate, a conductive thin film such as a transparent conductive oxide or a metal thin film is previously prepared. It is desirable to make a deposition.

The surface property of the strip substrate may be a so-called smooth surface or may have a minute uneven surface. In the case of forming a minute concavo-convex surface, it has a spherical shape, a conical shape, a pyramidal shape, and the maximum height (Rmax) is preferably 50.
When the thickness is set to nm to 500 nm, the light reflection on the surface becomes irregular reflection, and the optical path length of the reflected light on the surface increases.

(Gas Gate) In the fifth configuration of the present invention, the vacuum container for feeding and winding the strip-shaped substrate and the vacuum container for semiconductor film formation are separated and independent, and the strip-shaped substrate is pierced through them to be continuous. A gas gate means is preferably used for efficient transport. The cross-sectional shape of the gas gate is a slit shape or a shape similar to this, and the dimensions thereof are calculated and designed using a general conductance calculation formula in combination with the entire length thereof and the exhaust capacity of the exhaust pump used. Further, it is preferable to use a gate gas together to enhance the separation ability. For example, Ar and H
A rare gas such as e, Ne, Kr, Xe, or Rn, or a diluent gas for producing a semiconductor film such as H ₂ may be used. The gate gas flow rate is appropriately determined depending on the conductance of the entire gas gate, the capacity of the exhaust pump used, and the like. For example, a pressure gradient as shown in FIG. 43 may be created. In FIG. 43, if a point at which the pressure is maximized is provided approximately in the center of the gas gate, the gate gas flows from the center of the gas gate to the vacuum container side on both sides, and mutual gas diffusion between the containers on both sides is minimized. Can be suppressed to In practice, the optimum conditions are determined by measuring the amount of gas that diffuses using a mass spectrometer and analyzing the composition of the semiconductor film.

Each of FIGS. 44 to 46 is a schematic explanatory view showing a typical example of a photovoltaic element manufactured using the deposited film forming apparatus of the fifth constitution of the present invention.

In the example shown in FIG. 44, the strip substrate 4401, the lower electrode 4402, the first conductivity type layer 4403 and the i type layer 44 are used.
04, a second conductivity type layer 4405, an upper electrode 4406, and a collector electrode 4407.

The example shown in FIG. 45 is a so-called tandem type in which two photovoltaic elements 4511 and 4512 using two types of semiconductor layers having different band gaps and / or layer thicknesses as i-type layers are laminated. It is a photovoltaic element, and is a strip substrate 4501, a lower electrode 4502, and a first conductivity type layer 4.
503, an i-type layer 4504, a second conductivity type layer 4505, a first conductivity type layer 4503, an i-type layer 4504, a second conductivity type layer 4505, an upper electrode 4506, and a collector electrode 4507.

The example shown in FIG. 46 is formed by stacking three photovoltaic elements 4611, 4612, 4613 using three types of semiconductor layers having different band gaps and / or layer thicknesses as i-type layers. It is a so-called triple type photovoltaic device, and includes a strip substrate 4601, a lower electrode 4602, and a first electrode.
Conductivity type layer 4603, i type layer 4604, second conductivity type layer 4605, first conductivity type layer 4603, i type layer 4604,
Second conductivity type layer 4605, first conductivity type layer 4603, i
Type layer 4604, second conductivity type layer 4605, upper electrode 46
06 and a collector electrode 4607.

The construction of these photovoltaic elements will be described below.

Band- shaped substrate The band-shaped substrate (4401, 4501, 4601) is preferably made of a flexible material, and may be conductive or electrically insulating.
Furthermore, they may be translucent or non-translucent, but if the light is incident from the side of the strip substrate, it is of course translucent. is necessary.

[0312] appropriate electrodes are selected and used by the configuration form of the electrode photovoltaic device. Examples of those electrodes include a lower electrode, an upper electrode (transparent electrode), and a collector electrode (however, the upper electrode here means one provided on the light incident side, and the lower electrode is The one provided facing the upper electrode with the semiconductor layer sandwiched therebetween is shown).

These electrodes will be described in detail below.

(I) Lower electrode As the lower electrode (4402, 4502, 4602),
The surface of the strip-shaped substrate (4401, 4501, 4601) that is irradiated with light for generating photovoltaic power varies depending on whether or not the material of the strip-shaped substrate (4401, 4501, 4601) is transparent (for example, the strip-shaped substrate is non-translucent such as metal). 44-46, when the upper electrode (4406, 4506, 4606) is formed as a transparent electrode, light for generating photovoltaic power is emitted from the upper electrode side. , The installation location is different.

Specifically, in the case of the layer structure as shown in FIGS. 44 to 46, the strip substrates (4401, 4501, 460) are used.
1) and the first conductivity type layer (4403, 4503, 460)
3) and is provided. However, when the strip-shaped substrate is conductive, the strip-shaped substrate can also serve as the lower electrode. However, even if the strip-shaped substrate is conductive, if the sheet resistance is high, the lower electrode may be used as a low-resistance electrode for current extraction or for the purpose of effectively utilizing incident light by increasing the reflectance on the substrate surface. (4402, 4502, 460
2) may be installed.

As electrode materials, Ag, Au, Pt, N
Examples thereof include metals such as i, Cr, Cu, Al, Ti, Zn, Mo, and W, or alloys thereof. Thin films of these metals are formed by vacuum evaporation, electron beam evaporation, sputtering, or the like. Further, the produced metal thin film must be considered so as not to 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 10Ω or less.

Lower electrodes (4402, 4502, 460)
2) and the first conductivity type layer (4403, 4503, 460)
Although not shown in the figure, a buffer layer for preventing short-circuiting and diffusion of ZnO or the like may be provided between the same and 3). The effect of the buffer layer is not only to prevent the metal element forming the lower electrode from diffusing into the first conductivity type layer, but also to provide a small resistance value so that the lower portion provided with the semiconductor layer sandwiched therebetween. The effects of preventing a short circuit caused by a defect such as a pinhole between the electrode and the upper (transparent) electrode, and causing multiple interference due to a thin film to confine the incident light in the photovoltaic element are given. be able to.

(II) Upper Electrode (Transparent Electrode) The upper (transparent) electrode (4406, 4506, 4606) has a light transmittance for efficiently absorbing light from the sun or white fluorescent lamps into the semiconductor layer. Is preferably 85% or more, and the sheet resistance value is 100 so that it does not electrically become a resistance component to the output of the photovoltaic element.
Ω or less is desirable. Materials having such characteristics include SnO ₂ , In ₂ O ₃ , ZnO, CdO, Cd ₂
Examples thereof include metal oxides such as SnO ₄ and ITO (In ₂ O ₃ + SnO ₂ ), and metal thin films in which a metal such as Au, Al, and Cu is formed into an extremely thin semitransparent film. Since the transparent electrode is laminated on the second conductivity type layer 505 layer in FIG. 8, it is necessary to select those having good adhesion to each other.
A resistance heating vapor deposition method, an electron beam heating vapor deposition method, a sputtering method, a spray method, or the like can be used as a method for manufacturing these, and they are appropriately selected as needed.

(III) Collector Electrode The collector electrode (4407, 4507, 4607) is provided on the upper (transparent) electrode for the purpose of reducing the surface resistance value of the upper (transparent) electrode (4406, 4506, 4606). To be As electrode material, Ag, Cr, Ni, Al, A
Examples thereof include thin films of metals such as g, Au, Ti, Pt, Cu, Mo and W or alloys thereof. These thin films can be laminated and used. The shape and area of the semiconductor layer are appropriately designed so that a sufficient amount of light is incident on the semiconductor layer.

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

The sheet resistance value is preferably 50Ω or less, more preferably 10Ω or less.

[0322] As a material used for the first and second conductivity type layers first and second conductivity type layer,
A non-single-crystal semiconductor composed of one or more kinds of atoms of Group IV of the periodic table is suitable. Furthermore, the conductive layer on the light irradiation side is most preferably a microcrystallized semiconductor. The grain size of the fine crystals is preferably 3 nm to 20 nm, and most preferably 3 n.
m to 10 nm.

When the conductivity type of the first or second conductivity type layer is n-type, as the additive contained in the first or second conductivity type layer, an atom of Group VA of the periodic table is suitable. There is. Among them, phosphorus (P), nitrogen (N), arsenic (As) and antimony (Sb) are most suitable.

When the conductivity type of the first or second conductivity type layer is p-type, the group IIIA element of the periodic table is suitable as the additive contained in the first or second conductivity type layer. . Among them, boron (B), aluminum (Al), and gallium (Ga) are most suitable.

The layer thickness of the first and second conductivity types is preferably 1 nm to 50 nm, optimally 3 nm to 10 nm.

Further, in order to further reduce light absorption in the conductive layer on the light irradiation side, it is preferable to use a semiconductor layer having a band gap larger than that of the semiconductor forming the i-type layer. For example, when the i-type layer is amorphous silicon, it is optimal to use non-single crystal silicon carbide for the conductive type layer on the light irradiation side.

I-Type Layer As the semiconductor material used for the i-type layer, Si, Ge, which is composed of one or more atoms of Group IV of the periodic table,
Semiconductors such as C, SiC, GeC, SiSn, GeSn, and SnC can be given. As a III-V group compound semiconductor,
GaAs, GaP, GaSb, InP, InAs, II-
ZnSe, ZnS, ZnT as group VI compound semiconductor
e, CdS, CdSe, CdTe, CuAlS ₂ , CuAlSe ₂ CuAl as a group I-III-VI compound semiconductor
Te ₂ , CuInS ₂ , CuInSe ₂ , CuInTe ₂ ,
CuGAs ₂ , CuGaSe ₂ , CuGaTe, AgIn
Se ₂ , AgInTe ₂ , II-IV-V group compound semiconductors include ZnSiP ₂ , ZnGeAs ₂ , CdSiAs ₂ ,
CdSnP ₂ , Cu ₂ O, Ti as oxide semiconductor
O ₂ , In ₂ O ₃ , SnO ₂ , ZnO, CdO, Bi ₂ O ₃ ,
CdSnO ₄ may be mentioned respectively.

Furthermore, the layer thickness of the i-type layer is the same as that of the fifth aspect of the present invention.
It is an important parameter that influences the characteristics of the photovoltaic element having the above structure. The preferable layer thickness of the i-type layer is 100 nm to 100 nm.
0 nm and the optimum layer thickness is 200 nm to 600 nm. It is desirable that these layer thicknesses be designed within the above range in consideration of the absorption coefficient of the i-type layer and the interface layer and the spectrum of the light source.

The following are source gases suitable for the microwave glow discharge decomposition method for forming the first and second conductivity type layers, i-type layer and interface layer.

As the source gas for supplying Si, Si
In the gas state of H ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H _10, etc.,
In addition, silicon hydrides (silanes) that can be gasified are mentioned as being effectively used, and in particular, SiH ₄ , Si ₂ H _{6 and the} like are easy to handle in layer formation work and good in Si supply efficiency.
Are preferred.

Many halogen compounds are effective as the raw material gas for supplying halogen atoms. For example, a halogen gas, a halide, an interhalogen compound, a halogen-substituted silane derivative, or the like in a gas state or a gasifiable halogen. A compound is preferably mentioned.

Further, a silicon compound containing halogen atoms, which contains silicon atoms and halogen atoms as constituent elements and is in a gas state or which can be gasified, can be cited as an effective one.

Specific examples of the halogen compound that can be preferably used include halogen gas of fluorine, chlorine, bromine and iodine, BrF, ClF, ClF ₃ , BrF ₅ and BrF ₃ .
Interhalogen compounds such as IF ₃ , IF ₇ , ICl and IBr can be mentioned.

As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom,
Specifically, for example, SiF ₄ , Si ₂ F ₆ , SiCl ₄ , Si
A halogenated silicon such as Br ₄ can be mentioned as a preferable one.

The above-mentioned halogen compounds or silicon compounds containing halogen atoms are effectively used as the raw material gas for supplying halogen atoms, but in addition, halogenated compounds such as HF, HCl, HBr and HI are used. Hydrogen, SiH ₃ F, SiH ₂ F ₂ , SiHF ₃ , SiH ₂ I ₂ ,
SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHB
Halogen-substituted silicon hydrides such as r _{3 and the} like, and halides having a hydrogen atom as one of the constituent elements, which are in a gas state or can be gasified, can also be cited as effective raw material gases.

Halides containing these hydrogen atoms are as follows:
Since a hydrogen atom, which is extremely effective for controlling electrical or photoelectric properties, is supplied simultaneously with the supply of the halogen atom into the layer formed during the layer formation, the preferable halogen atom in the fifth structure of the present invention. Used as a source gas for supply.

As the source gas for supplying hydrogen atoms,
Besides H₂, Or SiH_Four, Si ₂H₆, Si₃H₈, S
i_FourH_TenAnd hydrogenated silicon.

As a gas for supplying germanium atoms, G
eH_Four, Ge₂H₆, Ge₃H₈, Ge_FourH_Ten, Ge_FiveH₁₂,
Ge₆H₁₄, Ge₇H₁₆, Ge₈H₁₈, Ge₉H₂₀Etc. hydrogen
Germanium oxide and GeHF₃, GeH₂F₂, GeH
₃F, GeHCl₃, GeH₂Cl ₂, GeH₃Cl, Ge
HBr₃, GeH₂Br₂, GeH₃Br, GeHI₃, G
eH₂I₂, GeH₃Hydrogenated halogenated germanium such as I
A halide containing a hydrogen atom, such as aluminum, as one of the constituent elements,
GeF_Four, GeCl_Four, GeBr_Four, GeI_Four, GeF ₂,
GeCl₂, GeBr₂, GeI₂Halogenated germanium
Examples thereof include germanium compounds such as nickel.

Examples of the carbon atom-containing compound as a raw material for supplying carbon atoms include saturated hydrocarbons having 1 to 4 carbon atoms,
Examples thereof include ethylene-based hydrocarbons having 2 to 4 carbon atoms and acetylene-based hydrocarbons having 2 to 3 carbon atoms.

Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C
₃ H ₈ ), n-butane (n-C ₄ H ₁₀ ), pentane (C ₅ H
₁₂ ), ethylene-based hydrocarbons include ethylene (C
₂ H ₄ ), propylene (C ₃ H ₆ ), butene-1 (C
₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C
₄ H ₈ ), pentene (C ₅ H ₁₀ ), and acetylene hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like.

Examples of the raw material gas containing Si, C and H as constituent atoms include alkyl silicides such as Si (CH ₃ ) ₄ and Si (C ₂ H ₄ ) ₄ .

When glow discharge is used to form a layer containing a group III atom or a group V atom, the starting material used as a source gas for forming the layer is the starting material for the silicon atom described above. A starting material for supplying a group III atom or a group V atom is added to an appropriately selected material. The starting material for supplying such a group III atom or a group V atom may be a gas-state substance containing a group III atom or a group V atom as a constituent atom or a gasified substance capable of being gasified. Any of them may be used.

What is effectively used as a starting material for supplying a Group III atom is specifically B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H for supplying a boron atom. ₁₁ , B
Boron hydride such as ₆ H ₁₀ , B ₆ H ₁₂ and B ₆ H ₁₄ , BF ₃ and BC
l _3, there may be mentioned BBr ₃ boron halide such as such as the other _{AlCl 3, GaCl 3, InCl 3} , Tl
Cl ₃ etc. can also be mentioned.

As a starting material for supplying a group V atom, those effectively used are, specifically, for supplying a phosphorus atom, phosphorus hydride such as PH ₃ , P ₂ H ₄ or the like, PH ₄ I. , P
F ₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , P
_{I 3, AsH 3, AsF 3} , AsCl 3, AsBr 3, As
F ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbC
_{l 5, BiH 3, BiCl 3} , BiBr 3, N 2, NH 3, H
_{2 NNH 2, HN 3, NH} 4 N 3, F 3 N, F 4 N 2 or the like can also be mentioned.

Gases for supplying oxygen atoms include oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N ₂ O), and nitrogen trioxide ( N ₂ O ₃ ), trinitrogen oxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitric oxide (NO ₃ ), silicon atom (S
i), oxygen atom (O) and hydrogen atom (H) as constituent atoms, for example, lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ) are listed. it can.

Gases for supplying nitrogen atoms include nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NN)
H ₂ ), hydrogen azide (HN ₃ ), ammonium (NH
There may be mentioned nitrogen compounds such as gaseous or gasifiable nitrogen such as ₄ N ₃ ), nitrogen compounds and azides. In addition to these, halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be mentioned in terms of supplying halogen atoms in addition to supplying nitrogen atoms. be able to.

Compounds containing a Group II atom of the periodic table, which are used for forming a II-VI group compound semiconductor, include:
Specifically, Zn (CH ₃ ) ₂ , Zn (C ₂ H ₅ ) ₂ , Zn
(OCH ₃ ) ₂ , Zn (OC ₂ H ₅ ) ₂ , Cd (CH ₃ ) ₂ ,
Cd (C ₂ H ₅ ) ₂ , Cd (CH ₃ ) ₂ , Cd (C ₂ H ₅ ) ₂ ,
_{Cd (C 3 H 7) 2} , Cd (C 4 H 9) 2, Hg (CH 3) 2,
Hg (C ₂ H ₅ ) ₂ , Hg (C ₆ H ₅ ) ₂ , Hg [(C = (C
₆ H ₅ )] _{2 and the} like. Specific examples of the compound containing an atom of Group VI of the periodic table include NO, N ₂ O, CO ₂ ,
CO, H ₂ S, SCl ₂ , S ₂ Cl ₂ , SOCl ₂ , Se
_{H 2, SeCl 2, Se 2} Br 2, Se (CH 3) 2, Se
(C ₂ H ₅ ) ₂ , TeH, Te (CH ₃ ) ₂ , Te (C
₂ H ₅ ) _{2 and the} like. Of course, these raw materials are 1
It is possible to use not only one kind but also a mixture of two or more kinds.

Examples of the valence electron control agent used for controlling the valence electrons of the II-VI group compound semiconductor include Periodic Tables I and II.
Compounds containing a group I, IV, or V atom can be cited as effective compounds. Specifically, as including a group I atom, LiCHLi (sec-CHg) _Lee SLi
Preferred examples include N and the like.

Further, as a compound containing a group III atom,
BX₃, B₂H₆, B_FourH_Ten, B_FiveH₉, B_FiveH₁₁, B₆H_Ten,
B (CH₃)₃, B (C₂H_Five)₃, B₆H₁₂, AlX₃, A
l (CH₃)₂Cl, Al (CH₃)₃, Al (OC
H₃)₃, Al (CH₃) Cl₂, Al (C₂H_Five)₃, Al
(OC₂H_Five)₃, Al (CH₃)₃Cl₃, Al (i-C_Four
H₉)₃, Al (i-C₃H₇)₃, Al (C₃H₇)₃, Al
(OC_FourH₉)₃, GaX₃Ga (OCH₃)₃, Ga (OC
₂H_Five)₃, Ga (OC₃H₇), Ga (OC_FourH₉)₃, Ga
(CH₃)₃, Ga₂H₆, GaH (C₂H_Five)₂, Ga (O
C₂H_Five), (C₂H_Five)₂, In (CH₃)₃, In (C_FourH
₇)₃, In (C_FourH₉)₃, As a compound containing a group V atom
Is NH₃, HN₃, N₂H_FiveN₃, N₂H_Four, NH_FourN₃, P
X₃, P (OCH₃)₃, P (OC₂H_Five)₃, P (C₃H₇)
₃, P (OC_FourH₉)₃, P (CH₃)₃, P (C₂H _Five)₃,
P (C_FourH₉)₃, P (OCH₃)₃, P (OC₂H_Five)₃, P
(OC₂H_Five)₃, P (OC₃H₇)₃, P (OC_FourH₉)₃,
P (SCN)₃, P₂H_Four, PH₃, AsH, AsH₃, A
s (OCH₃)₃, As (OC₂H_Five)₃, As (OC
₃H₇)₃, As (OC_FourH₉)₃, As (CH₃)₃, As
(C₆H_Five)₃, SbX₃, Sb (OCH₃)₃, Sb (OC
₂H_Five)₃, Sb (OC₃H₇)₃, Sb (OC_FourH₉)₃, S
b (CH₃) ₃, Sb (C₃H₇)₃, Sb (C_FourH₉)₃Etc.
Can be mentioned. [However, X is a halogen atom, specifically,
Show at least one selected from F, Cl, Br, and I
You ] Of course, these raw materials are not only one type, but two or more types.
It can also be used as a mixture.

As the valence electron controlling agent used for controlling the valence electrons of the III-V group compound semiconductor, periodic table II,
Compounds containing atoms of groups IV and VI can be cited as effective ones.

Specifically, as a compound containing a group II atom,
Is Zn (CH₃)₂, Zn (C₂H_Five)₂, Zn (OC
H₃)₂, Zn (C₂H_Five)₂, Cd (CH₃)₂, Cd (C₂
H_Five)₂, Cd (C₃H₇)₂, Cd (C_FourH₉)₂, Hg (C
H₃)₂, Hg (C₂H_Five)₂, Hg (C₆H_Five)₂, Hg [C
〓 C (C₆H_Five)]₂Etc. can be listed as effective
it can. Further, as the compound containing a group VI atom, NO,
N₂O, CO₂, CO, H ₂S, SCl₂, S₂Cl₂, SO
Cl₂, SeH₂, SeCl₂, Se₂Br₂, Se (C
H₃)₂, Se (C₂H_Five)₂, TeH, Te (CH₃)₂,
Te (C₂H_Five)₂Etc. Of course, these raw materials
Not only one substance but also two or more substances can be mixed and used.
it can. Further, the compound containing a group IV atom has been described above.
A compound can be mentioned.

The above-mentioned raw material compounds are He, Ne, Ar,
Noble gases such as Kr, Xe, Rn, and H ₂ , H
It may be introduced by mixing with a diluting gas such as F or HCl.

As a material forming the gas introducing means arranged in the fifth structure of the present invention, a material which is not damaged in plasma is preferably used. In particular,
Heat-resistant metals such as stainless steel, nickel, titanium, niobium, tantalum, tungsten, vanadium, and molybdenum, and those obtained by thermal spraying ceramics such as alumina, silicon nitride, and quartz, and alumina, silicon nitride, quartz, etc. Ceramics alone, and
Examples thereof include those composed of a complex.

In the fifth structure of the present invention, in order to control the plasma potential of the plasma generated in the film forming chamber, the bias voltage may be applied to the film forming chamber by the bias voltage applying means made of a conductive member. As the bias voltage, it is preferable to apply a DC voltage, a pulsating current, and an AC voltage alone or in combination with each other. By controlling this plasma potential, plasma stability, reproducibility,
In addition, the film characteristics are improved and the defects are reduced.

By using the microwave plasma CVD apparatus having the above-mentioned fifth structure of the present invention, the above-mentioned problems can be solved and the above-mentioned requirements can be satisfied, and high quality can be obtained on a continuously moving strip-shaped substrate. Thus, a deposited film with few defects can be formed.

Specific examples of the apparatus for continuously producing the photovoltaic element having the fifth structure of the present invention will be shown below, but the present example is not limited to these examples.

[Example 5-1] Photovoltaic devices were continuously manufactured using the apparatus shown in FIG.

First, a vacuum container 4301 having a substrate delivery mechanism is thoroughly degreased and washed, and a silver thin film of 100 nm and Z is formed as a lower electrode by a sputtering method.
SUS430BA strip substrate 4019 (width 120 mm x length 200 m x thickness 0.
13 mm) wound bobbin 4303 is set, the strip-shaped substrate 4019 is used as a gas gate, a vacuum container 4000n for producing a first conductivity type layer, a vacuum container 4000 for producing an i-type layer, and a second conductivity type layer. Vacuum container 4000p
Via a vacuum container 41 having a belt-like substrate winding mechanism.
The tension was adjusted to such an extent that slack did not occur by passing through 02.

Therefore, each vacuum container 4301, 4000
n, 4000, 4000p, and 4102 were evacuated to 1 × 10 ⁻⁶ Torr or less by a vacuum pump (not shown).

Next, the gas gates 4138, 4139, 4
117, 4118 at gate gas introduction pipes 4119, 412
H ₂ as a gate gas was made to flow from 0, 4121 and 4122 at 700 sccm each to heat the infrared lamp heater 4
128, 4129 and 4130 allow the strip-shaped substrate 4019
Were each heated to 350 ° C. And the gas introduction means 4
From 140, SiH ₄ gas 20 sccm, PH ₃ / H ₂
(1%) gas 200 sccm, H ₂ gas 200 sccm
cm, gas introducing means 4011, 4012, 4013 (see FIG. 40), 200 Scc of SiH ₄ gas, respectively.
m, H ₂ gas 200 sccm, gas introduction means 4141
The SiH ₄ gas at 30 sccm and BF ₃ / H ₂ (1
%) Gas and H ₂ gas at 250 sccm were introduced. The pressure in the vacuum container 4000n is 30 mTorr
The opening of the throttle valve 4111n was adjusted while observing the pressure gauge (not shown) so as to be r. Vacuum container 4000
The opening of the throttle valves 4111 and 4112 was adjusted while observing the pressure gauge (not shown) so that the internal pressure was 6 mTorr. The pressure in the vacuum container 4000p is 30
The opening of the throttle valve 4112p was adjusted while observing the pressure gauge (not shown) so as to be mTorr.

Thereafter, the microwave power is applied to the applicators 4005n, 4005, 4006, 4007, 4005.
The microwave power of 2.45 GHz is introduced into p, and the microwave power is 1 through each of the microwave permeable members.
000W, 300W, 300W, 300W, 1000W
Then, the strip-shaped substrate 4004 is conveyed in the direction of the arrow in the figure, and the first conductivity type layer, the i-type layer, and the second layer are formed on the strip-shaped substrate.
The conductivity type layer of was produced. Next, on the second conductivity type layer,
As a transparent electrode, ITO (In ₂ O ₃ + SnO ₂ ) was deposited by vacuum deposition to a thickness of 70 nm.
Was vacuum-deposited to a thickness of 2 μm to prepare a photovoltaic element. (Element No. Ex 1) Table 13 shows the above-mentioned conditions for producing the photovoltaic element.

[0362]

[Table 13] Here, the first conductivity type layer is an n-type layer, and the second conductivity type layer is a p-type layer.

In the carrying-in part 4035 and the carrying-out part 4036 of the strip-shaped substrate in the discharge chamber 4001 of the apparatus of FIG. 40, the wall surface of the discharge chamber extends over a length of 12 cm (microwave wavelength) in the moving direction of the strip-shaped substrate. , 3 cm from the deposition film formation surface of the strip substrate (1 / the microwave wavelength)
It was close to the distance of 4).

Further, the strip substrate 401 in the discharge chamber 4001
The distance between the strip-shaped substrate 4019 and the wall surface of the discharge chamber facing the strip-shaped substrate 4019 (the lower surface in FIG. 41) other than the carry-in part 4017 and the carry-out part 4018 of No. 9 was 15 cm.

[Comparative Example 5-1] Same as Example 5-1 except that the distance between the wall surface of the discharge chamber 4001 facing the strip substrate 4004 and the strip substrate 4004 was 15 cm over the entire length of the discharge chamber 4001. Then, a photovoltaic device having a nip structure was prepared. (Element No. ratio 1) [Example 5-2] Strip substrate 4004 in discharge chamber 4001
Under the same production conditions as in Example 5-1, except that the distance between the wall surface of the discharge chamber and the deposited film formation surface of the strip-shaped substrate was set to 3 cm only in the carry-in section 4035. A layer, an i-type layer, a second conductivity type layer, a transparent electrode, and a collector electrode were formed to prepare a photovoltaic element. (Element No. Ex 2) Photovoltaics created in Example 5-1 (Element No. Ex 1), Example 5-2 (Element No. Ex 2) and Comparative Example 5-1 (Element No. Ex 1) The photoelectric conversion efficiency, the characteristic uniformity, and the defect density of the power element were evaluated.

The photoelectric conversion efficiency and the uniformity of characteristics are as shown in Example 5-.
1 (element No. Ex 1), Example 5-2 (Element No. Ex 2) and Comparative Example 5-1 (Element No. Ratio 1), the photovoltaic elements on the strip-shaped substrate were set every 10 m. It was cut out in an area of 5 cm square, placed under AM-1.5 (100 mW / cm ² ) light irradiation, the photoelectric conversion efficiency was measured, and its average value and its variation were evaluated. The photoelectric conversion efficiencies of the photovoltaic elements of Example 5-1 (element No. Ex 1) and Example 5-2 (element No. Ex 2) were the same as those of Comparative Example 5-1 (element No. ratio 1). 1.12 times each based on the power device,
It was found to be excellent with 1.08 times. Also,
Table 14 shows the results of the characteristic evaluation in which the reciprocal of the magnitude of variation was obtained with the photovoltaic device of Comparative Example 5-1 (device No. ratio 1) as a reference.

[0367]

[Table 14] Note) The characteristic uniformity and the defect density are relative values based on Comparative Example 1. The defect densities are Example 5-1 (Element No. Ex 1), Example 5-2 (Element No. Ex 2), and Comparative Example 5-1 (Element N
o. The presence or absence of a defect in each photovoltaic element is detected by cutting out 100 areas of 5 cm square in the area of the central portion 5 m of the photovoltaic element on the strip-shaped substrate prepared in the ratio 1) and measuring the reverse current. Then, the defect density was evaluated. Table 14 shows the characteristic evaluation in which the reciprocal of the number of defects was obtained with the photovoltaic device of Comparative Example 1 (device No. ratio 1) as a reference.

As shown in Table 14, Example 5-1 was applied to the photovoltaic element of Comparative Example 5-1 (element No. ratio 1).
The photovoltaic element of (Element No. Ex 1) is excellent in conversion efficiency, characteristic uniformity and defect density,
It was found that the photovoltaic element manufactured by the manufacturing method of the fifth structure of the present invention has excellent characteristics, and the effect of the fifth structure of the present invention was verified.

[Embodiment 5-3] Next, a deposited film forming apparatus having a fifth structure of the present invention for forming a film forming chamber by bending a belt-shaped substrate in the carrying direction will be described.

In FIG. 47, reference numeral 4701 is a belt-like substrate, and supporting / conveying rollers 4702, 4703, 470.
4, 4705 and a supporting / transporting ring (not shown) keep the shape curved in a cylindrical shape, and the film is transported in the direction of the arrow in the drawing to continuously form the film forming chamber 4716. Four
Reference numeral 706 is a temperature control mechanism for heating or cooling the strip substrate 4701. Applicator 470 with this device
7, 4708 are provided so as to face each other, a microwave permeable member is provided at each of the tips thereof, and the rectangular waveguides are provided on the surface including the central axis of the supporting / conveying rollers. On the other hand, the planes including the long sides are arranged so as not to be vertical, and the planes including the long sides are not parallel to each other. Reference numeral 4709 denotes a gas introduction unit, which introduces the source gas into the film forming chamber by a gas supply facility (not shown). Supporting / transporting rollers 4702, 4703
The transport speed detection mechanism and the tension detection adjustment mechanism (not shown) are built in 4704 and 4705 to keep the transport speed of the belt-shaped substrate 4701 constant and the curved shape thereof constant.

Supporting / transporting rollers 4702, 4
703, 4704, 4705, the strip substrate 4701
In the carry-in part and the carry-out part of the strip-shaped substrate 4701 of the discharge chamber formed by the above, the discharge chamber wall (strip-shaped substrate) and the deposited film formation surface of the strip-shaped substrate are arranged close to each other at a distance L4 over the length L3. And the wavelength of the introduced microwave is λ
Then, the relationship of L3 ≧ λ / 2 L4 ≦ λ / 2 is satisfied.

FIG. 48 shows the film formation space shown in FIG. 47 as a vacuum container 4800n for forming a first conductivity type layer, a vacuum container 4800 for forming an i-type layer, and a vacuum container 4 for forming a second conductivity type layer.
This device is applied to 800p and continuously forms a functional deposited film.

The vacuum containers 4802 and 4803 for feeding and winding the belt-shaped substrate 4801 include the bobbin 4804 for feeding the belt-shaped substrate 4801 and the belt-shaped substrate 48.
01 winding bobbin 4805 is provided. Then, the strip substrate is conveyed in the direction of the arrow in the figure. Of course, this can also be reversed and conveyed. Further, the vacuum containers 4802 and 4803 may be provided with winding and feeding means of interleaving paper used for surface protection of the belt-shaped substrate 4801. As a material for the interleaving paper, heat-resistant resins such as polyimide, Teflon, and glass wool are preferably used. Reference numerals 4806 and 4807 are transport rollers for adjusting tension and positioning the belt-shaped substrate, 481.
Reference numeral 8,4819 is a pressure gauge.

4810, 4811, 4812, 480
8, 4809 is a throttle valve for adjusting conductance, 4815, 4816, 4817, 4813, 481.
Reference numeral 4 denotes an exhaust pipe, which is connected to an exhaust pump (not shown).

The microwave applicator is the same as that described above with reference to FIG.

Support / transport rollers 4802, 4
Band substrate 4801 by 803, 4804, 4805
Is a length (l3) of a portion of the loading / unloading portion of the strip-shaped substrate into / out of the discharge chamber in the vicinity of the strip-shaped substrate with respect to the moving direction of the strip-shaped substrate, and a distance (l4) between the strip-shaped substrates.
Was 4 cm.

Photovoltaic devices were continuously manufactured using the apparatus shown in FIG.

First, a vacuum container 4802 having a substrate feeding mechanism was thoroughly degreased and washed, and a silver thin film of 100 nm and Z was formed as a lower electrode by a sputtering method.
SUS430BA strip-shaped substrate 4801 (width 120 mm x length 200 m x thickness 0.
(13 mm) wound bobbin 4804 is set and passed through the belt-shaped substrate 4801, the gas gate, and the vacuum containers 4800n, 4800, 4800p for forming each layer to a vacuum container 4803 having a belt-shaped substrate winding mechanism, and a slack The tension was adjusted to the extent that there was not.

Therefore, each vacuum container 4802, 4803,
4800n, 4800 and 4800p were evacuated to 1 × 10 ⁻⁶ Torr or less by a vacuum pump (not shown).

Next, a gate gas introducing pipe 48 is attached to the gas gate.
H ₂ as a gate gas was made to flow at 700 sccm from 20,4821, 4822, and 4823, respectively, by a temperature adjusting mechanism and a heater (not shown) provided in each vacuum container.
Band-shaped substrate 4801 is set at 350 ° C, 350 ° C, 300
Heating to ℃, and Si from the gas introduction means 4813n
40 sccm of H ₄ gas and _{2 of} PH ₃ / H ₂ (1%) gas
00sccm, 400 sccm of H ₂ gas, 400 sccm of SiH ₄ gas and 200 sc of H ₂ gas in total from the gas introduction means tubes 4813n, 4813, 4813p.
cm, gas introduction means 4813p, SiH ₄ gas 2
0 sccm, BF ₃ (1%) gas 100 sccm, H ₂
Gas was introduced at 500 sccm.

The pressure in the vacuum container 4800n is 40 mT.
The opening of the throttle valve for adjusting the conductance was adjusted while observing the pressure gauge (not shown) so as to be orr.
The pressure inside the vacuum container 4800 is adjusted to 5 mTorr while watching the pressure gauge (not shown) and the conductivity valve 48.
The aperture of 06 was adjusted. The opening of the throttle valve 4812 was adjusted while observing the pressure gauge (not shown) so that the pressure in the vacuum container 4800p was 40 mTorr. And, the applicator 4824, 4825, 4826, 4827, 4 connected to each vacuum container with microwave power
828, 4829 through the microwave transparent member,
800 W of microwave power of 2.45 GHz,
800W, 500W, 500W, 800W, 800W were introduced.

Next, the strip substrate 4801 is conveyed in the direction of the arrow in the figure, and the first conductivity type layer, the i-type layer, and the
A second conductivity type layer was produced.

Next, ITO (In ₂ O ₃ + SnO ₂ ) as a transparent electrode was formed on the second conductivity type layer by vacuum evaporation to 70%.
nm was vapor-deposited, and Al was further vapor-deposited by vacuum vapor-depositing to a thickness of 2 μm as a collector electrode to prepare a photovoltaic element. (Element N
o. Ex. 3) Table 15 shows the conditions for making the above photovoltaic element.

[0384]

[Table 15] Here, the first conductivity type layer is an n-type layer, and the second conductivity type layer is a p-type layer.

The stacking order is from the upper column to the lower column in the table.

[Comparative Example 5-2] A photovoltaic element was prepared in the same manner as in Example 5-3, except that L3 was shortened to 3 cm. (Element No. ratio 2) [Example 5-4] Example 5 except that L3 was set to 15 cm.
A photovoltaic element was prepared in the same manner as in -3. (Element N
o. Ex 4) Photovoltaic elements of the photovoltaic devices prepared in Example 5-3 (Element No. Ex 3), Example 5-4 (Element No. Ex 4) and Comparative Example 5-2 (Element No. Ratio 2) The conversion efficiency, property uniformity, and defect density were evaluated.

The uniformity of characteristics is as shown in Example 5-3 (device No.
Ex 3), Example 5-4 (Element No. Ex 4) and Comparative Example 5-2 (Element No. Ratio 2) were applied to the photovoltaic elements on the strip-shaped substrate with an area of 5 cm square every 10 m. Cut out, A
Installed under M-1.5 (100 mW / cm ² ) light irradiation,
The photoelectric conversion efficiency was measured to obtain an average, and the variation in the photoelectric conversion efficiency was evaluated.

The photoelectric conversion efficiencies of the photovoltaic elements of Example 5-3 (element No. Ex 3) and Example 5-4 (element No. Ex 4) are comparative Example 5-2 (element No. ratio 2). It was found that they were excellent, being 1.06 times and 1.07 times, respectively, based on the photovoltaic element of.

Table 15 shows the results of the characteristic evaluation in which the reciprocal of the magnitude of variation was obtained with the photovoltaic device of Comparative Example 5-2 (device No. ratio 2) as a reference.

The defect densities are as shown in Example 5-3 (element No. Ex 3), Example 5-4 (element No. Ex 4) and Comparative Example 5.
-2 (element No. ratio 2), the photovoltaic element on the belt-shaped substrate was cut out from the central portion 5m in an area of 5 cm square, and 100 pieces of 5 cm square area were cut out to measure the reverse current. The defect density was evaluated by detecting the presence or absence of defects. The result of characteristic evaluation in which the reciprocal of the number of defects was obtained based on the photovoltaic element of Comparative Example 5-2 (element No. ratio 2) was the 16th value.
Shown in the table.

[0391]

[Table 16] Note) The characteristic uniformity and the defect density are relative values based on Comparative Example 2 as shown in Table 16, as compared with Example 3 for the photovoltaic element of Comparative Example 2 (element No. ratio 2). , 4 (element Nos. 3 and 4) are excellent in both characteristic uniformity and defect density, and the photovoltaic element manufactured according to the fifth constitution of the present invention is excellent. It was found to have characteristics, and the effect of the fifth configuration of the present invention was demonstrated.

[0390]

Since the present invention is constructed as described above, it has the following effects.

According to the first and second aspects, a film is formed on the microwave introduction window by providing a large number of gas diffusion suppressing tubes typified by ceramic tubes and controlling the diffusion of the raw material gas. There is an effect that it is possible to provide a film-forming apparatus capable of mass production, which can prevent this from occurring and can stably maintain plasma.

According to the third and fourth aspects, a film is formed on the microwave introduction window by providing a gas diffusion suppressing plate typified by a ceramic plate and controlling the diffusion of the raw material gas. Therefore, there is an effect that it is possible to provide a film forming apparatus capable of mass production, which can prevent the above-mentioned phenomenon and stably maintain plasma.

In the apparatus described in claim 5, the length of the p-type or n-type semiconductor thin film doped with impurities is not increased without destabilizing the plasma discharge and without unnecessarily increasing the size of the exhaust system. There is an effect that time continuous formation can be realized.

In the apparatus described in claims 6 and 7, by changing the electric field direction of the microwave before and after the discharge occurrence, discharge occurrence and stable discharge can be easily obtained, and high quality is achieved over a large area. The effect is that a uniform and uniform deposited film can be obtained.

Further, since the microwave power applied at the time of microwave generation is reduced, the microwave power source can be made to have a low output specification, and the device cost can be reduced.

In the apparatus described in claims 8 and 9, the microwave power input means is arranged parallel to the moving direction of the strip-shaped substrate forming the side wall of the film formation space, and the plasma is confined in the film formation chamber. By this, there is an effect that a large-area compositionally controlled functional deposition film can be continuously formed with good reproducibility.

Further, the apparatus of the present invention has an effect that a functional deposited film having an arbitrary band gap profile and doping profile can be efficiently and continuously formed on a continuously moving strip substrate.

By confining the plasma in the film forming chamber by the apparatus of the present invention, the stability and reproducibility of the plasma can be improved and the utilization efficiency of the deposited film forming raw material gas can be improved. Furthermore, by continuously transporting the belt-shaped substrate, a deposited film having an arbitrary composition distribution and film thickness can be continuously deposited over a large area with good uniformity. According to the apparatus of the present invention, it is possible to continuously form a functionally deposited film having a composition controlled with good uniformity on the surface of a strip substrate. Therefore, it can be suitably used as a mass-production machine of particularly high-efficiency large-area solar cells.

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

Further, since a deposited film can be formed under a low pressure, generation of polysilane powder can be suppressed, and polymerization of active species can be suppressed, so that defects can be reduced, film characteristics can be improved, and film characteristics can be improved. It is possible to improve stability.

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

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

According to the tenth aspect of the present invention, it is possible to continuously form a deposited film having excellent electric characteristics, particularly interface characteristics, over a large area while uniformly reducing characteristic unevenness and defects. Become.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view in the vicinity of a microwave introduction window, which is a main part of one embodiment according to the first configuration of the present invention.

FIG. 2 is a side view of what is shown in FIG.

FIG. 3 is a schematic perspective view of a microwave plasma CVD apparatus with an adhesion-preventing structure according to the first configuration of the present invention.

FIG. 4 is a modification of the main part of one embodiment according to the first configuration of the present invention.

FIG. 5 is a modification of the main part of one embodiment according to the first configuration of the present invention.

FIG. 6 is a schematic sectional view in the vicinity of a microwave introduction window, which is a main part of a second embodiment according to the first configuration of the present invention.

FIG. 7 is a perspective explanatory diagram as seen from the side of the one shown in FIG.

FIG. 8 is a diagram of one embodiment according to a second configuration of the present invention.

FIG. 9 is a diagram showing an apparatus used in an experiment conducted for completing the third configuration of the present invention.

FIG. 10 is a diagram showing a polarization plane rotator used in an example of the third configuration of the present invention.

FIG. 11 shows an apparatus for implementing the apparatus according to the third aspect of the present invention.

FIG. 12 shows an apparatus for implementing the apparatus according to the third aspect of the present invention.

FIG. 13 shows a device for implementing the device according to the third configuration of the invention.

14A to 14D are diagrams showing specific examples of bandgap profiles.

FIG. 15 is a diagram showing a typical hole of a circular waveguide used in a fourth structure of the present invention.

FIG. 16 is a diagram showing a typical hole of a circular waveguide used in a fourth structure of the present invention.

FIG. 17 is a diagram showing a typical hole of a rectangular waveguide used in the fourth configuration of the present invention.

FIG. 18 is a diagram showing a typical hole of a rectangular waveguide used in the fourth configuration of the present invention.

19 (a) to (c) are each a fourth embodiment of the present invention.
It is a figure which shows the typical shape of the shutter used for the structure of FIG.

FIG. 20 (a) to (d) are each a fourth embodiment of the present invention.
It is a figure which shows the typical shape of the shutter used for the structure of FIG.

FIG. 21 is a diagram showing an example of a film forming chamber for carrying out the fourth configuration of the present invention.

FIG. 22 is a diagram showing an example of a film forming chamber for carrying out the fourth configuration of the present invention.

FIG. 23 is a diagram showing a schematic configuration of an apparatus for carrying out a fourth configuration of the present invention.

FIG. 24 is a diagram showing a configuration of a continuous microwave plasma CVD apparatus according to a fourth configuration of the present invention.

FIG. 25 is a diagram showing film forming conditions in Experimental Example 4-1.

FIG. 26 is a diagram showing a depth profile of the element manufactured in Experimental Example 4-1.

FIG. 27 is a diagram showing film forming conditions in Experimental Example 4-2.

FIG. 28 is a diagram showing a depth profile of an element manufactured in Experimental Example 4-2.

FIG. 29 is a diagram showing film forming conditions in Experimental Example 4-3.

FIG. 30 is a diagram showing a depth profile of an element manufactured in Experimental Example 4-3.

FIG. 31 is a diagram showing film forming conditions in Experimental Example 4-4.

FIG. 32 is a diagram showing a depth profile of an element manufactured in Experimental Example 4-4.

FIG. 33 is a diagram showing a layer structure of a pin type photovoltaic element manufactured in Example 4-1.

FIG. 34 is a diagram showing a configuration of a continuous deposited film forming apparatus used in Example 4-1.

FIG. 35 is a diagram showing deposition film forming conditions in Example 4-1.

FIG. 36 is a diagram showing the layer structure of the photovoltaic element produced in Example 4-2.

FIG. 37 is a diagram showing conditions for forming a deposited film in Example 4-2.

FIG. 38 is a diagram showing the structure of a continuously deposited film forming apparatus used in Example 4-3.

FIG. 39 is a diagram showing conditions of deposited film formation in Example 4-3.

FIG. 40 is a schematic diagram showing a main configuration of a fifth configuration of the present invention.

41 is a schematic cross-sectional view of an apparatus for continuously forming a multilayer deposited film, which incorporates the deposited film forming apparatus shown in FIG. 40.

FIG. 42 is a diagram showing a structure of a microwave applicator preferably used in the fifth configuration of the present invention.

FIG. 43 is a diagram showing a pressure gradient of a gate gas flow rate in the fifth configuration of the present invention.

FIG. 44 is a schematic explanatory view showing a typical example of a photovoltaic element manufactured using the deposited film forming apparatus having the fifth structure of the present invention.

FIG. 45 is a schematic explanatory view showing a typical example of a photovoltaic element manufactured using the deposited film forming apparatus having the fifth structure of the present invention.

FIG. 46 is a schematic explanatory view showing a typical example of a photovoltaic element manufactured using the deposited film forming apparatus having the fifth structure of the present invention.

FIG. 47 is a diagram showing a structure of a film forming chamber used in Example 5-3.

FIG. 48 is a diagram showing the structure of an apparatus for continuously forming a functional deposited film used in Example 5-3.

FIG. 49 is a diagram showing a conventional deposition-inhibitory structure.

FIG. 50 is a diagram showing a conventional deposition-inhibitory structure.

FIG. 51 is a diagram showing a conventional deposition-inhibitory structure.

FIG. 52 is a diagram showing a conventional deposition-inhibitory structure.

FIG. 53 is a diagram showing a conventional microwave introduction method compatible with large-area film formation.

[Explanation of symbols]

100, 303, 801, 1301, 2409, 91
0, 2104, 4716 Film forming chamber 101 Circular waveguide 102, 602, 802 Microwave introduction window 103 Gas diffusion suppression tube 104 Gas pipe 106 Gas nozzle 107, 301, 911, 1102, 2101, 220
1,2301,2404,4019,4401,450
1, 4601, 4701, 4801 Belt-shaped substrate 108 Exhaust direction 101b Circular waveguide 102b Microwave introduction window 103b Ceramic tube 302a, 302b Support transport rollers 304a, 304b Support transport disk 305, 1310, 2203, 2305 Bias electrode 306 Gap 307 , 901 to 903, 1001 Rectangular waveguide 401, 501 Ceramic taper portion 601 Gas diffusion suppressing plate 701 Non-deposition gas suppressing plate 803 Microwave waveguide 804 Microwave power source 805, 4115n, 4115, 4116p, 411
6, 4113, 4114, 4813-4817 Exhaust pipe 806, 809 Raw material gas supply pipe 807, 3301, 3601 Substrate 808 Heater 810 Metal mesh 904-906, 1111a, 1111b, 1201-
1204, 1302 to 1309, 2102, 2202
2306, 2410, 4005n, 4005-400
7,4005p, 4200,4707,4708,48
24n, 4826, 4828p, 4825n, 482
7, 4829 Applicator 907-909, 1116-11119 Electric field direction 912 Exhaust board 1002 Cylindrical waveguide 1003 Polarization plane rotator 1004 Cylinder 1006, 1114 Coil 1101 Outer wall 1103 Transport direction 1104 Gas discharge port 1105 Gas supply means 1106 Raw material gas 1107 , 2304, 2414, 2415 Exhaust port 1108 Exhaust direction 1112, 4008-4010, 4201, 4202
Microwave permeable member 1113 Ferrite 1115 Microwave introduction direction 1303 Raw material gas release rod 1501, 1601, 1701, 1801, 4123-
4127 Waveguide 1502, 1503, 16021702, 1703, 1
802 holes 1901 to 1903, 2001 to 2004 Shutter 2103 Partition plate 2302 Side wall 2303 End face wall 4140, 4141, 4709 Gas introduction means 2307 Separation means 2308, 2411 Wire mesh 2401, 402, 2406, 3403 to 1403,
3801-3803, 4000, 4000n, 4000
p, 4101, 4102, 4800n, 4800, 48
00p, 4802, 4803 Vacuum container 2403 Bobbin 2412, 2413, 4119-4122, 4820
n, 4821, 4823p, 4822 Gate gas introduction pipes 2405, 2407, 4138n, 4139, 411
8,4117 Gas gate 2408,4706 Temperature control mechanism 3300,4511,4512,4611-4613
Photovoltaic device 3302, 3602, 4402, 4502, 4602
Lower electrode 3303, 3603, 3614, 3617 N-type semiconductor layer 3304, 3604, 3615, 3618 i-type semiconductor layer 3305, 3605, 3616, 3619 p-type semiconductor layer 3306, 3606 Transparent electrode 3307, 3507, 4407, 4507, 4607
Current collecting electrode 2620, 3621, 3623 pin junction type photovoltaic element 3624 Triple type photovoltaic element 4001, 4001n, 4001p Discharge chamber 4002 First film forming chamber 4003 Second film forming chamber 4004 Third film forming chamber 4005 1st applicator 4006 2nd applicator 4007 3rd applicator 4011 1st gas introduction means 4012 2nd gas introduction means 4013 3rd gas introduction means 4111n, 4111, 4112p, 4112, 410
7,4108 Exhaust throttle valve 4014-4016 Exhaust punching board 4129,4128n, 4130p Infrared lamp heater 4132,4131n, 4133p Lamp house 4134n, 4135,4136p, 4137 Thermocouple 4017 Carry-in part 4018 Carry-out part 4203,4208 Microwave matching circle Plate 4204 Inner cylinder 4205 Outer cylinder 4206 Fixing ring 4207 Choke flange 4209 Refrigerant 4210 O-ring 4211 Groove 4213 Discharge hole 4214 Inlet hole 4103, 4804 Sending bobbin 4104, 4805 Winding bobbin 4105, 4106, 4806, 4807 Transfer roller 4109, 4110, 4818, 4819 Pressure gauge 4403, 4503, 4603 First conductivity type layer 4404, 4504 4604 i-type layer 4405,4505,4605 second conductivity type layer 4702～4705,4803 support, transport rollers 4808 to 4812 throttle valve 4830 to 4832 gas inlet tube

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Adachi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Akio Koganei 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. Co., Ltd. (72) Inventor Yasushi Fujioka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Naoshi Yoshiri, 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Shotaro Okabe 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Akira Sakai 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Invention Person Yoshino Gojin 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (10)

[Claims] 1. In a microwave plasma CVD apparatus including a microwave power input means, a source gas supply means, an exhaust means, and a film forming chamber, a microwave transparent member is provided on a surface of a microwave introduction window exposed to plasma. 1. A microwave plasma CVD apparatus with a deposition structure, characterized in that a multi-columnar structure constituted by 1. is provided, and an axis of symmetry of each columnar structure is perpendicular to a surface exposed to plasma. 2. The microwave plasma CVD apparatus with an adhesion-preventing structure according to claim 1, wherein each columnar structure is a plurality of ceramic capillaries parallel to and in close contact with each other. 3. In a microwave plasma CVD apparatus provided with a microwave power input means, a source gas supply means, an exhaust means, and a film forming chamber, a microwave transparent member is provided on the surface of the microwave introduction window exposed to the plasma. A microwave plasma CVD apparatus with a deposition-inhibitory structure, characterized in that a multi-layered structure constituted by 1. is provided, and each layer is parallel to the surface exposed to the plasma. 4. The microwave plasma CVD apparatus with an adhesion-preventing structure according to claim 3, wherein each of the layers has a large number of through holes, and the layers are arranged in parallel and at intervals. Structured microwave plasma CVD equipment. 5. A p-type or n-type doped with an impurity element by applying microwave power to a film formation chamber through a microwave introduction window.
In a microwave plasma CVD apparatus for forming a semiconductor thin film, a raw material gas containing a main element of the semiconductor thin film and containing no impurity element is blown onto the microwave introduction window.
VD device. 6. A microwave plasma CVD apparatus comprising a plurality of microwave power input means arranged in parallel, wherein electric fields of microwaves in adjacent microwave power input means are orthogonal to each other before discharge and parallel to each other after discharge. A microwave plasma CVD apparatus characterized by: 7. The microwave plasma C according to claim 6.
In the VD apparatus, a microwave plasma CVD apparatus in which the microwave radiating direction of the microwave power input means is one direction parallel to the strip-shaped substrate. 8. A roll-to-roll type microwave plasma CVD apparatus having a belt-shaped substrate, wherein the moving belt-shaped substrate is used as one wall surface of a quadrangular prism-shaped film forming chamber, and the belt-shaped substrate is moved into the film forming chamber. A roll-to-roll type microwave plasma CVD apparatus characterized in that a microwave power input means is arranged parallel to the direction. 9. The roll-to-roll type microwave plasma CVD apparatus according to claim 8, wherein each of the gas supply means is arranged parallel to a width direction of the strip-shaped substrate, and the deposited film forming raw material gas is provided. Is a roll-to-roll microwave plasma CVD device that radiates unidirectionally toward adjacent strip substrates. 10. A microwave plasma CVD apparatus for continuously forming a deposited film on a belt-shaped substrate, a vacuum container, a discharge chamber provided in the vacuum container, and penetrating the belt-shaped substrate.
The wall surface of the discharge chamber is disposed so as to face the strip-shaped substrate in at least one of the loading / unloading portion of the strip-shaped substrate of the discharge chamber, and the length of the wall surface of the discharge chamber is equal to or less than 1
/ 2 or more and the distance from the strip substrate is 1/2 or less of the wavelength of the microwave.