JPH10209479A - Manufacturing apparatus of semiconductor thin film and photovoltaic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus for manufacturing a semiconductor thin film and a photovoltaic device, wherein the semiconductor thin film can be formed at a high speed and power generated in plasma is hardly stuck to the surface of a board. SOLUTION: An apparatus for manufacturing a semiconductor thin film is equipped with a cathode electrode 1002 where a high-frequency power is applied, a belt-like member 1000 at a ground potential, and an anode electrode 104 arranged in a plasma discharge space, wherein the surface area of the cathode electrode 1002 in larger than the sum of those of the belt-like member 1000 and the anode electrode 104. When a glow discharge starts, the potential (self-bias) of the cathode electrode 1002 is kept positive to the grounded belt-like member 1000 and the anode electrode 1004, partitioning electrodes 1003 comprises in the cathode electrode 1002 are formed like fins or blocks so as not to impede a flow of material gas, and a high-frequency power is applied to the cathode 1002 in pulses.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an apparatus for manufacturing a semiconductor thin film and a photovoltaic element. More specifically, while maintaining a high deposition rate, fine particles generated in plasma (hereinafter, referred to as
(Also referred to as powder) on a semiconductor thin film and a photovoltaic element manufacturing apparatus.

In particular, an apparatus for manufacturing a semiconductor thin film and a photovoltaic element according to the present invention is suitable as an apparatus for mass-producing a photovoltaic element such as a solar cell using a roll-to-roll method.

[0003]

2. Description of the Related Art Conventionally, an amorphous silicon film (hereinafter referred to as a
As a method for manufacturing a photovoltaic element using (e.g., -Si film) or the like, a plasma CVD method is generally widely used and commercialized.

In the plasma CVD method, a high-quality i-type amorphous
Material for forming a fuzzy semiconductor layer or an n-type semiconductor layer
Silane (SiH_Four), Band gap
CH as adjustment gas_Four, GeH_FourEtc.
Further, this mixed gas is converted to hydrogen (H _Two) For dilution (1 to 1)
(Approximately 00 times). Also high frequency
By turning on the power low, many long-lived radicals are generated,
A method of obtaining a high-quality film through a surface reaction has also been performed.

[0005] However, in order to increase the deposition rate in the plasma CVD method, it is necessary to supply a large amount of necessary radicals and to promote a surface reaction for relaxing the structure. For this reason, prescriptions such as raising the substrate temperature have been studied, but this method is not suitable for application to industrialization because it is disadvantageous for the formation of a PIN junction.

As another method of increasing the deposition rate, there is a method of increasing the density of high frequency power in order to perform a large amount of decomposition of the source gas. However, radicals decomposed and generated under the condition that the density of the high frequency power is high include SiH
Active substances such as ₂ are contained in large quantities, and sufficient structural relaxation cannot be obtained. As a result, a high-quality semiconductor film cannot be obtained. In addition, these active radicals easily grow into clusters, and when they grow further, they cause the generation of fine particles (hereinafter referred to as powder). As a countermeasure, for example, a method of applying a high-frequency power in a pulse shape to suppress generation of powder and exhausting powder generated by temporarily stopping plasma without being taken into a deposited film has been attempted. I have.

Further, in order to establish a photovoltaic device as one that can meet the power demand, the photovoltaic device must have high photoelectric conversion efficiency, excellent characteristic stability, and excellent mass productivity. Is basically required.

For this purpose, in the production of a photovoltaic element using an a-Si film or the like, electrical, optical, photoconductive or mechanical properties, fatigue properties when repeatedly used, or use environment. It is necessary to improve characteristics and the like. It is also necessary to achieve reproducible mass production by high-speed film formation while achieving a large area, uniform film thickness and film quality.

In the photovoltaic element, the semiconductor layer, which is an important component thereof, has a semiconductor junction such as a so-called pn junction or pin junction. When a thin film semiconductor such as a-Si is used, phosphine (PH ₃ ), diborane (B ₂
A semiconductor film having a desired conductivity type is obtained by mixing a source gas containing an element serving as a dopant such as H ₆ ) with silane or the like as a main source gas and subjecting the mixture to glow discharge decomposition to obtain a semiconductor film having a desired conductivity type. It is known that the above-described semiconductor junction can be easily achieved by sequentially stacking and manufacturing semiconductor films. In the case of manufacturing such an a-Si-based photovoltaic element, a method has been proposed in which an independent film formation chamber is provided for forming each semiconductor layer, and each semiconductor layer is formed for each film formation chamber. ing.

[0010] For example, US Pat. No. 4,400,409 discloses a continuous plasma CVD apparatus employing a roll-to-roll method.
According to this apparatus, a plurality of glow discharge regions are provided, and a sufficiently long flexible substrate having a desired width is arranged along a path through which the substrate sequentially passes through each of the glow discharge regions. It is described that an element having a semiconductor junction can be manufactured continuously by continuously transporting the substrate in the longitudinal direction while depositing a conductive semiconductor layer required in a discharge region. Note that, in this specification, a gas gate is used to prevent a dopant gas used in manufacturing each semiconductor layer from diffusing or mixing into another glow discharge region. Specifically, means for separating the respective glow discharge regions from each other by a slit-shaped separation passage and forming a flow of a scavenging gas such as Ar or H _{2 in the} separation passage is employed. .

[0011] As a method of obtaining a good quality film recently, a capacitively coupled plasma CVD method has been used.
There is a research report on forming a high-quality film using a self-bias generated between a cathode and an anode and ionic species. This research report can solve the following two problems in the prior art. (1) In a typical internal structure of a discharge vessel of the prior art, the area of the whole grounded anode electrode including the substrate is often much larger than the area of the cathode electrode.
In such a cathode electrode, most of the input high-frequency power is consumed near the cathode electrode. As a result, the excitation and decomposition reactions of the material gas become active only in a certain limited portion near the cathode electrode, and the thin film formation rate increases only on the high frequency power input side, that is, near the cathode electrode. Even so, high-frequency power to the substrate side, which is the anode electrode, is not supplied sufficiently large, and it is extremely difficult to obtain a high-quality amorphous semiconductor thin film at the desired high deposition rate. Met. (2) In a typical discharge vessel structure of the prior art, that is, in a discharge vessel having a structure in which the entire area of the grounded anode electrode including the substrate is very large compared to the area of the cathode electrode, a direct current (DC) power supply or the like is used. Although a method of applying a positive potential (bias) to the cathode electrode by using a DC power supply is also performed, in such a system, a DC current flows through the plasma discharge as a result of using a secondary means such as a DC power supply. It is a system that will be. As a result, when the DC voltage bias is increased, abnormal discharge such as spark occurs, and it has been extremely difficult to suppress this and maintain stable discharge. Therefore, it was unclear whether the effect of applying a DC voltage to the plasma discharge was effective. This is because the DC voltage and the DC current cannot be separated. That is, means for effectively applying only a DC voltage to plasma discharge has been desired.

However, even when the technology described in the above research report is employed, under high-speed deposition conditions, powder is still generated in the film formation space and is taken into the semiconductor thin film being deposited, which adversely affects the film quality of the semiconductor thin film. The problem of giving was not solved.

It is indispensable to produce a semiconductor thin film of higher quality by suppressing the generation of the powder and developing a technique in which the powder is not taken into the semiconductor thin film being deposited. In particular, the p-type semiconductor layer and n
In many cases, the thickness of the mold semiconductor layer is set to be very thin, at most several hundred angstroms, from the viewpoint of device characteristics.
Therefore, when forming a photovoltaic device, especially a stacked photovoltaic device, the uniformity of the layer thickness, the adhesion of the film, the doping efficiency of the dopant, the uniformity of the characteristics, and the reproducibility affect the characteristics of the device. Not only that, it greatly affects the yield of the device, so it is important to suppress the above-mentioned powder generation and prevent the powder from being taken into the film being deposited.

Therefore, in order to obtain a semiconductor thin film such as an a-Si thin film which is uniform in space and time and has good reproducibility, it is necessary to further improve discharge stability over a long period of time and improve reproducibility. Therefore, a forming method and an apparatus having improved uniformity are required. In order to further improve the throughput of the apparatus and reduce costs, a forming method and apparatus capable of increasing the deposition rate while maintaining the quality of the semiconductor thin film are required.

In particular, under the above-mentioned high deposition rate manufacturing conditions, development of means for suppressing generation of powder and forming a high-quality amorphous semiconductor thin film has been awaited.

[0016]

SUMMARY OF THE INVENTION The present invention relates to an apparatus for manufacturing a semiconductor thin film and a photovoltaic element which can suppress the powder generated in plasma from adhering to the substrate surface while maintaining a high film forming rate. The purpose is to provide. In addition, by using this manufacturing apparatus, the amount of powder incorporated in the film being deposited is reduced, so that an amorphous semiconductor thin film having excellent photodegradation characteristics can be formed. An object is to enable mass production of electromotive force elements.

[0017]

DISCLOSURE OF THE INVENTION The present invention has been completed as a result of intensive studies by the present inventors to solve the problems in the prior art and to achieve the above object.

That is, the present invention provides (1) a plasma discharge space having a cathode electrode to which high-frequency power is applied, a band-shaped member and an anode electrode at a ground potential, and a surface area of the cathode electrode in the plasma discharge space. Is larger than the sum of the surface areas of the strip member and the anode electrode in the plasma discharge space, and the potential of the cathode electrode at the time of glow discharge generation (hereinafter referred to as self-bias) is at the ground potential. A positive potential can be maintained with respect to the anode electrode, and the shape of the cut-off electrode forming a part of the cathode electrode is a fin shape or a block shape that does not hinder the flow of the material gas flowing through the cut-off electrode. An apparatus for producing a semiconductor thin film having the cathode electrode having a structure, wherein the plasma discharge space In order to generate a loose plasma, a high-frequency power is applied in a pulsed manner to the cathode electrode, thereby producing a semiconductor thin film that suppresses the incorporation of powder into the deposited film even under high-speed deposition conditions. Device.

Further, as an advanced type in which this is applied to a continuous production apparatus, (2) when a belt-shaped member continuously passes through a plurality of connected vacuum vessels, a plasma CVD method is used.
In a photovoltaic device manufacturing apparatus in which a plurality of different thin films are stacked and formed on the surface of the strip-shaped member, a high-frequency wave is supplied to a capacitively coupled plasma discharge space for manufacturing a semiconductor thin film to be a constituent layer of the photovoltaic element. A cathode electrode to which power is applied, a band member and an anode electrode at a ground potential, and a surface area of the cathode electrode in the plasma discharge space is a surface area of the band member and the anode electrode in the plasma discharge space. The potential of the cathode electrode when a glow discharge occurs (hereinafter referred to as
Self-bias) can maintain a positive potential with respect to the strip-shaped member and the anode electrode at the ground potential, and the shape of the cut-off electrode forming a part of the cathode electrode is the same as that of the strip-shaped member. A fin-shaped or block-shaped photovoltaic element having a cathode electrode having a structure that does not hinder the flow of a material gas flowing in the transport direction of the photovoltaic element, wherein pulsed plasma is generated in the plasma discharge space. Therefore, a high-frequency power is applied in a pulsed manner to the cathode electrode, thereby providing a photovoltaic device manufacturing apparatus that suppresses the incorporation of powder into a deposited film even under high-speed deposition conditions.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION In the apparatus for manufacturing a semiconductor thin film according to the present invention, the excitation or decomposition reaction of the material gas is not promoted only in a certain limited portion near the cathode electrode, and the entire discharge space is not increased. For example, the excitation and decomposition reaction of the above-mentioned material gas is promoted on the anode electrode side including the end member, and a thin film can be efficiently deposited on the band member at a relatively high deposition rate. That is, the amount of high-frequency power supplied to the cathode is properly adjusted, the material gas introduced into the discharge space is efficiently excited and decomposed by using the supplied high-frequency power more effectively, and a high-quality non-single crystal is obtained. A semiconductor thin film can be formed on the belt-like member uniformly and with good reproducibility at a relatively high deposition rate.

In the manufacturing apparatus of the present invention, as the material of the cathode electrode, stainless steel and its alloys, aluminum and its alloys, etc. can be considered, but other materials having conductive properties are particularly limited. It does not need to be a material. The same applies to the anode electrode material.

In the apparatus for manufacturing a photovoltaic element according to the present invention, the belt-shaped member is successively moved in the longitudinal direction while sequentially passing through the film forming space of the photovoltaic element to continuously manufacture the photovoltaic element. In the apparatus for producing a stacked type photovoltaic element continuously by sequentially passing through the film formation space of a plurality of photovoltaic elements, the potential of the cathode electrode (self- Bias) has a structure capable of maintaining a positive potential with respect to a ground (anode) electrode including the strip-shaped member, and the fin-shaped or block-shaped cut-off electrode is disposed in the transport direction of the strip-shaped member. Are arranged in parallel or perpendicularly to each other, and have a cathode structure in which the distance between the threshold electrodes is sufficient to maintain and maintain the discharge between the adjacent threshold electrodes. It is the location.

The present invention is characterized in that the surface area of the cathode electrode in the plasma discharge space is made larger than the sum of the surface areas of the band-shaped member and the anode electrode in the plasma discharge space. The potential (self-bias) of the cathode electrode of
An apparatus characterized in that a semiconductor thin film is deposited while maintaining a positive potential, more preferably +5 V or more, by adjusting the applied high frequency power.

Further, in the present invention, a plurality of the cut-off electrodes are provided in the conveying direction of the band-shaped member, and the interval between the cut-off electrodes is sufficient to generate and maintain a discharge between the adjacent cut-off electrodes. By providing an interval, a relatively large positive potential can be generated and maintained at the cathode electrode by a self-bias. This means
Unlike a bias application method using a separately provided direct current (DC) power supply or the like, occurrence of abnormal discharge due to sparks or the like can be suppressed. As a result, it is possible to stably generate and maintain the discharge, and furthermore, a part of the cathode electrode where the positive self-bias is generated, that is, the tip of the cut-off electrode is relatively close to the band-shaped member. Therefore, the generated relatively large positive potential can be efficiently and stably applied to the strip-shaped deposition film via the discharge space. This is because in a parallel plate type cathode electrode structure, in which the cathode electrode area is smaller than the anode (ground) electrode area, which is a typical example of the conventional type, for example, by simply shortening the distance between the cathode and the substrate or by using a DC power supply together It is a self-bias potential that is clearly different from the method of applying a DC voltage to the cathode, etc.
This is a DC bias application effect.

This positive self-bias is characterized in that the potential is maintained for a while even when the plasma maintenance power is lost. Fine particles such as clusters and powders charged to a negative charge existing in the plasma discharge are efficiently accelerated in the direction of the cathode partition plate, which holds the potential at the positive potential, at the moment when the plasma disappears. As a result, the probability that fine particles such as clusters and powder will be taken into the semiconductor thin film during deposition is greatly reduced. Further, it is important to efficiently exhaust the fine particles such as the clusters and the powder. For this purpose, the flow direction of the material gas introduced into the discharge space is caused to flow in the same or opposite direction as the conveying direction of the belt-like member. At this time, the shape of the partition electrode does not hinder the flow while ensuring a sufficient cathode area. It is important to have a structure.

In the present invention, the discharge device is of the capacitive coupling type, and a sine wave of 13.56 MHz is preferably used industrially. By modulating the period and the peak value of 13.56 MHz of the sine wave serving as the fundamental frequency, pulsed plasma can be generated in the discharge space.
As shown in FIG. 2A, for example, a sine wave 13.56M
When a rectangular wave of 1 Hz and an on / off ratio of 20% are superimposed on the Hz, a plasma discharge occurs once per second for 0.2 seconds in the discharge space and disappears for 0.8 seconds. Among the active species generated during this 0.2 second, those that are particularly active grow as clusters and powders. When the plasma discharge for the next 0.8 seconds is interrupted, fine particles such as negatively charged clusters and powders are accelerated in a direction away from the belt-like member due to the positive potential residual effect of the cathode. Then, the air is quickly exhausted according to the flow defined by the shape of the partition electrode arranged so as not to obstruct the exhaust flow. As a result,
It becomes possible to reduce the incorporation of fine particles such as powders and clusters that grow in plasma and degrade the characteristics of the semiconductor thin film into the film.

With the interruption of the plasma, the supply amount of the active species contributing to the film formation decreases, so that the film formation rate and the gas utilization rate decrease. As a method of compensating for these reductions, a method of increasing the peak value of the modulated wave, that is, increasing the number of moles of material gas decomposition by generating instantaneous high-density plasma and limiting the progress of decomposition is known. No.
For example, in the case of SiH ₄ , the progress of decomposition in plasma
It is considered that the time progresses from SiH ₃ → SiH ₂ → SiH with time, and the active species is changed to a more chemically active species. It is considered that this altered active species leads to the generation and growth of powder.

The instantaneous formation of high-density plasma leads to an increase in deposition rate, an improvement in the utilization rate of material gas, and
It is considered that the restriction of the decomposition time suppresses the generation of powder.

In the present invention, the material gas Si
H _4, H _2, it is possible to realize an intermittent process of occurrence decompose and exhaust the pulsed plasma by applying a sine wave 13.56MHz high-frequency power to be used industrially pulsed doping gas .

Further, the pulsed plasma of the present invention can be realized by modulating the sinusoidal wave 13.56 Hz in time and the peak value. In the present invention, in order to optimize the decomposition and evacuation processes of the source gas described above, the pulse frequency is determined by experimentally changing the modulation frequency and confirming the desired characteristic improvement of the resulting semiconductor thin film. The modulation shape of the plasma is appropriately determined. Specifically, a modulation frequency of 0.1
The frequency can be appropriately selected in the range of 1 Hz to 1 MHz, and is preferably selected in the range of 1 Hz to 100 kHz. Further, with respect to the peak value of the sine wave of 13.56 MHz, the shape of the pulse applied to the sine wave of 13.56 MHz is optimized by a sine wave, a rectangular wave, a triangular wave, and the like. May be appropriately selected to determine the conditions of the plasma for forming the plasma. FIG. 2B shows an example in which modulation is performed using a triangular wave, and FIG. 2C shows an example in which modulation is performed using a sine wave with an on / off ratio of 20%. FIG. 2D shows an example in which a sawtooth wave is modulated at an on / off ratio of 30%.

As described above, the manufacturing apparatus of the present invention optimizes the active species generated by changing the plasma formation conditions over time, interrupts the plasma, and exhausts the active powder to achieve high speed. It is possible to improve deposition, gas utilization and film quality.

Further, by using the manufacturing apparatus of the present invention, a uniform and highly reproducible discharge state is maintained over a long film forming time such as forming a semiconductor layer on a belt-shaped member of several hundred meters. It is possible to form a semiconductor layer by controlling the semiconductor layer, and it is possible to form a high-quality, high-quality, uniform semiconductor deposited film continuously and with high yield over the entire length of the long strip from the beginning to the end.

Further, using the manufacturing apparatus of the present invention
It is also effective when the p-type semiconductor layer or n-type semiconductor layer of the photovoltaic element is realized by a microcrystalline silicon thin film, improves discharge stability over a long time, improves reproducibility, and improves uniformity. In addition, it is possible to realize a high-quality semiconductor thin film that is uniform spatially and temporally and has good reproducibility.

Further, using the manufacturing apparatus of the present invention
In particular, in a stacked photovoltaic element, an extremely good pn junction can be realized, and a higher-quality photovoltaic element can be formed uniformly and continuously with good reproducibility. Further, the use of the apparatus of the present invention makes it possible to realize a high-quality thin film layer at a relatively high deposition rate, particularly when a p-type semiconductor layer or an n-type semiconductor layer is formed of a microcrystalline silicon thin film. Thus, the throughput of the apparatus can be greatly improved.

By manufacturing a photovoltaic element by using the above-described apparatus for continuously manufacturing a photovoltaic element according to the present invention, the above-mentioned problems can be solved and the belt-shaped member which is continuously moved can be transported at a high speed. A photovoltaic element having high quality and excellent uniformity can be manufactured. Hereinafter, an apparatus for manufacturing a semiconductor thin film and a photovoltaic element according to the present invention will be described.

FIG. 1 is a schematic sectional view showing the characteristics of the inside of the discharge vessel of the present invention. A cathode electrode 1002 having a structure similar to that of the cathode electrode example shown in FIG. 3C is provided on a ground (anode) electrode 1004 so as to be electrically insulated by an insulating insulator 1009. On the cathode electrode, a conductive strip member 1000 is supported by a plurality of magnet rollers (not shown), and is indicated by an arrow without physically touching the cathode electrode located below and the lamp heater 1005 located above. It is a structure that moves to the direction in which A material gas is introduced from a gas introduction pipe 1007, passes between the belt-shaped member and the cathode electrode, and is evacuated.
From 06, the air is exhausted by a vacuum pump (not shown). As the cathode and anode electrode materials, SUS31
6 was used.

In FIG. 1, reference numeral 1100 denotes a high frequency of 13.5.
6 MHz oscillator, 1101 is an oscillator for modulation, 110
Reference numeral 2 denotes an amplifier, which is electrically connected to the cathode electrode 1002 via a high-frequency cable. Here, a high frequency 13.56 MHz is supplied from the high frequency oscillator 1100 to the amplifier 1102.
And the output waveform is cycled by the modulation oscillator 1101,
The on / off ratio, the peak value, and the waveform can be arbitrarily controlled.

The discharge region of the glow discharge generated while modulating the high-frequency power is a gap between a plurality of grounded strip-shaped electrodes 1003 which is a part of the cathode electrode and a gap between the strip-shaped member and the cathode electrode. And is a region confined by the upper conductive strip member.

When a discharge vessel having such a structure is used,
The ratio of the surface area of the cathode electrode to the sum of the surface areas of the strip member and the anode electrode is obviously larger than 1. Further, it is effective that the closest distance (l _{1 in the} figure) between the band-shaped member 1000 and the fin-shaped or block-shaped cut-off electrode 1003 which is a part of the cathode electrode is within 5 cm or less. is there. Further, the interval between the plurality of set-up electrodes 1003 has a sufficient interval for generating and maintaining the discharge, and an appropriate interval (l _{2 in the} figure) is within a range of 3 cm or more and 10 cm or less. Is effective.

FIGS. 4 and 5 are schematic diagrams of a general conventional cathode electrode. As is clear from this figure,
The surface area of the cathode electrode 2002 in contact with the discharge space has a structure smaller than the entire surface area of the grounded anode electrode 2004 including the conductive strip member 2000 also in contact with the discharge space. That is, the ratio of the surface area of the cathode electrode to the sum of the surface areas of the strip-shaped member and the anode electrode is:
Obviously it will be smaller than one.

The shape of the cathode electrode of the present invention is not limited to this. For example, FIGS.
The shape of the cathode electrode shown schematically in (f) may be used. In each case, SUS316 was used as the cathode electrode material.

FIG. 3A shows an example of a structure in which two strip electrodes are provided at both ends in the city direction in a direction parallel to the transport direction of the belt-shaped member. The gap between the end-shaped electrodes at both ends has a structure through which a material gas can pass.

FIGS. 3B and 3F show an example of a structure in which a plurality of cut-off electrodes are provided in a direction perpendicular to the conveying direction of the belt-like member. A structure in which a plurality of ventilation holes 1010 through which a material gas can pass is provided on the boundary electrode. The vent hole may have a size that allows a material gas to pass therethrough and does not impair the function as a cathode electrode. For example, a structure example as shown in FIG. 3C may be used.

FIG. 3D shows an example of a structure in which a plurality of cut-off electrodes are provided in a direction parallel to the direction in which the belt-shaped member is conveyed.

FIG. 3 (e) shows an example of a structure in which a plurality of cut-off electrodes are provided so as to meander in the conveying direction of the belt-like member and to be parallel to the belt-like member.

FIGS. 3 (a) to 3 (f) show examples in which the cross-sectional shape of a plurality of strip-shaped electrodes provided in a direction perpendicular and parallel to the strip-shaped member is rectangular. However, the cross-sectional shape of the cut-off electrode is not limited to a rectangle as long as local deviation of the gas flow and the plasma can be prevented. Moreover,
In FIGS. 3A to 3F described above, a rectangular shape constituted by straight sides is shown. However, although not illustrated, a shape constituted by curved sides may be employed. . In short, any structure may be used as long as the shape is such that the surface area of the cathode electrode is larger than the surface area of the anode electrode and the flow of gas is not hindered.

By manufacturing a photovoltaic element using the above-described manufacturing apparatus of the present invention, the above-mentioned problems can be solved, and the above-mentioned requirements can be satisfied. A photovoltaic device having excellent uniformity in quality and few defects can be manufactured.

In Example 1 to be described later, the cathode electrode structure having the shape shown in FIG. 3A and the ratio of the surface area of the cathode electrode to the sum of the surface areas of the conductive strip member and the anode electrode was 2.1 times. Are used as a first conductive layer forming container and a second conductive layer forming container in a continuous plasma CVD method employing a roll-to-roll method shown in FIG. A single type photovoltaic device was manufactured.

Hereinafter, the present invention will be described with reference to FIG.
Detailed explanation of the manufacturing equipment for single type photovoltaic elements
I do. (1) Connecting part In the present invention, feeding and winding of the belt-shaped member
The vacuum container for semiconductor and the vacuum container for semiconductor film production are separated and independent,
And the belt-like members are continuously penetrated through them.
For transportation, the connecting part is preferably a gas gate means.
It is. The capacity of the gas gate means is between
Due to the pressure difference that occurs, the semiconductor film
Have the ability not to diffuse the atmosphere of the raw material gas etc.
Is necessary. Therefore, the basic concept is
Gas gate means disclosed in 4,438,723
Can be adopted, but the ability is further improved
There is a need. Specifically, a pressure difference of up to about 106 times
It must be able to withstand, and the exhaust pump
High power oil diffusion pump, turbo molecular pump, mechanic
A booster pump or the like is preferably used. Also gas
The cross-sectional shape of the gate is slit-like or similar
The overall length and the exhaust capacity of the exhaust pump used
Using the general conductance calculation formula together with the force, etc.
Their dimensions are calculated and designed. In addition, the separation capacity
It is preferable to use a gate gas in combination to increase
For example, rare gases such as Ar, He, Ne, Kr, Xe, and Rn
Is H_TwoAnd the like. Game
The gas flow rate depends on the conductance and
And the capacity of the exhaust pump used
However, for example, the maximum pressure is almost at the center of the gas gate.
If a gate point is provided, the gate gas will be
To the vacuum vessel on both sides, and between the vessels on both sides.
Of each other can be minimized. Actual
Measure the amount of gas diffused using a mass spectrometer.
The optimum conditions by analyzing the composition of the semiconductor film.
To determine. (2) Band-shaped member As the material of the band-shaped member suitably used in the present invention,
Is deformed at the temperature required during semiconductor film fabrication,
Low distortion, desired strength, and conductivity
Preferably, specifically, stainless steel
Teal, aluminum and its alloys, iron and its alloys,
Thin sheets of metals such as copper and its alloys and their composites, and
On these surfaces, metal thin films of different materials and / or Si
O_Two, Si_ThreeN _Four, Al_TwoO_ThreeInsulating thin film such as
Surface coating treatment by putter method, vapor deposition method, plating method, etc.
What has been done. In addition, polyimide, polyamide, polye
Sheets made of heat-resistant resin such as ethylene terephthalate and epoxy
Glass fiber or carbon fiber
On the surface of the composite with carbon fiber, boron fiber, metal fiber, etc.
Simple metal or alloy, and transparent conductive oxide (TCO)
Conductive treatment by plating, evaporation, sputtering, coating, etc.
Are performed.

The thickness of the band-shaped member can be set in consideration of cost, storage space, and the like, as long as the thickness is within a range in which the curved shape produced at the time of carrying by the carrying means exhibits a strength for maintaining the curved shape. It is desirable to be as thin as possible. Specifically, the thickness is preferably from 0.01 mm to 5 mm, more preferably from 0.02 mm to 2 mm, and most preferably from 0.05 mm to 1 mm. Desired strength is easily obtained even when thin.

The width of the band-shaped member is not particularly limited, and is determined by the size of the semiconductor film forming means or the size of the container or the like.

The length of the belt-shaped member is not particularly limited, and may be a length that can be wound up in a roll shape. It may be.

When the band-shaped member is electrically conductive such as a metal, it may be used as an electrode for direct current extraction, and when the band-shaped member is electrically insulating such as a synthetic resin, the surface of a snapper on which a semiconductor film is formed. To Al, Ag, Pt, Au, Ni, Ti,
Mo, W, Fe, V, Cr, Cu, stainless steel, brass, _{nichrome, SnO 2, In 2 O 3} , ZnO, SnO 2 -
A so-called single metal or alloy such as In ₂ O ₃ (ITO) or a transparent conductive oxide (TCO) is subjected to a surface treatment in advance by plating, vapor deposition, sputtering, or the like to produce an electrode for extracting current. It is desirable to keep.

When the band-shaped member is a non-translucent material such as a metal, a reflective conductive film for improving the reflectance of the long-wavelength light on the substrate surface is formed on the band-shaped member. Preferred as set forth. Ag, Al, Cr and the like are preferably used as the material of the reflective conductive film.

Further, for the purpose of preventing mutual diffusion of constituent elements between the substrate material and the semiconductor film and forming a buffer layer for preventing short circuit, a metal layer or the like is used as a reflective conductive film. It is preferably provided on the side where the semiconductor film is deposited. As a material preferably used as the material of the buffer layer, Zn
O.

In the case where the band-shaped member is relatively transparent and a solar cell having a layer structure in which light is incident from the side of the band-shaped member, the conductive thin film such as the transparent conductive oxide or the metal thin film is used. Is desirably deposited in advance.

The surface of the belt-shaped member may be a so-called smooth surface or a fine uneven surface.
In the case of forming a fine uneven surface, the shape is spherical, conical, pyramidal, or the like, and its maximum height (Rmax) is preferably 5
By setting the angle between 00 ° and 5000 °, the light reflection on the surface becomes irregular reflection, thereby increasing the optical path length of the light reflected on the surface. (3) Photovoltaic element FIG. 7 is a schematic diagram showing the configuration of a photovoltaic element manufactured according to the present invention.

The example shown in FIG.
4), lower electrode 4003, first conductivity type layer 4004, i
Mold layer 4005, second conductivity type layer 4006, upper electrode 40
07, and a collecting electrode 4008.

The example shown in FIG. 8 is a so-called triple type photovoltaic device in which three photovoltaic devices using three types of semiconductor layers having different band gaps and / or layer thicknesses as i-type layers are stacked. It is a power element, and is a belt-shaped member 5001 (10
4), lower electrode 5003, first conductivity type layer 5004, first i-type layer 5005, second conductivity type layer 5006, first conductivity type layer 5007, second i-type layer 5008, second Conductive type layer 5009, first conductive type layer 5010, thirdly i-type layer 5011, second conductive type layer 5012, upper electrode 501
3. It is composed of a collecting electrode 5014.

Hereinafter, each layer constituting the photovoltaic element will be described. (3-1) First and second conductivity type layers Materials used for the first and second conductivity type layers in the photovoltaic device of the present invention include Group III or V of the periodic table.
Non-single-crystal semiconductors comprising one or more group atoms are suitable. Further, as the conductive layer on the light irradiation side, a microcrystallized semiconductor is optimal. The particle size of the microcrystal is preferably from 3 nm to 20 nm, and most preferably from 3 nm 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, a Group III element of the periodic table is suitable. I have. Among them, phosphorus (P), nitrogen (N), arsenic (As), and antimony (Sb) are particularly suitable.

When the conductivity type of the first or second conductivity type layer is p-type, a Group V element of the periodic table is suitable as an additive contained in the first or second conductivity type layer. . Among them, boron (B), aluminum (Al), gallium (G
a) is optimal.

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

Further, light absorption in the conductive layer on the light irradiation side is improved.
In order to reduce the number of semiconductors,
Semiconductor layer having a band gap larger than the gap
It is preferable to use For example, if the i-type layer is an amorphous
In the case of silicon, non-single-crystal carbon
It is optimal to use silicon halide. (3-2) i-type layer Semiconductor used for i-type layer in photovoltaic device of the present invention
As the body material, one or more atoms of Group IV of the periodic table may be used.
Si, Ge, C, SiC, GeC, Si
Semiconductors, such as Sn, GeSn, and SnC, are mentioned. III
GaAs, GaP, GaS as a group V compound semiconductor
b, InP, InAs, II-VI compound semiconductor as Z
nSe, ZnS, ZnTe, CdS, CdSe, CdT
e, CuAlS as I-III-VI compound semiconductor_Two,
CuAlSe_Two, CuAlTe_Two, CuInS_Two, CuIn
Se_Two, CuInTe_Two, CuGaAs_Two, CuGaS
e_Two, CuGaTe, AgInSe_Two, AgInTe_Two, I
As the I-IV-V compound semiconductor, ZnSiP_Two, Zn
GeAs_Two, CdSiAs_Two, CdSnP_Two, Oxide semiconductor
Cu as a body_TwoO, TiO_Two, In_TwoO_Three, SnO_Two, Z
nO, CdO, Bi_TwoO _Three, CdSnO_FourAre each listed
Can be

[0065]

EXAMPLE In the following, a photovoltaic element was formed using the apparatus for producing a semiconductor thin film and a photovoltaic element according to the present invention, and various characteristics of the obtained photovoltaic element were evaluated. However, the present invention is not limited by these examples.

Example 1 In this example, a single cell type photovoltaic device shown in FIG. 7 was used, using a continuous plasma CVD apparatus employing the roll-to-roll method shown in FIG. An element was manufactured. At this time, the shape of the cathode electrode of the vacuum vessel for forming the i-type layer was the partition plate shape shown in FIG. In this cathode electrode structure,
The ratio of the surface area of the cathode electrode to the sum of the surface areas of the conductive strip member and the anode electrode was 2.9 times.

The first conductive type layer forming container and the second conductive type layer forming container
As the conductive layer forming container, a forming container having a parallel plate type RF electrode was used.

The manufacturing apparatus shown in FIG. 6 comprises vacuum containers 301 and 302 for feeding and winding the belt-like member 101,
Of the conductive type layer forming vacuum container 601, the i-type layer forming vacuum container 100, and the second conductive type layer forming vacuum container 602 via a gas gate.

Each structure of the cathode electrode 603 in the vacuum vessel 601 and the cathode electrode 604 in the vacuum vessel 602 has the above-described cathode electrode structure.

Using the manufacturing apparatus shown in FIG.
The first conductivity type layer, the i-type layer, and the
And the second conductivity type layer by the following manufacturing procedure.
A single type photovoltaic element (element-actual 1)
). (1) First, a vacuum vessel 301 having a substrate delivery mechanism
Then, the bobbin 303 around which the belt-shaped member 101 is wound is
I did it. The belt-shaped member 101 is sufficiently degreased and washed.
And the lower electrode is made of silver by a sputtering method.
S deposited with a thin film of 100 nm and ZnO thin film of 1 μm
US430BA band-shaped member (width 120 mm x length 20
0 m x thickness 0.13 mm). (2) Fabricating the band-shaped member 101 with a gas gate and each non-single-crystal layer
Through a vacuum container for
Pass through the empty container 302 and adjust the tension so that there is no slack.
went. (3) Each vacuum vessel 301, 601, 100, 602, 3
02 was evacuated with a vacuum pump (not shown). (4) Each gas gate has a gate gas introduction pipe 131n, 1
31, 132, 131p, H_TwoTo
Flow 700 sccm each, and lamp heaters 124n, 12
4, 124p, the belt-shaped member 101
It heated to 350 degreeC, 250 degreeC. (5) SiH from the gas introduction pipe 605_Four40 sc gas
cm, PH_ThreeGas (2% H _Two50sccm, H
_Two200 sccm of gas, gas introduction pipes 104a, 104
b, 104c, SiH_Four100 sccm of gas,
H_TwoEach gas is supplied at a flow rate of 500 sccm from the gas introduction pipe 606.
SiH_Four10 sccm gas, BF_ThreeGas (2% H_TwoDilution
Product) at 100 sccm, H_TwoIntroduce 500 sccm of gas
did. (6) When the pressure in the vacuum vessel 301 is 1.
With the conductance valve 307 so that it becomes 0 Torr
It was adjusted. The pressure in the vacuum vessel 601 is measured by a pressure gauge (not shown).
Conductance (not shown) so that the pressure becomes 1.5 Torr
Adjusted with a valve. The pressure in the vacuum vessel 100 is not shown
(Not shown) so that the pressure gauge becomes 1.8 Torr
It was adjusted with a reactance valve. Pressure in vacuum vessel 602
However, a pressure gauge (not shown) is used so that the pressure becomes 1.6 Torr.
It was adjusted with the indicated conductance valve. Vacuum container 302
So that the internal pressure becomes 1.0 Torr with the pressure gauge 315
Was adjusted by the conductance valve 308. (7) After the pressure adjustment shown in step (6), the cathode electrode
RF power of 500 W is supplied to the cathode electrode 603.
200 W RF power, and 6
An RF power of 00 W was each introduced. (8) The belt-shaped material 101 is transported in the direction of the arrow in the figure,
A first conductive type layer, an i-type layer and a second conductive layer on the belt-shaped member;
Mold layers were made sequentially. (9) A transparent film is formed on the second conductive type layer formed in step (8).
ITO (In)_TwoO_Three+ SnO_Two) Vacuum steaming
After deposition by 80 nm, A was further used as a current collecting electrode.
1 was vacuum-deposited at 2 μm, and a photovoltaic device (device-
(Referred to as “Exact 1”).

Table 1-1 shows the conditions for manufacturing the photovoltaic device according to this example.

[0072]

[Table 1-1] (Comparative Example 1) This example is different from Example 1 in that the shape of the cathode electrode of the vacuum vessel forming the i-type layer was a parallel plate type structure and the cathode electrode structure shown in FIGS. 4 and 5 was used. . In this cathode electrode structure, the ratio of the surface area of the cathode electrode to the sum of the surface areas of the conductive strip member and the anode electrode was 0.6 times.

However, the conditions for producing the photovoltaic element were the same as those in Example 1 (Table 1-1).

The other points were the same as in Example 1, and a single-cell type photovoltaic element (referred to as element-ratio 1) was manufactured.

In the following, the evaluation of the uniformity of the characteristics, the defect density, and the photodegradation of the photovoltaic elements manufactured in Example 1 and Comparative Example 1, ie, (element-actual 1) and (element-ratio 1), were performed. The result of the above will be described.

The uniformity of the characteristics refers to the photovoltaic element on the belt-shaped member produced in Example 1 and Comparative Example 1, that is, (Element-
Example 1) and (element-ratio 1) were cut out at an area of 5 cm square every 10 m, placed under AM-1.5 (100 mW / cm ² ) light irradiation, the photoelectric conversion efficiency was measured, and the photoelectric conversion was performed. It is the result of evaluating the variation in efficiency. The variance of the photovoltaic element of Example 1 (element-actual 1) is shown with the variance of the photovoltaic element of Comparative Example 1 (element-ratio 1) as the reference 1.00.

The defect density refers to the range of the photovoltaic element on the belt-shaped member produced in Example 1 and Comparative Example 1, that is, the range of the central part 5 m between (element-real 1) and (element-ratio 1). 5cm
This is the result of evaluating the defect density by cutting out 100 corner areas and measuring the reverse current to detect the presence or absence of a defect in each photovoltaic element. Example 1 with the defect density of the photovoltaic element of Comparative Example 1 (element-ratio 1) as the reference 1.00.
3 shows the defect density of the photovoltaic element (element-actual 1).

The photo-deterioration characteristic refers to the photovoltaic element on the belt-shaped member manufactured in Example 1 and Comparative Example 1, that is, (Element-
The range of the central part 5m between the actual 1) and (element-ratio 1) is 5c
AM-1.5 (100mW
/ Cm ² ) Installed under light irradiation, left for 10,000 hours,
It is a result of measuring the photoelectric conversion efficiency and evaluating the rate of decrease in the photoelectric conversion efficiency. Photovoltaic device of Comparative Example 1 (device
The reduction rate of the photovoltaic element of Example 1 (element-actual 1) was shown with the reduction rate of ratio 1) as the reference 1.00.

Table 1-2 shows the photovoltaic elements manufactured in Example 1 and Comparative Example 1, that is, (Element-Example 1) and (Element-
This is a result of examining the above-described variation in the photoelectric conversion efficiency, the defect density, and the light deterioration rate with respect to the ratio 1).

[0080]

[Table 1-2] From Table 1-2, the photovoltaic element of Comparative Example 1 (element-ratio 1)
On the other hand, the photovoltaic element of Example 1 (element-actual 1)
It was found that the photovoltaic element formed by the manufacturing method of the present invention had excellent characteristics in terms of the variation in conversion efficiency, defect density, and photodegradation rate.

(Embodiment 2) This embodiment is different from Embodiment 1 in that the shape of the cathode electrode of the vacuum vessel for forming the i-type layer is a partition plate shape shown in FIG. 3B. In this cathode electrode structure, the ratio of the surface area of the cathode electrode to the sum of the surface areas of the conductive strip member and the anode electrode is 2.9.
Doubled. Table 2-1 shows the conditions for producing the photovoltaic element.
And

The first conductive type layer forming container and the second conductive type layer forming container
As the conductive layer forming container, a forming container having a parallel plate type RF electrode was used.

The other points were the same as in Example 1, and a single type photovoltaic element (referred to as Element-Example 2) was produced.

[0084]

[Table 2-1] The photovoltaic elements produced in Example 2 and Comparative Example 1, ie, (element-real 2) and (element-ratio 1),
In the same manner as in the above, evaluations were made on the property uniformity, defect density, and light degradation. The results are shown in Table 2-2.

[0085]

[Table 2-2] From Table 2-2, the photovoltaic element of Comparative Example 1 (element-ratio 1)
On the other hand, the photovoltaic element of Example 2 (element-real 2)
It was found that variations in conversion efficiency, defect density, and light degradation rate were all excellent.

(Embodiment 3) This embodiment is different from Embodiment 1 in that the shape of the cathode electrode of the vacuum vessel for producing the i-type layer is a partition plate shape shown in FIG. 3 (c). In this cathode electrode structure, the ratio of the surface area of the cathode electrode to the sum of the surface areas of the conductive strip member and the anode electrode is 2.9.
Doubled. Table 3-1 shows the conditions for producing the photovoltaic element.
And

The first conductive type layer forming container and the second conductive type layer forming container
As the conductive layer forming container, a forming container having a parallel plate type RF electrode was used.

The other points were the same as in Example 1, and a single type photovoltaic device (referred to as device-actual 3) was produced.

[0089]

[Table 3-1] In contrast to the photovoltaic elements produced in Example 3 and Comparative Example 1, ie, (Element-Real 3) and (Element-Ratio 1), Example 1
In the same manner as in the above, evaluations were made on the property uniformity, defect density, and light degradation. The results are shown in Table 3-2.

[0090]

[Table 3-2] From Table 3-2, the photovoltaic element of Comparative Example 1 (element-ratio 1)
On the other hand, the photovoltaic element of Example 3 (Element-Real 3)
It was found that variations in conversion efficiency, defect density, and light degradation rate were all excellent.

(Embodiment 4) This embodiment is different from the embodiment 1 in that the shape of the cathode electrode of the vacuum vessel for producing the i-type layer is the partition plate shape shown in FIG. In this cathode electrode structure, the ratio of the surface area of the cathode electrode to the sum of the surface areas of the conductive strip member and the anode electrode is 2.9.
Doubled. Table 4-1 shows the conditions for producing the photovoltaic element.
And

The first conductive type layer forming container and the second conductive type layer forming container
As the conductive layer forming container, a forming container having a parallel plate type RF electrode was used.

The other points were the same as in Example 1, and a single type photovoltaic element (referred to as Element-Example 4) was produced.

[0094]

[Table 4-1] In contrast to the photovoltaic elements produced in Example 4 and Comparative Example 1, ie, (Element-Real 4) and (Element-Ratio 1), Example 1
In the same manner as in the above, evaluations were made on the property uniformity, defect density, and light degradation. The results are shown in Table 4-2.

[0095]

[Table 4-2] From Table 4-2, the photovoltaic element of Comparative Example 1 (element-ratio 1)
On the other hand, the photovoltaic element of Example 4 (element-real 4)
It was found that variations in conversion efficiency, defect density, and light degradation rate were all excellent.

(Embodiment 5) In this embodiment, the shape of the cathode electrode of the vacuum vessel for forming the first conductivity type layer is shown in FIG.
3 is different from that of the first embodiment. In this cathode electrode structure, the ratio of the surface area of the cathode electrode to the sum of the surface areas of the conductive strip member and the anode electrode was 2.9 times. Also, the manufacturing conditions of the photovoltaic element are as follows:
The results are shown in Table 5-1.

As the second conductive layer forming container and the i-type layer forming container, a forming container having a parallel plate type RF electrode was used.

The other points were the same as in Example 1, and a single type photovoltaic element (referred to as Element-Example 5) was produced.

[0099]

[Table 5-1] In contrast to the photovoltaic elements manufactured in Example 5 and Comparative Example 1, that is, (Element-Real 5) and (Element-Ratio 1), Example 1
In the same manner as in the above, evaluations were made on the property uniformity, defect density, and light degradation. The results are shown in Table 5-2.

[0100]

[Table 5-2] From Table 5-2, the photovoltaic element of Comparative Example 1 (element-ratio 1)
On the other hand, the photovoltaic element of Example 5 (element-actual 5)
It was found that variations in conversion efficiency, defect density, and light degradation rate were all excellent.

(Embodiment 6) In this embodiment, the shape of the cathode electrode of the vacuum vessel for producing the second conductivity type layer is shown in FIG.
3 is different from that of the first embodiment. In this cathode electrode structure, the ratio of the surface area of the cathode electrode to the sum of the surface areas of the conductive strip member and the anode electrode was 2.9 times. Also, the manufacturing conditions of the photovoltaic element are as follows:
The results are shown in Table 6-1.

As the first conductive layer forming container and the i-type layer forming container, a forming container having a parallel plate type RF electrode was used.

The other points were the same as in Example 1, and a single type photovoltaic element (referred to as Element-Example 6) was produced.

[0104]

[Table 6-1] In contrast to the photovoltaic elements produced in Example 6 and Comparative Example 1, that is, (Element-Real 6) and (Element-Ratio 1), Example 1
In the same manner as in the above, evaluations were made on the property uniformity, defect density, and light degradation. The results are shown in Table 6-2.

Table 6-2 shows that the open-circuit voltage Voc was significantly improved among the conversion efficiencies.
The results of Example 6 (Element-Real 6) are shown with the open-circuit voltage value of (Element-Ratio 1) as the reference 1.00.

[0106]

[Table 6-2] From Table 6-2, the photovoltaic element of Comparative Example 1 (element-ratio 1)
On the other hand, the photovoltaic element of Example 6 (Element-Real 6)
It was found that variations in conversion efficiency, defect density, and light degradation rate were all excellent, and the open-circuit voltage was high.

(Embodiment 7) In this embodiment, a continuous plasma CVD apparatus employing a roll-to-roll method shown in FIG. 8 was fabricated. At that time, the shape of the cathode electrode of the vacuum vessel for producing each i-type layer was the partition plate shape shown in FIG. In this cathode electrode structure, the ratio of the surface area of the cathode electrode to the sum of the surface areas of the conductive strip member and the anode electrode was 2.1 times.

The first conductive type layer forming container and the second conductive type layer forming container
As the conductive layer forming container, a forming container having a parallel plate type RF electrode was used.

In the manufacturing apparatus shown in FIG. 6, although not shown, the first vacuum container 601 for forming the conductive layer, the vacuum container 100 for forming the i-type layer, and the vacuum container 6 for forming the second conductive layer are formed.
02 was connected via a gas gate as one set, and this was further expanded by two sets, and a total of three sets of the apparatus were used in series. In addition, among them, the above-mentioned formation containers were installed in all the first conductivity type layer formation containers and the second conductivity type layer formation containers, and triple type photovoltaic elements were manufactured.

Using such an apparatus (not shown), the first conductivity type layer and the first conductive type layer were formed on the lower electrode under the manufacturing conditions shown in Table 7.
I-type layer, second conductivity type layer, first conductivity type layer, second i
Example 1 A pattern layer, a second conductivity type layer, a first conductivity type layer, a third i-type layer, and a second conductivity type layer were sequentially stacked and deposited.
According to the same manufacturing procedure as described above, a triple-type photovoltaic element (element-Example 7) was continuously manufactured.

Table 7-1 shows the manufacturing conditions of the photovoltaic device according to this example.

[0112]

[Table 7-1] (Comparative Example 2) The present embodiment differs from the first embodiment in that the cathode electrode of the vacuum vessel for forming each i-type layer has a parallel plate structure and the cathode electrode structure shown in FIGS. different. In this cathode electrode structure, the ratio of the surface area of the cathode electrode to the sum of the surface areas of the conductive strip member and the anode electrode was 0.6 times.

However, the conditions for producing the photovoltaic element were the same as those in Example 7 (Table 7-1).

The other points were the same as in Example 7, and a triple cell type photovoltaic element (referred to as element ratio 2) was produced.

The photovoltaic elements produced in Example 7 and Comparative Example 2, ie, (element-actual 7) and (element-ratio 2), in the same manner as in Example 1, had uniformity in characteristics, defect density and The light degradation was evaluated. The results are shown in Table 7-2.

[0116]

[Table 7-2] From Table 7-2, the photovoltaic element of Comparative Example 2 (element-ratio 2)
On the other hand, the photovoltaic element of Example 7 (Element-Real 7)
All of the variation in conversion efficiency, the defect density, and the light degradation rate were excellent, and it was found that the triple photovoltaic device having excellent characteristics was obtained by the manufacturing method of the present invention.

[0117]

As described above, according to the present invention,
Fabrication of semiconductor thin film and photovoltaic element capable of producing large quantities of semiconductor thin film and photovoltaic element with high quality and excellent uniformity with few defects over a large area with high throughput. The device is obtained.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an apparatus for manufacturing a semiconductor thin film using a cathode electrode according to the present invention, and is a conceptual schematic view used to explain an example of a discharge space in the manufacturing apparatus. is there.

FIG. 2 is a schematic diagram showing an example of a pulse modulation waveform according to the present invention.

FIG. 3 is a schematic view showing an example of a cathode electrode according to the present invention.

FIG. 4 is a schematic cross-sectional view of a conventional apparatus for producing a semiconductor thin film using a cathode electrode.

FIG. 5 is a conceptual schematic diagram used to describe an example of a discharge space in the manufacturing apparatus.

FIG. 6 is a schematic cross-sectional view of an apparatus for manufacturing a photovoltaic element using the apparatus for manufacturing a semiconductor thin film according to the present invention.

FIG. 7 is a conceptual sectional view of a single-cell type photovoltaic device according to the present invention.

FIG. 8 is a conceptual sectional view of a triple-cell type photovoltaic device according to the present invention.

[Explanation of symbols]

100 vacuum vessel, 101 belt-shaped member, 103a, 103b, 103c heating heater, 104a, 104b, 104c gas introduction tube, 107 cathode electrode, 124n, 124, 124p lamp heater, 129n, 129, 129p, 130 gas gate, 131n, 131, 131p, 132 gas gate introduction pipe, 301, 302 vacuum vessel, 303, 304 bobbin, 305, 306 idling roller, 307, 308 conductance valve, 310, 311 exhaust pipe, 314, 315 pressure gauge, 513 exhaust pipe, 601, 602 vacuum Container, 603, 604 cathode electrode, 605, 606 gas introduction pipe, 607, 608 exhaust pipe, 1000 conductive strip member, 1001 vacuum vessel, 1002 cathode electrode, 1003 cut-off electrode, 1 004 Anode electrode, 1005 lamp heater, 1006 exhaust port, 1007 gas introduction pipe, 1008 gas gate, 1009 insulating insulator, 1010 high frequency oscillator, 1011 modulation oscillator, 1012 amplifier, 2000 conductive strip member, 2001 vacuum vessel 2002 cathode electrode, 2004 Anode electrode, 2005 lamp heater, 2006 exhaust port, 2007 gas inlet tube, 2008 gas gate, 2009 insulating insulator, 4001 SUS substrate, 4002 Ag thin film, 4003 ZnO thin film, 4004 first conductivity type layer, 4005 i-type layer, 4006 first 2, 4007 ITO, 4008 collector electrode, 5001 SUS substrate, 5002 Ag thin film, 5003 ZnO thin film, 5004 first conductive type layer, 5005 first i-type layer, 006 second conductivity type layer, 5007 first conductivity type layer, 5008 second i-type layer, 5009 second conductivity type layer, 5010 first conductivity type layer, 5011 third i-type layer, 5012 2, conductivity type layer, 5013 ITO, 5014 current collecting electrode.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shotaro Okabe 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Takahiro Yajima 3-30-2 Shimomaruko, Ota-ku, Tokyo (72) Inventor Yasushi Fujioka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Masahiro Kanai 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (2)

[Claims] 1. A plasma discharge space having a cathode electrode to which high-frequency power is applied, a band-shaped member at a ground potential, and an anode electrode, wherein the surface area of the cathode electrode in the plasma discharge space is the plasma discharge space. And the potential of the cathode electrode (hereinafter, referred to as self-bias) when a glow discharge occurs is positive with respect to the strip member and the anode electrode at the ground potential. It can maintain a potential, and has a structure in which the shape of the cut-off electrode forming a part of the cathode electrode is a fin shape or a block shape that does not hinder the flow of the material gas flowing through the cut-off electrode. An apparatus for producing a semiconductor thin film having the cathode electrode, wherein a pulsed plasma is supplied to the plasma discharge space. An apparatus for producing a semiconductor thin film, wherein high-frequency power is applied in a pulse shape to the cathode electrode to generate the power. 2. A photovoltaic element comprising a plurality of different thin films laminated on the surface of a strip-shaped member by a plasma CVD method when the strip-shaped member continuously passes through a plurality of connected vacuum vessels. In the manufacturing apparatus, a cathode electrode to which high-frequency power is applied, a band-shaped member at a ground potential, and an anode electrode are connected to a capacitively coupled plasma discharge space for manufacturing a semiconductor thin film to be a constituent layer of the photovoltaic element. The surface area of the cathode electrode in the plasma discharge space is larger than the sum of the surface areas of the strip-shaped member and the anode electrode in the plasma discharge space, and the potential of the cathode electrode at the time of glow discharge occurrence (hereinafter, referred to as
Self-bias) can maintain a positive potential with respect to the strip-shaped member and the anode electrode at the ground potential, and the shape of the cut-off electrode constituting a part of the cathode electrode is the same as that of the strip-shaped member. A fin-shaped or block-shaped photovoltaic element having a cathode electrode having a structure that does not hinder the flow of a material gas flowing in the transport direction of the photovoltaic element, wherein a pulsed plasma is generated in the plasma discharge space. An apparatus for manufacturing a photovoltaic element, wherein high-frequency power is applied in a pulsed manner to the cathode electrode.