JP2716633B2 - Photovoltaic element, method of manufacturing the same, and power generator using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pin type photovoltaic element made of a silicon-based non-single-crystal semiconductor material, a method of manufacturing the same, and a power generator. In particular, the present invention relates to a pin-type photovoltaic element in which a band gap in an i-type layer is changed, and also relates to a power generation system using the photovoltaic element.

[0002]

2. Description of the Related Art Conventionally, in a photovoltaic device having a pin structure made of a silicon-based non-single-crystal semiconductor material, light whose i-layer contains silicon atoms and germanium atoms and whose band gap changes in the i-type layer. Various proposals have been made for electromotive force elements as described below. For example, (1) “Optimum deposition conditions for a- (Si, G
e): H using a triode-configurated rf glow discharge
system ”, JA Bragagnolo, P. Littlefield, A. Mas
trovito and G. Storti, Conf. Rec. 19th IEEE Photov
oltaic Specilists Conference-1987, pp.878, (2) “Efficiency improvement in amorphous-SiGe: H
solar cells and its application to tandem type so
lar cells ”, S. Yoshida, S. Yamanaka, M. Konagai a
nd K. Takahashi, Conf. Rec.19th IEEE Photovoltaic
Specilists Conference-1987, pp.1101, (3) “Stability and terrestrial application of a
-Si tandem type solarcells ”, A. Hiroe, H. Yamagis
hi, H. Nishio, M. Kondo and Y. Tawada, Conf. Rec.
19th IEEE Photovoltaic Specilists Conference-1987,
pp.1111, (4) “Preparation of high quality a-SiGe: H films
and its application to the high efficiency triple
-junction amorphous solar cells ”, K. Sato, K. Kawa
bata, S. Terazono, H. Sasaki, M. Deguchi, T. Itaga
ki, H. Morikawa, M. Aiga and K. Fujikawa, Conf. Re
c. 20th IEEE Photovoltaic SpecilistsConference-198
8 pp. 73, (5) USP 4,816,082, (6) USP 4,471,155, (7) USP 4,782,376 and the like have been reported.

A theoretical study of the characteristics of a photovoltaic device having a changed band gap is described in, for example, (8) “A novel design for amorphous silicon alloy”.
solar cells ”, S. Guha, J. Yang, A. Pawlikiewicz,
T. Glatfelter, R. Ross and SR Ovshinsky, Conf.
Rec. 20th IEEE Photovoltaic Specilists Conference-
1988 pp.79, (9) “Numerical modeling of multijunction, amorp
hous silicon based PIN solar cells ”, AH Pawl
ikiewicz and S. Guha, Conf. Rec. 20th IEEE Photovo
ltaic Specilists Conference-1988 pp.251, etc. have been reported.

In such a conventional photovoltaic element, p
A layer having a variable band gap is inserted at the interface for the purpose of preventing recombination of photoexcited carriers near the / i, n / i interface, increasing the open-circuit voltage, and improving the hole carrier range. doing.

[0005]

A conventional photovoltaic device containing silicon atoms and germanium atoms and having a changed band gap requires higher performance and reliability in practical use, and recombination of photoexcited carriers. It is desired to further improve the suppression of the voltage drop, the open circuit voltage and the hole carrier range.

In addition, the conventional photovoltaic element has a problem that the conversion efficiency is reduced when the light applied to the photovoltaic element is weak. Further, the conventional photovoltaic element has a problem that the photoelectric conversion efficiency is reduced when the i-layer has a strain and is annealed where there is vibration or the like. An object of the present invention is to provide a photovoltaic element that solves the above-mentioned conventional problems. That is, an object of the present invention is to provide a photovoltaic element in which recombination of photoexcited carriers is prevented and the open voltage and the carrier range of holes are improved.

It is another object of the present invention to provide a photovoltaic device having improved conversion efficiency when the light applied to the photovoltaic device is low. It is a further object of the present invention to provide a photovoltaic element in which the photoelectric conversion efficiency is unlikely to decrease when annealing is performed under vibration for a long period of time. Still another object of the present invention is to provide a photovoltaic element whose photoelectric conversion efficiency hardly changes with temperature change.

Still another object of the present invention is to provide a system using a photovoltaic device which has achieved the above-mentioned object.

[0009]

According to the present invention, there is provided a photovoltaic device comprising a pin type photovoltaic device having an amorphous or microcrystalline structure, wherein an i-type layer is located on a side of the p-type layer and the microwave and 1 to 3 A first i-type layer deposited by the CVD method in the presence of a high frequency of 100 MHz and a second i-type layer located on the side of the n-type layer and deposited by the CVD method in the presence of a high frequency of 1 to 100 MHz. And wherein the first i-type layer contains silicon atoms and germanium atoms, and the minimum value of the band gap of the first i-type layer is closer to the p-type layer than the center. The second i-type layer includes amorphous silicon or microcrystalline silicon and has a thickness of 30 nm or less, and the microwave energy is more than the microwave energy that decomposes the source gas by 100%. Low Is set, the said high frequency energy applied simultaneously, wherein said set higher than the microwave energy.

[0010] In the manufacturing method, an n-type semiconductor is formed, and high-frequency energy of 1 to 100 MHz is applied for forming a plasma containing silicon atoms.
Thus, the step of depositing the RF-i type semiconductor and the simultaneous application of microwave energy for forming a plasma and high-frequency energy of 1 to 100 MHz to the gas containing silicon atoms and germanium atoms, whereby silicon atoms and Depositing an MW-i type semiconductor containing germanium atoms in this order, wherein the microwave energy in the step of depositing the MW-i type semiconductor is the silicon atom And the microwave energy for decomposing the gas containing germanium atoms by 100% is set lower than the microwave energy, and the high-frequency energy in the step is set higher than the microwave energy. Method.

[0011]

The operation and the configuration will be described in detail below with reference to the drawings. FIG. 1 is a schematic explanatory view showing one example of the photovoltaic element of the present invention. The photovoltaic device of the present invention includes a conductive substrate 101 having a light reflection layer and a light reflection enhancement layer, an n-type silicon-based non-single-crystal semiconductor layer 102, and RF plasma CVD.
Layer 109 formed by the method, substantially i by the microwave plasma method containing silicon atoms and germanium atoms.
A non-single-crystal semiconductor layer 103 of a type, an i-type layer 108 by an RF plasma CVD method, a p-type silicon-based non-single-crystal semiconductor layer 104, a transparent electrode 105, a current collecting electrode 106, and the like.

In the i-type layer formed by microwave plasma CVD, the minimum value of the band gap is deviated in the direction of the p-type layer, and the electric field of the conduction band is large on the p-type layer side of the i-type layer. Is efficiently performed, and recombination of electrons and holes near the interface between the p-type layer and the i-type layer can be reduced. Further, since the electric field in the valence band increases from the i-type layer toward the n-type layer,
Recombination of electrons and holes excited by light in the vicinity of the mold layer can be reduced.

Further, by simultaneously adding a valence electron controlling agent serving as a donor and a valence electron controlling agent serving as an acceptor to an i-type layer formed by microwave plasma CVD, the carrier range of electrons and holes can be increased. it can. In particular, by including a relatively large amount of the valence electron controlling agent at the minimum band gap, the carrier range of electrons and holes can be effectively extended. As a result n
A high electric field near the interface between the i-type layer and the i-type layer formed by the microwave plasma CVD method can be used more effectively, and the collection efficiency of the photo-excited electrons and holes in the i-type layer can be significantly improved. Comes out. Further, in the vicinity of the interface between the n-type layer and the i-type layer, defect levels (so-called D− and D +) are compensated by a valence electron controlling agent, so that hopping conduction via the defect levels causes dark current (reverse). Bias). In particular, in the vicinity of the interface, the internal stress such as strain caused by a sudden change of the constituent element peculiar to the interface is reduced by containing a larger amount of the valence electron controlling agent than in the i-type layer. As a result, defect levels near the interface can be reduced. As a result, the open voltage and the fill factor of the photovoltaic element can be improved.

In addition, the durability against light degradation is increased by simultaneously including a valence electron controlling agent serving as a donor and a valence electron controlling agent serving as an acceptor in the i-type layer by microwave plasma CVD. Although the details of the mechanism are unknown, it is considered as follows. That is, it is generally considered that the dangling bonds generated by light irradiation deteriorate the characteristics of the photovoltaic element due to the recombination centers of carriers. In the case of the present invention, both the valence electron controlling agent serving as a donor and the valence electron controlling agent serving as an acceptor in the i-type layer are contained, and they are not 100% activated. As a result, even if dangling bonds are generated by light irradiation, it is considered that they react with the inactive valence electron controlling agent to compensate for dangling bonds.

In addition, even when the light intensity applied to the photovoltaic element is low, the probability that the photoexcited electrons and holes are trapped is reduced because the defect levels are compensated by the valence electron controlling agent. Further, as described above, since the dark current at the time of reverse bias is small, a sufficient electromotive force can be generated. As a result, excellent photoelectric conversion efficiency is exhibited even when the intensity of light irradiated on the photovoltaic element is low.

In addition, the photovoltaic element of the present invention has a low photoelectric conversion efficiency even when it is annealed under vibration for a long time. Although the detailed mechanism is unknown, it is considered as follows. That is, the photovoltaic element is formed by changing the constituent elements in order to continuously change the band gap. Therefore, strain is accumulated inside the photovoltaic element. That is, many weak couplings exist inside the photovoltaic element. Then, the weak bond in the i-type non-single-crystal semiconductor is broken by vibration, and an unbonded bond is formed. However, the simultaneous addition of a valence electron controlling agent as a donor and a valence electron controlling agent as an acceptor increases local flexibility and suppresses a decrease in photoelectric conversion efficiency of the photovoltaic element even during annealing due to long-term vibration. It is thought that we can do it. In addition, it is conceivable that an unactivated donor or acceptor is mainly coordinated with three, thereby increasing local flexibility. As a result, it is considered that annealing occurs for a long period of time under vibration and the photoelectric conversion efficiency does not easily decrease. However, unactivated donors and acceptors must be reduced to a certain amount or less to form defects.
That is, the preferred amount of the unactivated donor or acceptor is 0.1 to 100 ppm.

In addition, by providing an i-type layer by RF plasma CVD at a deposition rate of 2 nm / sec or less and 30 nm or less between the p-type layer and the i-type layer by microwave plasma CVD, the photovoltaic element is further improved. Can be improved in photoelectric conversion efficiency. In particular, the photovoltaic element of the present invention has a small change in photoelectric conversion efficiency when used in an environment with a large temperature change.

The i-type non-single-crystal semiconductor layer deposited by the RF plasma CVD method has a deposition rate of 2 nm / sec or less.
The gas phase reaction is unlikely to occur and deposits with low power. As a result, the packing density of the deposited film is high, and when the i-type layer is laminated with the deposited film by the microwave plasma CVD method, the interface state between the i-type layers is reduced. In particular, when the deposition rate of the deposited film by the microwave plasma CVD method is 5 nm / sec or more, after the microwave plasma is stopped, the surface level near the surface of the i-type layer is not sufficiently relaxed, so that the surface state is low. Very much. RF plasma CV is applied to the surface of such an i-type layer.
By forming a deposition film having a low deposition rate by the D method, it is possible to reduce the surface state of the deposition film by the microwave plasma CVD method by annealing by diffusion of hydrogen atoms which occurs simultaneously with the formation of the deposition film by the RF plasma CVD method. It is considered possible.

Furthermore, by inserting an i-type layer by RF plasma CVD at a deposition rate of 2 nm / sec or less at 30 nm or less between the n-type layer and the i-type layer by microwave plasma CVD, the photovoltaic power is further increased. The photoelectric conversion efficiency of the device can be improved. In particular, the photovoltaic element of the present invention,
When used in an environment with a large temperature change, the photoelectric conversion efficiency is unlikely to change.

In the deposition by the microwave plasma CVD method, the kinetic energy of ions is larger than that in the RF plasma CVD method, and therefore, it is considered that the lower semiconductor layer is damaged. Therefore, it is necessary to use a semiconductor layer having resistance to ion damage as the lower semiconductor layer. Further, the deposited film deposited by the microwave plasma CVD method is of good quality as a semiconductor, and the deposition conditions are lower than that of the lower semiconductor layer. It is necessary to deposit under conditions that are unlikely to cause damage. The deposition conditions for the photovoltaic device of the present invention are suitable to achieve this purpose.

As a result, a photovoltaic element having a small interface state can be formed at the interface between the n-type layer and the i-type layer by RF plasma CVD, and the open-circuit voltage and short-circuit current of the photovoltaic element can be reduced. It will improve. FIG. 2 is a diagram schematically illustrating an example of a change in the band gap of the photovoltaic device of the present invention. This figure shows half of the band gap (E
The change of the band gap in the i-type layer is shown based on _G / 2). In the figure, the right side is an n-type layer (not shown) side, and the left side is a p-type layer (not shown) side. The example of FIG. 2 is configured such that the minimum value of the band gap is near the p-type layer and the maximum value of the band gap is in contact with the p-type layer and the n-type layer. i-type layer 211 and i-type layer 212
Is a layer deposited by microwave plasma CVD, and the i-type layer 213 is a non-single-crystal silicon layer deposited by RF plasma CVD. i-type layer 211 and i-type layer 2
13 is an i-type layer 2 so that the band gaps are substantially equal.
11 and 213 were adjusted for the hydrogen content.

FIG. 3 is a schematic illustration of the change in the band gap drawn in the same manner as FIG. 3, the minimum value of the band gap is p as in FIG.
Although it is closer to the mold layer, the maximum value of the band gap is configured so as to be in contact with the p-type layer. i-type layer 221
The i-type layer 222 is a layer deposited by a microwave plasma CVD method, and the i-type layer 223 is an RF plasma CVD
It is a non-single-crystal silicon layer deposited by a method. i-type layer 2
21 and the band gap of the i-type layer 223 are discontinuously connected. With the band gap configuration shown in FIG. 3, the open circuit voltage can be particularly increased.

FIG. 4 to FIG. 10 show that an RF plasma CVD method is used between the n-type layer and the i-type layer formed by the microwave plasma CVD and between the p-type layer and the i-type layer formed by the microwave plasma CVD. It is a schematic explanatory view of a change of a band gap of a photovoltaic element having an i-type non-single-crystal layer. Each figure depicts a change in band gap based on E _G / 2. The right side of the band diagram is an n-type layer, and the left side is a p-type layer.

FIG. 4 shows a microwave plasma CVD in which the i-type layer 312 formed by the RF plasma CVD method is provided in the i-type layer on the p-type layer side, and the band gap decreases from the n-type layer side toward the p-type layer. In this example, there is an i-type layer 311 formed by a method and an i-type layer 313 formed by RF plasma CVD near the n-type layer. And the minimum value of the band gap is the i-type layer 31.
2 and an i-type layer 311 at the interface. Further, the bonding of the bands between the i-type layer 311 and the i-type layer 312 is such that the bands are discontinuously connected. Thus, by providing the i-type layer by the RF plasma CVD method, the dark current due to hopping conduction via the defect level at the time of reverse bias of the photovoltaic element can be suppressed as much as possible. As a result, the open-circuit voltage of the photovoltaic element increases.

The i-type layer 3 is formed by RF plasma CVD.
The layer thickness of 12 is a very important factor, and the preferred range of the layer thickness is 1 to 30 nm. I with constant band gap
If the thickness of the mold layer is less than 1 nm, dark current due to hopping conduction via defect levels cannot be suppressed, and improvement in the open voltage of the photovoltaic element cannot be expected.
On the other hand, when the layer thickness of the i-type layer 312 by RF plasma CVD is larger than 30 nm, photoexcited holes are likely to be accumulated near the interface between the i-type layer 312 and the i-type layer 311 having a changed band gap. Therefore, the collection efficiency of photoexcited carriers decreases. That is, the short-circuit photocurrent is reduced.

The layer thickness of the i-type layer 313 by RF plasma CVD is a very important factor, and the preferable layer thickness is 1 to 30 nm. When the thickness of the i-type layer having a constant band gap is smaller than 1 nm, dark current due to hopping conduction via a defect level cannot be suppressed, and an improvement in the open-circuit voltage of the photovoltaic element cannot be expected. On the other hand, when the layer thickness of the i-type layer 313 by RF plasma CVD is greater than 30 nm, holes excited by light are accumulated near the interface between the i-type layer 312 and the i-type layer 311 having a changed band gap. As a result, the collection efficiency of photoexcited carriers decreases. That is, the short-circuit photocurrent decreases.

FIG. 5 shows that an i-type layer 322 having a constant band gap is provided between the p-type layer and the i-type layer 321 by microwave CVD, and the n-type layer and the i-type layer 321 by microwave plasma CVD. In this example, an i-type layer 323 is formed between the i-type layer 321 and the i-type layer 321 by RF plasma CVD, the band gap of which is equal to that of the i-type layer 321.

FIG. 6 shows a p-type layer and a microwave RF plasma C.
RF between the i-type layer 331 by the VD method and between the n-type layer and the i-type layer 331 by the microwave plasma CVD method.
This is an example in which i-type layers 332 and 333 are provided by a plasma CVD method. When a reverse bias is applied to the photovoltaic element, the dark current further decreases and the open voltage of the photovoltaic element increases.

FIGS. 7 to 10 show bands between the p-type layer and the i-type layer formed by the microwave plasma CVD method and between the n-type layer and the i-type layer formed by the microwave plasma CVD method. It has an i-type layer having a constant gap, and has an i-type layer formed by microwave plasma CVD.
This is an example of a photovoltaic element having a region where the band gap changes rapidly in the direction of the mold layer or the n-type layer. In the figure, the band diagram is 1/2 of the band gap (E _G / 2)
, And the right side of the band diagram is the n-type layer, and the left side is the p-type layer.

FIG. 7 shows a p-type layer and a microwave plasma CV.
RF plasma C is applied between the i-type layer 341 and the n-type layer by the D method and the i-type layer 341 by the microwave plasma CVD method.
I-type layers 342, 34 having a constant band gap by VD method
3, the band gap of the i-type layer 341 is changed, and the position of the minimum band gap of the i-type layer 341 is offset toward the p-type layer side. This is an example in which the band gaps of the i-type layers 342 and 343 are continuous. By continuing the band gap, electrons and holes photoexcited in the i-type layer in which the band gap of the i-type layer is changed can be efficiently collected in the n-type layer and the p-type layer, respectively. In particular, when the i-type layers 342 and 343 each having a constant band gap are as thin as 5 nm or less, the i-type layer in which the band gap of the i-type layer changes rapidly becomes darker when a reverse bias is applied to the photovoltaic element. The current can be reduced, so that the open-circuit voltage of the photovoltaic element can be increased.

FIG. 8 shows that the i-type layer 351 whose band gap is changed by the microwave plasma CVD method is an RF type.
I-type layer 3 with constant band gap by plasma CVD
This is an example in which the connection is discontinuously and relatively loosely connected to 52 and 353. However, the i-type layer 352 having a constant band gap,
Since the 353 and the i-type layer 351 having the changed band gap are gently connected in the direction in which the band gap is widened, the carriers photoexcited in the i-type layer 351 having the changed band gap can efficiently have a constant band gap. I
It is injected into the mold layers 352, 353. As a result, the collection efficiency of the photoexcited carriers increases.

Whether the i-type layer having a constant band gap and the i-type layer having a changing band gap are connected continuously or discontinuously depends on whether the i-type layer having a constant band gap and the band gap are rapidly changed. It depends on the thickness of the i-type layer that is changing. 5n i-type layer with constant band gap
When the thickness of the i-type layer whose band gap is rapidly changing is as thin as 10 m or less, the i-type layer having a constant band gap and the i-type layer whose band gap is changing are continuous. Connected, the photoelectric conversion efficiency of the photovoltaic element increases, while the i-type layer having a constant band gap has a thickness of 5 nm or more, and the i-type layer has a rapidly changing band gap. In the case where the layer thickness is 10 to 30 nm, the conversion efficiency of the photovoltaic element is improved when the i-type layer having a constant band gap and the i-type layer having a changed band gap are connected discontinuously. Is what you do.

FIG. 9 shows an i-type layer 36 having a fixed band gap.
I-type layer 36 whose band gap is changed to 2,363
1 is an example in which connection is made in two stages. In this example, the position where the band gap is minimal is closer to the p-type layer. By connecting to the constant i-type layers 362 and 363 having a wide band gap through a step of gradually expanding the band gap from a position where the band gap is extremely small and a step of rapidly expanding the band gap, light excitation is performed in a region where the band gap is changed. The collected carriers can be collected efficiently. FIG.
In this case, the i-type layer 361 has an i-type layer 361 whose band gap changes rapidly toward the i-type layer 363.

FIG. 10 shows a photovoltaic element having i-type layers 373 and 374 formed by RF plasma CVD between an i-layer 371 formed by microwave plasma CVD and p-type and n-type layers. An i-type layer 372 having a constant band gap by microwave plasma CVD is provided between the i-type layer 373 and the i-type layer 371. i-type layer 37
This is an example in which 2 and the i-type layer 371 are continuously connected via a two-step band gap change.

The internal strain can be reduced by connecting the above-described region having a constant band gap and the i-type layer whose band gap is changed in a state where the constituent elements are similar. As a result, even if annealing is performed under vibration for a long period of time, a phenomenon in which a weak bond in the i-layer is broken and the defect level increases to lower the photoelectric conversion efficiency is less likely to occur, and high photoelectric conversion efficiency is maintained. Is what you can do.

Further, as described above, the incorporation of the valence electron controlling agent in the i-type layer can increase the carrier range of the carriers in the i-type layer, thereby increasing the carrier collection efficiency. In particular, the collection efficiency of photoexcited carriers can be further increased by increasing the number of valence electron controlling agents in a narrow band gap and decreasing the number in a wide band gap corresponding to a change in the band gap. Further, in the i-type layer having a constant band gap, the valence electron controlling agent is contained in the p-type layer and the n-type layer side more than the band gap minimum, so that the photoexcitation near the p / i interface and the n / i interface is achieved. It can prevent the recombination of carriers and can improve the photoelectric conversion efficiency of the photovoltaic element.

In the present invention, the preferable range of the band gap at the minimum band gap of the i-type layer containing silicon atoms and germanium atoms is variously selected depending on the spectrum of the irradiation light, but 1.1. ~ 1.
6 eV is desirable. Further, in the photovoltaic device of the present invention in which the band gap is continuously changed, the inclination of the tail state of the valence band is an important factor that affects the characteristics of the photovoltaic device. It is preferable that the slope of the tail state at the minimum value is smoothly continuous from the slope of the tail state at the maximum band gap.

The photovoltaic element having the pin structure has been described above, but the present invention can also be applied to a photovoltaic element having a pin structure such as a pinpin structure or a pinpinpin structure. FIG. 11 is a schematic explanatory view of a deposited film forming apparatus suitable for performing the method for forming a deposited film of a photovoltaic element of the present invention. The deposition film forming apparatus includes a deposition chamber 1001, a dielectric window 1002, a gas introduction pipe 1003, a substrate 1004,
Heater 1005, vacuum gauge 1006, conductance valve 1007, auxiliary valve 1008, leak valve 1009, waveguide 1010, bias power supply 1011, bias rod 1012, shutter 1013, source gas supply device 1020, mass flow controller 1021 to 1
029, gas inflow valves 1031-1039, source gas cylinder valves 1051-1059, pressure regulator 106
1 to 1069, source gas cylinders 1071 to 1079, and the like.

Although the details of the deposition mechanism in the preferred method of depositing a photovoltaic device of the present invention are unknown, it is considered as follows. By applying microwave energy lower than the microwave energy required to decompose the source gas to 100% on the source gas, high RF energy is simultaneously applied to the microwave energy on the source gas to form a deposited film. It is believed that a suitable active species can be selected. Further, it is considered that when the internal pressure in the deposition chamber when the source gas is decomposed is 50 mTorr or less, the mean free path of active species suitable for forming a high-quality deposited film is sufficiently long, so that the gas phase reaction is suppressed as much as possible. .
When the internal pressure in the deposition chamber is 50 mTorr or less, it is considered that the RF energy hardly affects the decomposition of the source gas, and controls the potential between the plasma in the deposition chamber and the substrate. That is, the microwave plasma C
In the case of the VD method, although the potential difference between the plasma and the substrate is small, the potential difference between the plasma and the substrate (+ on the plasma side and − on the substrate side) can be increased by applying RF energy simultaneously with microwave energy. it can. Since the plasma potential is positive and high with respect to the substrate, active species decomposed by the microwave energy are deposited on the substrate, and at the same time, + ions accelerated by the plasma potential collide with the substrate and generate It is considered that the relaxation reaction is promoted and a high-quality deposited film is obtained. In particular, this effect becomes remarkable when the deposition rate is several nm / sec or more.

Further, since RF has a high frequency unlike DC, the difference between the plasma potential and the substrate potential is determined by the distribution of ionized ions and electrons. That is, the potential difference between the substrate and the plasma is determined by the synergistic effect between the ions and the electrons. Therefore, there is an effect that spark is less likely to occur in the deposition chamber. As a result, a stable glow discharge can be maintained for 10 hours or longer.

In addition, in depositing a layer having a changed band gap, the flow rate and the flow rate ratio of the source gas change with time or spatially.
It is necessary to appropriately change the C voltage over time or spatially. However, in the method for forming a deposited film according to the present invention, the ratio of ions changes due to a temporal or spatial change in the flow rate and the flow rate ratio of the source gas. The RF self-bias automatically changes accordingly. As a result, when the source gas flow rate and the source gas flow rate ratio are changed by applying RF to the bias rod, the discharge is very stable as compared with the case of DC bias.

In addition, in order to obtain a desired change in band gap in the method of forming a deposited film, it is preferable to mix a gas containing silicon atoms and a gas containing germanium at a distance of 5 m or less from the deposition chamber. It is.
If the source gases are mixed at a distance of more than 5 m, even if the mass flow controller is controlled in response to a desired change in band gap, the source gas mixing positions are far apart, so that the source gas changes late and the source gases may not be mixed. Diffusion occurs, causing a deviation from a desired band gap. That is, if the mixing positions of the source gases are too far apart, the controllability of the band gap is reduced.

Further, in order to change the hydrogen content contained in the i-type layer in the layer thickness direction, the RF energy applied to the bias rod is increased where the hydrogen content is desired to be increased, and the hydrogen content is reduced. The RF energy applied to the bias rod may be reduced where it is desired to reduce it. On the other hand, when the DC energy is applied simultaneously with the RF energy, the DC voltage applied to the bias rod may be increased by applying a large voltage with a positive polarity where the content of hydrogen atoms is to be increased, and when the hydrogen content is to be reduced, What is necessary is just to apply a small voltage with a positive polarity to the DC voltage applied to the bias rod.

The photovoltaic element of the present invention is formed, for example, as follows. First, the deposition chamber 100 shown in FIG.
A substrate 1004 for forming a deposited film is mounted in the chamber 1, and the inside of the deposition chamber is sufficiently evacuated to a level of 10 ^-5 Torr or less. A turbo molecular pump is suitable for this exhaust, but an oil diffusion pump may be used. In the case of an oil diffusion pump, the internal pressure of the deposition chamber 1001 is set to 10 so that oil does not diffuse back into the deposition chamber.
^-4 Torr or less, H ₂ , He, Ar, Ne, K
A gas such as r or Xe is preferably introduced into the deposition chamber. After sufficiently exhausting the deposition chamber, H ₂ , He, Ar, N
Gases such as e, Kr, and Xe are introduced into the deposition chamber so that the pressure in the deposition chamber is substantially the same as when the source gas for forming the deposited film is flowed. The pressure in the deposition chamber is 0.5 to 50
mTorr is the optimal range. When the internal pressure in the deposition chamber is stabilized, the substrate heater 1005 is turned on to heat the substrate to 100 to 500 ° C. When the substrate temperature is stabilized at a predetermined temperature, H ₂ , He, Ar, Ne, Kr, and Xe are used.
Then, a predetermined amount of a raw material gas for forming a deposited film is introduced from a gas cylinder into the deposition chamber via a mass flow controller.

The supply amount of the source gas for forming the deposited film introduced into the deposition chamber is appropriately determined by the deposition in the deposition chamber. The internal pressure in the deposition chamber is a very important factor, and the optimal internal pressure in the deposition chamber is 0.5 to 50 mTorr.
It is. In the method of forming a deposited film for a photovoltaic device according to the present invention, the microwave energy input into the deposition chamber for forming the deposited film is an important factor. The microwave energy is appropriately determined according to the flow rate of the source gas introduced into the deposition chamber.
The energy is smaller than the microwave energy required for decomposition, and a preferable range is 0.02.
１1 W / cm ³ . A preferable frequency range of the microwave energy is 0.5 to 10 GHz. Particularly, a frequency around 2.45 GHz is suitable. Further, in order to form a deposited film with reproducibility by a deposited film forming method and to form a deposited film over several hours to several tens of hours, the stability of the frequency of microwave energy is very important. It is preferable that the fluctuation of the frequency be in the range of ± 2%. Further, the ripple of the microwave is preferably in a range of ± 2%. RF energy is simultaneously turned further the microwave energy into the deposition chamber, a preferable range of the a factor very important In combination with the microwave energy RF energy, 0.04~2W / cm ³ It is.

A preferable frequency range of the RF energy is 1 to 100 MHz. Especially 13.56
MHz is optimal. RF frequency fluctuation is ± 2%
A smooth waveform is preferable within the range. R
When F energy is supplied, it is appropriately selected according to the area ratio between the area of the bias rod for supplying RF energy and the area of the ground. In particular, the area of the bias rod for supplying RF energy is larger than the area of the ground. If narrow,
Self-bias on power supply side for RF energy supply (DC
It is better to ground the component). Further, when the self-bias (DC component) on the power supply side for supplying the RF energy is not grounded, it is preferable that the area of the bias rod for supplying the RF energy be larger than the area of the ground contacting the plasma.

Such microwave energy is introduced from the waveguide 1010 through the dielectric window 1002 into the deposition chamber, and at the same time, RF energy is introduced from the bias power supply 1011 through the bias rod 1012 into the deposition chamber. In such a state, the source gas is decomposed for a desired time to form a deposited film having a desired thickness on the substrate. Thereafter, the input of microwave energy and RF energy is stopped, the deposition chamber is evacuated, and sufficiently purged with a gas such as H ₂ , He, Ar, Ne, Kr, or Xe. Take out.

A DC voltage may be applied to the bias rod 1012 in addition to the RF energy. It is preferable to apply the voltage so that the bias bar becomes positive as the polarity of the DC voltage. The preferable range of the DC voltage is 10 to 300 V. FIG. 12 is a schematic explanatory view of a deposition film forming apparatus suitable for depositing an i-type layer of the photovoltaic element of the present invention by RF plasma CVD. The deposition film forming apparatus includes a deposition chamber 1101, a cathode 1102, a gas introduction pipe 1103, a substrate 1104,
Heater 1105, vacuum gauge 1106, conductance valve 1107, auxiliary valve 1108, leak valve 1109, RF power supply 1111, RF matching box 1112, source gas supply device 1020, mass flow controllers 1021 to 1029, gas inflow valve 103
1 to 1039, valves 1051 to 10 of raw material gas cylinders
59, pressure regulators 1061 to 1069, source gas cylinders 1071 to 1079, and the like.

RF plasma CV of photovoltaic device of the present invention
The i-type layer by the method D is formed, for example, as follows. First, a substrate deposited up to an i-type layer by a microwave plasma CVD method is mounted as a substrate 1104 on a heater in a deposition chamber 1101. The door is closed and the inside of the deposition chamber 1101 is sufficiently evacuated to a level of 10 ⁻³ Torr or less. H ₂ , H
A substrate heating gas such as e, Ar, Ne, Kr, Xe or the like is flowed at the same flow rate and pressure as when RF plasma CVD is performed. At the same time, the switch of the substrate heater 1105 is turned on, and the heater 11 is set to a desired substrate temperature.
Set the temperature at 05. When the temperature of the substrate is stabilized at a predetermined temperature, the gas for heating the substrate is stopped, and a predetermined amount of a raw material gas for forming a deposited film is introduced from a gas cylinder into the deposition chamber 1101 via a mass flow controller. When the internal pressure of the deposition chamber is stabilized at a desired pressure by the source gas, desired RF energy is supplied from the RF power source to the matching box 11.
12 to the cathode electrode 1102. Then, plasma is generated and deposition is continued for a predetermined time. After deposition for a predetermined time, the supply of RF energy is stopped, the heater for heating the substrate is stopped, the source gas is stopped, and the deposition chamber is sufficiently purged. When the substrate temperature has dropped to about room temperature, the substrate is taken out of the deposition chamber.

When the i-type layer is deposited by the RF plasma CVD method, the substrate temperature is 100 to 350 ° C. and the internal pressure is 0.1 to
10 Torr, RF power is 0.01 to 5.0 W / cm
^{2. The} optimum condition for the deposition rate is 0.01 to ² nm / sec. A more preferable apparatus for depositing the photovoltaic element of the present invention is an apparatus in which a microwave plasma CVD apparatus and an RF plasma CVD apparatus are continuously connected as shown in FIGS. 4-3 and 4-4. . Deposition chamber and microwave plasma CVD by microwave plasma CVD
The deposition chamber by the method is preferably separated by a gate. The gate is preferably a mechanical gate valve or gas gate.

In the above-described method for forming a deposited film, the following compounds are suitable as compounds that can be mentioned as a source gas for silicon deposition. Specifically, gaseous compounds containing silicon atoms include SiH ₄ , Si
_{2 H 6, SiF 4, SiFH} 3, SiF 2 H 2, SiF 3 H,
Si ₃ H ₈ , SiD ₄ , SiHD ₃ , SiH ₂ D ₂ , SiH ₃
D, SiFD ₃ , SiF ₂ D ₂ , SiD ₃ H, Si ₂ D ₃ H ₃
And the like.

The following compounds are suitable as compounds listed as source gases for germanium deposition. Specifically, gaseous compounds containing germanium atoms include GeH ₄ , GeD ₄ , GeF ₄ , GeFH ₃ , and GeF _2.
H ₂ , GeF ₃ H, GeHD ₃ , GeH ₂ D ₂ , GeH ₃ D,
Ge ₂ H ₆ and Ge ₂ D ₆ are exemplified.

In the present invention, examples of the valence control agent introduced into the non-single-crystal semiconductor layer for controlling the valence electrons of the non-single-crystal semiconductor layer include Group III atoms and Group V atoms of the periodic table. . In the present invention, examples of the valence electron controlling agent introduced into the non-single-crystal semiconductor layer for controlling the valence electrons of the non-single-crystal semiconductor layer include Group III and V atoms of the periodicity.

In the present invention, a material effectively used as a starting material for introducing a group III atom, specifically, for introducing a boron atom, is B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H
_{9, B 5 H 11, B} 6 H 10, B 6 H 12, B 6 H 14 , etc. borohydride, may be mentioned BF _3, BCl ₃ or the like boron halide or the like. In addition, AlCl ₃ , GaCl ₃ , In
Cl ₃ and TlCl ₃ can also be mentioned.

In the present invention, the starting material for introducing a group V atom is effectively used. Specifically, for the purpose of introducing a phosphorus atom, a hydrogenated phosphorus such as PH ₃ or P ₃ H ₄ , PH ₄ I, P
F ₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , P
Halogenated phosphorus such as I ₃ and the like. In addition, As
H ₃ , AsF ₃ , AsCl ₃ , AsBr ₅ , AsF ₅ , Sb
H ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , Bi
H ₃ , BiCl ₃ , BiBr _{3 and the} like can also be mentioned.

It is preferable that the introduction amount of Group III and Group V atoms of the periodic table introduced into the i-type layer of the non-single-crystal semiconductor layer to achieve the object of the present invention is 1000 ppm or less. In order to achieve the object of the present invention, it is preferable to add the group III atom and the group V atom in the periodic table so that they are simultaneously compensated. In addition, the compound capable of being gasified is H ₂ , D ₂ , He, Ne, Ar, X
It may be appropriately diluted with a gas such as e or Kr and introduced into the deposition chamber. In particular, H ₂ and He are mentioned as the most suitable gas for diluting the gasifiable compound.

As the nitrogen-containing gas, N ₃ , NH ₃ , N
D ₃ , NO, NO ₃ , and N ₂ O are mentioned. Examples of the oxygen-containing gas include O ₂ , CO, CO ₂ , NO, NO ₂ , N ₂ O, and CH.
₃ CH ₂ OH, CH ₃ OH and the like. Hereinafter, the configuration of the photovoltaic element of the present invention will be described in detail.

Conductive Substrate The conductive substrate may be a conductive material, or may be a support formed of an insulating material or a conductive material and then subjected to a conductive treatment. As the conductive support,
For example, NiCr, stainless steel, Al, Cr, Mo, A
Metals such as u, Nb, Ta, V, Ti, Pt, Pb, Sn and the like, or alloys thereof.

Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyethylene, and polyamide, and sheets, glass, ceramics, and paper. Is mentioned. It is preferable that at least one surface of these electrically insulating supports is subjected to conductive treatment, and a photovoltaic layer is provided on the conductive-treated surface side.

For example, in the case of glass, N
iCr, Al, Cr, Mo, Ir, Nb, Ta, V, T
i, Pt, Pb, In ₂ O ₃ , ITO (In ₂ O ₃ + SnO
₂ ) Conductivity is imparted by providing a thin film made of a material such as NiCr, Al, Ag, Pb, Zn, N if the film is a synthetic resin film such as a polyester film.
i, Au, Cr, Mo, Ir, Nb, Ta, V, Ti,
A thin metal film such as Pt is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, or the like, or the surface is laminated with the metal to impart conductivity to the surface. The shape of the support may be a sheet having a smooth surface or an uneven surface. The thickness is appropriately determined so that a desired photovoltaic element can be formed, but when flexibility as a photovoltaic element is required, the thickness can be set within a range where the function as a support can be sufficiently exhibited. It can be as thin as possible. However, the thickness is usually 10 μm or more from the viewpoints of production and handling of the support, mechanical strength and the like.

Light Reflecting Layer For the light reflecting layer, a metal such as Ag, Al, Cu, or AlSi having a high reflectance in the near infrared to near infrared region is suitable. These metals are suitably formed by a resistance heating vacuum evaporation method, an electron beam vacuum evaporation method, a co-evaporation method, a sputtering method, or the like. Suitable layer thicknesses of these metals as the light reflecting layer are 10 nm to 5000 nm. In order to texture these metals, the substrate temperature at the time of depositing these metals may be 200 ° C. or higher.

[0062] ZnO is a reflection enhancing layer reflection enhancing _{layer, SnO 2, In 2 O 3} , IT
O, TiO ₂ , CdO, Cd ₂ SnO ₄ , Bi ₂ O ₃ , Mo
O ₃ , Na _x WO _{3 and the} like are mentioned as the most suitable ones. As a method for depositing the reflection increasing layer, a vacuum deposition method, a sputtering method, a CVD method, a spray method, a spin-on method, a dipping method, and the like are mentioned as suitable methods.

The optimum thickness of the reflection-enhancing layer varies depending on the refractive index of the material of the reflection-enhancing layer, but a preferable range of the layer thickness is 50 nm to 10 μm. In order to further texture the reflection enhancement layer,
It is preferable to raise the substrate temperature to 300 ° C. or more when depositing the reflection enhancing layer.

The p-type layer or the n-type layer The p-type layer or the n-type layer is an important layer that affects the characteristics of the photovoltaic device. The amorphous material of the p-type layer or the n-type layer (a
(It is needless to say that a microcrystalline material (expressed as μc-) is also included in the category of an amorphous material.), For example, a-Si: H, a-Si: HX, a-Si
C: H, a-SiC: HX, a-SiGe: H, a-S
iGeC: H, a-SiO: H, a-SiN: H, a-
SiON: HX, a-SiOCN: HX, μc-Si:
H, μc-SiC: H, μc-Si: HX, μc-Si
C: HX, μc-SiGe: H, μc-SiO: H, μ
c-SiGeC: H, μc-SiN: H, μc-SiO
N: HX, μc-SiOCN: HX, etc., p-type valence electron controlling agents (Group III atoms B, Al, Ga, I
n, Ti) or a material in which an n-type valence electron controlling agent (group V atom P, As, Sb, Bi) in the periodic table is added at a high concentration, and as a polycrystalline material (denoted as poly-). Are, for example, poly-Si: H, poly-Si: H
X, poly-SiC: H, poly-SiC: HX,
poly-SiGe: H, poly-Si, poly-
SiC, poly-SiGe, etc., p-type valence electron controlling agents (Group III atoms B, Al, Ga, In, T
l) and n-type valence electron controlling agent (Group V atom P,
Materials to which As, Sb, Bi) are added at a high concentration can be given.

In particular, the p-type layer or the n-type layer on the light incident side includes:
A crystalline semiconductor layer with little light absorption or an amorphous semiconductor layer with a wide band gap is suitable. The optimum amount of the group III atom added to the p-type layer and the group V atom added to the n-type layer is 0.1 to 50 at%. Hydrogen atoms (H, D) or halogen atoms contained in the p-type layer or the n-type layer work to compensate for dangling bonds of the p-type layer or the n-type layer, and doping efficiency of the p-type layer or the n-type layer. Is to improve. A hydrogen atom or a halogen atom added to the p-type layer or the n-type layer is 0.1 to
40 at% is mentioned as the optimum amount. In particular, when the p-type layer or the n-type layer is crystalline, the optimum amount of hydrogen atoms or halogen atoms is 0.1 to 8 at%. And p
A preferable distribution form is one in which a large amount of hydrogen atoms and / or halogen atoms is distributed on each interface side of the n-type layer / i-type layer and the n-type layer / i-type layer. The preferred range of the content of atoms and / or halogen atoms is 1.1 to 2 times the content in the bulk. By increasing the content of hydrogen atoms or halogen atoms in the vicinity of each interface between the p-type layer / i-type layer and the n-type layer / i-type layer, the defect level and mechanical strain near the interface are reduced. Accordingly, the photovoltaic power and the photocurrent of the photovoltaic device of the present invention can be increased.

The p-type layer and the n-type layer of the photovoltaic element preferably have an activation energy of 0.2 eV or less, and most preferably have an activation energy of 0.1 eV or less. The specific resistance is preferably 100 Ωcm or less, and most preferably 1 Ωcm or less. Further, the layer thickness of the p-type layer and the n-type layer is 1 to
50 nm is preferred, and 3 to 10 nm is optimal.

As the source gas suitable for depositing the p-type layer or the n-type layer of the photovoltaic element, a gasizable compound containing a silicon atom, a gasizable compound containing a germanium atom, and a carbon atom were used. Examples thereof include a compound that can be gasified, and a mixed gas of the compound. Specific examples of the gasizable compounds containing silicon atoms include SiH ₄ , Si ₂ H ₆ , SiF ₄ , SiFH ₃ , and SiF _2.
H ₃ , SiF ₃ H, Si ₃ H ₈ , SiD ₄ , SiHD ₃ , Si
H ₂ D ₂ , SiH ₃ D, SiFD ₃ , SiF ₂ D ₂ , SiD ₃
H, Si ₂ D ₃ H _{3 and the} like.

Specific examples of the gasifiable compound containing a germanium atom include GeH ₄ , GeD ₄ , GeF ₄ ,
GeFH ₃ , GeF ₂ H ₂ , GeF ₃ H, GeHD ₃ , Ge
H ₃ D ₂ , GeH ₃ D, Ge ₂ H ₆ , Ge ₂ D _{6 and the} like can be mentioned. Specific examples of the gasizable compound containing a carbon atom include CH ₄ , CD ₄ , C ₂ H _{2n + 2} (n is an integer) and C _n H
_2n (n is an integer), C ₂ H ₂ , C ₆ H ₆ , CO ₂ , CO and the like.

As the nitrogen-containing gas, N ₂ , NH ₃ , N
D ₃ , NO, NO ₂ , and N ₂ O. Examples of oxygen-containing gases include O ₂ , CO, CO ₂ , NO, NO ₃ , N ₃ O, and CH.
₃ CH ₂ OH, CH ₃ OH and the like. As a substance introduced into the p-type layer or the n-type layer for controlling valence electrons, there may be mentioned a group III element and a group V atom of the periodic table.

Examples of useful starting materials for introducing Group III atoms include, specifically, boron atoms, such as B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , and B ₅ H. ₁₁ , B _{6
H 10, B 6 H 12,} B 6 H 14 , etc. borohydride, BF _3, B
Examples thereof include boron halide such as Cl ₃ .
In addition, AlCl ₃ , GaCl ₃ , InCl ₃ , TIC
l ₃ and the like can also be mentioned. Particularly, B ₂ H ₆ and BF ₃ are suitable.

Effectively used as a starting material for introducing a group V atom is, specifically, PH for introducing a phosphorus atom.
₃ , hydrogenated phosphorus such as P ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ , PC
and phosphorus halides such as l ₃ , PCl ₅ , PBr ₃ , PBr ₅ and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsC
l ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , Sb
_{F 5, SbCl 3, SbCl 5} , BiH 3, BiCl 3, B
iBr _{3 and the} like can also be mentioned. Particularly, PH ₃ and PF ₃ are suitable.

The p-type or n-type layer deposition method suitable for a photovoltaic element is an RF plasma CVD method or a microwave plasma CVD method. In particular, when depositing by RF plasma CVD, a capacitively coupled RF plasma CVD is suitable. When a p-type layer or an n-type layer is deposited by the RF plasma CVD method, the substrate temperature in the deposition chamber is 100 to 350
° C, internal pressure is 0.1-10 Torr, RF power is 0.0
1-5.0 W / cm ² , deposition rate 0.01-3 nm /
sec is an optimal condition.

The compounds capable of being gasified are H ₂ , H
The gas may be appropriately diluted with a gas such as e, Ne, Ar, Xe, or Kr and introduced into the deposition chamber. In particular, microcrystalline semiconductors and a-Si
When depositing a layer having a small light absorption or a wide band gap such as C: H, it is preferable to dilute the source gas by 2 to 100 times with hydrogen gas and to introduce a relatively high RF power. . RF frequency is 1MHz ~ 1
00 MHz is a suitable range, especially 13.56 MHz
Nearby frequencies are optimal.

When a p-type layer or an n-type layer is deposited by a microwave plasma CVD method, the microwave plasma CVD apparatus introduces a microwave into a deposition chamber through a dielectric window (alumina ceramics or the like) through a waveguide. The method is suitable. A film formation method of simultaneously depositing a p-type layer or an n-type layer by applying the above-mentioned microwave power and RF power to the source gas by microwave plasma CVD is also a suitable deposition method. A deposited film applicable to the electromotive element can be formed. That is, when a p-type layer or an n-type layer is deposited by a general microwave plasma CVD method, the substrate temperature in the deposition chamber is 100 to 400 ° C., the internal pressure is 0.5 to 30 mTorr, and the microwave power is 0.0.
1-1 W / cm ³ , microwave frequency is 0.5-10
GHz is a preferred range.

The compound capable of being gasified is H ₂ , H
The gas may be appropriately diluted with a gas such as e, Ne, Ar, Xe, or Kr and introduced into the deposition chamber. In particular, microcrystalline semiconductors and a-Si
When depositing a layer having a small light absorption or a wide band gap such as C: H or the like, it is preferable to dilute the source gas by 2 to 100 times with hydrogen gas and to introduce a relatively high microwave power. is there.

In the i-type layer photovoltaic device by the microwave plasma CVD method, the i-type layer by the microwave plasma CVD method is an important layer for generating and transporting carriers with respect to irradiation light. As the i-type layer, a slightly p-type or slightly n-type layer can be used. I of the photovoltaic device of the present invention
The type layer contains silicon atoms and germanium atoms, and the band gap changes smoothly in the layer thickness direction of the i-type layer. It is offset toward the interface of the mold layer. Also,
It is preferable that the i-type layer is simultaneously doped with a valence electron controlling agent serving as a donor and a valence electron controlling agent serving as an acceptor.

Hydrogen atoms (H, D) contained in the i-type layer
Alternatively, the halogen atom (X) works to compensate for dangling bonds of the i-type layer, and improves the product of the mobility and the lifetime of carriers in the i-type layer. Further, it has a function of compensating the interface state of each interface of the p-type layer / i-type layer, and has an effect of improving the photovoltaic power, the photocurrent, and the photoresponsiveness of the photovoltaic element. The optimal content of hydrogen atoms and / or halogen atoms contained in the i-type layer is 1 to 40 at%. In particular, a preferred distribution form includes a large distribution of hydrogen atoms and / or halogen atoms on each interface side of the p-type layer / i-type layer. The preferred range of the content of atoms is 1.1 to 2 times the content in the bulk. Further, it is preferable that the content of hydrogen atoms and / or halogen atoms is changed in accordance with the content of silicon atoms. Where the content of silicon atoms is the minimum, the content of hydrogen atoms or / halogen atoms is 1
A preferred range is 10 to 10 at%, and a preferred range is 0.3 to 0.8 times the maximum region of the content of hydrogen atoms and / or halogen atoms.

The content of hydrogen atoms and / or halogen atoms is changed corresponding to silicon atoms, that is, the content of hydrogen atoms and / or halogen atoms decreases in a narrow band gap corresponding to the band gap. Is what it is. Although the details of the mechanism are unknown, according to the method of forming a deposited film of the present invention, in the deposition of an alloy semiconductor containing silicon atoms and germanium atoms, each of them depends on the difference in ionization rate between silicon atoms and germanium atoms. It is considered that there is a difference in the RF energy obtained by the atoms, and as a result, even if the hydrogen content or / halogen content in the alloy-based semiconductor is small, the relaxation is sufficiently advanced and a good-quality alloy-based semiconductor can be deposited.

In addition, 100 pp of oxygen and / or nitrogen is added to the i-type layer containing silicon atoms and germanium atoms.
By adding a small amount of m or less, the durability of the photovoltaic element against annealing due to long-term vibration is improved. Although the details of the cause are unknown, it is considered as follows. That is, since the composition ratio of silicon atoms and germanium atoms changes continuously in the layer thickness direction, the residual strain tends to be larger than when silicon atoms and germanium atoms are mixed at a fixed ratio. It is considered something. By adding oxygen atoms and / or nitrogen atoms to such a system, the structural strain can be reduced, and as a result, the durability of the photovoltaic element against annealing due to long-term vibration is improved. it is conceivable that. As the distribution of oxygen atoms and / or nitrogen atoms in the layer thickness direction, a distribution that increases or decreases in accordance with the content of germanium atoms is preferable. This distribution is opposite to the distribution of hydrogen atoms and / or halogen atoms, but such a distribution is considered preferable in view of the effect of removing structural distortion and the effect of reducing dangling bonds. . Further, such hydrogen atom (or / and halogen atom) and oxygen atom (or /
And nitrogen atoms), the tail states of the valence band and the conduction band are smoothly and continuously connected.

The thickness of the i-type layer greatly depends on the structure of the photovoltaic element (for example, single cell, tandem cell, triple cell) and the band gap of the i-type layer.
1.0 μm is mentioned as the optimum layer thickness. The i-type layer containing silicon atoms and germanium atoms by the method of forming a deposited film of the present invention has a small valence band tail state even when the deposition rate is increased to 5 nm / sec or more, and the tail state inclination Is not more than 60 meV and the density of dangling bonds by electron spin resonance (esr) is 1
0 ¹⁷ / cm ³ or less.

The band gap of the i-type layer is p-type layer / i
It is preferable to design so as to be wider on each interface side of the mold layer and the n-type layer / i-type layer. With such a design, the photovoltaic power and the photocurrent of the photovoltaic element can be increased, and furthermore, it is possible to prevent light deterioration or the like when used for a long time. For the i-type layer of the photovoltaic element, the above-described method of applying a microwave and radio frequency (RF) simultaneously to form a deposited film is optimal.

I-Type Layer by RF Plasma CVD The i-type layer by RF plasma CVD is deposited at a deposition rate of 2 nm or less, and contains hydrogen atoms and / or halogen atoms contained in the deposited film. Amount is 1-40
The range of at% is preferable. The bonding state of a hydrogen atom and a halogen atom is preferably a state in which one hydrogen atom or one halogen atom is bonded to a silicon atom. Value the value of the half width divided by the peak height of the peak of the infrared absorption spectrum of 2000 cm ^-1 to the silicon atom is hydrogen atom represents one bound state, the i-type layer by microwave plasma CVD 2000 cm ^- larger than the value obtained by dividing the half-width of the ^first peak in the peak height is preferable.

Transparent Electrode As the transparent electrode, a transparent electrode of indium oxide or indium-tin oxide is suitable. For deposition of the transparent electrode, a sputtering method and a vacuum deposition method are the most suitable deposition methods.
The transparent electrode is deposited as follows.

In the case of depositing a transparent electrode made of indium oxide on a substrate in a DC magnetron sputtering device, a target such as metal indium (In) or indium oxide (In ₂ O ₃ ) is used. Further, when depositing a transparent electrode made of indium-tin oxide on a substrate, the target may be a target such as metal tin, metal indium or an alloy of metal tin and metal indium, tin oxide, indium oxide, and indium-tin oxide. They are used in an appropriate combination.

When depositing by sputtering, the substrate temperature is an important factor, and a preferred range is 25 ° C. to 600 ° C. Also, when depositing a transparent electrode by a sputtering method, as a sputtering gas,
An inert gas such as an argon gas (Ar), a neon gas (Ne), a xenon gas (Xe), a helium gas (He), and the like are preferable, and an Ar gas is particularly preferable. It is preferable to add oxygen gas (O ₂ ) to the inert gas as needed. Particularly when a metal is targeted, oxygen gas (O ₂ ) is essential.

Further, when sputtering the target with the inert gas or the like, the pressure in the discharge space is set to 0.1 to 50 mTorr in order to perform sputtering effectively.
Is a preferred range. In addition, as a power source in the case of the sputtering method, a DC power source and an RF power source are suitable. A suitable range for the electric power during sputtering is 10 to 1000 W.

The deposition rate of the transparent electrode depends on the pressure in the discharge space and the discharge power.
It is in the range of 1 to 10 nm / sec. Examples of a deposition source suitable for depositing a transparent electrode in a vacuum deposition method include metal tin, metal indium, and an indium-tin alloy. The substrate temperature for depositing the transparent electrode is 2
A range of 5 ° C to 600 ° C is a suitable range.

Further, when depositing a transparent electrode, the pressure of the deposition chamber is reduced to the order of 10 ⁻⁵ Torr or less, and then oxygen gas (O ₂ )
Must be introduced into the deposition chamber in the range of 5 × 10 ⁻⁵ Torr to 9 × 10 ⁻⁴ Torr. By introducing oxygen in this range, the metal vaporized from the evaporation source reacts with oxygen in the gas phase to deposit a good transparent electrode. Alternatively, plasma may be generated by introducing RF power at the degree of vacuum, and vapor deposition may be performed via the plasma.

The preferable range of the deposition rate of the transparent electrode under the above conditions is 0.01 to 10 nm / sec.
When the deposition rate is less than 0.01 nm / sec, the productivity is reduced, and when the deposition rate is more than 10 nm / sec, the film becomes a coarse film, and the transmittance, the conductivity and the adhesion are reduced. It is preferable that the transparent electrode is deposited under such conditions that the thickness of the antireflection film is satisfied. As a specific layer thickness of the transparent electrode, a preferable range is 50 to 300 nm.

A power generation system according to the present invention includes a photovoltaic element according to the present invention, and monitors the voltage and / or current of the photovoltaic element to transfer power from the photovoltaic element to a storage battery and / or an external load. It comprises a control system for controlling the supply, and a storage battery for storing power from the photovoltaic element and / or supplying power to an external load. FIG.
0 is an example of a power supply system of the present invention, which is a basic circuit when only a photovoltaic element is used as a power supply, and the power supply system includes a photovoltaic element 9001 of the present invention as a solar cell; It comprises a diode 9002 for controlling the voltage of the photovoltaic element, a capacitor 9003 for functioning as a storage battery and for stabilizing the voltage, a load 9004, and the like.

FIG. 21 shows an example of a power supply system according to the present invention, which is a basic charging circuit using a photovoltaic element. The circuit uses the photovoltaic element of the present invention in a solar cell 9101.
Backflow prevention diode 9102, voltage control circuit 9103 for monitoring voltage and controlling voltage, and secondary battery 91
04, a load 9105, and the like. A silicon diode, a Schottky diode, or the like is suitable as the backflow prevention diode. Examples of the secondary battery include a nickel cadmium battery, a rechargeable silver oxide battery, a lead storage battery, and a flywheel energy storage unit.
FIG. 22 illustrates an example of the voltage control circuit 9103. The voltage control circuit is substantially equal to the output of the solar cell until the battery is fully charged, but when the battery is fully charged, the charging current is stopped by the charge control IC.

The solar cell system utilizing such photovoltaic power can be used as a power source for an automobile battery charging system, a ship battery charging system, a streetlight lighting system, an exhaust system, and the like. FIG. 23 is a block diagram of a power supply system of a hybrid type using a solar cell and diesel power generation. The power generation system includes a diesel generator 9401, a solar cell 9402, a rectifier 9403, a charge / discharge control device 9404, a storage battery 9405, a DC / AC converter 9406, a switch 9407, an AC load 9408, and the like.

FIG. 24 is a block diagram of a commercial power supply backup solar cell power supply system. The power supply system includes a solar battery 9501, a charge / discharge control device 9502, a storage battery 9503, a DC / AC converter 9504, and a commercial power supply 950.
5, a non-instantaneous interruption switch 9506, a load 9507, and the like. FIG. 25 is a block diagram of a fully-coupled commercial power supply solar cell power supply system. The power supply system includes a solar cell 9601 and a DC / AC converter 960.
2, commercial power supply 9603, load 9604, reverse power flow 9605
And so on.

As described above, the power supply system using the photovoltaic device of the present invention as a solar cell can be used stably for a long period of time, and even when the irradiation light applied to the solar cell fluctuates. Since it functions sufficiently as an electromotive element, it shows excellent stability.

[0095]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. (Example 1) Source gas supply device 1020 and deposition device 10 shown in FIG.
The photovoltaic element of the present invention was manufactured using a manufacturing apparatus based on a microwave plasma CVD method consisting of a raw material gas supply apparatus 1020 and a deposition apparatus 1100 shown in FIG.

In the figures, gas cylinders 1071 to 1079 are made of p-type non-single-crystal semiconductor material of the present invention.
The source gas for producing the mold layer, the i-type layer and the n-type layer is sealed, and 1071 is a SiH ₄ gas cylinder, 107
2 is an H ₂ gas cylinder, 1073 is a BF ₃ gas diluted to 1% with H ₂ gas (hereinafter abbreviated as “BF ₃ (1%) / H ₂ ”), and 1074 is a 1% diluted H ₂ gas. Done P
H ₃ gas (hereinafter abbreviated as “PH ₃ (1%) / H ₂ ”) cylinder, 1075: Si ₂ H ₆ gas cylinder, 1076: Ge
The H ₄ gas cylinder and 1077 are BF ₃ gas diluted to 2000 ppm with H ₂ gas (hereinafter “BF ₃ (2000 ppm)
/ H ₂ )), 1078 is H ₂ gas at 2078.
PH ₃ gas diluted to 00 ppm (hereinafter PH ₃ (200
0 ppm) / H ₂ ") cylinder, 1079 is H
NO gas diluted to 1% with e gas (hereinafter “NO / H
e "). When the gas cylinders 1071 to 1079 are attached in advance, each gas is supplied from the valves 1051 to 1059 through the inflow valve 10.
31 to 1039 are introduced into the gas pipes.

In the figure, reference numerals 1004 and 1104 denote substrates.
50mm square, 1mm thick stainless steel (SUS430B
A), a mirror-finished surface is applied, and a textured silver (Ag) thin film is formed as a reflective layer by sputtering to a thickness of 100 nm, and further a zinc oxide (Z
nO) A 1 μm thin film is deposited. First, gas cylinder 1
071, SiH ₄ gas from gas cylinder 1072, H ₂ gas from gas cylinder 1073, BF ₃ (1%) / H ₂ gas from gas cylinder 1073,
PH ₃ (1%) / H ₂ gas from gas cylinder 1074, Si ₂ H ₆ gas, gas cylinder 1076 from gas cylinder 1075
GeH ₄ gas and BF ₃ (20
00ppm) / H ₂ , PH ₃ (2
000 ppm) / H ₂ , NO /
He is introduced by opening valves 1051 to 1059, and each gas pressure is adjusted to about 2 k by a pressure regulator 1061/1069.
g / cm ^{2 was} adjusted.

Next, the inflow valves 1031 to 1039 and the leak valves 1009 and 1 of the deposition chambers 1001 and 1101 are set.
109 is closed and outflow valves 1041 to 1049, auxiliary valves 1008 and 110
8 is opened, the conductance (butterfly type) valves 1007 and 1107 are fully opened, and the deposition chambers 1001 and 110 are opened by a vacuum pump (not shown).
1 and the gas pipe are evacuated, and vacuum gauges 1006 and 110
When the reading of No. 6 becomes about 1 × 10 ⁻⁴ Torr, the auxiliary valves 1008 and 1108 and the outflow valves 1041 to 104
9 was closed.

Next, the inlet valves 1031 to 1039 are gradually opened to allow each gas to flow through the mass flow controller 1.
021 to 1029. After the preparation for film formation is completed as described above, n
Mold layer, RF plasma CVD method and microwave plasma C
An i-type layer and a p-type layer were formed by the VD method.

In order to form an n-type layer, the substrate 1004 is heated to 350 ° C. by the heater 1005, the outflow valves 1041, 1044 and the auxiliary valve 1008 are gradually opened, and the SiH ₄ gas, PH ₃ (1%) / H ₂ gas was introduced into the deposition chamber 1001 through the gas introduction pipe 1003. At this time, the flow rate of the SiH ₄ gas is
The mass flow controllers 1021 and 1024 adjusted the flow rate of ₃ (1%) / H ₂ gas to 200 sccm. The pressure in the deposition chamber 1001 is 10 mTorr
The opening of the conductance valve 1007 was adjusted while watching the vacuum gauge 1006 so that

Thereafter, the shutter 1013 is closed, and the direct current (hereinafter abbreviated as “DC”) of the bias power source 1011 is closed.
The bias was set to 50 V and applied to the bias rod 1012, and then the power of the microwave power source (not shown) was set to 130 m.
W / cm ³ , and a waveguide (not shown)
Then, microwave power is introduced into the deposition chamber 1001 through the dielectric window 1002 to generate microwave glow discharge, the shutter 1013 is opened, and n
When the formation of the mold layer is started and the n-type layer having a thickness of 10 nm is formed, the shutter 1013 is closed to stop the microwave glow discharge, the outflow valves 1041 and 1044 and the auxiliary valve 1008 are closed, and the inside of the deposition chamber 1001 is introduced. Was stopped, and the fabrication of the n-type layer was completed.

Next, the substrate 1004 was taken out of the deposition chamber 1001 and placed in the deposition chamber 1101 of the deposition apparatus 1100 by the RF plasma CVD method shown in FIG. 12 to produce an i-type layer by the RF plasma CVD method. RF plasma CVD
In order to form an i-type layer by the method, the substrate 1104 is heated to 350 ° C.
041 and 1042 and the auxiliary valve 1108 were gradually opened to allow SiH ₄ gas and H ₂ gas to flow into the deposition chamber 1101 through the gas introduction pipe 1103. At this time, the mass flow controllers 1021 and 1021 were set so that the flow rate of the SiH ₄ gas was 8 sccm and the flow rate of the H ₂ gas was 100 sccm.
1022 was adjusted. The pressure in the deposition chamber 1101 is 0.5
The opening of the conductance valve 1107 was adjusted while watching the vacuum gauge 1106 so that the pressure became Torr.

Thereafter, the power of the RF power supply 1111 is reduced to 120
mW / cm ² and the RF matching box 111
2 to the cathode 1102 through RF power,
A glow discharge is generated and an i-type layer formed by microwave plasma CVD is used to form an i-type layer formed by RF plasma CVD.
When the production of the mold layer was started and the i-type layer having a thickness of 10 nm was produced, the RF glow discharge was stopped, and the outflow valve 104 was formed.
1, 1042 and the auxiliary valve 1108 were closed, the gas flow into the deposition chamber 1101 was stopped, and the fabrication of the i-type layer was completed.

Next, the substrate 1104 was taken out of the deposition chamber 1101 and placed in the deposition chamber 1001 of the deposition apparatus 1000 by the microwave plasma CVD method shown in FIG. 11 to produce an i-type layer by the microwave plasma CVD method. In order to form an i-type layer by a microwave plasma CVD method, the substrate 1004 is heated to 350 ° C. by the heater 1005, and the outflow valves 1041, 1042, 1046 and the auxiliary valve 1008 are gradually opened, and SiH ₄ gas, H _Two gases, GeH ₄ gas, were introduced into the deposition chamber 1001 through the gas introduction pipe 1003. At this time, the flow rate of SiH ₄ gas was 200 sccm, the flow rate of H ₂ gas was 500 sccm,
The mass flow controllers 1021, 1022, and 1026 were adjusted so that the H ₄ gas flow rate was 1 sccm. The pressure inside the deposition chamber 1001 is controlled by the conductance valve 1
The opening of 007 was adjusted.

Next, the shutter 1013 is closed, the power of the microwave power supply (not shown) is set to 170 mW / cm ³ , and the waveguide, the waveguide 1010 and the dielectric window 10 (not shown) are set.
02, a microwave power is introduced into the deposition chamber 1001 to generate a microwave glow discharge,
A high-frequency (hereinafter abbreviated as “RF”) bias of 011 was set to 350 mW / cm ³ , and a DC bias was set to 0 V via an RF cut coil, and the bias rod 1
012. Thereafter, the shutter 1013 is opened to start the production of the i-type layer by the microwave plasma CVD method on the i-type layer by the RF plasma CVD method. At the same time, the flow rates of the SiH ₄ gas and the GeH ₄ gas are shown in FIG. Mass flow controller 1 according to flow pattern
When the i-type layer having a layer thickness of 300 nm was prepared by adjusting at 021 and 1026, the shutter 1013 was closed, the output of the bias power supply 1011 was turned off, the microwave glow discharge was stopped, the outflow valves 1041, 1042, 1046, and the auxiliary valve 1008. Was closed, and the gas flow into the deposition chamber 1001 was stopped.

Subsequently, to form a p-type layer, the substrate 10
04 to 300 ° C. with a heater 1005,
Outflow valves 1041 to 1043 and auxiliary valve 1008
Is gradually opened, and SiH ₄ gas, H ₂ gas, BF ₃ (1
%) / H ₂ gas through the gas introduction pipe 1003 to the deposition chamber 1
001. At this time, the SiH ₄ gas flow rate is 1
0 sccm, H ₂ gas flow rate 700 sccm, BF ₃ (1
%) / H ₂ gas flow rate was adjusted to 30 sccm by each of the mass flow controllers 1021 to 1023. The pressure inside the deposition 1001 is controlled by the conductance valve 1 while watching the vacuum gauge 1006 so as to be 25 mTorr.
The opening of 007 was adjusted.

After that, the power of the microwave power supply (not shown) was set to 250 mW / cm ³ , and the deposition chamber 1001
Microwave power is introduced into the inside, a microwave glow discharge is generated, the shutter 1013 is opened, and the formation of a p-type layer on the i-type layer by microwave plasma CVD is started.
When a 10-nm-thick p-type layer was produced, shutter 1 was used.
013, the microwave glow discharge was stopped, the outflow valves 1041 to 1043 and the auxiliary valve 1008 were closed, the flow of gas into the deposition chamber 1001 was stopped, and the production of the p-type layer was completed.

When forming the respective layers, it goes without saying that the outflow valves 1041 to 1049 other than the necessary gas are completely closed, and the respective gases are supplied into the deposition chambers 1001 and 1101 and outflow valve 1041. ~
In order to avoid remaining in the piping from 1049 to the deposition chambers 1001 and 1101, the outflow valves 1041
1049 is closed, auxiliary valves 1008 and 1108 are opened, and conductance valves 1007 and 1107 are closed.
Is fully opened, and the operation of once evacuating the system to a high vacuum is performed as necessary.

Next, on the p-type layer, an IT
An O (In ₂ O ₃ + SnO ₂ ) thin film was vacuum-deposited with a 70 μm thin film, and an aluminum (Al) thin film was further vacuum-deposited with a thickness of 2 μm as a current collecting electrode to produce a photovoltaic element (element Nos. 1-1 to 1-1).
7, ratio 1-1). Table 1 shows the conditions for manufacturing the above-described photovoltaic element. The fabricated photovoltaic element (element N
o. Examples 1-1 to 7 and element Nos. The initial characteristics, the low illuminance characteristics, and the durability characteristics of the ratio 1-1) were measured.

The measurement of the initial characteristics was carried out by measuring the photovoltaic elements (element Nos. 1-1 to 7; ratio 1-1) produced by using AM-1.
5 (100 mW / cm ² )
The measurement was performed by the open-circuit voltage and the fill factor obtained by measuring the characteristics. Table 2 shows the measurement results. The measurement of the low illuminance characteristics was performed using the manufactured photovoltaic element (element No. 1-).
1 to 7, ratio 1-1) with AM-1.5 (10 mW / cm
² ) It was installed under light irradiation, and the measurement was performed based on the photoelectric conversion efficiency obtained by measuring the VI characteristics. Table 2 shows the measurement results.

The durability characteristics were measured by measuring the photovoltaic elements (element Nos. 1-1 to 7, ratio 1-1) produced at a humidity of 70%.
%, Placed in a dark place at a temperature of 60 ° C., and 1 m at 3600 rpm
The measurement was performed by changing the photoelectric conversion efficiency after applying vibration of m for 48 hours. Table 2 shows the measurement results. As can be seen from Table 2, it was found that a photovoltaic element having excellent characteristics was obtained by forming an i-type layer by microwave plasma CVD at a pressure in the deposition chamber 1001 of 50 mTorr or less.

Next, a device No. was prepared except that a barium borosilicate glass (7059, manufactured by Corning Incorporated) substrate was used and the SiH ₄ gas flow rate, GeH ₄ gas flow rate, and microwave power were set to the values shown in Table 3. The shutter 1 was manufactured under the same manufacturing conditions as those of the i-type layer by the microwave plasma CVD method of Example 1-5.
013 for 2 minutes and microwave plasma CV on the substrate
An i-type layer was prepared by the method D to prepare samples for measuring the efficiency of raw material gas decomposition (Sample Nos. 1-1 to 5).

The thickness of the prepared sample for measuring the decomposition efficiency of the raw material gas was measured with a layer thickness measuring instrument (TENCOINSTRUMENT).
The decomposition efficiency of the raw material gas was determined based on the layer thickness by measuring with alpha step 100 manufactured by TS. Table 3 shows the results. Next, when producing the i-type layer by the microwave plasma CVD method, the element No. Under the same manufacturing conditions as the photovoltaic element of Example 1-5, a reflection layer, a reflection enhancement layer, an n-type layer,
An i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode were formed to produce a photovoltaic element (element Nos. 1-8 to 10 and a ratio of 1).
-2-3).

The manufactured photovoltaic element (element No. 1-
8 to 10 and the ratios 1-2 to 3) were used for the device Nos. The initial characteristics, low illuminance characteristics, and durability characteristics were measured in the same manner as in Example 1-5. Table 4 shows the measurement results. As can be seen from Table 4,
It has been found that a photovoltaic element having excellent characteristics can be obtained by decomposing a source gas with microwave energy lower than that required for decomposing the source gas by 100%.

Next, when producing the i-type layer by the microwave plasma CVD method, except that the RF bias was set to the value shown in Table 5, the device No. Under the same manufacturing conditions as the photovoltaic element of Example 1-5, a reflection layer, a reflection enhancement layer, an n-type layer, i
A photovoltaic element was manufactured by forming a mold layer, a p-type layer, a transparent electrode, and a collecting electrode (element Nos. 1-11 to 14 and ratio 1).
-4).

The manufactured photovoltaic element (element No. 1-
Nos. 11 to 14 and the ratio 1-4) were assigned to the element Nos. The initial characteristics, low illuminance characteristics, and durability characteristics were measured in the same manner as in Example 1-5. Table 5 shows the measurement results. As can be seen from Table 5, it was found that a photovoltaic element having excellent characteristics was obtained by applying RF energy higher than microwave energy to the source gas.

Next, using a stainless steel substrate and a barium borosilicate glass (7059, manufactured by Corning Incorporated) substrate,
The element Nos. 1 and 2 except that the H ₄ gas flow rate and the GeH ₄ gas flow rate were set to the values shown in Table 6. Actual 1-5 microwave plasma CV
Under the same manufacturing conditions as for the i-type layer according to Method D, an i-type layer was formed on the substrate to a thickness of 1 μm to prepare samples for measuring physical properties (Sample Nos. 1-6 to 10).

Further, using a barium borosilicate glass (7059, manufactured by Corning Incorporated) substrate, the element No. Under the same manufacturing conditions as the i-type layer by the RF plasma CVD method of Example 1-5,
An i-type layer was formed on the substrate at 1 μm to prepare a sample for measuring physical properties (Sample No. 1-11). The band gap and composition of the prepared sample for measuring physical properties were analyzed, and S
The relationship between the composition ratio of i atoms and Ge atoms and the band gap was determined.

For the measurement of the band gap, the glass substrate on which the i-type layer was formed was placed on a spectrophotometer (type 330 manufactured by Hitachi, Ltd.).
And the wavelength dependence of the absorption coefficient of the i-type layer was measured, and the band gap of the i-type layer was determined by the method described on p. I asked. In the composition analysis, the stainless steel substrate on which the i-type layer was formed was placed on an Auger electron spectrometer (JEOL J
AMP-3), and the composition ratio of Si atoms and Ge atoms was measured. Table 6 shows the results of band gap and composition analysis.

Next, when producing an i-type layer by microwave plasma CVD, except that the SiH ₄ gas flow rate and the GeH ₄ gas flow rate were adjusted by the mass flow controllers 1021 and 1026 according to the flow pattern shown in FIG.
Element No. Under the same manufacturing conditions as the photovoltaic element of Example 1-5,
A reflective layer, a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode were formed on a substrate to produce a photovoltaic element (element number ratio 1-5).

The manufactured photovoltaic element (element No. ratio 1-
5) is replaced with the element No. The initial characteristics,
Low illuminance characteristics and durability characteristics were measured. As a result of the measurement, the element N
o. For the ratio 1-5, the device No. Example 1-5 had 1.02 times the open-circuit voltage of the initial characteristics, 1.03 times the fill factor, 1.08 times the low illuminance characteristics, and 1.07 times the durability characteristics.

Next, the device No. Example 1-5 and the element No. The composition analysis of Si atoms and Ge atoms in the layer thickness direction in the i-type layer by microwave plasma CVD at a ratio of 1-5 was performed in the same manner as the above-described composition analysis. Then, as described above, the sample No. Si atom and Ge determined by 1-6 to 10
From the relationship between the atomic composition ratio and the band gap, the change in the band gap in the thickness direction of the i-type layer by microwave plasma CVD was determined. FIG. 16 shows the result. FIG.
As can be seen from FIG. In the photovoltaic device of Ex. 1-5, the position of the minimum value of the band gap is shifted from the center position of the i-type layer toward the interface between the p-type layer and the i-type layer. In the photovoltaic element having the ratio of 1-5, it was found that the position of the minimum value of the band gap was shifted from the center position of the i-type layer toward the interface between the n-type layer and the i-type layer.

When an i-type layer was produced by the RF plasma CVD method, except that the flow rate of the SiH ₄ gas and the RF discharge power were set to the values shown in Table 7, the device Nos. Under the same manufacturing conditions as the photovoltaic device of Example 1-5, a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode were formed on a substrate, The element was produced (element No. actual 1-15 to 19 and ratio 1-6).

The manufactured photovoltaic element (element No. 1-
Nos. 15 to 19 and the ratio 1-6) were used for the device Nos. The initial characteristics, low illuminance characteristics, and durability characteristics were measured in the same manner as in Example 1-5. Table 7 shows the results. Next, using a barium borosilicate glass (7059 manufactured by Corning Incorporated) substrate,
₄ except that the gas flow rate and the RF discharge power were the values shown in Table 7. Under the same manufacturing conditions as the i-type layer by the RF plasma CVD method of Example 1-5, an i-type layer was formed on the substrate at 1 μm to prepare a sample for measuring the deposition rate (sample N).
o. 1-12-17). The deposition rate of the produced sample for measuring the deposition rate was designated as Sample No. It determined by the same method as 1-1 to 5. Table 7 shows the results.

As can be seen from Table 7, RF plasma CVD
It has been found that a photovoltaic element having excellent characteristics can be obtained by manufacturing the i-type layer at a deposition rate of 2 nm / sec or less by the method. When an i-type layer was produced by the RF plasma CVD method, except that the thickness of the i-type layer was set to the value shown in Table 8, the device No. Under the same manufacturing conditions as the photovoltaic element of Example 1-5, a reflective layer, a reflection increasing layer, an n-type layer, an i-type layer,
A p-type layer, a transparent electrode, and a collecting electrode were formed to produce a photovoltaic element (element numbers 1-20 to 22 and ratios 1 to 7).
8).

The manufactured photovoltaic element (element No. 1-
20 to 22 and the ratios 1 to 7 to 8) were used for the device Nos. The initial characteristics, low illuminance characteristics, and durability characteristics were measured in the same manner as in Example 1-5. Table 8 shows the measurement results. As can be seen from Table 8,
A photovoltaic element provided with an i-type layer having a layer thickness of 30 nm or less by an RF plasma CVD method (element Nos. 1-20 to 2)
2) was found to have excellent properties.

Next, the device Nos. 1 and 2 were manufactured using the single crystal silicon substrate and changing the RF discharge power to the values shown in Table 9. Actual 1-
5 under the same manufacturing conditions as the i-type layer formed by the RF plasma CVD method.
m to prepare samples for infrared spectrometry (Sample Nos. 1-18 to 22). Further, using a single crystal silicon substrate, the device No. Actual 1-5 microwave plasma CV
Under the same manufacturing conditions as the i-type layer by the D method, an i-type layer of 1 μm was formed on the substrate by the microwave plasma CVD method to prepare a sample for infrared spectrometry.
3).

The infrared spectrophotometer (sample Nos. 1-18 to 23) thus prepared was subjected to an infrared spectrophotometer (PERK).
It was installed on IN ELMER 1720-X), and the value obtained by dividing the half width at the peak of 2000 cm ^-1 of the infrared absorption spectrum by the peak height was obtained. Table 9 shows the results.
Next, when producing the i-type layer by the RF plasma CVD method, except that the RF discharge power was set to the value shown in Table 9, the device Nos. Under the same manufacturing conditions as those of the photovoltaic element of Example 1-5, a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode were formed on a substrate. The element was produced (element No. 1-23 to 26).

The manufactured photovoltaic element (element No. 1-
Nos. 23 to 26) as element Nos. The initial characteristics, low illuminance characteristics, and durability characteristics were measured in the same manner as in Example 1-5. Table 9 shows the measurement results. As can be seen from Table 9, the value obtained by dividing the half width at the peak of 2000 cm ^-1 of the infrared absorption spectrum by the peak height is closer to the i-type layer by the microwave plasma CVD method than the i-type layer by the RF plasma CVD method. It has been found that a photovoltaic element having a large value has excellent characteristics.

From the above measurement results, the microwave energy and the microwave energy lower than the microwave energy required to decompose the raw material gas by 100% at an internal pressure of 50 mTorr or less and the i-type layer by the microwave plasma CVD method of the present invention are shown. RF energy higher than that applied to the source gas, the band gap changes smoothly in the layer thickness direction, and the minimum value of the band gap is located between the center of the i-type layer and the p-type layer and the i-type. Offset towards the interface of the layer, R
A photovoltaic element (element Nos. 1-1 to 23) in which an i-type layer formed by F plasma CVD was formed at a deposition rate of 2 nm / sec or less and a thickness of 30 nm or less was replaced with a conventional photovoltaic element (element No. ratio 1-1 to 8), it was found to have excellent characteristics, and the effect of the present invention was demonstrated.

Example 2 When fabricating an i-type layer by microwave plasma CVD, the flow rates of SiH ₄ gas and GeH ₄ gas were changed in Example 1.
After the adjustment by the mass flow controllers 1021 and 1026 according to the flow pattern shown in FIG.
iH ₄ gas flow rate 200 sccm, GeH ₄ gas flow rate 1
Table 1 shows the region of the maximum band gap value maintained at sccm.
0, except that the device was manufactured to have the layer thickness shown in FIG. Under the same manufacturing conditions as in Example 1-5, a reflective layer, a transparent conductive layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode,
A collector electrode was prepared to produce a photovoltaic device (device N
o. Actual 2-1 to 8).

The manufactured photovoltaic element (element No. 2-
1) to 8), the initial characteristics, the low illuminance characteristics, and the durability characteristics were measured in the same manner as in Example 1. Table 10 shows the results. As can be seen from Table 10, it was found that the photovoltaic devices (device Nos. 2-1 to 7) in which the layer thickness in the band gap maximum value region of the present invention is 1 to 30 nm have excellent characteristics. The effects of the present invention have been demonstrated.

(Example 3) When producing an i-type layer by RF plasma CVD, B
F ₃ (2000 ppm) / H ₂ gas cylinder 1077 and P
Using a H ₃ (2000 ppm) / H ₂ gas cylinder 1078, the BF ₃ (2000 ppm) / H ₂ gas flow rate was set to 0.04.
sccm, PH ₃ (2000 ppm) / H ₂ flow rate 0.0
Except for flowing 2 sccm, the device No. of Example 1 was used. Actual 1-
Under the same manufacturing conditions as in 5, a reflective layer, a transparent conductive layer,
An n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode were produced to produce a photovoltaic element (element No. 3).

The initial characteristics, low illuminance characteristics and endurance characteristics of the photovoltaic device manufactured in Example 3 (element No. 3) were measured in the same manner as in Example 1. Real 1
Initial characteristics, low illuminance characteristics, and durability characteristics similar to -5 were obtained. In addition, the element No. The composition of Real 3 was analyzed by a secondary ion mass spectrometer (IMS-3F manufactured by CAMECA), and it was confirmed that B- and P-atoms were contained in the i-type layer by RF plasma CVD.

(Example 4) When producing an i-type layer by RF plasma CVD, P
H ₃ (2000ppm) / H ₂ in place of the gas cylinder AsH diluted to 2000ppm by H ₂ gas ₃ gas (hereinafter abbreviated as "AsH ₃ / H _2") using a cylinder, AsH ₃
A reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a collecting electrode were formed on a substrate under the same manufacturing conditions as in Example 3 except that a flow rate of / H ₂ gas was 0.1 sccm. Was fabricated to produce a photovoltaic element (element No. Ex. 4). Example 4
Example 1 shows the photovoltaic element manufactured in (Element No. 4).
The initial characteristics, low illuminance characteristics, and durability characteristics were measured in the same manner as in Example 1. The same initial characteristics, low illuminance characteristics, and durability characteristics as those of Example 3 were obtained.

Example 5 When producing an i-type layer by microwave plasma CVD and RF plasma CVD, a NO / He gas cylinder 1 was used.
No. 079 was used, and the flow rate of the NO / He gas was 0.5 sccm for the i-type layer formed by microwave plasma CVD and 0.05 sccm for the i-type layer formed by RF plasma CVD. Under the same manufacturing conditions as in Example 1-5, a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer,
A p-type layer, a transparent electrode, and a current collecting electrode were prepared to produce a photovoltaic element (element No. 5). The initial characteristics, low illuminance characteristics and durability characteristics of the fabricated photovoltaic element (element No. 5) were measured in the same manner as in Example 1.
o. The same initial characteristics, low illuminance characteristics, and durability characteristics as in Example 1-5 were obtained. In addition, the element No. The composition of Real 5 was analyzed by a secondary ion mass spectrometer, and it was confirmed that the i-type layer contained N atoms and O atoms.

Example 6 When producing an i-type layer by microwave plasma CVD, a Si ₂ H ₆ gas cylinder was used and the Si ₂ H ₆ gas flow rate was set to 4
The flow rate of the SiH ₄ gas was set to 0 sccm, and the mass flow controller 102 was set in accordance with the flow rate pattern shown in FIG.
1 except that the element No. 1 was adjusted. Under the same manufacturing conditions as in Example 1-5, a photovoltaic element was manufactured by manufacturing a reflective layer, a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode on a substrate. (Element No. Ex. 6).

The fabricated photovoltaic element (element No. 6)
Was measured for initial characteristics, low illuminance characteristics, and durability characteristics in the same manner as in Example 1. The same initial characteristics, low illuminance characteristics, and durability characteristics as in Example 1-5 were obtained. Further, the Si of the photovoltaic element of Example 6 (element No. 6) was used.
The distribution of atoms and hydrogen atoms in the i-type layer in the thickness direction is
Secondary ion mass spectrometer (IMEC-3 manufactured by CAMECA)
F). FIG. 18 shows the result. From the above results, it was found that the photovoltaic element in which the content of hydrogen atoms changed in accordance with the content of Si atoms had excellent characteristics, and the effect of the present invention was demonstrated.

(Embodiment 7) In a source gas supply device 1020, SiH ₄ gas and G
Element No. 1 of Example 1 was repeated except that the distance between the mixing point of the eH ₄ gas and the deposition chamber 1001 was set to the value shown in Table 11. Under the same manufacturing conditions as in Example 1-5, a reflective layer,
A photovoltaic element was produced by producing a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode (element No. 7).

The fabricated photovoltaic element (element No. 7)
Was measured for initial characteristics, low illuminance characteristics, and durability characteristics in the same manner as in Example 1. Table 11 shows the measurement results. Table 1
As can be seen from FIG. 1, it was found that by setting the distance between the point at which the SiH ₄ gas and the GeH ₄ gas are mixed and the deposition chamber 1001 to 5 m or less, a photovoltaic element having better characteristics could be obtained.

(Embodiment 8) A photovoltaic element was manufactured under the same manufacturing conditions as in Example 1-5, and using this, a solar cell module was manufactured, and an analog timepiece having a circuit configuration as shown in FIG. 21 was manufactured. In FIG. 22, a solar cell module 910 is shown.
The power generated in 1 is charged to the secondary battery 9104 via the backflow prevention diode 9102. 9103 is an overcharge prevention diode. Solar cell module 910
Power from the primary and secondary batteries 9104 is supplied to a drive circuit 9105 of the analog timepiece.

Comparative Example 2 As a comparative example, the device No. A photovoltaic element was manufactured under the same manufacturing conditions as in the ratio 1-7, and an analog timepiece similar to that of Example 8 was manufactured using the same. When the analog timepieces produced in Example 8 and Comparative Example 2 were installed on the indoor wall and the interior lights were turned on for 8.5 hours every day, the analog timepiece of Example 8 moved all day, but the analog timepiece of Comparative Example It was stationary all day, demonstrating the effect of the power generation system according to the invention.

Example 9 When fabricating an i-type layer by microwave plasma CVD, the flow rate of SiH ₄ gas and the flow rate of GeH ₄ gas were adjusted according to the flow pattern shown in FIG.
21, the device N of Example 1 was adjusted.
o. Under the same manufacturing conditions as in Example 1-5, a photovoltaic element was manufactured by manufacturing a reflective layer, a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode on a substrate. (Element No. 9). The initial characteristics, low illuminance characteristics, and durability characteristics of the fabricated photovoltaic element (element No. 9) were measured in the same manner as in Example 1. The same initial characteristics, low illuminance characteristics and durability as those of Example 1-5 were obtained, demonstrating the effects of the present invention.

Example 10 When an i-type layer was produced by RF plasma CVD, B
B ₂ H ₆ gas diluted to 1% with H ₂ gas instead of F ₃ (2000 ppm) / H ₂ gas cylinder (hereinafter “B ₂ H ₆ (1
%) / H ₂ )) and B ₂ H ₆ (1%) / H ₂ when forming an i-type layer by RF plasma CVD.
Except for flowing the gas at 0.05 sccm, the device N of Example 1 was used.
o. Under the same manufacturing conditions as in Example 1-5, a photovoltaic element was manufactured by forming a reflective layer, a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode on a substrate. (Element No. Actual 1
0). The initial characteristics, low illuminance characteristics, and durability characteristics of the fabricated photovoltaic element (element No. 10) were measured in the same manner as in Example 1. Real 1-5
The same initial characteristics, low illuminance characteristics and durability as those described above were obtained, demonstrating the effects of the present invention.

Example 11 The device of Example 1 was repeated except that the NO / He gas was adjusted by the mass flow controller 1029 in accordance with the flow pattern shown in FIG. 26 when the i-type layer was produced by the microwave plasma CVD method. No. Under the same manufacturing conditions as in Example 1-5, a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer,
A p-type layer, a transparent electrode, and a current collecting electrode were prepared to produce a photovoltaic element (element No. 11).

The fabricated photovoltaic element (element No. 1)
The initial characteristics, the low illuminance characteristics, and the durability characteristics of the element No. 1) of Example 1 were measured in the same manner as in Example 1.
The same initial characteristics, low illuminance characteristics and durability as those of Example 1-5 were obtained. The distribution of N atoms and O atoms in the i-type layer in the layer thickness direction of the photovoltaic element of Example 11 (element No. 11) was analyzed by a secondary ion mass spectrometer. FIG. 27 shows the result. From the above results, the effect of the present invention was demonstrated.

(Example 12) When manufacturing an i-type layer by microwave plasma CVD, the flow rate of SiH ₄ gas and the flow rate of GeH ₄ gas were changed according to the flow pattern shown in FIG.
21, 1026 and microwave plasma CV
After forming the i-type layer by the method D, an i-type layer was manufactured by the RF plasma CVD method under the manufacturing conditions shown in Table 12. Under the same conditions as in Example 1-5, a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode,
A collector electrode was prepared to produce a photovoltaic device (device N
o. Actual 12). The fabricated photovoltaic element (element No. 1)
2) The initial characteristics, low illuminance characteristics and durability characteristics were measured in the same manner as in Example 1.
The same initial characteristics, low illuminance characteristics, and durability characteristics as those of Example 1-5 were obtained, and the effect of the present invention was demonstrated.

(Example 13) When manufacturing an i-type layer by microwave plasma CVD, the RF bias of the bias power supply 1011 was set to 250 mW.
/ Cm ³ , a DC bias was set to 50 V through a coil for RF cut, and a bias was applied to the bias bar 1012 under the same manufacturing conditions as in Example 9 except that a reflection layer, a reflection increase A photovoltaic element was produced by producing a layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode and a current collecting electrode (element No. 13). The fabricated photovoltaic element (element N
o. Example 13) was measured for initial characteristics, low illuminance characteristics, and durability characteristics in the same manner as in Example 9. As a result, initial characteristics, low illuminance characteristics, and durability characteristics similar to those in Example 9 were obtained. Has been demonstrated.

Example 14 Example 1 was repeated except that a D ₂ gas (not shown) was used instead of the H ₂ gas cylinder when the i-type layer was produced by the microwave plasma CVD method, and D ₂ gas was flowed at 300 sccm. Element No. Under the same manufacturing conditions as in Example 1-5, a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode,
A collector electrode was prepared to produce a photovoltaic device (device N
o. Actual 14).

The fabricated photovoltaic element (element No. 1)
4) was measured for initial characteristics, low illuminance characteristics, and durability characteristics in the same manner as in Example 1.
The same initial characteristics, low illuminance characteristics, and durability characteristics as in Example 1-5 were obtained. Further, when the composition of the photovoltaic device of Example 14 (Element No. 14) was analyzed by a secondary ion mass spectrometer, it was confirmed that the i-type layer contained D atoms. The effect was demonstrated.

(Example 15) In manufacturing the n-type layer, the DC bias of the bias power supply 1011 was changed to 50 at the same time when the shutter 1013 was opened.
V of Example 1 except that the voltage was changed from V to 80 V at a constant rate. Under the same manufacturing conditions as in Example 1-5, on a substrate,
A photovoltaic element was produced by producing a reflective layer, a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode (element No. 15). The fabricated photovoltaic element (element No. 15) was measured for initial characteristics, low illuminance characteristics, and durability characteristics in the same manner as in Example 1.
o. The same initial characteristics, low illuminance characteristics, and durability characteristics as those of Example 1-5 were obtained, and the effect of the present invention was demonstrated.

(Example 16) The n-type layer of the photovoltaic device of the present invention was manufactured by the manufacturing apparatus based on the RF plasma CVD method shown in FIG. And a p-type layer were produced.

To form an n-type layer, the substrate 1104 is heated to 350 ° C. by the heater 1105, and the outflow valves 1042, 1044, 1045 and the auxiliary valve 110 are heated.
8 was gradually opened, and H ₂ gas, PH ₃ (1%) / H ₂ gas, and Si ₂ H ₆ gas were caused to flow into the deposition chamber 1101 through the gas introduction pipe 1103. At this time, the H ₂ gas flow rate is 50
sccm, PH ₃ (1%) / H ₂ gas flow rate is 5 sccm,
The mass flow controllers 1022, 1024, and 1025 adjusted the flow rates of the Si ₂ H ₆ gas to 3 sccm. The opening of the conductance valve 1107 was adjusted while watching the vacuum gauge 1106 so that the pressure in the deposition chamber 1101 became 1 Torr.

Thereafter, the power of the RF power supply 1111 is reduced to 120
mW / cm ² and the RF matching box 111
2 to the cathode 1102 through RF power,
Glow discharge is caused to start forming an n-type layer on the substrate 1104, and when an n-type layer having a thickness of 10 nm is formed, R
F glow discharge is stopped, and outflow valves 1042, 1044,
1045 and the auxiliary valve 1108 are closed, and the deposition chamber 11 is closed.
The flow of gas into 01 was stopped, and the formation of the n-type layer was completed.

Next, the device No. Under the same manufacturing conditions as in Example 1-5, an i-type layer was formed on the n-type layer by RF plasma CVD. Next, RF plasma C is deposited from the deposition chamber 1101.
The substrate 1104 on which the i-type layer was formed by the VD method was taken out and set in the same deposition apparatus 1000 by the microwave plasma CVD method as in the first embodiment. I by the RF plasma CVD method under the same manufacturing conditions as in Example 1-5.
An i-type layer was formed on the mold layer by microwave plasma CVD.

Next, the substrate 1004 on which the i-type layer has been formed by the microwave plasma CVD method is taken out from the deposition chamber 1000, and the deposition apparatus 1 by the above-described RF plasma CVD method is taken out.
100 and i by microwave plasma CVD method.
A p-type layer was formed on the mold layer. In order to form a p-type layer, the substrate 1104 is heated to 200 ° C. by the heater 1105, and the outflow valves 1041 to 1043 and 1108 are opened gradually, and SiH ₄ gas, H ₂ gas, BF ₃ (1%) /
H ₂ gas is introduced into the deposition chamber 1101 through the gas introduction pipe 1103.
Allowed to flow in. At this time, the flow rate of the SiH ₄ gas is 0.5 s.
ccm, H ₂ gas flow rate is 100 sccm, BF ₃ (1%)
Each of the mass flow controllers 1021 to 1023 was adjusted so that the / H ₂ gas flow rate became 1 sccm. The opening of the conductance valve 1107 was adjusted while watching the vacuum gauge 1106 so that the pressure in the deposition chamber 1101 became 1 Torr.

After that, the power of the RF power supply 1111 is reduced by 2 W /
cm ² , and RF power is introduced into the cathode 1102 through the RF matching box 1112 to generate an RF glow discharge, start forming a p-type layer on the i-type layer, and form a p-type layer having a thickness of 5 nm. When the RF glow discharge is stopped, the outflow valves 1041 to 1043 and the auxiliary valve 1
108 was closed, the gas flow into the deposition chamber 1101 was stopped, and the formation of the p-type layer was completed. Next, a transparent electrode and a current collecting electrode were deposited on the p-type layer in the same manner as in Example 1 to produce a photovoltaic element (element No. 16). Table 13 shows the conditions for manufacturing the photovoltaic element described above.

Comparative Example 3 A reflective layer was formed on a substrate under the same manufacturing conditions as in Example 16 except that an i-type layer was not formed by RF plasma CVD.
A photovoltaic element was produced by producing a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode and a current collecting electrode (element number ratio 3).

The fabricated photovoltaic element (element No. 16)
And element No. The ratio 3) was measured for initial characteristics, low illuminance characteristics and durability characteristics in the same manner as in Example 1. As a result of the measurement, the device No. For the photovoltaic element of ratio 3, the element N
o. The photovoltaic element of Example 16 has an open-circuit voltage of initial characteristics of 1.04 times, a fill factor of 1.03 times, a photoelectric conversion efficiency of low illuminance characteristics of 1.08 times, and a decrease in photoelectric conversion efficiency of durability characteristics. 1.09 times better, demonstrating the effect of the present invention.

Example 17 Under the manufacturing conditions shown in Table 14, a reflective layer, a reflection increasing layer, a first n-type layer, a first i-type layer, A first p-type layer, a second n-type layer, a second i-type layer, a second p-type layer, a transparent electrode, and a current collecting electrode were prepared to produce a photovoltaic element (element No. 17).

Comparative Example 4 The same manufacturing conditions as in Example 17 were used, except that the i-type layer 1 and the i-type layer 2 were not formed by the first RF plasma CVD method.
On a substrate, a reflection layer, a reflection enhancement layer, a first n-type layer, a first i-type layer, a first p-type layer, a second n-type layer, a second i-type layer,
A second p-type layer, a transparent electrode, and a current collecting electrode were prepared to produce a photovoltaic element (element number ratio 4).

The photovoltaic elements (element No. 17 and ratio 4) produced as described above were measured for initial characteristics, low illuminance characteristics and durability characteristics in the same manner as in Example 1. As a result of the measurement, the device No. With respect to the photovoltaic element having a ratio of 4, In the photovoltaic element of Example 17, the open-circuit voltage of the initial characteristics is 1.03 times, the fill factor is 1.03 times, the photoelectric conversion efficiency of the low illuminance characteristics is 1.08 times, and the decrease of the photoelectric conversion efficiency of the durability characteristics is small. 1.10 times better, demonstrating the effect of the present invention.

(Example 18) Under the manufacturing conditions shown in Table 15, a reflective layer, a reflection increasing layer, a first n-type layer, a first i-type layer, A first p-type layer, a second n-type layer, a second i-type layer, a second p-type layer, a third n-type layer, a third i-type layer, a third
A p-type layer, a transparent electrode, and a current collecting electrode were produced to produce a photovoltaic element (element No. 18).

Comparative Example 5 The first i-type layer and the second i-type layer formed by the RF plasma CVD method were used.
Except that the mold layer 1 and the i-type layer 2 are not formed, a reflective layer, a reflection increasing layer, a first n-type layer, a first i-type layer, a first
P-type layer, second n-type layer, second i-type layer, second p-type layer, third n-type layer, third i-type layer, third p-type layer, transparent electrode, A current collecting electrode was produced to produce a photovoltaic element (element number ratio 5).

The fabricated photovoltaic element (element No. 18)
The initial characteristics, the low illuminance characteristics, and the durability characteristics were measured in the same manner as in Example 1 with the ratio 5). As a result of the measurement, the element N
o. For element ratio No. 5, Actually, the open voltage of the initial characteristics is 1.03 times, the fill factor is 1.03 times, the photoelectric conversion efficiency of the low illuminance characteristics is 1.09 times, and the decrease of the photoelectric conversion efficiency of the durability characteristics is 1.07 times better. Thus, the effect of the present invention was demonstrated.

(Example 19) A photovoltaic element of the present invention was manufactured by a multi-chamber separation type deposition apparatus shown in FIG. In the figure, reference numerals 1201 and 1210 denote load and unload chambers, 1202, 1203, 1205-1.
Reference numerals 207 and 1029 denote chambers for depositing each layer by the same RF plasma CVD method as in Embodiment 16, 1204 and 1208 denote chambers for depositing each layer by the microwave plasma CVD method as in Embodiment 1, and 1211 to 1219 gates separating the chambers. The bulbs 1221, 1222, 1224-1226 and 1228 are cathode electrodes, and 1223 and 1227 are microwave waveguides and dielectric windows.

First, the substrate is set in the load chamber 1201,
After the inside of the load chamber 1201 is evacuated, the gate valve 1211 is opened, and the substrate is removed from the first n-type layer deposition chamber 1202.
And the gate valve 1211 was closed. Next, the first n-type layer was formed on the substrate under the same conditions as those of the first n-type layer of Example 17.
A mold layer was prepared. Next, the gate valve 1212 was opened, the substrate was moved to the i-type layer deposition chamber 1203 by the first RF plasma CVD method, and the gate valve 1212 was closed. Next, the first R-type layer 1 was formed on the first n-type layer under the same conditions as those of the i-type layer 1 by the first RF plasma CVD method in Example 17.
An i-type layer 1 was produced by the F plasma CVD method. next,
The gate valve 1213 was opened, the substrate was moved to the i-type layer deposition chamber 1204 by the first microwave plasma CVD method, and the gate valve 1213 was closed. Next, an i-type layer formed by the first microwave plasma CVD method is formed on the i-type layer 1 formed by the first RF plasma CVD method under the same conditions as those of the i-type layer formed by the first microwave plasma CVD method in Example 17. Produced. Next, the gate valve 1214 is opened, and the substrate is placed in the i-type layer deposition chamber 12 by the first RF plasma CVD method.
05, and the gate valve 1214 was closed. next,
Under the same conditions as the i-type layer 2 by the first RF plasma CVD method of Example 17, the i-type layer 2 by the first RF plasma CVD method was formed on the i-type layer by the first microwave plasma CVD method. .

The gate valve 1215 is opened, the substrate is moved to the first p-type layer deposition chamber 1206, and the gate valve 1215 is opened.
15 was closed. Next, a first p-type layer was formed on the i-type layer 2 by the first RF plasma CVD method under the same conditions as the first p-type layer of Example 17. Next, the gate valve 121
6 was opened, the substrate was moved to the second n-type layer deposition chamber 1207, and the gate valve 1216 was closed. Next, Example 17
Under the same conditions as the second n-type layer, a second n-type layer was formed on the first p-type layer. Next, the gate valve 1217 was opened, the substrate was moved to the second i-type layer deposition chamber 1208, and the gate valve 1217 was closed. Next, a second i-type layer was formed on the second n-type layer under the same conditions as the second i-type layer of Example 17. Next, the gate valve 1218 was opened, the substrate was moved to the second p-type layer deposition chamber 1209, and the gate valve 1218 was closed. Next, a second p-type layer was formed on the second i-type layer under the same conditions as the second p-type layer in Example 17. Next, the gate valve 1219 was opened, the substrate was moved to the unload chamber 1210, the gate valve 1219 was closed, the substrate was taken out of the unload chamber 1210, and a photovoltaic element was manufactured (element No. 19).

The fabricated photovoltaic element (element No. 1)
The initial characteristics, low illuminance characteristics, and durability characteristics were measured in the same manner as in Example 1 of 9). As a result of the measurement, the photovoltaic device of Example 17 (element No. 17)
The photovoltaic element (element No. 19) has an open-circuit voltage of 1.01 times, a fill factor of 1.02 times, a photoelectric conversion efficiency of low illuminance characteristics of 1.03 times, and a photoelectric characteristic of endurance characteristics. The reduction in conversion efficiency is 1.02 times better, and it has been found that a photovoltaic element having even more excellent characteristics can be obtained by manufacturing the photovoltaic element of the present invention with a multi-chamber separation type deposition apparatus. Thus, the effect of the present invention was demonstrated.

Example 20 A photovoltaic element was manufactured under the same manufacturing conditions as in Example 17, and
Using this, a solar cell module was produced, and an in-vehicle ventilation fan having a circuit configuration as shown in FIG. 21 was produced. FIG.
In, the electric power generated by the solar cell module 9101 attached to the hood of the automobile is charged into the secondary battery 9104 via the backflow prevention diode 9102. 9
103 is an overcharge prevention diode. The power from the solar cell module 9101 and the secondary battery 9104 is
It is supplied to the motor 9105 of the ventilation fan.

Comparative Example 6 As a comparative example, the device No. A photovoltaic element was produced under the same production conditions as in Ratio 4, and using this, a vehicle-mounted ventilation fan similar to that of Example 21 was produced. The vehicle equipped with the in-vehicle ventilation fan manufactured in Example 20 and Comparative Example 6 was left for 168 hours in an idling state in which the engine was rotated, and then left in a sunny state with the engine stopped and the ventilation fan operated, The temperature in the car interior was measured. As a result, the in-vehicle cooling fan of Example 20 had a room temperature lower by 3 degrees than the in-vehicle cooling fan of Comparative Example 6, and the effect of the power generation system according to the present invention was demonstrated.

(Example 21) A source gas supply device 1020 and a deposition device 10 shown in FIG.
The photovoltaic element of the present invention was manufactured using a manufacturing apparatus based on a microwave plasma CVD method consisting of a raw material gas supply apparatus 1020 and a deposition apparatus 1100 shown in FIG. In this embodiment, B is added to the i-type layer by microwave plasma CVD.
And P atoms were doped.

The device No. of Example 1 Under the same manufacturing conditions as in Example 1-5, a reflection layer, a reflection enhancement layer, and an n-type layer were formed on the substrate, and then an i-type layer was formed by RF plasma CVD and microwave plasma CVD as follows. A film was formed. The substrate 1004 is taken out of the deposition chamber 1001, and
-2 Deposition apparatus 110 by RF plasma CVD method
No. 0 deposition chamber 1101 to produce an i-type layer by RF plasma CVD.

In order to form an i-type layer by the RF plasma CVD method, the substrate 1104 is heated to 350 ° C. by the heater 1105, and the outflow valves 1041, 1042,
047, 1048 and the auxiliary valve 1108 are gradually opened, and SiH ₄ gas, H ₂ gas, BF ₃ (2000 ppm)
/ H ₂ gas and PH ₃ (2000 ppm) / H ₂ gas were introduced into the deposition chamber 1101 through the gas introduction pipe 1103. At this time, the SiH ₄ gas flow rate was 8 sccm, the H ₂ gas flow rate was 100 sccm, BF ₃ (2000 ppm) / H ₂ gas flow rate 0.04 sccm, PH ₃ (2000 ppm) /
Each of the mass flow controllers 1021, 1022, 1027, 102 is set so that the H ₂ gas flow rate becomes 1 sccm.
8 adjustments were made. The pressure in the deposition chamber 1101 is 0.5 Torr
The opening of the conductance valve 1107 was adjusted while watching the vacuum gauge 1106 so as to obtain r.

Thereafter, the power of the RF power supply 1111 is reduced to 120
mW / cm ² and the RF matching box 111
2 to the cathode 1102 through RF power,
Glow discharge is generated, and RF plasma CVD is performed on the n-type layer.
When the i-type layer is formed by the method and the i-type layer having a thickness of 10 nm is formed, the RF glow discharge is stopped, the outflow valves 1041 and 1042 and the auxiliary valve 1108 are closed, and the gas flows into the deposition chamber 1101. And the fabrication of the i-type layer was completed.

Next, the substrate 1104 was taken out of the deposition chamber 1101 and placed in the deposition chamber 1001 of the deposition apparatus 1000 by the microwave plasma CVD method shown in FIG. 11 to produce an i-type layer by the microwave plasma CVD method. In order to form an i-type layer by a microwave plasma CVD method, the substrate 1004 is heated to 350 ° C. by a heater 1005, and the outflow valves 1041, 1042, 1046 to 1046
48 and the auxiliary valve 1008 are gradually opened, and SiH ₄
Gas, H ₂ gas, GeH ₄ gas, BF ₃ (2000 pp
m) / H ₂ gas and PH ₃ (2000 ppm) / H ₂ were introduced into the deposition chamber 1001 through the gas introduction pipe 1003. At this time, SiH ₄ gas flow rate 200 sccm, H ₂
Gas flow rate is 500 sccm, GeH ₄ gas flow rate is 1 sc
cm, BF ₃ (2000 ppm) / H ₂ gas flow rate 0.2 s
ccm, PH ₃ (2000 ppm) / H ₂ gas flow rate 0.1
Each mass flow controller 1021, 1022, 1026 to 1028 was adjusted so as to be sccm. The pressure inside the deposition chamber 1001 is monitored by the conductance valve 100
The opening of No. 7 was adjusted.

Next, the shutter 1013 is closed, the power of the microwave power supply (not shown) is set to 170 mW / cm ³ , and the waveguide, the waveguide 1010 and the dielectric window 10 (not shown) are set.
02, a microwave power is introduced into the deposition chamber 1001 to generate a microwave glow discharge,
The RF bias of 011 was set to 350 mW / cm ³ , and the DC bias was set to 0 V via an RF cut coil, and applied to the bias bar 1012. After that, the shutter 1013 is opened to start the production of the i-type layer by the microwave plasma CVD method on the i-type layer by the RF plasma CVD method, and at the same time, the flow rate of SiH ₄ gas and GeH ₄
The gas flow rate was adjusted by the mass flow controllers 1021 and 1026 according to the flow rate pattern shown in FIG.
013, the output of the bias power supply 1011 is turned off, the microwave glow discharge is stopped, and the outflow valves 1041, 10
42, 1046 and the auxiliary valve 1008 were closed to stop the gas flow into the deposition chamber 1001.

Subsequently, a p-type layer was formed on the i-type layer by RF plasma CVD under the same conditions as in Example 1. Furthermore, p
ITO (In ₂ O ₃ + SnO) as a transparent electrode on the mold layer
₂ ) A thin film of 70 μm was further vacuum-deposited with an aluminum (Al) thin film of 2 μm as a current collecting electrode to produce a photovoltaic element (element Nos. 21-1 to 7; ratio 7-1). The fabricated photovoltaic devices (device Nos. 21-1 to 21-7 and device N
o. The initial characteristics, low illuminance characteristics, and durability characteristics of the ratio 7-1) were measured. Table 16 shows the results.

As can be seen from Table 16, the pressure in the deposition chamber 1001 was 5
It has been found that a photovoltaic element having excellent characteristics can be obtained by manufacturing at 0 mTorr or less. In addition, a barium borosilicate glass (Corning Co., Ltd. 7059) substrate was used, and the SiH ₄ gas flow rate, the GeH ₄ gas flow rate, and the microwave power were set to the values shown in Table 3, and the device Nos. Real 2
The shutter 1013 was opened for 2 minutes under the same manufacturing conditions as those of the i-type layer by the microwave plasma CVD method of 1-5 to form an i-type layer on the substrate by the microwave plasma CVD method. Was obtained, and the same result as in Table 3 was obtained.

Next, when producing an i-type layer by microwave plasma CVD, the power of the microwave power supply was
, Except that the values shown in FIG. A reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a collecting electrode are formed on a substrate under the same manufacturing conditions as those of the photovoltaic element of Example 21-5. An element was manufactured (Element No. 21-8).
-10 and 7-2-3).

The fabricated photovoltaic element (element No. 21)
-8 to 10 and 7-2 to 3) were used as element Nos. The initial characteristics, the low illuminance characteristics, and the durability characteristics were measured in the same manner as in Example 21-5. Table 17 shows the measurement results. As can be seen from Table 17, it was found that a photovoltaic element having excellent characteristics was obtained by decomposing the source gas with microwave energy lower than the microwave energy required to decompose the source gas by 100%.

Next, when producing the i-type layer by the microwave plasma CVD method, except that the RF bias was set to the value shown in Table 18, the device No. A reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a collecting electrode were formed on a substrate under the same manufacturing conditions as those of the photovoltaic element of Example 21-5. Elements were manufactured (element Nos. 21-11 to 14).
And 7-4).

The manufactured photovoltaic element (element No. 21)
-11 to 14 and 7-4) were replaced by element Nos. The initial characteristics, the low illuminance characteristics, and the durability characteristics were measured in the same manner as in Example 21-5. Table 18 shows the measurement results. As can be seen from Table 18, it was found that a photovoltaic element having excellent characteristics was obtained by applying RF energy higher than the microwave energy to the source gas.

Next, using a stainless steel substrate and a barium borosilicate glass (7059, manufactured by Corning Incorporated) substrate,
The element Nos. 1 and 2 except that the H ₄ gas flow rate and the GeH ₄ gas flow rate were set to the values shown in Table 6. Actual 21-5 microwave plasma C
Under the same manufacturing conditions as for the i-type layer by the VD method, an i-type layer was formed on the substrate at 1 μm to prepare a sample for measuring physical properties. Furthermore, barium borosilicate glass (705 made by Corning Co., Ltd.)
9) The device No. Under the same manufacturing conditions as those of the i-type layer by RF plasma CVD method in Ex. 21-5, an i-type layer was formed on the substrate at 1 μm to prepare a sample for measuring physical properties.

The bandgap and composition of the manufactured sample for measuring physical properties were analyzed, and the relationship between the composition ratio of Si atoms and Ge atoms and the bandgap was determined. The same results as in Table 6 were obtained. Next, when fabricating an i-type layer by microwave plasma CVD, the SiH ₄ gas flow rate and GeH ₄
The device Nos. 1 and 2 were prepared except that the gas flow rate was adjusted by the mass flow controllers 1021 and 1026 according to the flow pattern shown in FIG. Under the same manufacturing conditions as the photovoltaic element of Actual 21-5, a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer,
A p-type layer, a transparent electrode, and a current collecting electrode were formed, and a photovoltaic element was manufactured (element number ratio 7-5).

The fabricated photovoltaic element (element number ratio 7-
5) is replaced with the element No. The initial characteristics, the low illuminance characteristics, and the durability characteristics were measured in the same manner as in Example 21-5. As a result of the measurement, the device No. For the ratio 7-5, the device No. In the actual 21-5, the open-circuit voltage of the initial characteristics is 1.02 times, the fill factor is 1.03 times,
The low illuminance characteristics were 1.09 times better and the durability characteristics were 1.07 times better.

Further, the device No. Actual 21-5 and the element No.
When the composition analysis of Si atoms and Ge atoms in the layer thickness direction in the i-type layer by microwave plasma CVD at a ratio of 7-5 was performed in the same manner as the composition analysis, the element N
o. In the photovoltaic element of Actual 21-5, the position of the minimum value of the band gap is shifted from the center position of the i-type layer toward the interface between the p-type layer and the i-type layer. In the photovoltaic element having the ratio of 7-5, it was found that the position of the minimum value of the band gap was shifted more toward the interface between the n-type layer and the i-type layer than the center position of the i-type layer.

For comparison, BF ₃ (2000 pp) was used to form an i-type layer by microwave plasma CVD.
m) / H ₂ and PH ₃ (2000 ppm) / H ₂ except that element No. Under the same manufacturing conditions as the actual photovoltaic element of 21-5, a reflection layer, a reflection enhancement layer, an n-type layer,
A photovoltaic element was manufactured by forming a mold layer, a p-type layer, a transparent electrode, and a current collecting electrode (Element Nos. 21 to 15).

The fabricated photovoltaic element (element No. 21)
-15) for the element No. The initial characteristics, the low illuminance characteristics, and the durability characteristics were measured in the same manner as in Example 21-5. As a result of the measurement,
Element No. In contrast to 21-21, the element No. Real 21-5
Means that the open-circuit voltage of the initial characteristics is 1.02 times and the fill factor is 1.0
3 times, the low illuminance characteristic was 1.09 times, and the durability characteristic was 1.07 times.

The device No. The composition of the photovoltaic element No. 21-5 was analyzed by a secondary ion mass spectrometer, and it was confirmed that the i-type layer contained B and P atoms. When an i-type layer was produced by the RF plasma CVD method, the element No. was changed except that the SiH ₄ gas flow rate and the RF discharge power were set to the values shown in Table 19. Under the same manufacturing conditions as the photovoltaic element of Example 21-5, a reflection layer, a reflection enhancement layer,
An n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode were formed, and a photovoltaic device was manufactured (Element Nos. 21 to 16).
-20 and ratio 7-6).

The fabricated photovoltaic element (element No. 21)
-16 to 20 and the ratio 7-6) were used for the device No. The initial characteristics, the low illuminance characteristics, and the durability characteristics were measured in the same manner as in Example 21-5. Table 19 shows the results. As can be seen from Table 19, the deposition rate of the i-type layer by RF plasma CVD was 2
It has been found that a photovoltaic element having excellent characteristics can be obtained by manufacturing at a speed of nm / sec or less.

[0192] When an i-type layer was produced by an RF plasma CVD method, the element No. Under the same manufacturing conditions as the photovoltaic element of Actual 21-5, a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer,
A p-type layer, a transparent electrode, and a collecting electrode were formed to produce a photovoltaic element (element Nos. 21-21 to 23-23 and ratio 7-7).
To 8).

The fabricated photovoltaic element (element No. 21)
-21 to 23 and ratios 7-7 to 8) were used for the device Nos. Real 21-
The initial characteristics, low illuminance characteristics, and durability characteristics were measured in the same manner as in Example 5. Table 20 shows the measurement results. As can be seen from Table 20, a photovoltaic element (element No. 21-) provided with an i-type layer formed by an RF plasma CVD method having a layer thickness of 30 nm or less.
21-23) were found to have excellent properties.

Next, when producing the i-type layer by the RF plasma CVD method, except that the RF discharge power was set to the value shown in Table 21, element No. A reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a collecting electrode were formed on a substrate under the same manufacturing conditions as those of the photovoltaic element of Example 21-5. The element was produced (element No. actual 21-24 to 27). The produced photovoltaic elements (element Nos. 21-24 to 27) are referred to as element Nos. The initial characteristics, the low illuminance characteristics, and the durability characteristics were measured in the same manner as in Example 21-5. Table 21 shows the measurement results. As can be seen from Table 21, 20 in the infrared absorption spectrum
The value obtained by dividing the half-width at the peak of 00 cm ^-1 by the peak height indicates that the i-type layer formed by the RF plasma CVD method is larger than the i-type layer formed by the microwave plasma CVD method. Was found to have.

From the above measurement results, the microwave energy and the microwave energy lower than the microwave energy required to decompose the raw material gas by 100% at an internal pressure of 50 mTorr or less and the i-type layer by the microwave plasma CVD method of the present invention are shown. RF energy higher than that applied to the source gas, the band gap changes smoothly in the layer thickness direction, and the minimum value of the band gap is located between the center of the i-type layer and the p-type layer and the i-type. Offset towards the interface of the layer, i
A valence electron controlling agent serving as a donor and an acceptor is doped in the i-type layer, and the i-type layer is
It was found that a photovoltaic device formed with a layer thickness of 30 nm or less at a deposition rate of m / sec or less had superior characteristics to a conventional photovoltaic device, and the effect of the present invention was demonstrated. .

(Example 22) When fabricating an i-type layer by microwave plasma CVD, the flow rates of SiH ₄ gas and GeH ₄ gas were changed in Example 1.
After the adjustment by the mass flow controllers 1021 and 1026 according to the flow pattern shown in FIG.
iH ₄ gas flow rate 200 sccm, GeH ₄ gas flow rate 1
Table 2 shows the region of the maximum band gap value while maintaining the band gap at sccm.
Example 21 except that the layer thickness was as shown in FIG.
Element No. Under the same manufacturing conditions as the actual 21-5, on the substrate,
A photovoltaic element was produced by producing a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode (element Nos. 22-1 to 22-8).

The fabricated photovoltaic element (element No. 22
-1 to 8) were measured for initial characteristics, low illuminance characteristics, and durability characteristics in the same manner as in Example 21. Table 22 shows the results. As can be seen from Table 22, it was found that the photovoltaic devices (device Nos. 22-1 to 22-7) having a layer thickness of 1 to 30 nm in the band gap maximum value region of the present invention had excellent characteristics, The effects of the present invention have been demonstrated.

(Example 23) Microwave plasma CVD and RF plasma CVD
When producing an i-type layer by the method, PH ₃ (2000 pp
m) / H ₂ using AsH ₃ / H ₂ gas cylinder in place of the gas cylinder, the microwave plasma CVD method under the i-type layer by 0.2sccm the AsH ₃ / H ₂ gas, RF plasma CV
In the device No. of Example 21, except that the flow rate was 0.5 sccm in the i-type layer by the method D. Under the same manufacturing conditions as in Example 21-5, a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer,
A transparent electrode and a current collecting electrode were produced to produce a photovoltaic element (element No. 23). Example 23 (element No. actual 2)
The initial characteristics, low illuminance characteristics, and durability characteristics of the photovoltaic device manufactured in 3) were measured in the same manner as in Example 21. The same initial characteristics, low illuminance characteristics, and durability characteristics as those of Example 21-5 were obtained.

(Example 24) When producing an i-type layer by microwave plasma CVD, the flow rate of BF ₃ (2000 ppm) / H ₂ gas was set to PH ₃ (2000 ppm) / H _{2 according to the} flow pattern shown in FIG. The gas flow rate was adjusted by mass flow controllers 1027 and 1028 according to the flow rate pattern shown in FIG.
When fabricating an i-type layer by F plasma CVD, BF ₃
(2000 ppm) / H ₂ gas flow rate 0.06 scc
m, PH ₃ (2000 ppm) / H ₂ gas flow rate ₂ scc
m of the device of Example 21. Under the same manufacturing conditions as in Example 21-5, a reflection layer, a reflection enhancement layer, an n-type layer, i
A photovoltaic element was produced by producing a mold layer, a p-type layer, a transparent electrode, and a current collecting electrode (element No. 24).

The initial characteristics, low illuminance characteristics, and durability characteristics of the photovoltaic device manufactured in Example 24 (element No. 24) were measured in the same manner as in Example 21.
o. The same initial characteristics, low illuminance characteristics, and durability characteristics as those of Example 21-5 were obtained. Example 24 (element No. 2)
The distribution of B and P atoms in the i-type layer of the photovoltaic element of 4) was analyzed by a secondary ion mass spectrometer. FIG. 34 shows the results.
35 and FIG. From the above results, the effect of the present invention was demonstrated.

Example 25 When producing an i-type layer by microwave plasma CVD and RF plasma CVD, a NO / He gas cylinder 1 was used.
No. 079, and the flow rate of the NO / He gas was 0.5 sccm for the i-type layer by the microwave plasma CVD method and 0.05 sccm for the i-type layer by the RF plasma CVD method. Under the same manufacturing conditions as in Example 21-5, a photovoltaic element was manufactured by manufacturing a reflective layer, a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode on a substrate. (Element No. 25).

The manufactured photovoltaic element (element No. 2)
5) was measured for initial characteristics, low illuminance characteristics, and durability characteristics in the same manner as in Example 21. Real 21-
The same initial characteristics, low illuminance characteristics, and durability characteristics as in Example 5 were obtained. Further, when the composition of the photovoltaic device of Example 25 was analyzed by a secondary ion mass spectrometer, O and N atoms were confirmed in the i-type layer.

(Example 26) When an i-type layer was produced by microwave plasma CVD, an Si ₂ H ₆ gas cylinder was used and the Si ₂ H ₆ gas flow rate was set at 4%.
Element No. 21 of Example 21 except that the flow rate of the SiH ₄ gas was adjusted by the mass flow controller 1021 in accordance with the flow rate pattern shown in FIG. Under the same manufacturing conditions as in Example 21-5, a photovoltaic element was manufactured by manufacturing a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode on a substrate. (Element No. 26).

The fabricated photovoltaic element (element No. 2)
6) was measured for initial characteristics, low illuminance characteristics, and durability characteristics in the same manner as in Example 21. Real 21-
The same initial characteristics, low illuminance characteristics, and durability characteristics as in Example 5 were obtained. The distribution of Si atoms and hydrogen atoms in the i-type layer in the thickness direction of the photovoltaic element of Example 26 (element No. 26) was measured using a secondary ion mass spectrometer (manufactured by CAMECA).
Analysis by IMS-3F) showed the same tendency as in FIG. From the above results, the content of hydrogen atoms was S
It has been found that the photovoltaic element that changes corresponding to the i-atom content has excellent characteristics, demonstrating the effect of the present invention.

(Example 27) In a source gas supply apparatus 1020, SiH ₄ gas and G
The device No. of Example 21 was changed except that the distance between the mixing point of the eH ₄ gas and the deposition chamber 1001 was a value shown in Table 23. Under the same manufacturing conditions as in Example 21-5, a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode,
A collector electrode was prepared to produce a photovoltaic device (device N
o. Actual 27-1 to 5).

The fabricated photovoltaic element (element No. 27)
-1 to 5) were measured for initial characteristics, low illuminance characteristics, and durability characteristics in the same manner as in Example 21. Table 23 shows the measurement results.
Shown in As can be seen from Table 23, SiH ₄ gas and GeH ₄
It has been found that by setting the distance between the gas mixing point and the deposition chamber 1001 to be 5 m or less, a photovoltaic element having better characteristics can be obtained.

(Example 28) The device Nos. A photovoltaic element was manufactured under the same manufacturing conditions as in Examples 21-5 and 21-15, and
A solar cell module was manufactured, and an analog timepiece having a circuit configuration as shown in FIG. 21 was manufactured. When the produced analog timepiece was installed on a wall in a room, the element No. In comparison with the analog timepiece using the actual 21-15, the element No. The analog timepiece using the actual 21-5 showed even better performance.

Example 29 When producing an i-type layer by microwave plasma CVD, the flow rate of SiH ₄ gas and the flow rate of GeH ₄ gas were changed according to the flow pattern shown in FIG.
21, the element N of Example 21
o. Under the same manufacturing conditions as in Example 21-5, a reflective layer,
A photovoltaic element was produced by producing a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode (element No. 29). The initial characteristics, low illuminance characteristics, and durability characteristics of the fabricated photovoltaic device (device No. 29) were measured in the same manner as in Example 21. The same initial characteristics, low illuminance characteristics, and durability as those of Example 21-5 were obtained, and the effect of the present invention was demonstrated.

(Example 30) In preparing an i-type layer by microwave plasma CVD or RF plasma CVD, a B ₂ H ₆ gas diluted to 2000 ppm with H ₂ gas instead of a BF ₃ / H ₂ gas cylinder. (B ₂ H ₆ / H ₂ gas) using a bomb, B and B ₂ H ₆ / H ₂ gas during the formation of the i-type layer by microwave plasma CVD method 1 sccm, during the formation of the i-type layer by RF plasma CVD method ₂ Except for flowing H ₆ / H ₂ gas at 0.05 sccm,
The device No. Under the same manufacturing conditions as in Real 21-5,
On the substrate, a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode were prepared to produce a photovoltaic element (element No. 30). The initial characteristics, low illuminance characteristics, and durability characteristics of the manufactured photovoltaic device (Element No. 30) were measured in the same manner as in Example 21. The same initial characteristics, low illuminance characteristics, and durability as those of Example 21-5 were obtained, and the effect of the present invention was demonstrated.

Example 31 The device of Example 21 was prepared except that the NO / He gas was adjusted by the mass flow controller 1029 in accordance with the flow pattern shown in FIG. 26 when the i-type layer was produced by the microwave plasma CVD method. No. Under the same manufacturing conditions as in Example 21-5, a photovoltaic element was manufactured by manufacturing a reflective layer, a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode on a substrate. (Element No. 31).

The manufactured photovoltaic element (element No. 3)
1) The initial characteristics, the low illuminance characteristics, and the durability characteristics were measured in the same manner as in Example 21.
o. The same initial characteristics, low illuminance characteristics, and durability as those of Example 21-5 were obtained. Example 11 (Element No. 31)
When the distribution of N atoms and O atoms in the i-type layer of the photovoltaic element in the i-type layer in the layer thickness direction was analyzed by a secondary ion mass spectrometer, a tendency similar to that of FIG. 27 was shown. From the above results, the effect of the present invention was demonstrated.

Example 32 When fabricating an i-type layer by microwave plasma CVD, the flow rate of SiH ₄ gas and the flow rate of GeH ₄ gas were changed according to the flow pattern shown in FIG.
21, 1026 and microwave plasma CV
Example 2 except that after the i-type layer was formed by the D method, the i-type layer was formed by the RF plasma CVD method under the manufacturing conditions shown in Table 12.
Element No. 1 Under the same conditions as in Example 21-5, a photovoltaic element was produced by producing a reflective layer, a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode on a substrate ( Element No. 32). The initial characteristics, low illuminance characteristics, and durability characteristics of the fabricated photovoltaic device (Element No. 32) were measured in the same manner as in Example 21. The same initial characteristics, low illuminance characteristics, and durability characteristics as those of Example 21-5 were obtained, and the effect of the present invention was demonstrated.

(Example 33) When an i-type layer was produced by microwave plasma CVD, the RF bias of the bias power supply 1011 was set to 250 mW.
/ Cm ³ , a DC bias was set to 50 V via a coil for RF cut, and a bias was applied to the bias bar 1012 under the same manufacturing conditions as in Example 29. A photovoltaic element was produced by producing a layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode (element No. 33). The fabricated photovoltaic element (element N
o. Example 33) was obtained in the same manner as in Example 29 by using the initial characteristics,
When the low illuminance characteristic and the durability characteristic were measured,
The same initial characteristics, low illuminance characteristics and durability characteristics as
The effects of the present invention have been demonstrated.

Example 34 Example 21 was repeated except that, when an i-type layer was produced by microwave plasma CVD, a D ₂ gas cylinder (not shown) was used instead of the H ₂ gas cylinder and D ₂ gas was flowed at 300 sccm.
Element No. Under the same manufacturing conditions as the actual 21-5, on the substrate,
A photovoltaic element was produced by producing a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode (element No. 34).

The manufactured photovoltaic element (element No. 3)
4) The initial characteristics, the low illuminance characteristics, and the durability characteristics were measured in the same manner as in Example 21.
o. The same initial characteristics, low illuminance characteristics, and durability characteristics as those of Example 21-5 were obtained. Example 14 (element No. 3)
When the composition of the photovoltaic element of 4) was analyzed by a secondary ion mass spectrometer, it was confirmed that the i-type layer contained D atoms, and the effect of the present invention was demonstrated.

(Example 35) In manufacturing an n-type layer, the DC bias of the bias power supply 1011 was changed to 50 at the same time when the shutter 1013 was opened.
V of Example 21 except that the voltage was changed from V to 80 V at a constant rate. Under the same manufacturing conditions as in Example 21-5, a photovoltaic element was manufactured by manufacturing a reflective layer, a reflection increasing layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode on a substrate. (Element No. 35). The fabricated photovoltaic element (element N
o. Example 35) was obtained in the same manner as in Example 21 by using the initial characteristics,
When the low illuminance characteristic and the durability characteristic were measured,
Element No. The same initial characteristics, low illuminance characteristics, and durability characteristics as those of Example 21-5 were obtained, and the effect of the present invention was demonstrated.

(Example 36) In this example, an n-type layer and a p-type layer were produced under the same conditions as in Example 16 by using a deposition apparatus by the RF plasma CVD method shown in FIG. Element No. Real 21-
5 was manufactured under the same conditions as in Example 5 (Element No. 36-1).

[0218] Further, when producing an i-type layer by microwave plasma CVD, the procedure of Example 36-1 was repeated except that BF ₃ (2000 ppm) / H ₂ gas and PH ₃ (2000 ppm) / H ₂ gas were not used. Under the same manufacturing conditions, a photovoltaic element was manufactured by manufacturing a reflection layer, a reflection enhancement layer, an n-type layer, an i-type layer, a p-type layer, a transparent electrode, and a current collecting electrode on a substrate (element No. 36-2).

The fabricated photovoltaic element (element No. 36)
-1 and 2) were measured for initial characteristics, low illuminance characteristics, and durability characteristics in the same manner as in Example 21. As a result of the measurement, the element N
o. In contrast to the photovoltaic element of Ex. The photovoltaic element of Actual 36-1 has an open-circuit voltage of initial characteristics of 1.
03 times, the fill factor was 1.04 times, the photoelectric conversion efficiency of the low illuminance characteristics was 1.09 times, and the decrease of the photoelectric conversion efficiency of the durability characteristics was 1.08 times, which proved the effect of the present invention.

(Example 37) Under the manufacturing conditions shown in Table 24, a reflective layer, a reflection increasing layer, a first n-type layer, a first i-type layer, A first p-type layer, a second n-type layer, a second i-type layer, a second p-type layer, a transparent electrode, and a current collecting electrode were prepared to produce a photovoltaic element (element No. 37-1).

When an i-type layer was produced by the first microwave plasma CVD method, the device No. 1 was prepared except that BF ₃ (2000 ppm) / H ₂ gas and PH ₃ (2000 ppm) / H ₂ gas were not used. Under the same manufacturing conditions as in Example 37-1, a reflective layer, a reflection increasing layer, a first n-type layer, a first i-type layer, a first p-type layer, a second n-type layer, 2 i-type layer, 2nd
A p-type layer, a transparent electrode, and a current collecting electrode were produced to produce a photovoltaic element (element No. 37-2).

The initial characteristics, low illuminance characteristics and durability characteristics of the photovoltaic devices (element Nos. 37-1 and 37-2) manufactured as described above were measured in the same manner as in Example 21.
As a result of the measurement, the device No. For the photovoltaic element of Ex. The photovoltaic element of Example 37-1 has an open-circuit voltage of initial characteristics of 1.04 times, a fill factor of 1.03 times, a photoelectric conversion efficiency of low illuminance characteristics of 1.08 times, and a photoelectric conversion efficiency of endurance characteristics. The reduction was 1.09 times better, demonstrating the effect of the present invention.

(Example 38) Under the manufacturing conditions shown in Table 25, a reflective layer, a reflection increasing layer, a first n-type layer, a first i-type layer, A first p-type layer, a second n-type layer, a second i-type layer, a second p-type layer, a third n-type layer, a third i-type layer, a third
A p-type layer, a transparent electrode and a current collecting electrode were produced to produce a photovoltaic element (element No. 38-1).

Next, when fabricating the first i-type layer and the second i-type layer by the microwave plasma CVD method, BF
₃ (2000 ppm) / H ₂ gas and PH ₃ (2000p
pm) / H ₂ gas was not used. Real 38
In the same manner as -1, the reflective layer, the reflection increasing layer, the first n-type layer, the first i-type layer, the first p-type layer, the second n-type layer, and the second i-type layer are formed on the substrate. Mold layer, second p-type layer, third n-type layer, third
The i-type layer, the third p-type layer, the transparent electrode, and the current collecting electrode were produced to produce a photovoltaic element (element No. 38-2).

The fabricated photovoltaic element (element No. 38)
-1 and 2) were measured for initial characteristics, low illuminance characteristics, and durability characteristics in the same manner as in Example 21. As a result of the measurement, the element N
o. With respect to the element No. 38-2, Actual 38-1 has an open-circuit voltage of 1.03 times the initial characteristic and a fill factor of 1.04.
2 times, the photoelectric conversion efficiency of the low illuminance characteristics was 1.08 times, and the decrease of the photoelectric conversion efficiency of the durability characteristics was 1.07 times, which proved the effect of the present invention.

Example 39 A photovoltaic element of the present invention was manufactured using the multi-chamber separation type deposition apparatus shown in FIG. The conditions for forming each layer were the same as in Example 37, and a photovoltaic device was manufactured according to the procedure of Example 19 (Element No. 39). The initial characteristics, low illuminance characteristics, and durability characteristics of the manufactured photovoltaic element (element No. 39) were measured in the same manner as in Example 21. As a result of the measurement,
Compared to the photovoltaic element of Example 37 (Element No. 37), the photovoltaic element of Example 39 (Element No. 39) had an open-circuit voltage of 1.01 times the initial characteristic and a fill factor of 1.
The photovoltaic element of the present invention is manufactured with a multi-chamber separation type deposition apparatus because the photoelectric conversion efficiency of the low illuminance characteristic is 1.02 times and the reduction of the photoelectric conversion efficiency of the durability characteristic is 1.03 times. As a result, it was found that a photovoltaic element having more excellent characteristics was obtained, and the effect of the present invention was proved.

(Example 40) The device Nos. A photovoltaic element was produced under the same production conditions as in Examples 37-1 and 37-2, and a solar cell module was produced using the photovoltaic element, thereby producing a vehicle-mounted ventilation fan having a circuit configuration as shown in FIG. Element No. The vehicle equipped with the in-vehicle ventilation fan using the actual 37-1 and 37-2 was left for 168 hours in an idling state where the engine was rotated, and then left in a state where the engine was stopped and the ventilation fan was operated in fine weather, The room temperature was measured. As a result, the device No. Real 37
No.-2 is used for the in-vehicle cooling fan. Real 3
The indoor temperature of the in-vehicle cooling fan using 7-1 was lowered by 3 degrees.

[0228]

[Table 1] │ │substrate│SUS430BA 50mm square, 1mm thick │ ├─────┼────────────────────────────┤ │Reflection layer│Silver (Ag) thin film 100 nm │ │ │Reflection increasing layer│Zinc oxide (ZnO) thin film 1 μm │ ├層 │ │ layer │ gas │ microwave │ bias │ pressure power │ substrate │ thickness │ │ │ │ and flow │ discharge power │ │ │ temperature │ │ │ │ name │ (sccm) │ (mW / cm 3) │ A scan │ (mTorr) │ (℃) │ (nm ) │ │ ├───┼──────┼─────┼───┼────┼───┼──┤ │ │ │ │ SiH ₄ 50 │ │ DC │ │ │ │ │ each │ n-type layer │ PH ₃ / H ₂ 200 │ 130 │ │ 10 │ 350 │ 10 │ │ │ │ (1% dilution) │ │ 50V │ │ │ │ │ ＲＦ │ │RF │SiH ₄ 8 │ │ │ │ │ │ │ ││ plasma │ │ │ │ │ │ │ │ ￨CVD method _{│H 2 100 │RF 120 │ │ 500} │ 350 │ 10│ │ works │ in accordance ^{│ │ (mW / cm 2)} │ │ │ │ │ │ │i type layer │ │ │ │ │ │ │ │ │Production │ │Microwave│SiH ₄ 14 │ ￨RF │ │ │ │ │ conditions │ plasma │ reference │ │ 350 │ │ │ │ │ ￨CVD method _{│H 2 500 │ │ (mW /} │ table 2 refer │ │ │ │ matter by │ ￨GeH ₄ 14 │ 170 │ cm ³ ) │ │ 350 │ 300 │ │ │ │ i-type layer │ reference │ │ DC 0V│ │ │ │ │ ├───┼──── ├───┼──── H │ │ │SiH ₄ 10 │ │ │ │ │ │ │ │ │p-type layer │H ₂ 700 │ 250 │ │ 25 │ 300 │ 10 │ │ │ │ BF ₃ / H ₂ 30 │ │ │ │ │ │ │ │ │ │ (1% dilution) │ │ │ │ │ │ ├─┴───┼──────┴─ │ │Transparent electrode │ITO (In ₂ O ₃ + SnO ₂ ) thin film 70nm │ ├─────┼────── │ │Current collecting electrode │Aluminum (Al) thin film 2μm │ └─────┴──────── ────────────────────┘

[0229]

[Table 2] ┌────┬─────┬─────────┬─────┬──────┐ │ │ Initial characteristics in deposition chamber │ Low illumination Characteristics│Durability characteristics │ │ │ ├────┬────┼─────┼──────┤ │Device No. │Pressure│ │ │Photoelectric conversion │Photoelectric conversion efficiency│ │ │ │Open circuit voltage│Fill factor│ │ │ │ │ │ (mTorr) │ │ │ Decrease in efficiency │ │ ├────┼─────┼────┼────┼───── │ │Real 1-1│ 0.5 │ 1.02 │ 1.02 │ 1.06 │ 1.06 │ ├────┼─────┼────┼────┼────実 │Real 1-2│ 1 │ 1.02 │ 1.02 │ 1.06 │ 1.05 │ ├────┼─────┼────┼────┼─── │ │Real 1-3│ 2 │ 1.02 │ 1.02 │ 1.08 │ 1.06 │ ├────┼─────┼─── │ │Real 1-4│ 5 │ 1.03 │ 1.03 │ 1.07 │ 1.09 │ ├────┼─────┼─── │ │Real 1-5│ 10 │ 1.04 │ 1.02 │ 1.05 │ 1.08 │ ├────┼─────┼── │ │Real 1-6│ 20 │ 1.03 │ 1.02 │ 1.05 │ 1.07 │ ├────┼─────┼─ │ │Real 1-7│ 50 │ 1.03 │ 1.02 │ 1.04 │ 1.06 │ ├────┼─────┼ │ │ Ratio 1-1 │ 100 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ └────┴───── ┴────┴────┴─────┴──────┘ Note) Initial characteristics, low illuminance characteristics and durability are 1
Relative value based on -1

[0230]

[Table 3] ┌────┬───────┬───────────────────┐ │ │ Gas flow │ Each microwave power (W / cm │ │ sample │ in ³⁾ (sccm) decomposition efficiency │ raw material gas (%) │ │ No ├───┬───┼───┬───┬───┬───┬── │ │ │SiH ₄ │GeH ₄ │ 0.1 │ 0.2 │ 0.3 │ 0.4 │ 0.5 │ ├────┼───┼───┼───┼───┼───┼───┼ │ │ 1-1 │ 200 │ 1 │ 24 │ 45 │ 68 │ 93 │ 100 │ ├────┼───┼───┼───┼───┼───┼─ ──┼───┤ │ 1-2 │ 170 │ 20 │ 25 │ 48 │ 73 │ 97 │ 100 │ ├────┼───┼───┼───┼───┼── │ │ 1-3 │ 140 │ 40 │ 27 │ 51 │ 76 │ 99 │ 100 │ ├────┼───┼───┼───┼─ │ │ 1-4 │ 110 │ 60 │ 28 │ 53 │ 81 │ 100 │ 100 │ ├────┼───┼───┼─── │ │ 1-5 │ 80 │ 80 │ 31 │ 58 │ 88 │100 │ 100 │ └────┴───┴───┴ ───┴───┴───┴───┴───┘

[0231]

[Table 4] ┌────┬─────┬─────────┬─────┬──────┐ │ │ Microwave │ Initial characteristics │ Low illuminance characteristics │ Durability │ │Device No. │Power ├────┬────┼─────┼──────┤ │ │ (W / cm ³ ) │Open-circuit voltage│Fill factor│Photoelectric Conversion │ Photoelectric conversion efficiency │ │ │ │ │ │ Reduction of efficiency │ │ ├────┼─────┼────┼────┼─────┼───── │ │Real 1-8│ 0.1 │ 1.03 │ 1.02 │ 1.06 │ 1.08 │ ├────┼─────┼────┼────┼─────┼──── │ │Real 1-9│ 0.2 │ 1.03 │ 1.03 │ 1.07 │ 1.08 │ ├────┼─────┼────┼────┼─────┼─── │ │Real 1-10│ 0.3 │ 1.01 │ 1.02 │ 1.07 │ 1.07 │ ├────┼─────┼────┼────┼ │ │ Ratio 1-2 │ 0.4 │ 1.00 │ 1.01 │ 1.01 │ 1.01 │ ├────┼─────┼────┼────┼ │ │ Ratio 1-3 │ 0.5 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ └────┴─────┴────┴──── ┴─────┴──────┘ Note) Initial characteristics, low illuminance characteristics and durability are 1
Relative value based on -3

[0232]

[Table 5] ┌────┬─────┬─────────┬─────┬──────┐ │ │RF bias│ Initial characteristics │Low illumination characteristics │ durability │ │ element No. │ ├────┬────┼─────┼──────┤ │ │ (mW / cm 3) │ open circuit voltage │ fill factor │ photoelectric conversion │ photoelectric conversion efficiency │ │ │ │ │ │ efficiency │ decrease │ ├────┼─────┼────┼────┼─────┼────── │ │ Ratio 1-4 │ 150 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ ├────┼─────┼────┼────┼─────┼───── ─┤ │Real 1-11│ 200 │ 1.02 │ 1.01 │ 1.04 │ 1.06 │ ├────┼─────┼────┼────┼─────┼──── │ │Real 1-12│ 250 │ 1.03 │ 1.03 │ 1.06 │ 1.07 │ ├────┼─────┼────┼────┼─── ──┼──────┤ │Real 1-13│ 300 │ 1.04 │ 1.03 │ 1.06 │ 1.07 │ ├────┼─────┼────┼────┼── │ │Real 1-14│ 350 │ 1.02 │ 1.02 │ 1.07 │ 1.06 │ └────┴─────┴────┴────┴─ ────┴──────┘ Note) Initial characteristics, low illuminance characteristics and durability are 1
Relative value based on -4

[0233]

[Table 6] ┌─────┬──────────┬───────┬─────┐ │ │ gas flow rate (sccm) │ band gap │ composition ratio │ │ Sample ├────┬─────┤ ├──┬──┤ │ No. │SiH ₄ │GeH ₄ │ (eV) │Si│Ge│ │ │ 1- 6 │ 200 │ 1 │ 1.71 │ 100 │ 1 │ ├─────┼────┼─────┼───────┼──┼──┤ │ 1-7 │ 170 │ 20 │ 1.60 │8.7 │ 1 │ ├─────┼────┼─────┼───────┼──┼──┤ │ 1-8 │ 140 │ 40 │ 1.52 │3.3 │ 1 │ ├─────┼────┼─────┼───────┼──┼──┤ │ 1-9 │ 110 │ 60 │ 1.45 │1.9 │ 1 │ ├─────┼────┼─────┼───────┼──┼──┤ │ 1-10│ 80 │ 80 │ 1.38 │1.1 │ 1 │ ├─────┼────┼─────┼───────┼──┼──┤ │ 1-11│ │ │ 1.69 │ │ │ └─────┴ └─────┴ ── ─┴─────┴───────┴──┴──┘

[0234]

[Table 7] ┌────┬───┬───┬───┬─────┬────┬─────┐ │ │ SiH ₄゛ │ RF power │ deposition │ Initial characteristics │Low illuminance │Durability characteristics │ │Device No. │Flow rate │ │Speed ├──┬──┼────┼─────┤ │Sample No.│ (SCCM) │ (mW / │ (nm / │ open │ curve │ photoelectric conversion │ photoelectric conversion effect │ │ │ │ cm ² ) │ sec) │ voltage │ factor │ efficiency │ reduction of rate │ ├────┼───┼───┼ │ │Real 1-15│ 1 │ 15 │ 0.05 │1.02│1.04│ 1.07 │ 1.07 │ │ (1-12) │ │ │ │ │ │ │ │ │ ├────┼───┼───┼───┼──┼──┼────┼─────┤ │ Actual 1-16│ 2 │ 30 │ 0.1 │1.03│1.03│ 1.08 │ 1.06 │ │ (1-13) │ │ │ │ │ │ │ │ │ ├────┼───┼───┼───┼──┼──┼── ── │ │Real 1-17│ 10 │ 150 │ 0.5 │1.03│1.04│ 1.07 │ 1.07 │ │ (1-14) │ │ │ │ │ │ │ │ ├────┼─── ├────┼─── │ │Real 1-18│ 20 │ 300 │ 1.1 │1.02│1.03│ 1.07 │ 1.07 │ │ (1- 15) │ │ │ │ │ │ │ │ │ ├────┼───┼───┼───┼──┼──┼────┼─────┤ │ Actual 1-19 │ 40 │ 500 │ 2.0 │1.01│1.03│ 1.06 │ 1.05 │ │ (1-16) │ │ │ │ │ │ │ │ ├────┼───┼───┼───┼──┼ │ │ Ratio 1-6 │ 60 │ 1000 │ 2.8 │ │ │ │ │ │ │ │ 1.00 │ │ (1-17) │ │ │ │ │ │ │ │ └─ ───┴───┴───┴───┴──┴──┴────┴─────┘ Note) The initial characteristics, low illuminance characteristics and durability are 1
Relative value based on -6

[0235]

[Table 8] ┌────┬─────┬─────────┬─────┬──────┐ │ │RF plasm│ Initial characteristics │Low illuminance characteristics │ Endurance characteristics │ │ │Ma CVD method ├────┬────┼─────┼──────┤ │ i-type by device No. │ │ │ │ Photoelectric conversion │ Photoelectric conversion efficiency │ │ │ layer thickness │ open circuit voltage │ fill factor │ │ │ │ │ (nm) │ │ │ efficiency │ decrease │ ├────┼─────┼────┼─── │ │ Ratio 1-7 │ 0 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ ├────┼─────┼────┼── │ │Real 1-20│ 1 │ 1.02 │ 1.01 │ 1.03 │ 1.04 │ ├────┼─────┼────┼─ │ │Real 1-21│ 3 │ 1.03 │ 1.02 │ 1.04 │ 1.06 │ ├────┼ │ │Real 1-5│ 10 │ 1.03 │ 1.03 │ 1.07 │ 1.08 │ ├──── ┼─────┼────┼────┼─────┼──────┤ │Real 1-22│ 30 │ 1.03 │ 1.02 │ 1.05 │ 1.07 │ ├─── │ │ Ratio 1-8 │ 50 │ 1.01 │ 1.00 │ 1.01 │ 1.02 │ └── ──┴─────┴────┴────┴─────┴──────┘ Note) Initial characteristics, low illuminance characteristics and durability are 1
Relative value based on -7

[0236]

[Table 9] ┌────┬───┬──────┬─────┬────┬─────┐ │ │RF discharge│2000cm ^-1 peak│Initial characteristics │Low Illumination │Durability │ │Device No.│Power │Half width of │High │Sample No.│ (mW / │ Value │ open │ curve │ photoelectric conversion │ photoelectric conversion effect │ │ │ cm ² ) │ │ voltage │ factor │ efficiency │ reduction of rate │ ├────┼───┼──────┼── 23 │Real 1-23│ 90 │ 1.31 │1.02│1.03│ 1.04 │ 1.06 │ │ (1-18) │ │ │ │ │ │ │ │ ├─── │ │Real 1-5 │ 120 │ 1.16 │1.02│1.02│ 1.04 │ 1.06 │ │ ( 1-19) │ │ │ │ │ │ │ │ ├────┼───┼──────┼──┼──┼────┼─────┤ │ Actual −24│ 150 │ 1.07 │1.01│1.02│ 1.05 │ 1.05 │ │ (1-20) │ │ │ │ │ │ │ ├────┼───┼──────┼──┼──実 │Real 1-25│ 180 │ 0.95 │1.00│1.01│ 1.02 │ 1.01 │ │ (1-21) │ │ │ │ │ │ │ ├────┼─ ├────┼─ │ │Real 1-26│ 210 │ 0.88 │1.00│1.00│ 1.00 │ 1.00 │ │ (1-22 ) │ │ │ │ │ │ │ │ ├────┼───┼──────┼──┼──┼────┼─────┤ │1-23 │ │ │ 1.0 │ │ │ │ │ └────┴───┴──────┴──┴──┴────┴─────┘ Note) Initial characteristics, low illuminance characteristics and durability , Element No. 1-2
The relative value based on 6 and the value obtained by dividing the half width by the height are the relative values based on Sample No. 1-23.

[0237]

[Table 10] ┌────┬─────┬─────────┬─────┬──────┐ │ │ band │ initial characteristics │ low illuminance characteristics │ Endurance characteristics │ │ │ Gap ├────┬────┼─────┼──────┤ │ Device No. │ Maximum value │ │ │ Photoelectric conversion │ Photoelectric conversion efficiency │ │ │ │ Open voltage │ Fill factor │ │ │ │ │ Layer thickness (nm) │ │ │ Efficiency │ Reduction of area │ の│ │Real 2-1│ 1 │ 1.02 │ 1.02 │ 1.03 │ 1.03 │ ├────┼─────┼────┼────┼ │ │Real 2-2│ 2 │ 1.02 │ 1.03 │ 1.05 │ 1.04 │ ├────┼─────┼────┼────実 │Real 2-3│ 3 │ 1.03 │ 1.04 │ 1.06 │ 1.07 │ ├────┼ │ │Real 2-4│ 5 │ 1.04 │ 1.03 │ 1.06 │ 1.06 │ ├──── │ │Real 2-5│ 10 │ 1.03 │ 1.03 │ 1.05 │ 1.06 │ ├─── │ │Real 2-6│ 20 │ 1.03 │ 1.02 │ 1.04 │ 1.05 │ ├── │ │Real 2-7│ 30 │ 1.01 │ 1.02 │ 1.04 │ 1.04 │ ├─ │ │Real 2-8│ 50 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ └ ────┴─────┴────┴────┴─────┴──────┘ Note) The initial characteristics, low illuminance characteristics and durability Real 2
Relative value based on -8

[0238]

[Table 11] ┌────┬─────┬─────────┬─────┬──────┐ │ │ Gas mixture │ Initial characteristics │ Low illumination Characteristics │ Durability │ │ Device No. │ Point and ├────┬────┼─────┼──────┤ │ │ Opening voltage between deposition chamber │ Fill factor │ Photo Conversion │ photoelectric conversion efficiency │ │ │ distance (m) │ │ │ efficiency │ decrease │ ├────┼─────┼────┼────┼─────┼─実 │Real 7-1│ 1 │ 1.03 │ 1.04 │ 1.05 │ 1.07 │ ├────┼─────┼────┼────┼─────┼ │ │Real 7-2│ 2 │ 1.03 │ 1.03 │ 1.05 │ 1.06 │ ├────┼─────┼────┼────┼───── │ │Real 7-3│ 3 │ 1.02 │ 1.03 │ 1.04 │ 1.04 │ ├────┼─────┼── │ │Real 7-4│ 5 │ 1.01 │ 1.02 │ 1.04 │ 1.03 │ ├────┼─────┼── │ │Real 7-5│ 8 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ └────┴─────┴─ ───┴────┴─────┴──────┘ Note) The initial characteristics, low illuminance characteristics and durability
Relative value based on -5

[0239]

[Table 12] ┌─────┬───────┬─────┬────┬────┬────┐ │ │used gas and │RF │pressure │Substrate temperature│Layer thickness │ │ │Flow rate │Discharge power │ │ │ │ │ │RF plasm│ (sccm) │ (W / cm ² ) │ (Torr) │ (℃) │ (nm) │ │Ma CVD methodＣＶＤ i-type │SiH ₄ 8 According to ───────┼─────┼────┼────┼────┤ │ │ │ │ │ │ Preparation of │ layer Article │ H ₂ 100 │ │ │ │ │ │ │ case │BF ₃ / H ₂ 1 │ │ │ │ │ │ │ │ (2000ppm dilution) │ │ │ │ │ │ │PH ₃ / H ₂ 0.06│ 0.12 │ 500 │ 300 │ 10 │ │ │ (2000ppm dilution) │ │ │ │ │ └─────┴───────┴─────┴────┴────┴────┘

[0240]

[Table 13] │ │substrate│SUS430BA 50mm square 50mm thickness 1mm │ ├─────┼────────────────────────────┤ │Reflection layer│Silver (Ag) thin film 100 nm │ │ │Reflection increasing layer│Zinc oxide (ZnO) thin film 1 μm │ ├使用 │ │ layer │ used gas and │ RF │ pressure │ substrate Temperature │ Layer thickness │ │ Each │ │ Flow rate │ Discharge power │ │ │ │ │ │ Name │ (sccm) │ (W / cm ² ) │ (Torr) │ (℃) │ (nm) │ │ ──┼───────┼─────┼────┼────┼────┤ │ │ │Si ₂ H ₆ 3 │ │ │ │ │ │ n-type layer │ PH ₃ / H ₂ 5 │ 0.12 │ 1 │ 350 │ 10 │ │ │ │ (1% dilution) │ │ │ │ │ │ work │ H ₂ 50 │ │ │ │ │ │ │ │ │ made | i-type layer | Same as actual 1-5 │ │ ├───┼───────┬─────┬────┬────┬────┤ │ Article │ │SiH ₄ 0.5 │ │ │ │ │ │ │ p-type layer │ H ₂ 100 │ 2 │ 1 │ 200 │ 5 │ │ case │ │ BF ₃ / H ₂ 1 │ │ │ │ │ │ │ │ (1% dilution) │ │ │ │ │ │ │ ├─┴───┼───────┴─────┴────┴────┴────┤ │Transparent electrode │ITO (In ₂ O ₃ + SnO ₂ ) thin film 70nm │ ├─────┼────────────────────────────┤ │ Current collecting electrode │ Aluminum (Al) thin film 2μm │ └─────┴────────────────────────────┘

[0241]

[Table 14] │ | Base | SUS430BA 50mm square 1mm thick │ ├─────┼────────────────────────────┤ │Reflection layer│Silver (Ag) thin film 100 nm │ │ │Reflection increasing layer│Zinc oxide (ZnO) thin film 1 μm │ ├使用 │ │Layer │Used gas │ │Buy │Pressure │Substrate │Layer thickness│ │ │Name│ and flow rate │Discharge power│ │ │Temperature │ │ │ │ │ (sccm) │ │As│ (mTorr) │ (℃) │ (nm) │ │ ├───┼─ ─────┼────┼────┼────┼───┼──┤ │ │ │Si ₂ H ₆ 1│ RF │ │ │ │ │ │ the │ first _{│H 2 50│ 80 │ │ 1500 │} 370 │ 20 │ │ │n type layer _{│PH 3 / H 2 1│ (mW} / cm 2) │ │ │ │ │ │ layer │ │ (1% dilution) │ │ │ │ │ │ │ │ ├───┼──────┼────┼────┼────┼───┼──┤ │ First R│SiH ₄ 8 │ │ │ │ │ │ │ │ │F │ ₂ │H ₂ 100 │ │ │ │ │ │ │Work│Ma CVD method│BF ₃ / H ₂ 0.02│RF 120 │ │ 500 │ 350 │ 20 │ │ │ in accordance │ (2000ppm) │ (mW / cm 2) │ │ │ │ │ │ made │i type layer _{│PH 3 / H 2 0.4 │ │} │ │ │ │ │ │1 │ (2000ppm) │ │ │ │ │ │ │ Article ├───┼──────┼────┼────┼────┼───┼──┤ │ │ 1st machine │ SiH ₄ Fig. 29 Referring │ micro │ RF │ │ │ │ │ matter │ microwave off │H ₂ 500│ wave │ 350 │ │ │ │ │ │ ° plasma C￨GeH ₄ 29 see ^{│ 170 │ (mW / cm 3} ) │ 10 │ 350 │300 │ │ │VD According to the law │ │ (mW / cm ³ ) │DC 0V │ │ │ │ │ │ │I i│ │ │ │ │ │ │ │ │ │Type layer │ │ │ │ │ │ │ │ ├───┼───── ├───┼───── │ │ │First R│SiH ₄ 8 │ │ │ │ │ │ │ │ │F Plus ゜ │H ₂ 100 │ │ │ │ │ │ │ │Ma CVD method│BF ₃ / H ₂ 2 │RF 120 │ │ 500 │ 350 │ 10│ │ │ (2000ppm) │ (mW / cm ² ) │ │ │ │ │ │ │i type Layer │PH ₃ / H ₂ 0.05│ │ │ │ │ │ │ │ │2 │ (2000ppm) │ │ │ │ │ │ │ ├───┼──────┼────┼────┼ ├───┼──────┼────┼────┼ │ │ │ │SiH ₄ 0.05│ RF │ │ │ │ │ │ │ │First │H ₂ 100│ 1.5 │ │ 2000 │ 250 │ 10 │ │ │p-type layer│ BF ₃ / H ₂ 5 │ (W / cm ² ) │ │ │ │ │ │ │ │ │ (1% dilution) │ │ │ │ │ │ │ ├─┼───┼──────┼──── ┼────┼─── ┼───┼──┤ │ Each _{│ │Si 2 H 6 1│ RF │} │ │ │ │ │ │ second _{│H 2 50│ 80 │ │ 1500 │} 300 │ 10 │ │ layer │n type layer │ PH ₃ / H ₂ 1│ (mW / cm ² ) │ │ │ │ │ │ │ │ │ (1% dilution) │ │ │ │ │ │ │ │ │ │ │SiH ₄ 200 │ Micro │ RF │ │ │ │ │ │ Work │ Second │ H ₂ 700 │ Wave │ 250 │ │ │ │ │ │ │ i-type layer │ │ 130 │ (mW / cm ³ ) │ 5 │ 300 │ 150 │ │ │ │ │ │ (mW / cm ³ ) │ DC │ │ │ │ │ │ │ │ │ OV │ │ │ │ │ │ Article │ │ │ │SiH ₄ 0.05│ RF │ │ │ │ │ │ │ │Second │H ₂ 100│ 1.5 │ │ 2000 │ 200 │ 5 │ │ │ p-type layer │ BF ₃ / H ₂ 5 │ (W / cm ² ) │ │ │ │ │ │ │ │ (1% dilution) │ │ │ │ │ │ │ ├─┴───┼── │ │Transparent electrode │ITO (In ₂ O ₃ + SnO ₂ ) thin film 70nm │ ├─────┼ │ │Current collecting electrode │Aluminum (Al) thin film 2μm │ └─────┴── ──────────────────────────┘

[0242]

[Table 15] │ | Base | SUS430BA 50mm square 1mm thick │ ├─────┼────────────────────────────┤ │Reflection layer│Silver (Ag) thin film 100 nm │ │ │Reflection increasing layer│Zinc oxide (ZnO) thin film 1 μm │ ├層 │ │ layer │ gas │ microwave │ bias │ pressure │ │ temperature │ │ │ │ name │ (sccm) │ (mW / cm ³ ) │ AS │ (mTorr) │ (℃) │ (nm) │ │ ├───┼─────┼─────┼────┼────┼───┼──┤ │ │ 1 _{│SiH 4 50│ │ DC │ │ │} │ │ │n type layer _{│PH 3 / H 2 200│ 130 │} │ 10 │ 350 │ 10 │ │ the │ │ (1% dilution) │ │ 50V │ │ │ │ │ ├───┼─────┼─────┼────┼────┼───┼──┤ │ │First R│SiH ₄ 8 │ │ │ │ │ │ │ │Article│F Plus ゜ │H ₂ 100 │ │ │ │ │ │ │ │ │Ma CVD method │BF ₃ / H ₂ 0.05│ RF 120 │ │ 500 │ 350 │ 10│ │ Case │ (2000ppm) │ ( mW / cm ² ) │ │ │ │ │ │ │ │ i-type layer │PH ₃ / H ₂ 1 │ │ │ │ │ │ │ │ │1 │ (2000ppm) │ │ │ │ │ │ │ ├───┼─── ├───┼─── │ │ layer │ first mask │ SiH ₄ Fig. 30 │ │ │ │ │ │ │ │ │ │ Reference │ │ RF │ │ │ │ │ │ ゜ ゛ C C H H ₂ 500 │ │ 350 │ │ │ │ │ │ VD method │ GeH ₄ Fig. 30 │ 170 │ (mW / cm ³ ) │ 10 │ 350 │ 250 │ │ product │ yo │││ │ │ │ │ │ type layer │ │ │ │ │ │ │ │ R │ │ 1st R │ SiH ₄ 8 │ │ │ │ │ │ │ │ Article │ F ₂ │ │ │ │ │ │ │ │ │ │ Ma CVD method │ BF ₃ / H ₂ 0.5 │ RF 120 │ │ 500 │ 350 │ 10 │ │ | │ (2000 ppm) │ (mW / cm ² ) │ │ │ │ │ │ │ │ i-type layer │ PH ₃ / H ₂ 0.01 │ │ │ │ │ │ │ │ │2 │ (2000ppm) │ │ │ │ │ │ │ │ ├───┼─────┼─────┼────┼────┼───┼──┤ │ │ │SiH ₄ 10│ │ │ │ │ │ │ │ │First │H ₂ 700│ 250 │ │ 25 │ 350 │ 10 │ │ │ p-type layer │BF ₃ / H ₂ 30│ │ │ │ │ │ │ │ │ │ │ │ │ │ (1% dilution) │ │ │ │ │ │ │ ├─┼───┼─────┼─────┼────┼────┼───┼──┤ │ │ Second | SiH ₄ 50 │ │ DC │ │ │ │ │ │ │ PH ₃ / H ₂ 200 │ 130 │ 50V │ 10 │ 350 │ 10 │ │ │ n-type layer │ (1% dilution) │ │ │ │ │ │ │ ┼─────┼─────┼────┼────┼───┼──┤ │ made │ second R │ SiH ₄ 8 │ │ │ │ │ │ │ │ │ F ││H ₂ 100 │ │ │ │ │ │ │ │Article│Ma CVD method│BF ₃ / H ₂ 0.1│ RF 120 │ │ 500 │ 350 │ 10│ │ │ (2000ppm) │ (mW / cm ² ) │ │ │ │ │ │ case │ i-type layer │ PH ₃ / H ₂ 3 │ │ │ │ │ │ │ │ │ 1 │ (2000 ppm) │ │ │ │ │ │ │ ├───┼─────┼──マ │ │Second machine│SiH ₄ Fig.31│ │ │ │ │ │ │ │Layer│Micro wave│Reference │ │ RF │ │ │ │ │ │ ゜ ゛ C C │ H ₂ 500 │ │ 280 │ │ │ │ │ │ VD method │ GeH ₄ Fig. 31 │ │ (mW / cm ³ ) │ 10 │ 350 │ 200 │ │ │ i Reference │ 210 │DC 0V │ │ │ │ │ │Work│Type layer │ │ │ │ │ │ │ │ │ ├───┼─────┼─────┼────┼────┼─── ┼──┤ │ made │ second _{R│SiH 4 8 │ │ │ │ │} │ │ │F plasma ￨H ₂ 100 │ │ │ │ │ │ │ conditions │ Ma CVD method │BF ₃ / H ₂ 0.5│ RF 120 │ │ 500 │ 350 │ 10 │ │ │ (2000 ppm) │ (mW / cm ² ) │ │ │ │ │ │ case │ i-type layer │ PH ₃ / H ₂ 0.05 │ │ │ │ │ │ │ │2 │ (2000ppm) │ │ │ │ │ │ │ │ ├───┼─────┼─────┼────┼────┼───┼──┤ │ │ │SiH ₄ 10│ │ │ │ │ │ │ │ │Second │H ₂ 700 │ 250 │ │ 25 │ 350 │ 10 │ │ │ p-type layer │ BF ₃ / H ₂ 30 │ │ │ │ │ │ │ │ │ (1% Dilution) │ │ │ │ │ │ │ │ ├───┼─────┼─────┼────┼────┼───┼──┤ │ │ Third │ SiH _{4 50│} │ DC │ │ _{│ │ │ │PH 3 / H 2} 200│ 130 │ 50V │ 10 │ 300 │ 10 │ │ │n type layer │ (1% dilution) │ │ │ │ │ │ │ ├───┼─────┼ │ │ │ │ │ │ RF │ │ │ │ │ │ │ Third │ SiH ₄ 200 │ │ 300 │ │ │ │ │ │ │ │ │ 150 │ (mW / cm ³ ) │ 5 │ 300 │ 100 │ │ │ i-type layer │ H ₂ 700 │ │ DC │ │ │ │ │ │ │ │ │ OV │ │ │ │ ├───┼ ├───┼ ├───┼ ─────┼─────┼────┼────┼───┼──┤ │ │Third │SiH ₄ 10│ │ │ │ │ │ │ │ │ │H ₂ 700 │ 250 │ │ 25 │ 300 │ 5 │ │ │ p-type layer │ BF ₃ / H ₂ 30 │ │ │ │ │ │ │ │ │ (1% dilution) │ │ │ │ │ │ │ │ │ │ │ │ │ │ │ │ ├─┴───┼─────┴─────┴────┴────┴───┴──┤ │ Transparent electrode │ ITO (In ₂ O ₃ + SnO ₂ ) 70nm thin film │ ├─────┼────────────────────────────┤ │Current collecting electrode │Aluminum (Al) thin film 2μm │ │ ─────┴────────────────────────────┘

[0243]

[Table 16] ┌────┬─────┬─────────┬─────┬──────┐ │ │ Initial characteristics in deposition chamber │ Low illumination Characteristics│Durability characteristics │ │ │ ├────┬────┼─────┼──────┤ │Device No. │Pressure│ │ │Photoelectric conversion │Photoelectric conversion efficiency│ │ │ │Open circuit voltage│Fill factor│ │ │ │ │ │ (mTorr) │ │ │ Decrease in efficiency │ │ ├────┼─────┼────┼────┼───── │ │Real 21-1│ 0.5 │ 1.02 │ 1.02 │ 1.06 │ 1.06 │ ├────┼─────┼────┼────┼──── ─┼──────┤ │Real 21-2│ 1 │ 1.02 │ 1.02 │ 1.06 │ 1.06 │ ├────┼─────┼────┼────┼─── ──┼──────┤ │Real 21-3│ 2 │ 1.03 │ 1.03 │ 1.07 │ 1.06 │ ├────┼─────┼─── │ │Real 21-4│ 5 │ 1.03 │ 1.03 │ 1.07 │ 1.08 │ ├────┼─────┼─── │ │Real 21-5│ 10 │ 1.04 │ 1.02 │ 1.07 │ 1.08 │ ├────┼─────┼── │ │Real 21-6│ 20 │ 1.03 │ 1.02 │ 1.06 │ 1.07 │ ├────┼─────┼─ │ │Real 21-7│ 50 │ 1.03 │ 1.01 │ 1.06 │ 1.07 │ ├────┼─────┼ │ │ Ratio 7-1 │ 100 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ └────┴───── ┴────┴────┴─────┴──────┘ Note) Initial characteristics, low illuminance characteristics and durability are 7
Relative value based on -1

[0244]

[Table 17] ┌────┬─────┬─────────┬─────┬──────┐ │ │ Microwave │ Initial characteristics │ Low illuminance characteristics │ Endurance characteristics │ │ Device No. │ Power ├────┬────┼─────┼──────┤ │ │ (W / cm ³ ) │ Open-circuit voltage │ Fill factor │ Photoelectric Conversion │ Photoelectric conversion efficiency │ │ │ │ │ │ Reduction of efficiency │ │ ├────┼─────┼────┼────┼─────┼───── │ │Real 21-8│ 0.1 │ 1.03 │ 1.02 │ 1.07 │ 1.06 │ ├────┼─────┼────┼────┼─────┼──── │ │Real 21-9│ 0.2 │ 1.02 │ 1.02 │ 1.09 │ 1.09 │ ├────┼─────┼────┼────┼─────┼─── │ │Real 21-10│ 0.3 │ 1.02 │ 1.02 │ 1.06 │ 1.07 │ ├────┼─────┼────┼────┼ │ │ Ratio 7-2 │ 0.4 │ 1.00 │ 1.01 │ 1.01 │ 1.02 │ ├────┼─────┼────┼────┼ ─────┼──────┤ │ Ratio 7-3 │ 0.5 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ └────┴─────┴────┴──── ┴─────┴──────┘ Note) Initial characteristics, low illuminance characteristics, and durability are 7
Relative value based on -3

[0245]

[Table 18] ┌────┬─────┬─────────┬─────┬──────┐ │ │ RF bias │ Initial characteristics │ Low illuminance characteristics │ Endurance characteristics │ │Device No. │ ├────┬────┼─────┼──────┤ │ │ (mW / cm ³ ) │Open circuit voltage│Fill factor│Photoelectric conversion │ photoelectric conversion efficiency │ │ │ │ │ │ efficiency │ decrease │ ├────┼─────┼────┼────┼─────┼────── ┤ │ Ratio 7-4 │ 150 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ ├────┼─────┼────┼────┼─────┼───── │ │Real 21-11│ 200 │ 1.02 │ 1.02 │ 1.05 │ 1.06 │ ├────┼─────┼────┼────┼─────┼──── │ │Real 21-12│ 250 │ 1.02 │ 1.03 │ 1.06 │ 1.08 │ ├────┼─────┼────┼────┼── │ │Real 21-13│ 300 │ 1.03 │ 1.03 │ 1.06 │ 1.07 │ ├────┼─────┼────┼────┼── │ │Real 21-14│ 350 │ 1.02 │ 1.02 │ 1.07 │ 1.05 │ └────┴─────┴────┴────┴─ ────┴──────┘ Note) Initial characteristics, low illuminance characteristics, and durability are 7
Relative value based on -4

[0246]

[Table 19] ┌────┬───┬───┬───┬─────┬────┬─────┐ │ │ SiH ₄゛ │ RF power │ deposition │ Initial characteristics │Low illuminance │Durability characteristics │ │Device No. │open│curve│photoelectric conversion│photoelectric conversion effect│ │ │ │cm ² ) │sec) │voltage│factor│efficiency │ │Real 21-16│ 1 │ 15 │ 0.05 │1.03│1.03│ 1.08 │ 1.07 │ ├────┼───┼── │ │Real 21-17│ 2 │ 30 │ 0.1 │1.04│1.03│ 1.07 │ 1.07 │ ├────┼─ │ │Real 21-18│ 10 │ 150 │ 0.5 │1.04│1.02│ 1.07 │ 1.08 │ ├─ │ │Real 21-19│ 20 │ 300 │ 1.1 │1.03│1.02│ 1.07 │ 1.07 │ │ │ Real 21-20│ 40 │ 500 │ 2.0 │ 1.03│1.02│ 1.06 │ 1.06 │ ├────┼───┼───┼───┼──┼──┼────┼─────┤ │ Ratio 7-6 │ 60 │ 1000 │ 2.8 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ └────┴───┴───┴───┴──┴──┴────┴─────┘ └────┴───┴───┴───┴──┴──┴────┴─────┘ Note) Initial characteristics, low illuminance characteristics and durability are 7
Relative value based on -6

[0247]

[Table 20] ┌────┬─────┬─────────┬─────┬──────┐ │ │ RF plasm │ Initial characteristics │ Low illuminance characteristics │ Endurance characteristics │ │ │Ma CVD method ├────┬────┼─────┼──────┤ │ i-type by device No. │ │ │ │ Photoelectric conversion │ Photoelectric conversion efficiency │ │ │ layer thickness │ open circuit voltage │ fill factor │ │ │ │ │ (nm) │ │ │ efficiency │ decrease │ ├────┼─────┼────┼─── │ │ Ratio 7-7 │ 0 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ ├────┼─────┼────┼── │ │Real 21-21│ 1 │ 1.02 │ 1.02 │ 1.03 │ 1.05 │ ├────┼─────┼────┼─ ───┼─────┼──────┤ │Real 21-22│ 3 │ 1.03 │ 1.02 │ 1.05 │ 1.07 │ ├──── │ │Real 21-5│ 10 │ 1.03 │ 1.03 │ 1.06 │ 1.07 │ ├──── │ │Real 21−23│ 30 │ 1.02 │ 1.02 │ 1.06 │ 1.05 │ ├─── │ │ Ratio 7-8 │ 50 │ 1.01 │ 1.00 │ 1.02 │ 1.01 │ └── ──┴─────┴────┴────┴─────┴──────┘ Note) Initial characteristics, low illuminance characteristics and durability are 7
Relative value based on -7

[0248]

[Table 21] ┌────┬───┬──────┬─────┬────┬─────┐ │ │RF discharge│2000cm ^-1 peak│Initial characteristics │Low illuminance │Durability │ │Element No.│Power │Half width of power │ divided by high │ │ │ (mW / │ value│Open │Curve│Photoelectric conversion│Photoelectric conversion effect│ │ │cm ² ) │ │Voltage│Factor│Efficiency│Decrease in rate │ ├────┼───┼──────┼──┼── │ │Real 21-24│ 90 │ 1.31 │1.03│1.02│ 1.04 │ 1.05 │ ├────┼───┼──────┼──┼ │ │Real 21-5 │ 120 │ 1.16 │1.02│1.03│ 1.05 │ 1.06 │ ├────┼───┼──────┼─ │ │Real 21-25│ 150 │ 1.07 │1.01│1.01│ 1.04 │ 1.05 │ ├────┼───┼─ │ │Real 21−26│ 180 │ 0.95 │1.00│1.01│ 1.01 │ 1.02 │ ├────┼───┼ │ │Real 21-27│ 210 │ 0.88 │1.00│1.00│ 1.00 │ 1.00 │ └────┴── ─┴──────┴──┴──┴────┴─────┘ Note) The initial characteristics, low illuminance characteristics and durability
Relative value based on −27

[0249]

[Table 22] ┌────┬─────┬─────────┬─────┬──────┐ │ │ band │ initial characteristics │ low illuminance characteristics │ Endurance characteristics │ │ │ Gap ├────┬────┼─────┼──────┤ │ Device No. │ Maximum value │ │ │ Photoelectric conversion │ Photoelectric conversion efficiency │ │ │ │ Open voltage │ Fill factor │ │ │ │ │ Layer thickness (nm) │ │ │ Efficiency │ Reduction of area │ の│ │Real 45-1│ 1 │ 1.01 │ 1.02 │ 1.04 │ 1.03 │ ├────┼─────┼────┼────┼ │ │Real 45-2│ 2 │ 1.02 │ 1.03 │ 1.05 │ 1.04 │ ├────┼─────┼────┼──── │ │Real 45-3│ 3 │ 1.02 │ 1.03 │ 1.05 │ 1.06 │ ├────┼─ │ │Real 45-4│ 5 │ 1.03 │ 1.02 │ 1.05 │ 1.07 │ ├────┼ │ │Real 45-5│ 10 │ 1.04 │ 1.02 │ 1.06 │ 1.06 │ ├──── │ │Real 45-6│ 20 │ 1.04 │ 1.02 │ 1.05 │ 1.06 │ ├─── │ │Real 45-7│ 30 │ 1.02 │ 1.02 │ 1.04 │ 1.05 │ ├── │ │ Actual 45-8 │ 50 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ └─ ───┴─────┴────┴────┴─────┴──────┘ Note) The initial characteristics, low illuminance characteristics, and durability twenty two
Relative value based on -8

[0250]

[Table 23] ┌────┬─────┬─────────┬─────┬──────┐ │ │ Gas mixture │ Initial characteristics │ Low illumination Characteristics │ Durability │ │ Device No. │ Point and ├────┬────┼─────┼──────┤ │ │ Opening voltage between deposition chamber │ Fill factor │ Photo Conversion │ photoelectric conversion efficiency │ │ │ distance (m) │ │ │ efficiency │ decrease │ ├────┼─────┼────┼────┼─────┼─実 │Real 27-1│ 1 │ 1.03 │ 1.03 │ 1.06 │ 1.07 │ ├────┼─────┼────┼────┼─────┼ │ │Real 27-2│ 2 │ 1.03 │ 1.04 │ 1.05 │ 1.06 │ ├────┼─────┼────┼────┼───── │ │Real 27-3│ 3 │ 1.02 │ 1.03 │ 1.04 │ 1.06 │ ├────┼─────┼─── │ │Real 27-4│ 5 │ 1.02 │ 1.03 │ 1.02 │ 1.05 │ ├────┼─────┼─── │ │Real 27-5│ 8 │ 1.00 │ 1.00 │ 1.00 │ 1.00 │ └────┴─────┴── ──┴────┴─────┴──────┘ Note) The initial characteristics, low illuminance characteristics, and durability
Relative value based on -5

[0251]

[Table 24] │ | Base | SUS430BA 50mm square 1mm thick │ ├─────┼────────────────────────────┤ │Reflection layer│Silver (Ag) thin film 100 nm │ │ │Reflection increasing layer│Zinc oxide (ZnO) thin film 1 μm │ ├使用 │ │Layer │Used gas │ │Buy │Pressure │Substrate │Layer thickness│ │ │Name│ and flow rate │Discharge power│ │ │Temperature │ │ │ │ │ (sccm) │ │As│ (mTorr) │ (℃) │ (nm) │ │ ├───┼─ ─────┼────┼────┼────┼───┼──┤ │ │ │Si ₂ H ₆ 1│ RF │ │ │ │ │ │ │ first _{│H 2 50│ 80 │ │ 1500 │} 370 │ 20 │ │ │n type layer _{│PH 3 / H 2 1│ (mW} / cm 2) │ │ │ │ │ │ │ │ ( 1% dilution) │ │ │ │ │ │ │ │ each ├───┼──────┼────┼────┼────┼───┼──┤ │ │ first R│SiH ₄ 8 │ │ │ │ │ │ │ │ │F Plus H│H ₂ 100 │ │ │ │ │ │ │ Layer │ Ma CVD method │ BF ₃ / H ₂ 0.03 │ RF 120 │ │ 500 │ 350 │ 20 │ │ │ due (2000 ppm) │ (mW / cm ² ) │ │ │ │ │ │ │ │ i-type layer │ PH ₃ / H ₂ 0.5 │ │ │ │ │ │ │ │ 1 │ (2000 ppm) │ │ │ │ │ │ │ │ ├───┼──────┼────┼────┼────┼───┼──┤ │ │First machine│SiH ₄ See Fig.29│Micro │ RF │ │ │ │ │ operation │ microwave off │H ₂ 500│ wave │ 350 │ │ │ │ │ │ ° plasma C￨GeH ₄ 29 see ^{│ 170 │ (mW / cm 3} ) │ 10 │ 350 │300 │ │ │VD method _{BF 3 / H 2 0.3│ (mW} / cm 3) │DC 0V │ │ │ │ │ manufactured │ According i│ (2000ppm) │ │ │ │ │ │ │ │ type layer _{2 │PH 3 / H 2 0.5│ │} │ │ │ │ │ │ │ │ (2000ppm) │ │ │ │ │ │ │ │ ┤ │ │ first _{R│SiH 4 8 │ │ │ │ │} │ │ │F plasma _{│H 2 100 │ │ │ │ │} │ │ matter │ Ma CVD method _{│BF 3 / H 2 3 │RF 120} │ │ 500 │ 350 │ 10 │ │ │ (2000 ppm) │ (mW / cm ² ) │ │ │ │ │ │ │ i-type layer │ PH ₃ / H ₂ 0.05 │ │ │ │ │ │ │ │ (2000 ppm) │ │ │ │ │ │ │ ├───┼──────┼────┼────┼────┼───┼──┤ │ │ │ │SiH ₄ 0.05│ RF │ │ │ │ │ │ │ │ 1st │ H ₂ 100 │ 1.5 │ │ 2000 │ 250 │ 10 │ │ │ p-type layer │ BF ₃ / H ₂ 5 │ (W / cm ² ) │ │ │ │ │ │ │ │ (1 % Dilution) │ │ │ │ │ │ │ ├ _{┼───┼──────┼────┼────┼────┼───┼──┤ │ │ │Si 2 H 6 1│} RF │ │ │ │ │ │ each │ second _{│H 2 50│ 80 │ │ 1500 │} 300 │ 10 │ │ │n type layer _{│PH 3 / H 2 1│ (mW} / cm 2) │ │ │ │ │ │ layer │ │ (1% Dilution) │ │ │ │ │ │ │ │ ├───┼──────┼────┼────┼────┼───┼──┤ │ │ │ SiH ₄ 200 │ Micro │ RF │ │ │ │ │ │ │ Second │ H ₂ 700 │ Wave │ 250 │ │ │ │ │ Work │ i-type layer │ 130 │ (mW / cm ³ ) │ 5 │ 300 │ 150 │ │ │ │ │ (mW / cm ³ ) │ DC 0V │ │ │ │ │ │Production H │ │ │SiH ₄ 0.05│ RF │ │ │ │ │ │ │Second │H ₂ 100 │ 1.5 │ │ 2000 │ 200 │ 5 │ │ │p-type layer │ BF ₃ / H ₂ 5 │ (W / ^{cm 2) │ │ │ │ │} │ matter │ │ (1% dilution) │ │ │ │ │ ├─┴───┼──────┴────┴────┴────┴───┴──┤ │ transparent electrode │ITO (In ₂ O ₃ + SnO ₂ ) Thin film 70nm │ ├─────┼────────────────────────────┤ │ Current collecting electrode │ Aluminum (Al) Thin film 2μm │ └─────┴────────────────────────────┘

[0252]

[Table 25] │ | Base | SUS430BA 50mm square 1mm thick │ ├─────┼────────────────────────────┤ │Reflection layer│Silver (Ag) thin film 100 nm │ │ │Reflection increasing layer│Zinc oxide (ZnO) thin film 1 μm │ ├層 │ │ layer │ gas │ microwave │ bias │ pressure │ Name │ (sccm) │ (mW / cm ³ ) │ AS │ (mTorr) │ (℃) │ Power │ Substrate │ Layer Thickness │ │ │ │ and Flow Rate │ Discharge Power │ │ │ Temperature │ │ │ (nm) │ │ ├───┼─────┼─────┼────┼────┼───┼──┤ │ │ 1 _{│SiH 4 50│ │ DC │ │ │} │ │ │n type layer _{│PH 3 / H 2 200│ 130 │} │ 10 │ 350 │ 10 │ │ │ │ (1% dilution) │ │ 50V │ │ │ │ │ ├───┼─────┼─────┼────┼────┼───┼──┤ │ │First R│SiH ₄ 8 │ │ │ │ │ │ │ │ │F glass ゛ │H ₂ 100 │ │ │ │ │ │ │ │Each│Ma CVD method│BF ₃ / H ₂ 0.03│ RF 120 │ │ 500 │ 350 │ 10│ │ │ (2000ppm) │ (mW / cm ² ) │ │ │ │ │ │ layer │ i-type layer │ PH ₃ / H ₂ 2 │ │ │ │ │ │ │ │ │ 1 │ (2000 ppm) │ │ │ │ │ │ │ ├───┼─── ──┼─────┼────┼────┼───┼──┤ │ │ First machine │ SiH ₄ Fig. 30 │ │ │ │ │ │ │ Reference │ │ RF │ │ │ │ │ │ │ ゜ ゛ C C │ H ₂ 500 │ │ 350 │ │ │ │ │ VD method │ GeH ₄ Fig. 30 │ 170 │ (mW / cm ³ ) │ 10 │ 350 │ 250 │ │ │ yo i│ reference _{BF 3 / │ │DC 0V │ │} │ │ │ Conditions │-type layer _{│H 2 1 (200│ │ │ │} │ │ │ │ │0ppm) PH 3 / H│ │ │ │ │ │ │ │ │ matter ₂ 0.3 (2000│ │ │ │ │ │ │ │ │ │ppm) │ │ │ │ │ │ │ │ ├───┼─────┼─────┼────┼────┼─ │ │ │First R│SiH ₄ 8 │ │ │ │ │ │ │ │ │ │F ₂ │H ₂ 100 │ │ │ │ │ │ │ │Ma CVD method │BF ₃ / H ₂ 0.3│ RF 120 │ │ 500 │ 350 │ 10 │ │ │ (2000 ppm) │ (mW / cm ² ) │ │ │ │ │ │ │ i-type layer │PH ₃ / H ₂ 0.05│ │ │ │ │ │ │ │2 │ (2000ppm) │ │ │ │ │ │ │ │ ├───┼─────┼─────┼────┼────┼───┼──┤ │ │ │SiH ₄ 10 │ │ │ │ │ │ │ │ first _{│H 2 700│ 250 │ │ 25 │} 350 │ 10 │ │ │ p -type layer _{│BF 3 / H 2 30│ │ │} │ │ │ │ │ │ (1% dilution ) │ │ │ │ │ ├─┼───┼─────┼─────┼────┼────┼───┼──┤ │ │ second │SiH ₄ 50│ │ DC │ │ │ │ │ │ │PH ₃ / H ₂ 200 │ 130 │ 50V │ 10 │ 350 │ 10 │ │ │ n-type layer │ (1% dilution) │ │ │ │ │ │ │ │ │ │ │ │ │ │ │ │ │ │Second R│SiH ₄ 8 │ │ │ │ │ │ │ │ │F glass │ │H ₂ 100 │ │ │ │ │ │ │ │ │Ma CVD method │BF ₃ / H ₂ 0.1│ RF 120 │ │ 500 │ 350 │ 10│ │ │ due to (2000ppm) │ (mW / cm ² ││ │ │ │ │ │ │ i-type layer │PH ₃ / H ₂ 2 │ │ │ │ │ │ │ │1 │ (2000ppm) │ │ │ │ │ │ │マ │ │Second mask│SiH ₄ Fig.31│ │ │ │ │ │ │ │Layer│Micro wave│Reference │ │ RF │ │ │ │ │ │ ゜ ゛ C C │ H ₂ 500 │ │ 280 │ │ │ │ │ │ VD method │ GeH ₄ Fig. 31 │ │ (mW / cm ³ ) │ 10 │ 350 │ 200 │ │ │ i │ Reference │ │ 210 │DC 0V │ │ │ │ │Working │Type layer │BF ₃ / H ₂ 0.5│ │ │ │ │ │ │ │ │ (2000ppm) │ │ │ │ │ │ │Production │PH ₃ / H ₂ 0.1│ │ │ │ │ │ │ │ │ │ (2000ppm) │ │ │ │ │ │ │ │ R │ │Second R│SiH ₄ 8 │ │ │ │ │ │ │ ││Properties│F ₂ │H ₂ 100 │ │ │ │ │ │ │ │Ma CVD method│BF ₃ / H ₂ 1│ RF 120 │ │ 500 │ 350 │ 10 │ │ │ (2000 ppm) │ (mW / cm ² ) │ │ │ │ │ │ │ i-type layer │ PH ₃ / H ₂ 0.05 │ │ │ │ │ │ │ │ │ (2000 ppm) │ │ │ │ │ │ │ │ ├───┼─────┼─────┼────┼────┼───┼──┤ │ │ │SiH ₄ 10│ │ │ │ │ │ │ │ second _{│H 2 700│ 250 │ │ 25 │} 350 │ 10 │ │ │ p -type layer _{│BF 3 / H 2 30│ │ │} │ │ │ │ │ │ (1% dilution) │ │ │ │ │ │ │ ├───┼─────┼─────┼────┼────┼───┼──┤ │ │ Third │ SiH ₄ 50 │ │ DC │ │ │ │ │ │ │ │PH ₃ / H ₂ 200 │ 130 │ 50V │ 10 │ 300 │ 10 │ │ │ n-type layer │ (1% dilution) │ │ │ │ │ │ │ ├───┼─────┼ RF │ │ │ │ │ RF │ │ │ │ │ │ │ Third │ SiH ₄ 200 │ │ 300 │ │ │ │ │ │ │ │ │ 150 │ (mW / cm ³ ) │ 5 │ 300 │ 100 │ │ │ i-type layer │ H ₂ 700 │ │ DC │ │ │ │ │ │ │ │ │ OV │ │ │ │ ├───┼ ├───┼ ├───┼ ─────┼─────┼────┼────┼───┼──┤ │ │Third │SiH ₄ 10│ │ │ │ │ │ │ │ │ │H ₂ 700 │ 250 │ │ 25 │ 250 │ 5 │ │ │ p-type layer │ BF ₃ / H ₂ 30 │ │ │ │ │ │ │ │ │ (1% dilution) │ │ │ │ │ │ │ │ │ │ │ │ │ │ ├─┴── ├─┴── │ │Transparent electrode │ITO (In ₂ O ₃ + SnO ₂ ) thin film 70nm │ ├── │ │Current collecting electrode │Aluminum (Al) thin film 2μm │ └──── ─┴────────────────────────────┘

[0253]

As described above, according to the present invention, there is provided a photovoltaic device in which recombination of photoexcited carriers is prevented, open voltage and carrier range of holes are improved, and photoelectric conversion efficiency is improved. Can be. Further, the photovoltaic device of the present invention improves the conversion efficiency when the irradiation light is weak. The photovoltaic device of the present invention is one in which the photoelectric conversion efficiency does not easily decrease when annealing is performed under vibration for a long time.

Further, the power supply system using the photovoltaic element of the present invention exhibits excellent power supply capability even when the irradiation light is weak.

[Brief description of the drawings]

FIG. 1 is a schematic diagram for explaining a layer configuration of a photovoltaic element of the present invention.

FIG. 2 is a schematic diagram for explaining a change in a band gap of the photovoltaic device of the present invention.

FIG. 3 is a schematic diagram for explaining a change in a band gap of the photovoltaic device of the present invention.

FIG. 4 is a schematic diagram for explaining a change in a band gap of the photovoltaic device of the present invention.

FIG. 5 is a schematic diagram for explaining a change in a band gap of the photovoltaic device of the present invention.

FIG. 6 is a schematic diagram for explaining a change in a band gap of the photovoltaic device of the present invention.

FIG. 7 is a schematic diagram for explaining a change in a band gap of the photovoltaic device of the present invention.

FIG. 8 is a schematic diagram for explaining a change in band gap of the photovoltaic device of the present invention.

FIG. 9 is a schematic diagram for explaining a change in a band gap of the photovoltaic device of the present invention.

FIG. 10 is a schematic diagram for explaining a change in band gap of the photovoltaic device of the present invention.

FIG. 11 is a schematic view of an example of an apparatus for manufacturing a photovoltaic element of the present invention, which is a manufacturing apparatus using a microwave plasma CVD method.

FIG. 12 is a schematic view of an example of an apparatus for manufacturing a photovoltaic element of the present invention, which is a manufacturing apparatus using an RF plasma CVD method.

FIG. 13 is a schematic view of an example of an apparatus for manufacturing a photovoltaic element of the present invention, which is a manufacturing apparatus using a multi-chamber separation type deposition apparatus.

FIG. 14 is a graph showing a time change pattern of SiH ₄ and GeH ₄ gas flow rates.

FIG. 15 is a graph showing a time change pattern of SiH ₄ and GeH ₄ gas flow rates.

FIG. 16 is a graph showing a change in an i-type layer band gap in a layer thickness direction.

FIG. 17 is a graph showing a time change pattern of a SiH ₄ gas flow rate when an i-type layer is formed and a change in a thickness direction of Si and H atoms in the i-type layer.

FIG. 18 is a graph showing a time change pattern of a flow rate of a SiH ₄ gas at the time of forming an i-type layer and a change in a thickness direction of Si and H atoms in the i-type layer.

FIG. 19 is a graph showing a time change pattern of SiH ₄ and GeH ₄ gas flow rates.

FIG. 20 is a schematic explanatory diagram for explaining a power supply system of the present invention.

FIG. 21 is a schematic explanatory diagram for explaining a power supply system of the present invention.

FIG. 22 is a schematic explanatory diagram for explaining a power supply system of the present invention.

FIG. 23 is a schematic explanatory diagram for explaining a power supply system of the present invention.

FIG. 24 is a schematic explanatory diagram for explaining a power supply system of the present invention.

FIG. 25 is a schematic explanatory diagram for explaining a power supply system of the present invention.

FIG. 26 is a graph showing a time change of a flow rate of a NO / He gas introduced at the time of forming an i-type layer and a change in a thickness direction of N and O atoms contained in the i-type layer.

FIG. 27 is a graph showing a time change of a flow rate of a NO / He gas introduced at the time of forming an i-type layer and a change in a thickness direction of N and O atoms contained in the i-type layer.

FIG. 28 is a graph showing a time change pattern of SiH ₄ and GeH ₄ gas flow rates.

FIG. 29 is a graph showing a time change pattern of SiH ₄ and GeH ₄ gas flow rates.

FIG. 30 is a graph showing a time change pattern of SiH ₄ and GeH ₄ gas flow rates.

FIG. 31 is a graph showing a time change pattern of SiH ₄ and GeH ₄ gas flow rates.

FIG. 32 shows BF ₃ / H ₂ , PH introduced at the time of forming the i-type layer.
₃ / H ₂ gas flow rate change with time and B,
4 is a graph showing a change in a P atom thickness direction.

FIG. 33 shows BF ₃ / H ₂ , PH introduced during formation of an i-type layer.
₃ / H ₂ gas flow rate change with time and B,
4 is a graph showing a change in a P atom thickness direction.

FIG. 34 shows BF ₃ / H ₂ , PH introduced when forming an i-type layer.
₃ / H ₂ gas flow rate change with time and B,
4 is a graph showing a change in a P atom thickness direction.

FIG. 35 shows BF ₃ / H ₂ , PH introduced during formation of an i-type layer.
₃ / H ₂ gas flow rate change with time and B,
4 is a graph showing a change in a P atom thickness direction.

[Explanation of symbols]

Reference Signs List 101 conductive substrate 102 n-type silicon-based non-single-crystal semiconductor layer 103 i-type non-single-crystal semiconductor layer 104 p-type silicon-based non-single-crystal semiconductor layer 105 transparent electrode 106 current-collecting electrodes 211, 212, 221, 222, 311, 321, 3
31, 341, 351, 361, 371, 372 i-type layers 213, 223, 312, 313, 322, 323, 3 by microwave plasma CVD
32, 333, 342, 343, 352, 353, 36
2,363,373,374 i-type layer by RF plasma CVD method 1000 Deposition apparatus by microwave plasma CVD method 1001 Deposition chamber 1002 Dielectric window 1003 Gas introduction tube 1004 Substrate 1005 Heater 1006 Vacuum gauge 1007 Conductance valve 1008 Auxiliary valve 1009 Leak valve 1010 Wave guide unit 1011 Bias power supply 1012 Bias rod 1013 Shutter 1020 Source gas supply device 1021 to 1029 Mass flow controller 1031 to 1039 Gas inflow valve 1041 to 1049 Gas outflow valve 1051 to 1059 Source gas cylinder valve 1061 to 1069 Pressure regulator 1071-1079 Source gas cylinder 1100 Film forming apparatus by RF plasma CVD method 1101 Deposition chamber 1102 Caso Mode 1103 gas introduction pipe 1104 substrate 1105 heating heater 1106 vacuum gauge 1107 conductance valve 1108 auxiliary valve 1109 leak valve 1111 RF power supply 1112 RF matching box 1201, 1210 load, unload chamber 1202 to 1209 deposition chamber 1211 to 1219 gate valve 1221, 1222, 1224-1226, 1228
Cathode electrodes 1223, 1227 Microwave waveguide and dielectric window 9001 Photovoltaic element 9002 Voltage control diode 9003 Voltage stabilization capacitor 9004 Load 9101 Solar cell 9102 Backflow prevention diode 9103 Voltage control circuit 9104 Secondary battery 9105 Load 9401 Diesel generator 9402 Solar cell 9403 Rectifier 9404 Charge / discharge control device 9405 Storage battery 9406 DC / AC converter 9407 Switching device 9408 AC load 9501 Solar cell 9502 Charge / discharge control device 9503 Storage battery 9504 DC / AC converter 9505 Commercial power supply 9506 Switch 9507 Load 9601 Solar cell 9602 DC / AC converter 9603 Commercial power supply 9604 Load 9605 Reverse power flow.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor: Takashi Hayashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Masahiko Togaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Mitsuyuki Niwa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References US Patent 5,256,576 (US, A) US Patent 5,204,272 (US, A)

Claims (18)

(57) [Claims] 1. A pin having an amorphous or microcrystalline structure.
In the photovoltaic device, an i-type layer is provided on the side of the p-type layer, the first i-type layer being deposited by a CVD method in the presence of a microwave and a high frequency of 1 to 100 MHz, and an n-type layer. Side and C in the presence of a high frequency of 1 to 100 MHz
An i-type stacked structure including a second i-type layer deposited by a VD method, wherein the first i-type layer contains silicon atoms and germanium atoms, and has a minimum value of a band gap in the layer. Is located in the direction of the p-type layer from the center, the second i-type layer includes amorphous silicon or microcrystalline silicon, and has a thickness of 30 nm or less. A photovoltaic device, wherein the microwave energy is set lower than the microwave energy for decomposing gas by 100%, and the high-frequency energy applied at the same time is set higher than the microwave energy. 2. The semiconductor device according to claim 1, further comprising a third i-type layer deposited between the p-type layer and the first i-type layer by a CVD method in the presence of a high frequency of 1 to 100 MHz. Item 2. The photovoltaic element according to Item 1. 3. The device according to claim 1, wherein the first i-type layer has a region having a maximum band gap at an interface with an adjacent layer, and the region has a thickness of 1 to 30 nm. Photovoltaic element. 4. The photovoltaic device according to claim 1, wherein the i-type layer contains a group III element and a group V element at the same time. 5. The photovoltaic device according to claim 1, wherein the i-type layer contains oxygen and / or nitrogen. 6. The p-type amorphous or microcrystalline layer according to claim 1, wherein
2. The photovoltaic device according to claim 1, wherein the photovoltaic device has a laminated structure of an A layer containing a group II element as a main constituent element and a B layer containing a group III element and containing silicon atom as a main constituent element. 7. The method according to claim 1, wherein the n-type amorphous or microcrystalline layer
2. The photovoltaic device according to claim 1, wherein the photovoltaic device has a laminated structure of an A layer containing a group V element as a main constituent element and a B layer containing a group V element and containing silicon atom as a main constituent element. 8. A power generating apparatus having a pin-type photovoltaic element, a load, and means for supplying power from the photovoltaic element to the load, wherein the i-type layer is located on the side of the p-type layer. A first i-type layer deposited by a CVD method in the presence of a microwave and a high frequency of 1 to 100 MHz, and a CV in the presence of a high frequency of 1 to 100 MHz positioned on the side of the n-type layer.
An i-type stacked structure including a second i-type layer deposited by a method D, wherein the first i-type layer contains silicon atoms and germanium atoms, and has a minimum value of a band gap in the layer. Are located in the direction of the p-type layer from the center, and the second
The i-type layer has amorphous silicon or microcrystalline silicon and is set to a thickness of 30 nm or less, and the microwave energy is set lower than the microwave energy for decomposing the source gas by 100%. The applied high frequency energy is set higher than the microwave energy. 9. The semiconductor device according to claim 1, further comprising a third i-type layer deposited between the p-type layer and the first i-type layer by a CVD method in the presence of a high frequency of 1 to 100 MHz. Item 10. The photovoltaic element according to Item 8. 10. The device according to claim 8, wherein the first i-type layer has a region having a maximum band gap at an interface with an adjacent layer, and the region has a thickness of 1 to 30 nm. Power generator. 11. The power generator according to claim 8, wherein said i-type layer contains a group III element and a group V element simultaneously. 12. The power generator according to claim 8, wherein the i-type layer contains oxygen and / or nitrogen. 13. The p-type layer has a laminated structure of an A layer containing a group III element as a main constituent element and a B layer containing a group III element and containing silicon atom as a main constituent element. Item 9. The power generator according to Item 8. 14. The semiconductor device according to claim 1, wherein the n-type layer has a layered structure of a layer A containing a group V element as a main constituent element and a layer B containing a group V element and containing silicon atom as a main constituent element. Item 9. The power generator according to Item 8. 15. A process for forming an n-type semiconductor, and steps 1 to 10 for forming a plasma containing silicon atoms.
0 MHz high-frequency energy is applied, whereby R
Depositing an Fi-type semiconductor, and simultaneously applying microwave energy for forming a plasma and high-frequency energy of 1 to 100 MHz to a gas containing silicon atoms and germanium atoms, thereby forming silicon atoms and germanium atoms. And a step of depositing a MW-i type semiconductor containing: in this order, the microwave energy in the step of depositing the MW-i type semiconductor is the silicon atom and the germanium A method for manufacturing a photovoltaic device, wherein the microwave energy for decomposing 100% of a gas containing atoms is set lower than the microwave energy, and the high-frequency energy in the step is set higher than the microwave energy. 16. The method according to claim 1, wherein the pressure at the time of depositing the MW-i type semiconductor is 50 mTorr or less.
6. The method for manufacturing a photovoltaic element according to 5. 17. The deposition rate of the RF-i type semiconductor is 2
The method for manufacturing a photovoltaic device according to claim 15, wherein the speed is not more than nm / sec. 18. The film thickness of the RF-i type semiconductor is 30 n
The method for manufacturing a photovoltaic device according to claim 15, wherein m is equal to or less than m.