JPH07302921A - Method of forming photovoltaic device - Google Patents

Abstract

PURPOSE:To prevent impurities adsorbed or contained in the wall of a chamber from being taken in semiconductor layers and to restrain the semiconductor layers from being separated by a method wherein an interface between a P-type layer and an N-type layer and its vicinity are subjected to a hydrogen plasma treatment where hydrogen gas mixed with silicon-containing gas small enough in amount not to be conductive to deposits is used. CONSTITUTION:An interface between a P-type layer and an N-type layer and its vicinity are subjected to a hydrogen plasma treatment in which hydrogen plasma where 0.05 to 3% V element and silicon small enough in amount not to be substantially deposited are contained is used. By this setup, V element is sharply changed in distribution in the vicinity of the interface, so that the interface is enhanced in activation rate. Therefore, a photovoltaic device which is composed of a substrate 290, a first N-type layer 203, a first N/I buffer layer 251, a first I-type layer 204, a first P/I buffer layer 261, a first P-type layer 205, a second N-type layer 206, a second N/I buffer layer 252, a second I-type layer 207, a second P/I buffer layer 262, a second P-type layer 208, a transparent electrode 212, and a collector electrode 213, lessened in series resistance, and improved in characteristics can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention laminates a non-single-crystal n-type layer (or p-type layer) containing silicon atoms, a non-single-crystal i-type layer and a non-single-crystal p-type layer (or n-type layer). Formed by pi
The present invention relates to a method for forming a photovoltaic element such as a Taiyo battery or a sensor, which is formed by stacking at least two or more n structures.

[0002]

2. Description of the Related Art Conventionally, defects existing in semiconductors are closely related to the generation and recombination of electric charges and deteriorate the characteristics of the device. Hydrogen plasma treatment has been proposed as a method of compensating for such defect levels. For example USP
4113514 (JI Pankov et al., RCA, Sep. 12, 1978) describes hydrogen plasma treatment of completed semiconductor devices. See also “EF
FECT OF PLASMA TREATMENT OF THE TCO ON a-Si SOLAR
CELL PERFORMANCE ", F.Demichelis et.al., Mat.Res.So
c.Symp.Proc.Vol.258, p9O5,1992 shows a method of forming a pin-structured solar cell on a transparent electrode deposited on a substrate by hydrogen plasma treatment. Furthermore, "HYDR
OGEN-PLASMA REACTION FLUSHING F0R a-Si: H PIN SOL
AR CELL FABRlCATION ", YSTsuo et.al., Mat.Res.Soc.
Symp.Proc.Vol.149, p471,1989 shows that in a solar cell having a pin structure, the surface of the p layer is treated with hydrogen plasma before the deposition of the i layer. In the conventional hydrogen plasma treatment as described above, only hydrogen gas is introduced into the chamber,
Hydrogen gas was activated by RF power to perform hydrogen plasma treatment.

The hydrogen plasma is used for treating the substrate to be processed,
Not only spreads to act on unfinished devices and finished devices, but also spreads throughout the chamber. Since hydrogen plasma is extremely active, impurities (eg, oxygen, nitrogen, etc.) adsorbed on or contained in the wall surface of the chamber, which become defect levels when incorporated into the semiconductor layer, are generated.
There is a problem that carbon, iron, chromium, nickel, aluminum, etc. are taken out.

Further, it is more difficult for hydrogen gas to cause an electric discharge than other gases, and it is difficult for the plasma using only hydrogen gas to maintain the plasma as compared with other gases, so that stable hydrogen plasma treatment cannot be performed. There is a problem. Furthermore, in a photovoltaic element having a plurality of pin structures stacked, a layer having a high resistance due to mutual diffusion of Group III elements and Group V elements of the periodic table near the interface between the p-type layer and the n-type layer in contact with the pin structure. However, there is a problem that the characteristics of the photoelectrons are deteriorated due to the formation of

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems. That is, an object of the present invention is to provide a hydrogen plasma processing method in which the adsorption of impurities contained in the chamber wall surface or the incorporation of impurities contained therein does not substantially occur, and to provide a more stable method of hydrogen plasma processing. is there.

It is another object of the present invention to provide a method for forming a photovoltaic element in which the semiconductor layer is not substantially peeled off even when the photovoltaic element is placed in high temperature and high humidity. A further object of the present invention is to provide a method for forming a photovoltaic element in which the pin semiconductor layer is less likely to peel off even if the pin structure is formed on a flexible substrate even when the substrate is bent.

Furthermore, an object of the present invention is to provide a photovoltaic device which suppresses the deterioration of the characteristics of the photovoltaic device such as the separation of the substrate and the semiconductor layer and the increase of series resistance when irradiated with light under high temperature and high humidity. It is to provide a method for forming a power device. It is another object of the present invention to provide a photovoltaic element that has less deterioration in characteristics when used at high temperatures.

An object of the present invention is to provide a photovoltaic element which prevents diffusion of impurities from the p-type layer to the i-type layer and has improved initial efficiency. An object of the present invention is to provide a photovoltaic element that is hard to break when a reverse bias is applied to the photovoltaic element. An object of the present invention is to form a highly resistive layer in the vicinity of the interface by distributing the group V element of the periodic table so as to change abruptly in the vicinity of the interface between the p-type layer and the n-type layer. Not to provide a photovoltaic device.

[0009]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that the above object can be achieved by a method of forming a p-type layer and an n-type layer. . That is, the present invention provides a non-single-crystal n-type layer (or p-type layer) containing a silicon atom, a non-single-crystal i-type n / i buffer layer (or p / i buffer layer) on a substrate,
A non-single-crystal i-type layer, a non-single-crystal i-type p / i buffer layer (or n / i buffer layer), and a non-single-crystal p-type layer (or n-type layer) are stacked to form a pin structure of at least 2 In the method for forming a photovoltaic device having a structure or more,
In the vicinity of the interface where the p-type layer and the n-type layer are in contact with each other, the silicon atom-containing gas and the periodic table V
It is characterized in that plasma treatment is carried out with hydrogen gas containing a group element-containing gas.

Further, according to the present invention, the vicinity of the interface between the substrate and the n-type layer (or the vicinity of the interface between the substrate and the p-type layer).
Is subjected to plasma treatment with hydrogen gas containing a silicon atom-containing gas to the extent that substantially no deposition occurs.
Furthermore, the present invention provides the vicinity of the interface between the n / i buffer layer and the n-type layer, the vicinity of the interface between the n / i buffer layer and the i-type layer, and the p / i buffer layer and the i-layer.
The vicinity of the interface between the mold layers and the vicinity of the interface between the p / i buffer layer and the p-type layer are plasma-treated with hydrogen gas containing a silicon atom-containing gas that does not substantially deposit. .

According to the present invention, the silicon atom-containing gas is SiH ₄ , Si ₂ H ₆ , SiF ₄ , SiFH ₃ or SiF _2.
H ₂ , SiF ₃ H and SiC are ₂ H ₂ , SiCl ₃ H and SiC
It is characterized by containing at least one of l ₄ .
Further, the present invention is characterized in that the content ratio of the silicon atom-containing gas to the hydrogen gas is 0.1% or less.

[0012]

The above-mentioned object can be solved by forming a photovoltaic element by adding hydrogen-containing gas to the extent that silicon-containing gas does not substantially contribute to the deposition, performing hydrogen plasma treatment, and then depositing a semiconductor layer. is there. Although the detailed mechanism is not clear at present, the present inventors consider as follows.

That is, when hydrogen gas is added with a silicon atom-containing gas to an extent that does not substantially contribute to deposition and hydrogen plasma treatment is performed, the activated silicon atom-containing gas is adsorbed on the inner wall of the chamber. It acts on oxygen and water to generate stable silicon oxide and the like, which is more stable than that adsorbed on the inner wall of the chamber in the form of oxygen or water. As a result, when the silicon atom-containing gas is contained to the extent that it does not substantially contribute to the deposition and the plasma treatment is performed, it is possible to suppress the incorporation of impurities such as oxygen and water adsorbed on the chamber wall surface into the semiconductor to a very low level. It is thought that things can be done.

In addition, when hydrogen plasma treatment is performed with hydrogen gas containing a small amount of silicon atom-containing gas, hydrogen atoms on the chamber wall surface are suppressed from diffusing deeply into the chamber wall surface, and It is considered that it is possible to suppress as much as possible a reaction that takes out impurities that enter the semiconductor layer from the inside and form a defect level.

Further, hydrogen gas has a high ionization energy, and it is difficult to stably maintain plasma discharge for a long time. Depending on the matter
We believe that it will be easier to maintain the plasma discharge of hydrogen gas. By applying such a very stable hydrogen plasma discharge to the substrate or the element, the uniformity and reproducibility of the hydrogen plasma treatment are greatly improved. By improving the uniformity and reproducibility of such hydrogen plasma treatment, it is possible to prevent local peeling of the semiconductor layer and increase in series resistance under high temperature and high humidity and light irradiation for a hydrogen plasma treated substrate or element. It is possible.

In the hydrogen plasma treatment of the present invention, the surface of the substrate has a texture structure, and where the texture structure is locally sharply developed, the direction in which the silicon atom-containing gas is blunted is included. It works.
As a result, abnormal growth of the semiconductor layer can be substantially prevented even if the semiconductor layer is deposited on the textured structure substrate subjected to the hydrogen plasma treatment of the present invention. Therefore, when a photovoltaic element having a pin structure is formed, there is little unevenness in the characteristics of the photovoltaic element, and the adhesion between the substrate and the semiconductor layer is excellent,
In addition, a photovoltaic element having excellent durability under high temperature and high humidity can be obtained.

The hydrogen plasma treatment of the present invention is performed on the p-type layer and the n-type layer.
If it is carried out near the interface of the mold layer, the defects near the interface can be reduced, and the movement of charges excited by light can be facilitated. In particular, silicon atom-containing active species generated by plasma from a silicon atom-containing gas that does not substantially deposit are collided with or replaced by silicon atoms on the surface subjected to hydrogen plasma treatment, and structural relaxation proceeds, resulting in a surface condition. Will be improved. In particular, when light is irradiated from the p-type layer, a large number of charges excited by light are generated on the p-layer side, and thus many defects are likely to occur on the p-layer side. This can be relaxed by carrying out near the interface between the p-type layer and the n-type layer.

Further, when the hydrogen plasma treatment of the present invention is performed in the vicinity of the interface between the p-type layer and the n-type layer, mutual diffusion of the periodic table group III element and the periodic table group V element can be prevented. Therefore, it is possible to prevent a high resistance layer from being formed near the interface between the p-type layer and the n-type layer. As a result, the series resistance can be reduced. The hydrogen plasma treatment of the present invention is
When performed at the interface between the / i buffer layer and the p-type layer, the number of defects near the interface can be reduced, and the movement of charges excited by light can be facilitated. In particular, silicon atom-containing active species generated by plasma from a silicon atom-containing gas that does not substantially deposit are collided with or replaced by silicon atoms on the surface subjected to hydrogen plasma treatment, and structural relaxation proceeds, resulting in a surface condition. Will be improved.

[0019]

Embodiments Embodiments of the present invention will be described in detail below. First, a method and apparatus for forming a photovoltaic element according to the present invention will be described in detail with reference to the drawings. (Hydrogen Plasma Treatment Conditions) FIGS. 1 and 2 show examples of photovoltaic elements according to the present invention, which have been subjected to hydrogen plasma treatment with hydrogen gas containing a minute amount of silicon atom-containing gas.

FIG. 1 is a schematic explanatory view of a photovoltaic device having two pin structures. The photovoltaic element is a substrate 290.
(Support 200, reflection layer 201, reflection enhancement layer 202),
First n-type layer (or p-type layer) 203, first n / i buffer layer (or p / i buffer layer) 251, first
I-type layer 204, first p / i buffer layer (or n
/ I buffer layer) 261, first p-type layer (or n-type layer) 205, second n-type layer (or p-type layer) 206, second n / i buffer layer (or p / i buffer layer) )
252, second i-type layer 207, second p / i buffer layer (or n / i buffer layer) 262, second p-type layer (or n-type layer) 208, transparent electrode 212, current collecting electrode 2
It is composed of 13. When light is emitted from the substrate side, 200 is a transparent support, 201 is a transparent conductive layer, 202 is an antireflection layer, and 212 is a conductive layer that also serves as a reflective layer.

FIG. 2 is a schematic explanatory view of a photovoltaic element having three pin structures. The photovoltaic element is a substrate 390.
(Support 300, reflection layer 301, reflection enhancement layer 302),
First n-type layer (or p-type layer) 303, first n / i buffer layer (or p / i buffer layer) 351, first
I-type layer 304, the first p / i buffer layer (or n
/ I buffer layer) 361, first p-type layer (or n-type layer) 305, second n-type layer (or p-type layer) 306, second n / i buffer layer (or p / i buffer layer) )
352, the second i-type layer 307, the second p / i buffer layer (or n / i buffer layer) 362, the second p-type layer (or n-type layer) 308, the third n-type layer (or p-type layer) 309, third n / i buffer layer (or p / i)
Buffer layer) 353, third i-type layer 310, third p
/ I buffer layer (or n / i buffer layer) 36
3, third p-type layer (or n-type layer) 311, transparent electrode 3
12 and a collector electrode 313. When light is irradiated from the substrate side, 300 is a transparent support, 301 is a transparent conductive layer, 302 is an antireflection layer, and 312.
Is composed of a conductive layer that also serves as a reflective layer.

The plasma treatment with the hydrogen gas containing the silicon atom-containing gas and the group V element-containing gas of the periodic table of the present invention which does not substantially deposit is performed near the interface between the p-type layer and the n-type layer. It is effective to do. The hydrogen flow rate suitable for achieving the object of the present invention is appropriately optimized depending on the size of the processing chamber, but is 1 to 2000 s.
ccm is a suitable flow rate. When the hydrogen flow rate is less than 1 sccm, the electric power for maintaining the plasma discharge becomes large, the damage to the base slope becomes severe, and the impurities are easily taken in from the chamber wall surface. When the flow rate of hydrogen is more than 2000 sccm, the residence time of silicon-based active species or hydrogen active species in the plasma is shortened in the chamber, so that the hydrogen gas containing the silicon atom-containing gas is not substantially deposited. The effect of the plasma treatment in 1. becomes difficult to appear.

In the hydrogen plasma treatment method of the present invention,
The amount of the silicon atom-containing gas added to the hydrogen gas is preferably 0.001% to 0.1%.
The amount of silicon atom-containing gas added to hydrogen gas is
If it is less than 0.001%, the effect of the present invention will not appear, and if it is more than 0.1%, the deposition of silicon atoms will increase, and the original effect of hydrogen plasma treatment will not appear.

In the hydrogen plasma processing method of the present invention,
The ratio of the group V element-containing gas of the periodic table added to the hydrogen gas is preferably 0.05 to 3%. The vicinity of the interface between the p-type layer and the n-type layer is treated by treating the vicinity of the interface between the p-type layer and the n-type layer with hydrogen plasma containing a group V element of the periodic table in this range and containing silicon atoms in an amount not substantially deposited. The distribution of the group V element in the periodic table in can be sharply changed. Further, the hydrogen plasma treatment of the present invention improves the activation rate of the group V element of the periodic table in the vicinity of the interface, and particularly the interface between the p-type layer and the n-type layer, which is important for the photovoltaic of the pin structure. In the vicinity, the addition amount of the Group V element of the periodic table and the activation rate are increased, and as a result, the series resistance is reduced and the characteristics as a photovoltaic element are improved.

When the p-type layer is subjected to the hydrogen plasma treatment of the present invention at a relatively low temperature (280 ° C. or lower),
Substantially almost no diffusion of Group III of the periodic table into the n-type layer occurs, and a group V element of the periodic table has a high concentration and a high activation rate in the vicinity of the extreme surface of the p-type layer. It can be made to exist. Thus, in the hydrogen plasma treatment of the present invention,
Since the group V element of the periodic table can be contained in a large amount and with a high activation rate in the vicinity of the interface between the p-type layer and the n-type layer, the light with which the photovoltaic element is irradiated can be used more effectively. You can do things. Further, when the hydrogen plasma treatment of the present invention is performed on the n-type layer at a relatively low temperature (280 ° C. or lower), the diffusion of Group V of the periodic table into the p-type layer substantially occurs. Instead, it is possible to make the group V element of the periodic table exist in a state of high concentration and high activation rate in the vicinity of the extreme surface of the n-type layer. As described above, in the hydrogen plasma treatment of the present invention, the group V element of the periodic table can be contained in a large amount and at a high activation rate in the vicinity of the interface between the p-type layer and the n-type layer. The light can be made thin and the light applied to the photovoltaic element can be used more effectively.

Energy suitable for generating the hydrogen plasma of the present invention is electromagnetic waves, among which RF (r
adio frequency), VHF (very)
high frequency), MW (microrow)
ave) is a suitable energy. When the hydrogen plasma treatment of the present invention is performed by RF, the preferable frequency range is
It is in the range of 1 MHz to 50 MHz. When the hydrogen plasma treatment of the present invention is performed by VHF, a preferable frequency range is 51 MHz to 500 MHz. When the hydrogen plasma treatment of the present invention is performed in MW, the preferable frequency range is 0.51 GHz to 10 GHz.

In order to effectively carry out the hydrogen plasma treatment of the present invention, the degree of vacuum is an important factor, and the preferable range is the energy used to activate the hydrogen gas added with the silicon atom-containing gas. Greatly depends on. When the hydrogen plasma treatment is performed in the RF frequency band, the preferred vacuum degree is in the range of 0.05 Torr to 10 Torr. When performing the hydrogen plasma treatment in the VHF frequency band, the preferred vacuum degree is in the range of 0.0001 Torr to 1 Torr. A preferable degree of vacuum when hydrogen plasma treatment is performed in the MW frequency band is 0.0001T.
The range is from orr to 0.01 Torr.

In the hydrogen plasma treatment of the present invention, the power density introduced into the chamber to generate hydrogen plasma is an important factor for effectively performing the hydrogen plasma treatment of the present invention. Such power density depends on the frequency of the electromagnetic wave used. When using the RF frequency band, the power density is 0.01 to 1
W / cm ³ is a preferred range. When using the VHF frequency band, 0.01 to 1 W / cm ³ is a preferable range. Particularly in the VHF frequency band, there is a feature that plasma discharge can be maintained in a wide pressure range, and when performing hydrogen plasma treatment at high pressure, it is preferable to perform hydrogen plasma treatment at a relatively low power density. On the other hand, when performing hydrogen plasma treatment at a low pressure,
It is preferable to carry out at a relatively high power density.
When the hydrogen plasma treatment of the present invention is performed using the MW frequency band, 0.1 to 10 W / cm ³ is a preferable power density range. In carrying out the hydrogen plasma treatment of the present invention, there is a close relationship between the power density and the hydrogen plasma treatment time, and when the power density is high, it is preferable that the hydrogen plasma treatment time is relatively short. is there.

In the hydrogen plasma treatment of the present invention, the substrate temperature during the hydrogen plasma treatment is a very important factor for making the effect of the present invention effective. When hydrogen plasma treatment is performed using the RF frequency band, the substrate temperature is preferably relatively high, and 100 to 400 ° C. is a preferable temperature range. When the hydrogen plasma treatment of the present invention is performed using the VHF or MW frequency band, the substrate temperature is preferably a relatively low temperature. In this case, 50 to 300 ° C. is a preferable temperature range.
Further, the substrate temperature during the hydrogen plasma treatment of the present invention closely depends on the power density input into the chamber, and when the input power density is relatively high, the substrate temperature should be low. Is preferred.

When the hydrogen plasma treatment of the present invention is performed, the power density, gas flow rate, substrate temperature, pressure, etc. as described above are
It may be changed with respect to the processing time. Usually, the substrate has many defects and many impurities near the surface. Therefore, it is preferable that the hydrogen plasma treatment is performed at a relatively high power density and a high pressure at the start of the treatment.

In the hydrogen plasma treatment of the present invention, the silicon atom-containing gas added to the hydrogen gas is Si.
H ₄ , Si ₂ H ₆ , SiF ₄ , SiF ₃ H, SiF ₂ H ₂ , S
_{iF 3 H, Si 2 FH5,} SiCl 4, SiClH 3, Si
Suitable are silicon hydride compounds or halogenated silicon compounds such as Cl ₂ H ₂ , SlClH ₃ . These silicon atom-containing gases may be added alone to the hydrogen gas, or a plurality of them may be added in combination. In particular, the mixing ratio of the silicon atom-containing gas containing halogen atoms is preferably larger than that of the silicon atom-containing gas containing no halogen atoms.

What is effectively used as a starting material for introducing a Group V atom is specifically PH for introducing a phosphorus atom.
₃ , P ₂ H ₄ phosphorus hydride, PH ₄ I, PF ₃ , PF ₅ , PCl
Examples thereof include phosphorus halides such as ₃ , PCl ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsCl
₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ ,
SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr
₃ etc. can be mentioned. Particularly, PH ₃ and PF ₃ are suitable.

Further, the gasifiable compound is replaced by H ₂ , H
It may be appropriately diluted with a gas such as e, Ne, Ar, Xe, or Kr and introduced into the deposition chamber. The hydrogen plasma treatment of the present invention and n
It is also a preferred embodiment that the mold layers are deposited sequentially. By doing so, the interface state is further reduced and the series resistance of the photovoltaic element is further reduced.

(Forming Method and Apparatus) A method of forming the photovoltaic element of the present invention and a forming apparatus suitable for the method will be described. An example of the forming apparatus is shown in the schematic explanatory view of FIG. In FIG. 3, the forming apparatus 400 includes a load chamber 401, transfer chambers 402, 403, 404, an unload chamber 405, gate valves 406, 407, 408, 40.
9, substrate heating heaters 410, 411, 412, substrate transfer rails 413, n-type layer (or p-type layer) deposition chamber 417, i-type layer deposition chamber 418, p-type layer (or n-type layer) deposition chamber 419 , Plasma forming cups 420, 421, power supplies 422, 423, 42
4, microwave introduction window 425, waveguide 426, gas introduction pipes 429, 449, 469, valves 430, 431,
432, 433, 434, 441, 442, 443, 4
44, 450, 451, 452, 453, 454, 45
5, 461, 462, 463, 464, 465, 47
0, 471, 472, 473, 474, 481, 48
2, 483, 484, mass flow controller 43
6, 437, 438, 439, 456, 457, 45
8, 459, 460, 476, 477, 478, 47
9, a shutter 427, a bias rod 428, a substrate holder 490, an exhaust device (not shown), a microwave power source (not shown), a vacuum gauge (not shown), a controller (not shown), and the like.

A method of forming a photovoltaic element to which the hydrogen plasma processing method of the present invention is applied is performed as follows using the forming apparatus shown in FIG. All the chambers of the deposition apparatus 400 are pulled up to a vacuum degree of 10 ^-6 Torr or less by a turbo molecular pump (not shown) connected to each chamber. When the hydrogen plasma treatment of the present invention is performed by RF, it is performed as follows. A base plate having a reflective layer of silver or the like vapor-deposited on a stainless support and a reflection-increasing layer of zinc oxide or the like is vapor-deposited on the base plate holder 490. The substrate holder 4
90 is put in the load chamber 401. The door of the load chamber 401 is closed, and the load chamber 401 is pulled up to a predetermined vacuum degree by a mechanical booster pump / rotary pump (MP / RP) not shown. When the load chamber reaches a predetermined vacuum degree, the MP / RP is switched to a turbo molecular pump to raise the vacuum degree to 10 ^-6 Torr or less. Load chamber is 10 ^-6 Torr
When the degree of vacuum reaches the following level, the gate valve 406 is opened, the substrate holder 490 on the substrate transfer rail 413 is moved to the transfer chamber 402, and the gate valve 406 is moved.
Close. The substrate heating heater 410 of the transfer chamber 402 is raised so that the substrate holder 490 does not hit it. Position the substrate holder so that the substrate is directly under the heater. The heater 410 for heating the substrate is lowered, and the substrate is placed in the n-type layer deposition chamber.

The substrate temperature is changed to a temperature suitable for depositing the n-type layer, and a silicon atom-containing gas such as SiH ₄ and Si ₂ H ₆ for depositing the n-type layer and the periodic table V for depositing the n-type layer. Gas containing group element valve 443, mass flow controller 43
8. Introduce into the deposition chamber 417 via the valve 433. Further, it is preferable that the flow rate of hydrogen gas is also appropriately adjusted according to the n-type layer. In this way, the source gas for n-type layer deposition is introduced into the deposition chamber 417, and the opening / closing degree of the exhaust valve (not shown) is changed to bring the inside of the deposition chamber 417 to a desired vacuum degree of 0.1 to 10 Torr. Then, the RF power source 422 transfers the RF to the plasma forming cup 420.
Power is introduced, plasma discharge is generated, and the discharge is maintained for a desired time. In this way, an n-type semiconductor layer is deposited on the substrate to a desired thickness.

After the deposition of the n-type layer is completed, the introduction of the source gas into the deposition chamber 417 is stopped and the inside of the chamber is purged with hydrogen gas or helium gas. Once purged sufficiently, supply of hydrogen gas or helium gas is stopped and the inside of the deposition chamber is replaced by a turbo molecular pump.
Raise it to 0 ^-6 Torr. The gate valve 407 is opened, the substrate holder 490 is moved to the transfer chamber 403, and the gate valve 407 is closed. The substrate holder position is adjusted so that the substrate can be heated by the substrate heating heater 411. A substrate heating heater is brought into contact with the substrate to heat the substrate to a predetermined temperature. At the same time, an inert gas such as hydrogen gas or helium gas is introduced into the deposition chamber 418. The vacuum degree at that time is preferably the same as that at the time of depositing the n / i buffer layer. When the substrate temperature reaches a desired temperature, the gas for heating the substrate is stopped, and the source gas for n / i buffer layer deposition is supplied to the deposition chamber 418 from the gas supply device. For example, a hydrogen gas, a silane gas, and a germane gas are respectively supplied to the valve 46.
2, 463, 464 are opened, the desired settings are made with the mass flow controllers 457, 458, 459, and the valve 45
2, 453, 454, 450 are opened to open a gas introduction pipe 449
To the deposition chamber 418 via. At the same time, the supply gas is evacuated by a diffusion pump (not shown) so that the vacuum degree of the deposition chamber 418 becomes a desired pressure. When the degree of vacuum in the chamber 418 stabilizes at the desired degree of vacuum,
A desired power is introduced from an RF power source (not shown) to the bias rod for applying the bias. Then, using the RF plasma CVD method,
/ I deposit a buffer layer. The n / i buffer layer is
It is preferable to deposit at a slower deposition rate than the i-type layer deposited thereafter.

Next, the substrate temperature is heated to a predetermined temperature for i-type layer deposition. It is preferable that the valve 461 be opened with an inert gas such as hydrogen gas or helium gas to be set to a desired flow rate with a mass flow controller, and the valves 451 and 450 be opened to flow the substrate while heating. The vacuum degree at that time is preferably the same as the vacuum degree when depositing the i-type layer.

When the substrate temperature reaches a desired temperature, the gas for heating the substrate is stopped, and the source gas for depositing the i-type layer is supplied to the deposition chamber 418 from the gas supply device. For example, hydrogen gas, silane gas, and germane gas are opened with valves 462, 463, and 464, respectively, a desired flow rate is set with mass flow controllers 457, 458, and 459, and valves 452, 453, 454, and 450 are opened, and gas introduction pipe 449 is opened. Through the deposition chamber 418. At the same time, the supply gas is evacuated by a diffusion pump (not shown) so that the vacuum degree of the deposition chamber 418 becomes a desired pressure.
When the degree of vacuum in the chamber 418 stabilizes at the desired degree of vacuum, desired power is introduced from the microwave power source (not shown) into the deposition chamber 418 via the waveguide 426 and the microwave introduction window 425. Simultaneously with the introduction of microwave energy, as shown in the enlarged view of the deposition chamber 418, an external DC, RF or VH is applied to the bias applying bias rod.
It is also preferable to introduce the desired bias power from the F power source 424 into the deposition chamber 418. In this way, the i-type layer is deposited to a desired layer thickness. When the i-type layer has been deposited to a desired layer thickness, the microwave power and bias are stopped. Deposition chamber 418 as needed
The inside is purged with an inert gas such as hydrogen gas or helium gas.

Thereafter, a p / i buffer layer is deposited to a desired layer thickness in the same manner as the n / i buffer layer is deposited. Then, if necessary, the inside of the deposition chamber 418 is purged with an inert gas such as hydrogen gas or helium gas. The inside of the deposition chamber was purged, the exhaust gas was changed from a diffusion pump to a turbo molecular pump, and the vacuum degree in the deposition chamber was adjusted to 10
^-6 Make the degree of vacuum below Torr. At the same time, raise the heater for heating the substrate so that the substrate holder can move. Open the gate valve 408, move the Kisaka slope from the transfer chamber 403 to the transfer chamber 404,
The gate valve 408 is closed.

The substrate holder is attached to the heater 412 for heating the substrate.
And the substrate is heated by the Kisaka heating heater 412. It is a more preferable form that the exhaust gas is changed from the turbo molecular pump to MP / RP and the substrate is heated by flowing an inert gas such as hydrogen gas or helium gas at a pressure at the time of deposition of the p-type layer during heating. is there. When the substrate temperature stabilizes at the desired substrate temperature, the supply of the substrate heating gas such as the hydrogen gas or the inert gas for heating the substrate is stopped, and the source gas for p-type layer deposition, such as H ₂ or SiH. ₄ , the group III element-containing gas of the periodic table such as BF ₃ is supplied with valves 482, 483, 48.
4 open, mass flow controllers 477, 478,
Further, valves 472, 473, 474 are opened via 479, and a desired flow rate is supplied to the deposition chamber 419 through the gas introduction pipe 469. The exhaust valve is adjusted so that the internal pressure of the deposition chamber 419 becomes a desired degree of vacuum. When the internal pressure of the deposition chamber 419 becomes stable at a desired degree of vacuum, the RF power source 423 supplies RF power to the plasma forming cup. Then, the p-type layer is deposited by depositing for a desired time. After the deposition is completed, the RF power and the supply of the source gas are stopped, and the inside of the deposition chamber is sufficiently purged with an inert gas such as hydrogen gas or helium gas.

The substrate holder holding the substrate deposited up to the p-type layer is moved to the transfer chamber 402 by opening the gate valves 408 and 407, and the gate valve is closed. The hydrogen plasma treatment of the present invention is carried out on the p-type layer as follows. The hydrogen gas, the silicon atom-containing gas, and the group V element-containing gas of the periodic table, which are necessary for performing the hydrogen plasma treatment of the present invention, are introduced into the chamber by valves 431, 432, and 4.
33, mass flow controller 4376, 437, 4
A predetermined flow rate is introduced into the deposition chamber 417 through the valve 38, the valves 441, 442, 443, and the valve 430.
The opening / closing degree of an exhaust valve (not shown) is changed to deposit chamber 417.
The inside is made a desired vacuum degree. When the degree of vacuum in the chamber 417 becomes stable, RF power is introduced from the RF power source 422 into the plasma forming cup 420 to generate plasma. Thus, the hydrogen plasma treatment of the present invention is performed for a predetermined time.
Depending on the surface condition of Kisaka and the condition of the inner wall of the chamber, it is desirable to appropriately change the flow rate of hydrogen gas, the flow rate of silicon atom-containing gas, the RF power, the substrate temperature, etc. during the hydrogen plasma treatment. is there. The preferred form of change in these parameters is initially to increase the hydrogen flow rate and decrease the hydrogen flow rate over time. As a form of change in the flow rate of the silicon atom-containing gas, the flow rate of the silicon atom-containing gas is initially small and the flow rate of the silicon atom-containing gas increases with time. The RF power is a form of change in which it is preferable that the RF power is initially high and then becomes low over time.

In this way, the plasma treatment of the present invention is performed on the p-type layer, and the pin structure is laminated thereon in the same manner as described above to form a photovoltaic element. In the case of stacking a plurality of pin structures, it is a more preferable embodiment to perform the hydrogen plasma treatment of the present invention near the interface where each p-type layer and the n-type layer are in contact with each other. After laminating the final p-type layer and after purging, change the exhaust from MP / RP to turbo molecular pump and
Evacuate to a vacuum degree of 0 ^-6 Torr or less. At the same time, the heater 412 for heating the substrate is raised, the gate valve 409 is opened, and the substrate holder 490 is moved to the unload chamber 4
Move to 05. The gate valve 409 is closed, and when the temperature of the substrate holder becomes 100 ° C. or lower, the door of the unload chamber is opened and the substrate is taken out. In this way, the pin semiconductor layer subjected to the hydrogen plasma treatment of the present invention is formed. p
The substrate on which the in semiconductor layer is formed is set in a vacuum vapor deposition device for depositing a transparent electrode to form a transparent electrode on the semiconductor layer.
Next, the photovoltaic element having the transparent electrode formed thereon is set in a vacuum vapor deposition device for depositing a collecting electrode, and the collecting electrode is deposited. In this way, the photovoltaic element is formed.

When the hydrogen plasma treatment of the present invention is performed by MW, for example, it is performed as follows. After depositing the p-type layer, the gate valve 408 is opened, the substrate holder 490 is moved to the transfer chamber 403, and the gate valve is closed.
Position the substrate holder so that the substrate is directly under the heater. The heater 411 for heating the substrate is lowered, and the substrate is placed in the i-type layer deposition chamber. Substrate heating heater 411
To raise the substrate temperature to the desired substrate temperature. The turbo molecular pump is switched to MP / RP, and the hydrogen gas, the silicon atom-containing gas, and the Group V element-containing gas of the periodic table, which are necessary for performing the hydrogen plasma treatment of the present invention in the chamber, are valves 461, 462, 463, Mass flow controllers 456, 457, 458, valves 451, 452,
A predetermined flow rate is introduced into the deposition chamber 418 via the valve 453 and the valve 450. The degree of opening and closing of an exhaust valve (not shown) is changed to bring the inside of the deposition chamber 418 to a desired vacuum degree. When the degree of vacuum in the chamber 418 becomes stable, MW power is introduced from a MW power source (not shown) into the deposition chamber 418 through the microwave introduction window 425 to generate plasma. Thus, the hydrogen plasma treatment of the present invention is performed for a predetermined time. It is desirable to appropriately change the flow rate of hydrogen gas, the flow rate of silicon atom-containing gas, the MW power, the substrate temperature, etc. during the hydrogen plasma treatment depending on the surface condition of the substrate and the condition of the inner wall of the chamber. . The preferred form of change in these parameters is initially to increase the hydrogen flow rate and decrease the hydrogen flow rate over time. As a form of change in the flow rate of the silicon atom-containing gas, the flow rate of the silicon atom-containing gas is initially small and the flow rate of the silicon atom-containing gas increases with time. The MW power is a form of change in which it is preferable that the MW power is initially high and then becomes low over time. When the hydrogen plasma treatment of the present invention is performed by VHF, it is preferable that the hydrogen plasma treatment is performed in the same manner as in the case of MW.

Furthermore, it is also preferable that the vicinity of the interface between the substrate and the n-type layer is also subjected to hydrogen plasma treatment with hydrogen gas containing a silicon atom-containing gas in an amount not substantially deposited. In order to perform the hydrogen plasma treatment in the vicinity of the interface between the substrate and the n-type layer, the substrate is transferred to the n-type layer deposition chamber or the i-type layer deposition chamber in the above procedure to maintain the substrate at a predetermined substrate temperature. A silicon atom-containing gas and hydrogen gas are introduced into the deposition chamber at a predetermined flow rate by the above procedure. The pressure is adjusted by the pressure adjusting valve so that the degree of vacuum is suitable for the type of introduced power such as RF, VHF or / and MW power. RF, VHF or / and MW power is introduced to cause plasma discharge, and the hydrogen plasma treatment of the present invention is performed on the substrate for a predetermined time. Also n
Even in the vicinity of the interface between the / i buffer layer and the i-type layer, the characteristics of the photovoltaic element are further improved by performing the plasma treatment with the hydrogen gas containing the silicon atom-containing gas to the extent that it does not contribute to the deposition. The hydrogen plasma treatment of the present invention is performed on the n, i-type layer as follows. The hydrogen gas and the silicon atom-containing gas necessary for performing the hydrogen plasma treatment of the present invention are introduced into the chamber by the valve 4
61, 462, mass flow controller 456, 45
A predetermined flow rate is introduced into the deposition chamber 418 via the No. 7, valves 451, 452 and the valve 450. The degree of opening and closing of an exhaust valve (not shown) is changed to bring the inside of the deposition chamber 418 to a desired vacuum degree. When the degree of vacuum in the chamber 418 becomes stable, RF power is introduced from the RF power source 424 to the bias electrode 428 to generate plasma. Thus, the hydrogen plasma treatment of the present invention is performed for a predetermined time. Depending on the surface condition of the substrate and the condition of the inner wall of the chamber, it is desirable to appropriately change the flow rate of hydrogen gas, the flow rate of silicon atom-containing gas, the RF power, the base slope temperature, etc. during the hydrogen plasma treatment. is there. The preferred form of change in these parameters is initially to increase the hydrogen flow rate and decrease the hydrogen flow rate over time. As a form of change in the flow rate of the silicon atom-containing gas, the flow rate of the silicon atom-containing gas is initially small and the flow rate of the silicon atom-containing gas increases with time. The RF power is a form of change in which it is preferable that the RF power is initially high and then becomes low over time.

The hydrogen plasma treatment of the present invention on the i-type layer is performed as follows. A hydrogen gas and a silicon atom-containing gas necessary for performing the hydrogen plasma treatment of the present invention are introduced into the chamber by valves 461 and 462 and a mass flow 45.
A predetermined flow rate is introduced into the deposition chamber 418 through 6, 457, valves 451, 452, and valve 450. The degree of opening and closing of an exhaust valve (not shown) is changed to bring the inside of the deposition chamber 418 to a desired vacuum degree. When the degree of vacuum in the chamber 418 becomes stable, the RF power is supplied from the RF power source 424 to the bias rod 42.
8 is introduced and plasma is generated. Thus, the hydrogen plasma treatment of the present invention is performed for a predetermined time. It is desirable to appropriately change the flow rate of the hydrogen gas, the flow rate of the silicon atom-containing gas, the RF power, the substrate temperature, etc. during the hydrogen plasma treatment depending on the surface condition of the substrate and the condition of the inner wall of the chamber. . The preferred form of change in these parameters is initially to increase the hydrogen flow rate and decrease the hydrogen flow rate over time. As a form of change in the flow rate of the silicon atom-containing gas, the flow rate of the silicon atom-containing gas is initially small and the flow rate of the silicon atom-containing gas increases with time. The RF power is a form of change in which it is preferable that the RF power is initially high and then becomes low over time.

The hydrogen plasma treatment of the present invention on the p / i buffer layer is performed as follows. Valves 461 and 462, mass flow controllers 456 and 457, and valve 45 are used to supply hydrogen gas and a silicon atom-containing gas necessary for performing the hydrogen plasma treatment of the present invention in the chamber.
1, a predetermined flow rate is introduced into the deposition chamber 418 via the valve 450. The degree of opening and closing of an exhaust valve (not shown) is changed to bring the inside of the deposition chamber 418 to a desired vacuum degree.
When the vacuum degree of the chamber 418 becomes stable, the RF power source 424
RF power is introduced into the bias rod 428 to generate a plasma. Thus, the hydrogen plasma treatment of the present invention is performed for a predetermined time. It is desirable to appropriately change the flow rate of the hydrogen gas, the flow rate of the silicon atom-containing gas, the RF power, the substrate temperature, etc. during the hydrogen plasma treatment depending on the front condition of the substrate and the condition of the inner wall of the chamber. . The preferred form of change in these parameters is initially to increase the hydrogen flow rate and decrease the hydrogen flow rate over time. As a form of change in the flow rate of the silicon atom-containing gas, the flow rate of the silicon atom-containing gas is initially small and the flow rate of the silicon atom-containing gas increases with time. The RF power is a form of change in which it is preferable that the RF power is initially high and then becomes low over time.

As described above, one pin structure is formed, then the substrate holder holding the substrate on which the pin structure is formed is moved to the transfer chamber 402, and the pin structure is formed by the operation procedure of depositing each layer of the pin. Stack. In the case of a triple cell, it suffices to repeat such an operation again. In a photovoltaic device in which a plurality of pin structures are stacked, it is preferable to stack the photovoltaic device so that the band gap of the i-type layer becomes narrower in order from the light incident side.

In the above-described method for forming a photovoltaic element for performing hydrogen plasma treatment of the present invention, the gas cylinder may be used by appropriately replacing it with a necessary gas cylinder. In that case, it is preferable that the gas line be sufficiently heated and purged. Next, the components of the photovoltaic element will be described in detail. (Substrate) The material of the support preferably used in the present invention is one that has little deformation and distortion at the temperature required for forming the deposited film, has desired strength, and has conductivity. A support is preferred, and a support whose adhesion to the support of the reflection layer or the reflection increasing layer is not deteriorated by the hydrogen plasma treatment of the present invention performed after depositing the reflection layer or the reflection increasing layer is preferable.

Specifically, thin films of metals such as stainless steel, aluminum and its alloys, iron and its alloys, copper and its alloys, and their composites, and metal thin films of different materials and / or SiO _{2 on} their surfaces, Si ₃ N ₄ , Al ₂
An insulating thin film of O ₃ , AlN or the like, which has been subjected to surface coating treatment by a sputtering method, a vapor deposition method, a plating method or the like, or a heat-resistant resinous sheet of polyimide, polyamide, polyethylene terephthalate, epoxy or the like or glass fiber with these, Carbon fibers, boron fibers, metal fibers or the like, on the surface of which a simple metal or alloy, and a transparent conductive oxide or the like have been subjected to a conductive treatment by a method such as plating, vapor deposition, sputtering or coating. .

Further, the thickness of the support is within a range where the curved shape formed when the support is moved can be maintained and the strength is maintained as much as possible in consideration of cost, storage space and the like. It is desirable to be thin. Specifically, it is preferably 0.01 mm to 5 mm, more preferably 0.02.
The thickness is preferably 2 mm to 2 mm, and more preferably 0.05 mm to 1 mm, but when a thin film of metal or the like is used, the desired strength can be easily obtained even if the thickness is relatively thin.

The width of the support is not particularly limited and is determined by the size of the vacuum container and the like. The length of the support is not particularly limited, and may be such a length that it can be wound into a roll, or a longer one that is further lengthened by welding or the like. Good.

In the present invention, the support is heated and cooled in a short time.
However, it is preferable that the temperature distribution spreads in the longitudinal direction of the support.
Heat conduction in the moving direction of the support
It is desirable that the surface temperature of the support follow heating and cooling.
For this reason, it is preferable that the heat conduction is large in the thickness direction. Support
To increase the heat conduction of
Can be made thin, and if the support is uniform,
Conduction) × (thickness) is preferably 1 × 10 ^-1W / K or less,
More preferably 0.5 × 10^-1W / K or less
desirable.

(Reflective layer) As the material of the reflective layer, Ag,
Au, Pt, Ni, Cr, Cu, Al, Ti, Zn, M
Examples thereof include metals such as o and W or alloys thereof, and thin films of these metals are formed by vacuum vapor deposition, electron beam vapor deposition, sputtering or the like. In addition, care must be taken so that the formed metal thin film does not become a resistance component to the output of the photovoltaic element, and the sheet resistance value of the reflective layer is preferably 50Ω or less, more preferably 10Ω or less. Is desirable.

When the support is transparent and the photovoltaic element is irradiated with light from the transparent support, it is preferable to form a transparent conductive layer instead of the reflective layer. It is a thing. As a transparent conductive layer suitable for such a purpose, tin oxide, indium oxide, an alloy thereof, or the like is suitable. Further, it is preferable that the light-transmissive conductive layer is deposited so as to satisfy the antireflection condition. The sheet resistance of these translucent conductive layers is preferably 50 Ω or less, more preferably 10 Ω or less.
It is desirable that it is Ω or less.

(Reflection Increasing Layer) The reflection increasing layer preferably has a light reflectance of 85% or more in order to efficiently absorb the reflected light from the substrate which has passed through the semiconductor layer into each semiconductor layer. Further, electrically, the sheet resistance value is preferably 100Ω or less so as not to be a resistance component to the output of the photovoltaic element. Materials having such characteristics include SnO ₂ , In ₂ O ₃ , ZnO, CdO, and Cd ₂ S.
Examples thereof include metal oxides such as nO ₄ and ITO (In ₂ O ₃ + SnO ₂ ). In the photovoltaic device, the reflection enhancing layer is laminated in contact with the p-type layer or the n-type layer, and it is necessary to select a layer having good mutual adhesion. Further, it is preferable that the reflection increasing layer is deposited in a layer thickness that meets the conditions for increasing the reflection. As a method for forming the reflection increasing layer, a resistance heating vapor deposition method, an electron beam heating vapor deposition method, a sputtering method, a spray method, or the like can be used, and is appropriately selected as desired.

(I-type layer) Particularly in a photovoltaic element using a group IV or group IV alloy amorphous semiconductor material, p
The i-type layer used for in-junction is an important layer for generating and transporting carriers with respect to irradiation light. For the i-type layer, only p
Type, slightly n-type layers can also be used. Hydrogen atoms (H, D) or halogen atoms (X) are contained in the amorphous semiconductor material, and this has an important function.

The hydrogen atom (H, D) or halogen atom (X) contained in the i-type layer serves to compensate dangling bonds in the i-type layer, and the carrier in the i-type layer. It improves the product of the mobility and the life of the. Also p
A layer having an effect of compensating for the interface state of each interface of the n-type layer / i-type layer and the n-type layer / i-type layer, and having an effect of improving the photovoltaic power, the photocurrent and the photoresponsiveness of the photovoltaic element. Is. The number of hydrogen atoms and / or halogen atoms contained in the i-type layer is 1 to
The optimum content is 40 at%. In particular, p
A preferable distribution form is one in which the content of hydrogen atoms and / or halogen atoms is largely distributed on each interface side of the n-type layer / i-type layer and the n-type layer / i-type layer, and hydrogen near the interface is mentioned. The content of atoms and / or halogen atoms is preferably in the range of 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 corresponding to the content of silicon atoms.

When the photovoltaic element of the present invention has a plurality of pin structures, it is preferable to stack them so that the band gap of the i-type layer becomes smaller from the light incident side. Amorphous silicon or amorphous silicon carbide is used for the i-type layer having a relatively wide bandgap, and amorphous silicon germanium is used for the i-type semiconductor layer having a relatively narrow bandgap. Amorphous silicon and amorphous silicon germanium are a-Si: H, a-Si: F, a depending on the element that compensates for the dangling bond.
-Si: H: F, a-SiGe: H, a-SiGe:
It is written as F, a-SiGe: H: F, or the like.

When amorphous silicon germanium is used as the i-type layer, it is preferable to change the germanium content in the thickness direction of the i-type layer. In particular, it is a preferable distribution form of germanium that the germanium content continuously decreases in the direction of the n-type layer and / or the p-type layer. The distribution state of germanium atoms in the layer thickness is
This can be performed by changing the flow rate ratio of the germanium-containing gas contained in the raw material gas. As a method of changing the content of germanium atoms in the i-type layer by the MW plasma CVD method, in addition to a method of changing the flow rate ratio of the germanium-containing gas, the flow rate of the hydrogen gas that is the dilution gas of the source gas is changed. By doing so, it is possible to do the same. It is possible to increase the germanium content in the deposited film (i-type layer) by increasing the hydrogen dilution amount.

The hydrogen plasma treatment of the present invention particularly improves the electrical connection between the so-called graded band gap layer in which germanium atoms are continuously changed as described above and the buffer layer in contact with the layer. is there. More specifically, for example, a pin suitable for the photovoltaic device of the present invention
Examples of the i-type semiconductor layer of the junction include i-type hydrogenated amorphous silicon (a-Si: H), and its characteristics are:
The optical band gap (Eg) is 1.60 eV-1.
85 eV, hydrogen atom content (CH) is 1.0 to 2
The photoconductivity (σp) under irradiation of artificial sunlight of 5.0%, AM1.5, 100 mW / cm ² is 1.0 × 10 ⁻⁵ S / c.
m or more, dark conductivity (σd) is 1.0 × 10 ^-9 S / cm
Below, Constant Photocurrent Method (CPM)
It is preferable that the inclination of the urback tail due to the above is 55 meV or less and the local level density is 10 ¹⁷ / cm ³ or less.

The amorphous silicon germanium semiconductor material, which constitutes the i-type semiconductor layer having a relatively narrow bandgap of the photovoltaic element of the present invention, has a characteristic optical bandgap (Eg) of 1.20 eV. ~ 1.60e
The content of V and hydrogen atoms (CH) is 1.0 to 25%, the slope of the arback tail by the constant photocurrent method (CPM) is 55 meV or less, and the localized level density is 10 ¹⁷ cm ³ or less. Are preferred.

The i-type layer suitable for the present invention is preferably deposited under the following conditions. The amorphous semiconductor layer is preferably deposited by RF, VHF or MW plasma CVD method. When depositing by the RF plasma CVD method, the substrate temperature is 100 to 350 ° C., the vacuum degree in the deposition chamber is 0.05 to 10 Torr, and the RF frequency is 1 to 50 MHz. Especially RF
The frequency of 13.56 MHz is suitable. The RF power applied to the deposition chamber is 0.01 to 5 W / cm ²
Is a preferable range. Further, the self-bias applied to the substrate by the RF power is preferably in the range of 0 to 300.

When depositing by the VHF plasma CVD method, the substrate temperature is 100 to 450 ° C., the degree of vacuum in the deposition chamber is 0.0001 to 1 Torr, and the VHF frequency is 6.
A suitable range is 0 to 500 MHz. In particular, 100 MHz is suitable for the VHF frequency. Further, the VHF power supplied to the deposition chamber is preferably in the range of 0.01 to 1 W / cm ³ . In addition, the self bias applied to the substrate by the VHF power is preferably in the range of 10 to 1000V. Further, the characteristics of the deposited amorphous film are improved by introducing a DC or RF into the deposition chamber by providing a bias rod on top of VHF or separately. When introducing a DC bias using a bias rod,
It is preferred that the bias rod be positive. When the DC bias is introduced to the substrate side, it is preferable to introduce the DC bias so that the substrate side becomes the negative electrode. When introducing RF bias, RF is more than substrate area
It is preferable to reduce the area of the electrode into which is introduced.

In the case of depositing by the MW plasma CVD method, the substrate temperature is 100 to 450 ° C., the vacuum degree in the deposition chamber is 0.0001 to 0.05 Torr, and the MW frequency is 501 MHz to 10 GHz. . 2.45 GHz is particularly suitable for the MW frequency. The MW power input into the deposition chamber is 0.01 to 1 W / c.
m ³ is a suitable range. The MW power is optimally introduced into the deposition chamber with a waveguide. In addition to the MW, a bias rod is separately provided, and DC or RF is introduced into the deposition chamber to improve the characteristics of the deposited amorphous film. If the DC bias is introduced using a bias rod, it is preferred that the bias rod be positive. When the DC bias is introduced to the substrate side, it is preferable to introduce the DC bias so that the substrate side becomes the negative electrode. When introducing the RF bias, it is preferable to make the area of the electrode for introducing the RF smaller than the area of the substrate.

Silane source gases such as SiH ₄ , Si ₂ H ₆ , SiF ₄ and SiF ₂ H ₂ are suitable for depositing the i-type layer suitable for the plasma treatment of the present invention. Further, in order to widen the band gap, it is preferable to add carbon, nitrogen or an oxygen-containing gas. The carbon, nitrogen, or oxygen-containing gas is not contained in the i-type layer uniformly,
It is preferable to add a large amount in the vicinity of the mold layer and / or the n-type layer. By doing so, the open-circuit voltage can be improved without impairing the running property of charges in the i-type layer. As the carbon-containing gas, C
_n H _{2n + 2} , C _n H _2n , C ₂ H _{2 and the} like are suitable. The nitrogen-containing _{gas, N 2, NO, N 2} 0, NO 2, NH 3 or the like are suitable. O ₂ , CO ₂ , O _3, etc. are suitable as the oxygen-containing gas. Also, a combination of a plurality of these gases may be introduced. A suitable amount of the source gas added to increase the band gap is 0.1 to 50%.

Further, the characteristics of the i-type layer are improved by adding an element of Group III or / and Group V of the periodic table. The Group III elements of the periodic table are B,
Al, Ga, etc. are suitable. In particular, when B is added, it is preferable to add it by using a gas such as B ₂ H ₆ or BF ₃ . Further, as the Group V element of the periodic table,
N, P, As and the like are suitable. Particularly when P is added, PH ₃ is mentioned as a suitable one. The suitable amount of the group III element and / or the group V element of the periodic table added to the i-type layer is 0.1 to 1000 ppm.

For the i-type layer, an n / i buffer layer or p
By providing the / i buffer layer, the characteristics of the photovoltaic element are improved. As the buffer layer,
A semiconductor layer similar to the i-type layer can be used, in particular i
It is preferable to deposit at a slower deposition rate than the mold layer. A semiconductor having a wider bandgap than the i-type layer is suitable for the buffer layer. The band gap is
It is preferable that it is smoothly continuous from the i-type layer to the buffer layer. As a method for continuously changing the bandgap in the buffer layer, the bandgap can be narrowed by increasing the content of germanium atoms contained in the silicon-based non-single-crystal semiconductor. On the other hand, the band gap can be continuously widened by increasing the content of carbon atoms, oxygen atoms and / or nitrogen atoms contained in the silicon-based non-single crystal semiconductor. The ratio of the narrowest band gap to the widest band gap is 1.01 to 1.
A preferred range is 5.

When an element of Group III or / and Group V of the periodic table is added to the buffer layer, an element of Group III of the periodic table is added to the n / i buffer layer and p / i is added.
It is preferable to add a Group V element of the periodic table to the buffer layer. By doing so, it is possible to prevent deterioration of characteristics due to diffusion of impurities from the n-type layer and / or the p-type layer into the i-type layer.

(N-type layer, p-type layer) The p-type layer or the n-type layer is also an important layer which influences the characteristics of the photovoltaic device of the present invention. Examples of the amorphous material of the p-type layer or the n-type layer (denoted as a−) (microcrystalline material (denoted as μc−) also fall into the category of amorphous materials) are, for example, a-Si: H, a-Si: HX, a-SiC: H,
a-SiC: HX, a-SiGe: H, a-SiGe
C: H, a-SiO: H, a-SiN: H, a-SiO
N: HX, a-SiOCN: HX, μc-Si: H, μ
c-SiC: H, μc-Si: HX, μc-SiC: H
X, μc-SiGe: H, μc-SiO: H, μc-S
iGeC: H, μc-SiN: H, μc-SiON: H
X, μc-SiOCN: HX, etc., p-type valence electron control agent (Group III atom B, Al, Ga, In, TI of the periodic table)
And n-type valence electron control agents (group V atoms P, As,
A material to which Sb, Bi) is added at a high concentration can be cited, and a polycrystal material (indicated as poly-) is, for example, po.
ly-Si: H, poly-Si: HX, poly-S
iC: H, poly-SiC: HX, poly-SiG
e: H, poly-Si, poly-SiC, poly
-SiGe, p-type valence electron control agent (periodic table III
Group atom B. Examples of the material include Al, Ga, In, Tl) and an n-type valence electron control agent (atoms P, As, Sb, Bi of Group V of the periodic table) in high concentration.

Particularly, in the p-type layer or the n-type layer on the light incident side,
A crystalline semiconductor layer with little light absorption or an amorphous semiconductor layer with a wide band gap is suitable. Periodic table for p-type layers
The optimum amount of the group III atom added and the amount of the group V atom added to the n-type layer are 0.1 to 50 at%. Further, hydrogen atoms (H, D) or halogen atoms contained in the p-type layer or the n-type layer act to compensate dangling bonds of the p-type layer or the n-type layer, and the doping efficiency of the p-type layer or the n-type layer. Is to improve. The hydrogen atom or halogen atom added to the p-type layer or the n-type layer is 0.1 to
An optimum amount is 40 at%. Especially 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%. Further p
A preferable distribution form is one in which the content of hydrogen atoms and / or halogen atoms is largely distributed on each interface side of the n-type layer / i-type layer and the n-type layer / i-type layer, and hydrogen near the interface is mentioned. The content of atoms and / or halogen atoms is preferably in the range of 1.1 to 2 times the content in the bulk. Thus, by increasing the content of hydrogen atoms or halogen atoms in the vicinity of each interface of 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. It is possible to increase the photovoltaic power and the photocurrent of the photovoltaic device of the present invention.

Regarding the electrical characteristics of the p-type layer and the n-type layer of the photovoltaic element, the activation energy is preferably 0.2 eV or less, and most preferably 0.1 eV or less. The specific resistance is preferably 100 Ωcm or less, and most preferably 1 Ωcm or less. Furthermore, the layer thickness of the p-type layer and the n-type layer is 1 to
50 nm is preferable and 3 to 10 nm is optimum. Group IV and I suitable as semiconductor layers of the photovoltaic device of the present invention
The most preferable manufacturing method for forming the group V alloy-based amorphous semiconductor layer is the microwave plasma CVD method, and the next preferable manufacturing method is the RF plasma CVD method.

In the microwave plasma CVD method, a material gas such as a source gas and a diluent gas is introduced into the deposition chamber,
While evacuating with a vacuum pump, the internal pressure of the deposition chamber was kept constant, and microwaves oscillated by a microwave power source were guided by a waveguide and introduced into the deposition chamber through a dielectric window (alumina ceramics etc.). A plasma of material gas is generated and decomposed to form a desired deposited film on the substrate placed in the deposition chamber, and a deposited film applicable to a photovoltaic device is formed under a wide range of deposition conditions. be able to.

As a source gas suitable for depositing a group IV and group IV alloy-based amorphous semiconductor layer suitable for the photovoltaic device of the present invention, a gasifiable compound containing a silicon atom, germanium atom, is used. A gasifiable compound containing,
A gasifiable compound containing a carbon atom, a compound preliminarily gasifying containing a nitrogen atom, a gasifiable compound containing an oxygen atom, and the like, and a mixed gas of the compounds can be used.

A chain or cyclic silane compound is specifically used as the gasifiable compound containing a silicon atom. Specific examples include SiH ₄ , Si ₂ H ₆ and Si.
F 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, SiF
D ₃ , SiF ₂ D ₂ , SiD ₃ H, Si ₂ D ₃ H ₃ , (Si
F ₂ ) ₅ , (SiF ₂ ) ₆ , (SiF ₂ ) ₄ , Si ₂ F ₆ , Si
₃ F ₈ , Si ₂ H ₂ F ₄ , Si ₂ H ₃ F ₃ , SiCl ₄ , (Si
Cl ₂ ) ₅ , SiBr ₄ , (SiBr ₂ ) ₅ , Si ₂ Cl ₆ ,
SiHCl ₃ , SiH ₂ Br ₂ , SiH ₂ Cl ₂ , Si ₂ Cl
Examples thereof include those in a gas state such as ₃ F ₃ or those which can be easily gasified.

Specifically, a gas containing germanium atoms
GeH is a compound that can be converted into_Four, GeD_Four, GeF_Four,
GeFH₃, GeF₂H₂, GeF₃H, GeHD₃, Ge
H₂D ₂, GeH₃D, Ge₂H₆, Ge₂D₆Etc.
It Specifically, a gasifiable compound containing a carbon atom and
Then CH_Four, CD_Four, C _nH_{2n + 2}(N is an integer), C_nH
_2n(N is an integer), C₂H₂, C₆H₆, CO₂, CO, etc.
You can

As the nitrogen-containing gas, N ₂ , NH ₃ , N
D ₃ , NO, NO ₂ and N ₂ O can be mentioned. Oxygen-containing gas includes O ₂ , CO, CO ₂ , NO, NO ₂ , N ₂ O, CH
₃ CH ₂ OH, CH ₃ OH, etc. are struck. In addition, examples of the substance introduced into the p-type layer or the n-type layer for controlling the valence electrons include Group III atoms and Group V atoms of the periodic table.

The substances effectively used as a starting material for introducing a Group III atom are specifically B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ and B ₅ for introducing a boroso atom. H ₁₁ , B ₆
Hydrogenated borohydride such as H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ , B
Examples thereof include halogenated halo such as Cl ₃ .
In addition, AlCl ₃ , GaCl ₃ , InCl ₃ , TlC
Examples include l _{3 and the} like. In particular, B ₂ H ₆ and BF ₃ are effectively used as a suitable starting material for introducing a Group V atom, specifically, PH ₃ and P ₂ for introducing a phosphorus atom.
H ₄ Phosphorus hydride, PH ₄ I, PF ₃ , PF ₅ , PCl ₃ , P
Examples thereof include phosphorus halides such as Cl ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsCl ₃ , A
sBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ , Sb
Other examples include Cl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ and BiBr ₃ . Particularly, PH ₃ and PF ₃ are suitable.

Further, the gasifiable compound is replaced by H ₂ , H
It may be appropriately diluted with a gas such as e, Ne, Ar, Xe, or Kr and introduced into the deposition chamber. Especially microcrystalline semiconductors and a-Si
When depositing a layer such as C: H that has little light absorption or has a wide band gap, dilute the source gas 2 to 100 times with hydrogen gas and introduce relatively high microwave power or RF power. Is preferred.

(Transparent Electrode) The transparent electrode preferably has a light transmissivity of 85% or more in order to efficiently absorb light from the sun or a white fluorescent lamp into each semiconductor layer.
Further, electrically, the sheet resistance value is preferably 100Ω or less so as not to be a resistance component to the output of the photovoltaic element. As a material having such characteristics, S
nO ₂ , In ₂ O ₃ , ZnO, CdO, Cd ₂ SnO ₄ , I
Metal oxides such as TO (In ₂ O ₃ + SnO ₂ ) and A
Examples thereof include a metal thin film in which a metal such as u, Al, or Cu is formed into an extremely thin film in a semitransparent state. In the photovoltaic device, the transparent electrode is laminated on the p-type layer or the n-type layer to form the photovoltaic device on the translucent support, and to irradiate light from the translucent support side. Is laminated on the support, so it is necessary to select those having good mutual adhesion. Further, it is preferable that the transparent electrode is deposited in a layer thickness suitable for the antireflection condition. As a method for producing the transparent electrode, a resistance heating evaporation method, an electron beam heating evaporation method,
A sputtering method, a spray method, or the like can be used and is appropriately selected as desired.

(Collecting Electrode) As the collecting electrode of the photovoltaic element subjected to the hydrogen plasma treatment of the present invention, silver paste is formed by screen printing, or Cr, Ag, Au,
It may be formed by vacuum vapor deposition using a mask of Cu, Ni, M, Al or the like. Alternatively, a metal wire of Cu, Au, Ag, Al or the like may be attached with carbon or Ag powder together with a resin and attached to the surface of the photovoltaic element to form a collecting electrode.

When a photovoltaic device having a desired output voltage and output current is manufactured using the photovoltaic element of the present invention, the photovoltaic elements of the present invention are connected in series or in parallel, A protective layer is formed on the front and back surfaces, and output extraction electrodes and the like are attached. Further, when the photovoltaic elements of the present invention are connected in series, a diode for preventing backflow may be incorporated.

[0083]

EXAMPLES A method for forming a photovoltaic element of the present invention will be described in detail below with respect to a solar cell made of a non-single crystal silicon semiconductor material, but the present invention is not limited to this. (Example 1) The tandem solar cell of FIG. 1 was produced using the deposition apparatus shown in FIG. First, a substrate was manufactured.
A stainless support (200) having a thickness of 0.5 mm and 50 × 50 mm ² was ultrasonically cleaned with acetone and isopropanol, and dried with warm air.

On the surface of the stainless support (200) at room temperature using the sputtering method, Ag having a layer thickness of 0.3 μm was used.
Light reflection layer (201) and a layer thickness of 1.0 on it at 350 ° C.
A reflection-increasing layer (202) of ZnO having a thickness of 200 μm was formed, and the fabrication of the substrate was completed. Next, each semiconductor layer was formed on the reflection increasing layer using the deposition apparatus 400. The deposition apparatus 400 is MW
Both PCVD and RFPCVD methods can be performed.

A source gas cylinder (not shown) is connected to the deposition apparatus through a gas introduction pipe. The raw material gas cylinders were all purified to ultra-high purity. SiH ₄ gas cylinder, SiF ₄ gas cylinder, CH ₄ gas cylinder, GeH ₄ gas cylinder, GeF ₄ gas cylinder, Si ₂ H ₆ gas cylinder,
PH ₃ / H ₂ (Dilution: 2000ppm, 1%, 10%)
Gas cylinder, PF ₃ / H ₂ (dilution: 2000ppm, 1
%, 10%) gas cylinder, B ₂ H ₆ / H ₂ (dilution: 10
00ppm) gas cylinder, BF ₃ / H ₂ (dilution 1000
ppm) gas cylinder, H ₂ gas cylinder, He gas cylinder, SiCl ₂ H ₂ gas cylinder, SiH ₄ / H ₂ (dilution degree:
1000 ppm) gas cylinder was connected.

Next, the substrate 490 on which the reflection layer 201 and the reflection increasing layer 202 are formed is placed on the substrate transfer rail 413 in the load chamber 401, and the load chamber 401 is pressurized by a vacuum exhaust pump (not shown). Is about 1
It was evacuated to × 10 ^-5 Torr. Next, the gate valve 406 was opened and the film was transferred into the transfer chamber 402 and the deposition chamber 417 which were evacuated by a vacuum exhaust pump (not shown) in advance. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 410 and heated, and the inside of the deposition chamber 417 was evacuated by a vacuum exhaust pump (not shown) to a pressure of about 1 × 10 ⁻⁵ Torr.

Preparation for film formation is completed as described above.
After that, the RFn-type layer 203 made of μc-Si was formed.
To form an RFn-type layer made of μc-Si, H₂Moth
Gas through the gas introducing pipe 429 into the deposition chamber 417.
Introduced, H₂So that the gas flow rate is 300 sccm
Open valves 441, 431, and 430 to open the mass flow controller.
It was adjusted with the tracker 436. In the deposition chamber 417
Conductor (not shown) so that the pressure becomes 1.1 Torr
Adjusted with a closet valve. The temperature of the substrate 490 is 380 ° C
Set the heater for heating Kisaka 410 so that
When the temperature stabilizes, SiH _FourGas, PH₃/ H
₂(Dilution: 1%) Gas is deposited in the deposition chamber 417.
Gas by operating the valves 443, 433, 444, 434.
It was introduced through the inlet pipe 429. At this time, SiH_FourGas flow
1.5sccm, H₂Gas flow rate is 300sccm,
PH₃/ H₂(Dilution: 1%) Gas flow rate is 20 sccm
Mass flow controllers 438, 436,
439, and the pressure in the deposition chamber 417 is 1.
It was adjusted to be 1 Torr. RF power source 422 power
Power is 0.05W / cm³Set to the plasma formation cup.
Introduce RF power to the 420 to cause glow discharge,
The formation of the RFn-type layer is started on the substrate, and the R thickness of 20 nm is applied.
When the Fn type layer is formed, turn off the RF power source
The discharge was stopped and the formation of the RF n-type layer 203 was completed. Heap
SiH into chamber 417_FourGas, PH₃/ H₂Of gas
Stop the inflow for 4 minutes H into the deposition chamber₂Kept flowing gas
Later, H₂Stop the inflow of gas, and
1 x 10^-FiveEvacuated to Torr.

Next, an n / i buffer layer 251 made of a-Si was formed by the RFPCVD method. First, the transfer chamber 403 and the i-type layer deposition chamber 41 that have been evacuated by a vacuum exhaust pump (not shown) in advance.
8, the gate valve 407 was opened and the substrate 490 was transported. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 411 and heated, and the i-type layer deposition chamber 418 was evacuated to a pressure of about 1 × 10 ⁻⁵ Torr by a vacuum exhaust pump (not shown).

To prepare the n / i buffer layer 251, the substrate heating heater 411 is set so that the temperature of the substrate 490 becomes 360 ° C., and when the substrate is sufficiently heated, the valves 464, 454, 450, 463. , 453 are gradually opened to introduce Si ₂ H ₆ gas and H ₂ gas into the gas introduction pipe 4
It was made to flow into the i-type layer deposition chamber 418 through 49. At this time, the Si ₂ H ₆ gas flow rate was 2.5 sccm, and H ₂
The mass flow controllers 459 and 458 were adjusted so that the gas flow rate was 100 sccm. The pressure inside the i-type layer deposition chamber 418 was adjusted to 0.7 Torr by adjusting the opening of a conductance valve (not shown). Next, the RF power source 424 is set to 0.08 W / cm ³ , a bias rod 428 is applied to cause glow discharge, and a shutter 427 is opened to open an n-type layer on the RF n-type layer.
/ I buffer layer production was started and the layer thickness was 10 nm.
When the i buffer layer was produced, the RF glow discharge was stopped, the output of the RF power source 424 was cut off, and the production of the n / i buffer layer 251 was completed. By closing the valves 464 and 454, the flow of Si ₂ H ₆ gas into the i-type layer deposition chamber 418 is stopped, and H _{2 is} introduced into the i-type layer deposition chamber 418 for 2 minutes.
After continuing to flow ₂ gases, the valves 453 and 450 were closed, and the inside of the i-type layer deposition chamber 418 and the inside of the gas pipe were evacuated to 1 × 10 ⁻⁵ Torr. Next, a-SiG
The MWi-type layer 204 made of e was formed by the MWPCVD method. To prepare the MWi type layer, the substrate heating heater 411 is set so that the temperature of the substrate 490 becomes 380 ° C., and when the substrate is sufficiently heated, the valve 461,
451, 450, 462, 452, 463, 453 were gradually opened, and SiH ₄ gas, GeH ₄ gas, and H ₂ gas were caused to flow into the i-type layer deposition chamber 418 through the gas introduction pipe 449. At this time, the SiH ₄ gas flow rate is 37 scc
m, GeH ₄ gas flow rate is 38 sccm, H ₂ gas flow rate is 1
The mass flow controllers 456, 457, and 458 were adjusted to 80 sccm. The pressure inside the i-type layer deposition chamber 418 was adjusted to 5 mTorr by adjusting the opening of a conductance valve (not shown). Next, a high frequency (hereinafter abbreviated as “RF”) power source 424 was set to 0.6 W / cm ³ and applied to the bias rod 428. After that, the power of the MW power source (not shown) is set to 0.28 W / c.
m ³ and the waveguide 426 and the microwave introduction window 4 are set.
25, the MW power is introduced into the i-type layer deposition chamber 418 to cause glow discharge, and the shutter 427 is opened to start the preparation of the MWi-type layer on the n / i buffer layer. When the mold layer was formed, the MW glow discharge was stopped, the output of the bias power source 424 was cut off, and the formation of the MWi type layer 204 was completed. Valve 451,
452 is closed and S into the i-type layer deposition chamber 418
The inflow of iH ₄ gas and GeH ₄ gas was stopped, and H ₂ gas was continued to flow into the i-type layer deposition chamber 418 for 2 minutes, then the valves 453 and 450 were closed, and the i-type layer deposition chamber 41
The inside of 8 and the inside of the gas pipe were evacuated to 1 × 10 ⁻⁵ Torr.

Next, a p / i buffer layer 261 made of a-Si was formed by the RFPCVD method. To prepare the p / i buffer layer 261, the temperature of the substrate 490 is set to 2
The substrate heating heater 411 was set to 50 ° C., and when the substrate was sufficiently heated, the valves 464 and 45
4, 450, 463, 453 are gradually opened and Si ₂ H ₆
Gas and H ₂ gas were caused to flow into the i-type layer deposition chamber 418 through the gas introduction pipe 449. At this time, the Si ₂ H ₆ gas flow rate was 2.5 sccm, and the H ₂ gas flow rate was 80 sccm.
Each mass flow controller 459,
Adjusted at 458. The pressure inside the i-type layer deposition chamber 418 was adjusted to 0.7 Torr by adjusting the opening of a conductance valve (not shown). Next, the RF power source 424 is set to 0.07 W / cm ³ , a bias rod 428 is applied to cause glow discharge, and a shutter 427 is opened to produce a p / i buffer layer 261 on the MWi type layer. When the p / i buffer layer having a layer thickness of 20 nm was produced, the RF glow discharge was stopped, the output of the RF power source 424 was cut off, and the production of the p / i buffer layer 261 was completed.
The valves 464 and 454 are closed to stop the flow of Si ₂ H ₆ gas into the i-type layer deposition chamber 418, and after the H ₂ gas is continuously flowed into the i-type layer deposition chamber 418 for 2 minutes,
The valves 453 and 450 are closed, and the i-type layer deposition chamber 4
The inside of 18 and the inside of the gas pipe were evacuated to 1 × 10 ⁻⁵ Torr.

Next, the RF p-type layer 205 made of a-SiC
In order to form the substrate, the gate valve 408 is opened into the transfer chamber 404 and the p-type layer deposition chamber 419 which have been evacuated by a vacuum exhaust pump (not shown) in advance, and the substrate 490 is transferred. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 412 and heated, and the inside of the p-type layer deposition chamber 419 was evacuated to a pressure of about 1 × 10 ⁻⁵ Torr by a vacuum exhaust pump (not shown).

The heater 412 for heating the substrate is set so that the temperature of the substrate 490 becomes 250 ° C., and when the substrate temperature becomes stable, H ₂ gas, SiH ₄ / H ₂ gas, B ₂ H ₆ / H ₂ gas is added.
Gas and CH ₄ gas into the deposition chamber 419 by the valve 4
81, 471, 470, 482, 472, 483, 47
3, 484 and 474 were operated and introduced through the gas introduction pipe 469. At this time, the flow rate of H ₂ gas was 60 scm, Si
H ₄ / H ₂ gas flow rate is 0.5 sccm, B ₂ H ₆ / H ₂ gas flow rate is 10 sccm, CH ₄ gas flow rate is 0.3 sccm
Mass flow controllers 476, 47
7, 478, 479, and the pressure inside the deposition chamber 419 was adjusted to 1.7 Torr by adjusting the opening of a conductance valve (not shown). The power of the RF power source 423 was set to 0.07 W / cm ³ , and the RF power was introduced into the plasma forming cup 421 to cause glow discharge, and p
The formation of the RF p-type layer on the / i buffer layer was started, and when the RF p-type layer having a layer thickness of 10 nm was formed, the RF power supply was turned off, the glow discharge was stopped, and the formation of the RF p-type layer 205 was completed. Valves 472, 482, 473, 483, 47
4, 484 are closed to stop the inflow of SiH ₄ / H ₂ gas, B ₂ H ₆ / H ₂ gas, and CH ₄ gas into the p-type layer deposition chamber 419, and into the p-type layer deposition chamber 419 for 3 minutes. H ₂
After continuing to flow the gas, valves 471, 481, 470
Closed to stop the flow of H ₂ and the p-type layer deposition chamber 419
The inside and the gas pipe were evacuated to 1 × 10 ⁻⁵ Torr.

Next, in order to perform the trace amount group V element-containing hydrogen plasma treatment of the present invention, the transfer chamber 402 and the deposition chamber 417 are passed through the transfer chamber 403 which has been evacuated by a vacuum exhaust pump (not shown) in advance.
The gate valves 408 and 407 were opened and conveyed. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 410 and heated, and the inside of the deposition chamber 417 was evacuated by a vacuum exhaust pump (not shown) to a pressure of about 1 × 10 ⁻⁵ Torr.

Next, the hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed under the conditions shown in Table 1 (1). To carry out the trace amount group V element-containing hydrogen plasma treatment of the present invention, PH ₃ / H ₂ (dilution: 1%) gas as the group V element containing gas, SiH ₄ gas, H ₂ as the silicon atom containing gas. Gas was introduced into the deposition chamber 417 through a gas introduction pipe 429, valves 441, 431 and 430 were opened and the mass flow controller 436 adjusted so that the H ₂ gas flow rate was 1300 sccm. The mass flow controller 43 is opened by opening the valves 444 and 434 so that the group V element-containing gas PH ₃ gas becomes 0.3% of the total H ₂ gas flow rate.
Adjusted at 9. The silicon atom-containing gas was adjusted with a mass flow controller (not shown) by opening a valve (not shown) so that SiH ₄ was 0.01% with respect to the total H ₂ gas flow rate. The pressure in the deposition chamber 417 is 0.8 Torr
Was adjusted with a conductance valve (not shown). The heater 410 for heating the substrate is set so that the temperature of the substrate 490 becomes 250 ° C., and when the substrate temperature becomes stable, the power of the RF power source 422 is set to 0.06 W / cm ³ and the plasma forming cup 421 is set. RF was introduced to cause glow discharge, and the hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed for 4 minutes. Then turn off the RF power,
The glow discharge is stopped, and PH ₃ in the deposition chamber 417 is stopped.
/ H _2, SiH ₄ stop the flow of gas, 5 minutes, deposition After continued to flow H ₂ gas into the chamber 417, stopping the inflow of the H ₂ gas, the deposition chamber 417 and in the gas pipe 1 × 10 ^{- It} was evacuated to ⁵ Torr.

Next, the RFn-type layer 206 made of μc-Si.
Was formed. In order to form the RFn-type layer made of μc-Si, H ₂ gas is introduced into the deposition chamber 417 through the gas introduction pipe 429, and the H ₂ gas flow rate is 200 sccm.
The valves 441, 431, and 430 were opened so as to be set, and the mass flow controller 436 adjusted. The conductance valve (not shown) was used to adjust the pressure in the deposition chamber 417 to 1.1 Torr. The substrate heating heater 410 is set so that the temperature of the substrate 490 becomes 250 ° C., and when the substrate temperature becomes stable, SiH ₄ gas,
PH ₃ / H ₂ (dilution: 1%) gas is deposited in chamber 41
The valves 443, 433, 444, and 434 were operated into the chamber 7 and introduced through the gas introduction pipe 429. At this time, SiH
₄ gas flow rate is 1.5 sccm, H ₂ gas flow rate is 280 sc
cm, PH ₃ / H ₂ (dilution degree: 1%) gas flow rate is 25sc
Mass flow controllers 438, 4 to be cm
The pressure inside the deposition chamber 417 was adjusted to 1.1 Torr. RF power supply 42
The power of 2 was set to 0.05 W / cm ³ , RF power was introduced into the plasma-forming cup 420 to cause glow discharge, and formation of the RFn-type layer on the RFp-type layer was started. When the RFn-type layer was formed, the RF power supply was turned off to stop the glow discharge, and the formation of the RFn-type layer 206 was completed. SiH ₄ gas, PH ₃ into the deposition chamber 417
/ H ₂ was stopped, H ₂ gas was continuously flowed into the deposition chamber for 2 minutes, H ₂ was stopped, and the deposition chamber and the gas pipe were evacuated to 1 × 10 ⁻⁵ Torr.

Next, an n / i buffer layer 252 made of a-SiC was formed by the RFPCVD method. First, the transfer chamber 403 and the i-type layer deposition chamber 4 which have been evacuated by a vacuum exhaust pump (not shown) in advance.
The gate valve 407 was opened into the substrate 18 and the substrate 490 was transported. The back surface of the substrate 490 is brought into close contact with the substrate heating heater 411 to heat it, and the pressure inside the i-type layer deposition chamber 418 is adjusted to about 1 × 10 ⁻⁵ Torr by a vacuum exhaust pump (not shown).
It was evacuated until.

To manufacture the n / i buffer layer 252, the substrate heating heater 411 is set so that the temperature of the substrate 490 becomes 250 ° C., and when the substrate is sufficiently heated, the valves 464, 454, 450, 463. , 453,
465 and 455 were gradually opened, and Si ₂ H ₆ gas, H ₂ gas, and CH ₄ gas were caused to flow into the i-type layer deposition chamber 418 through the gas introduction pipe 449. At this time, the Si ₂ H ₆ gas flow rate was 0.4 sccm, and the H ₂ gas flow rate was 90 sccc.
The mass flow controllers 459, 458, and 460 adjusted the flow rates of m and CH ₄ gas to be 0.2 sccm.

The pressure inside the i-type layer deposition chamber 418 is
The opening of the conductance valve (not shown) was adjusted so as to be 1.0 Torr. Next, set the RF power source 424 to 0.0
The bias bar 428 is applied to the RF n-type layer at 6 W / cm ³ to generate glow discharge, and the shutter 427 is opened to start preparation of the n / i buffer layer on the RF n-type layer. When the buffer layer is prepared, R
Stop the F glow discharge, turn off the output of the RF power source 424, n
/ I buffer layer 252 was completed. Valve 46
4, 454, 465, 455 are closed to stop the inflow of Si ₂ H ₆ gas and CH ₄ gas into the i-type layer deposition chamber 418, and H ₂ gas is continued to flow into the i-type layer deposition chamber 418 for 2 minutes. After that, the valves 453 and 450 are closed and the inside of the i-type layer deposition chamber 418 and the inside of the gas pipe are set to 1 × 10.
Evacuated to ^-5 Torr.

Next, an RFi type layer 207 made of a-Si is formed.
It was formed by the RFPCVD method. Produces RFi type layer
The temperature of the substrate 490 to 200 ° C.
The heating heater 411 was set to sufficiently heat the substrate.
By the way, valves 464, 454, 450, 463, 45
Open 3 gradually, Si₂H₆Gas, H₂Gas introduction
Flow into i-type layer deposition chamber 418 through pipe 449
Let At this time, Si ₂H₆Gas flow rate is 2.5 sccm,
H₂Each mass flow rate should be 85sccm.
Adjusted with the low controllers 459 and 458. i-type layer
The pressure in the deposition chamber 418 is 0.5 Torr.
Adjust the opening of the conductance valve (not shown) so that
It was Next, the RF power source 424 is set to 0.07 W / cm.³Set to
And apply it to the bias rod 428 to cause glow discharge.
The shutter 427 to open the n / i buffer.
Fabrication of the RFi-type layer is started on the layer 252, and the layer thickness is 110 n.
When the i-type layer of m was produced, the RF glow discharge was stopped,
The output of the RF power source 424 is turned off, and the RFi type layer 207 is produced.
Finished. Close valves 464, 454 to deposit i-type layer
Si into chamber 418₂H₆Stop gas inflow, 2
H into the i-type layer deposition chamber 418₂Continue to flow gas
After that, the valves 453 and 450 are closed, and the i-type layer deposition check is performed.
1 x 10 in chamber 418 and gas piping^-FiveTor
It was evacuated to r.

Next, a p / i buffer consisting of a-Sic
The layer 262 was formed by the RFPCVD method. p / i
The temperature of the substrate 490 is required to form the stuffer layer 262.
Set the heater 411 for heating the substrate to 200 ° C.
Then, when the substrate is sufficiently heated, the valves 464 and 45 are
4, 450, 463, 453, 465, 455 gradually
Open, Si₂H₆Gas, H₂Gas, CH_FourGas introduction
Flow into i-type layer deposition chamber 418 through pipe 449
Let At this time, Si₂H₆Gas flow rate is 0.4 sccm,
H₂Gas flow rate is 65 sccm, CH_FourGas flow rate is 0.3s
Each mass flow controller 4 to be ccm
It was adjusted at 59, 458 and 460. i-type layer deposition chamber
-The pressure inside 418 is not adjusted so that it becomes 1.1 Torr.
The conductance valve opening shown was adjusted. Then R
F power supply 424 0.06 W / cm ³Set to bias
Apply to bar 428 to cause glow discharge, shutter
By opening 427, p / i buffer is placed on the RFi type layer.
Starting the layer preparation, a p / i buffer layer with a layer thickness of 15 nm
The RF power source 4
The output of 24 is cut off to prepare the p / i buffer layer 262.
finished. Close valves 464, 454, 465, 455
Si into the i-type layer deposition chamber 418 ₂H₆gas,
CH_FourStop the flow of gas for 2 minutes i-type layer deposition chamber
H into 418₂After continuing to flow the gas, the valve 453,
450 is closed and inside the i-type layer deposition chamber 418 and
1 x 10 inside the piping^-FiveEvacuated to Torr.

Next, the RF p-type layer 208 made of a-SiC is used.
In order to form the substrate, the gate valve 408 is opened into the transfer chamber 404 and the p-type layer deposition chamber 419 which have been evacuated by a vacuum exhaust pump (not shown) in advance, and the substrate 490 is transferred. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 412 and heated, and the inside of the p-type layer deposition chamber 419 was evacuated to a pressure of about 1 × 10 ⁻⁵ Torr by a vacuum exhaust pump (not shown).

The temperature of the substrate 490 should be 170 ° C.
Set the substrate heating heater 412 to stabilize the substrate temperature.
By the way, H₂Gas, SiH_Four/ H₂Gas, B₂H₆/ H₂
Gas, CH_FourValve 4 for depositing gas in deposition chamber 419
81, 471, 470, 482, 472, 483, 47
Operate 3, 484, 474 through the gas introduction pipe 469
Introduced. At this time, H₂Gas flow rate is 70scm, Si
H_Four/ H₂Gas flow rate is 0.5 sccm, B₂H₆/ H₂gas
Flow rate is 8 sccm, CH_FourGas flow rate is 0.3sccm
Mass flow controllers 476, 477,
The pressure in the deposition chamber 419 adjusted by 478 and 479.
Force not equal to 1.7 Torr, not shown
The opening of the sub valve was adjusted. The power of the RF power source 423
0.07W / cm³Set to, plasma forming cup 4
RF power is introduced to 21 to cause glow discharge and p /
forming an RF p-type layer on the i buffer layer 262,
RF power source when an RF p-type layer having a layer thickness of 10 nm is formed
To turn off the glow discharge and form the RF p-type layer 208
Finished. Valves 472, 482, 473, 483, 4
74, 484 closed and into p-type layer deposition chamber 419
SiH_Four/ H₂Gas, B ₂H₆/ H₂Gas, CH_FourGas flow
Turn off the gas for 2 minutes into the p-type layer deposition chamber 419.
₂After continuing to flow the gas, valves 471, 481, 47
Close 0 and H₂The inflow of hydrogen, and the p-type layer deposition chamber 4
1 × 10 inside 19 and gas piping^-FiveVacuum up to Torr
Exhausted.

Next, the gate valve 409 is opened into the unload chamber 405 which has been evacuated by a vacuum exhaust pump (not shown) in advance, the substrate 490 is transferred, and the leak valve (not shown) is opened to open the unload chamber 40.
Leaked 5. Next, ITO having a layer thickness of 70 nm was vacuum-deposited on the RF p-type layer 205 as a transparent conductive layer 212 by a vacuum vapor deposition method.

Next, a mask having comb-shaped holes is placed on the transparent conductive layer 212, and Cr (40 nm) / Ag (1000 n
m) / Cr (40 nm) comb-shaped collector electrode 213
Was vacuum deposited by the vacuum deposition method. This completes the production of the solar cell. We will call this solar cell (SC Ex 1),
Hydrogen plasma treatment conditions containing a trace amount of Group V element of the present invention, R
Fn type layer, RFn / i buffer layer, MWi type layer, RF
Table 1 shows the conditions for forming the p / i buffer layer and the RF p-type layer.
Shown in (1) and 1 (2).

Comparative Example 1 A solar cell (SC ratio 1) was produced under the same conditions as in Example 1 except that the hydrogen plasma treatment containing a trace amount of Group V element of the present invention was not performed. Seven solar cells (SC Ex 1) and (SC ratio 1) were produced, and the initial photoelectric conversion efficiency (photovoltaic power / incident optical power), vibration deterioration, light deterioration, and high temperature and high humidity when bias voltage was applied. Vibration deterioration and light deterioration in the environment were measured.

The initial photoelectric conversion efficiency can be obtained by placing the manufactured solar cell under AM1.5 (100 mW / cm ² ) light irradiation and measuring the VI characteristic. As a result of the measurement, the fill factor (FF) of the initial photoelectric conversion efficiency and the series resistance (Rs) of (SC ex 1) against (SC ratio 1)
And the characteristic unevenness was as follows. Fill factor Series Resistance Characteristic unevenness (SC Ex. 1) 1.16 times 0.89 times 0.83 times The vibration deterioration was measured with a solar cell whose initial photoelectric conversion efficiency was measured in advance at a humidity of 56% and a temperature of 26 ° C. Installed in a dark place of the
AM1.5 (100 mW / cm ² ) after adding for 0 hours
It was determined by the rate of decrease in photoelectric conversion efficiency under irradiation (photoelectric conversion efficiency after vibration deterioration test / initial photoelectric conversion efficiency).

The photodegradation was measured by setting a solar cell whose initial photoelectric conversion efficiency had been measured in advance in an environment of a humidity of 56% and a temperature of 26 ° C., and AM1.5 (100 mW / cm ² ) light for 550 hours. AM1.5 (100mW / c after irradiation)
m ² ) The decrease rate of the photoelectric conversion efficiency under irradiation (photoelectric conversion efficiency after photodegradation test / initial photoelectric conversion efficiency) was used. As a result of the measurement, the reduction rate of the photoelectric conversion efficiency after the photodegradation and the reduction rate of the photoelectric conversion efficiency after the vibration degradation of (SC ratio 1) to (SC ex. 1) were as follows.

[0108] We measured vibration deterioration and light deterioration under high temperature and high humidity environment with bias applied. Two solar cells whose initial photoelectric conversion efficiency was measured in advance were placed in a dark place with a humidity of 93% and a temperature of 86 ° C., and a forward bias voltage of 0.72 V was applied. The above vibration was applied to one of the solar cells to measure the vibration deterioration, and AM1.
The light deterioration was measured by irradiating light of No. 5. As a result of the measurement, the reduction rate of the photoelectric conversion efficiency after vibration deterioration and the reduction rate of the photoelectric conversion efficiency after photodegradation of (SC ratio 1) were as follows with respect to (SC ex. 1).

[0109] The state of delamination was observed using an optical microscope. Delamination was not observed in (SC Ex 1), but slight delamination was observed in (SC ratio 1). As described above, the solar cell of the present invention (SC Ex 1) has a fill factor, series resistance, characteristic unevenness, photodegradation characteristic, adhesiveness in the photoelectric conversion efficiency of the solar cell that is higher than that of the conventional solar cell (SC ratio 1). It was found that it has more excellent durability characteristics.

Example 2 The tandem solar cell of FIG. 1 was produced using the deposition apparatus shown in FIG. A reflection layer 201 and a reflection enhancement layer 20 prepared by the same method as in Example 1.
The base chamber 490 where the 2 is formed is the load chamber 40
1 was placed on the substrate transfer rail 413, and the inside of the load chamber 401 was evacuated to a pressure of about 1 × 10 ⁻⁵ Torr by a vacuum exhaust pump (not shown).

Next, the gate valve 406 was opened to carry the wafer into the transfer chamber 402 and the deposition chamber 417 which had been evacuated by a vacuum exhaust pump (not shown) in advance. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 410 and heated, and the inside of the deposition chamber 417 was evacuated by a vacuum exhaust pump (not shown) to a pressure of about 1 × 10 ⁻⁵ Torr.

Preparation for film formation was completed as described above.
After that, the RFn-type layer 203 made of μc-Si was formed.
To form an RFn-type layer made of μc-Si, H₂Moth
Gas through the gas introducing pipe 429 into the deposition chamber 417.
Introduced, H₂So that the gas flow rate is 300 sccm
Open valves 441, 431, and 430 to open the mass flow controller.
It was adjusted with the tracker 436. In the deposition chamber 417
Conductor (not shown) so that the pressure becomes 1.1 Torr
Adjusted with a closet valve. The temperature of the substrate 490 is 380 ° C
Set the heater for heating Kisaka 410 so that
When the temperature stabilizes, SiH_FourGas, PF₃/ H
₂(Dilution: 1%) Gas is deposited in the deposition chamber 417.
Gas by operating the valves 443, 433, 444, 434.
It was introduced through the inlet pipe 429. At this time, SiH_FourGas flow
The amount is 1.2 sccm, H₂Gas flow rate is 290sccm,
PF₃/ H₂(Dilution: 1%) Gas flow rate is 20 sccm
Mass flow controllers 438, 436,
439, and the pressure in the deposition chamber 417 is 1.
It was adjusted to be 1 Torr. RF power source 422 power
Power 0.06W / cm³Set to the plasma formation cup.
Introduce RF power to the 420 to cause glow discharge,
The formation of the RFn-type layer is started on the substrate, and the R thickness of 20 nm is applied.
When the Fn type layer is formed, turn off the RF power source
The discharge was stopped and the formation of the RF n-type layer 203 was completed. Heap
SiH into chamber 417_FourGas, PF₃/ H ₂Of gas
Stop the inflow for 4 minutes H into the deposition chamber₂Kept flowing gas
Later, H₂Stop the inflow of gas, and
1 x 10^-FiveEvacuated to Torr.

Next, an n / i buffer layer 251 made of a-Si was formed by the RFPCVD method. First, the transfer chamber 403 and the i-type layer deposition chamber 41 that have been evacuated by a vacuum exhaust pump (not shown) in advance.
8, the gate valve 407 was opened and the substrate 490 was transported. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 411 and heated, and the i-type layer deposition chamber 418 was evacuated to a pressure of about 1 × 10 ⁻⁵ Torr by a vacuum exhaust pump (not shown).

To prepare the n / i buffer layer 251, the substrate heating heater 411 is set so that the temperature of the substrate 490 becomes 360 ° C., and when the substrate is sufficiently heated, the valves 464, 454, 450, 463 are formed. , 453 are gradually opened to introduce Si ₂ H ₆ gas and H ₂ gas into the gas introduction pipe 4
It was made to flow into the i-type layer deposition chamber 418 through 49. At this time, the Si ₂ H ₆ gas flow rate was 2.5 sccm, and H ₂
The mass flow controllers 459 and 458 were adjusted so that the gas flow rate was 100 sccm. The pressure inside the i-type layer deposition chamber 418 was adjusted to 0.8 Torr by adjusting the opening of a conductance valve (not shown). Next, the RF power source 424 is set to 0.08 W / cm ³ , a bias rod 428 is applied to cause glow discharge, and a shutter 427 is opened to open an n-type layer on the RF n-type layer.
/ I buffer layer production was started and the layer thickness was 10 nm.
When the i buffer layer was produced, the RF glow discharge was stopped, the output of the RF power source 424 was cut off, and the production of the n / i buffer layer 251 was completed. By closing the valves 464 and 454, the flow of Si ₂ H ₆ gas into the i-type layer deposition chamber 418 is stopped, and H _{2 is} introduced into the i-type layer deposition chamber 418 for 2 minutes.
After continuing to flow ₂ gases, the valves 453 and 450 were closed, and the inside of the i-type layer deposition chamber 418 and the inside of the gas pipe were evacuated to 1 × 10 ⁻⁵ Torr.

Next, the MWi type layer 20 made of a-SiGe.
4 was formed by the MWPCVD method. To prepare the MWi type layer, the substrate heating heater 411 is set so that the temperature of the substrate 490 becomes 380 ° C., and when the substrate is sufficiently heated, the valves 461, 451, 450, 462,
452, 463, and 453 were gradually opened, and SiH ₄ gas, GeH ₄ gas, and H ₂ gas were caused to flow into the i-type layer deposition chamber 418 through the gas introduction pipe 449. At this time,
SiH ₄ gas flow rate is 43 sccm, GeH ₄ gas flow rate is 4
Mass flow controllers 456, 457, and 4 so that the flow rate of ₂ sccm and H ₂ gas is 150 sccm.
Adjusted at 58. The pressure inside the i-type layer deposition chamber 418 was adjusted to 5 mTorr by adjusting the opening of a conductance valve (not shown). Next, the RF power source 424 is turned on.
It was set to 60 W / cm ³ and applied to the bias rod 428. After that, the power of the MW power source (not shown) is changed to 0.25 W / c.
m ³ and the waveguide 426 and the microwave introduction window 4 are set.
25, the MW power is introduced into the i-type layer deposition chamber 418 to cause glow discharge, and the shutter 427 is opened to start the preparation of the MWi-type layer on the n / i buffer layer. When the mold layer was formed, the MW glow discharge was stopped, the output of the bias power source 424 was cut off, and the formation of the MWi type layer 204 was completed. Valve 451,
452 is closed and S into the i-type layer deposition chamber 418
The inflow of iH ₄ gas and GeH ₄ gas was stopped, and H ₂ gas was continued to flow into the i-type layer deposition chamber 418 for 2 minutes, then the valves 453 and 450 were closed, and the i-type layer deposition chamber 41
The inside of 8 and the inside of the gas pipe were evacuated to 1 × 10 ⁻⁵ Torr.

Next, the p / i buffer layer 261 made of a-Si was formed by the RFPCVD method. To prepare the p / i buffer layer 261, the temperature of the substrate 490 is set to 2
The substrate heating heater 411 was set to 50 ° C., and when the substrate was sufficiently heated, the valves 464 and 45
4, 450, 463, 453 are gradually opened and Si ₂ H ₆
Gas and H ₂ gas were caused to flow into the i-type layer deposition chamber 418 through the gas introduction pipe 449. At this time, the mass flow controllers 459 and 45 are controlled so that the Si ₂ H ₆ gas flow rate is 3 sccm and the H ₂ gas flow rate is 75 sccm.
Adjusted at 8. The pressure inside the i-type layer deposition chamber 418 was adjusted to 0.7 Torr by adjusting the opening of a conductance valve (not shown). Next, the RF power source 424 is set to 0.07 W / cm ³ , a bias rod 428 is applied to cause glow discharge, and a shutter 427 is opened to produce a p / i buffer layer 261 on the MWi type layer. When the p / i buffer layer having a layer thickness of 20 nm was produced, the RF glow discharge was stopped, the output of the RF power source 424 was cut off, and the production of the p / i buffer layer 261 was completed.
The valves 464 and 454 are closed to stop the flow of Si ₂ H ₆ gas into the i-type layer deposition chamber 418, and after the H ₂ gas is continuously flowed into the i-type layer deposition chamber 418 for 2 minutes,
The valves 453 and 450 are closed, and the i-type layer deposition chamber 4
The inside of 18 and the inside of the gas pipe were evacuated to 1 × 10 ⁻⁵ Torr.

Next, the RF p-type layer 205 made of a-SiC
In order to form the substrate, the gate valve 408 is opened into the transfer chamber 404 and the p-type layer deposition chamber 419 which have been evacuated by a vacuum exhaust pump (not shown) in advance, and the substrate 490 is transferred. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 412 and heated, and the inside of the p-type layer deposition chamber 419 was evacuated to a pressure of about 1 × 10 ⁻⁵ Torr by a vacuum exhaust pump (not shown).

The heater 412 for heating the substrate was set so that the temperature of the substrate 490 became 250 ° C., and when the substrate temperature became stable, H ₂ gas, SiH ₄ / H ₂ (dilution degree: 100
0ppm) gas, BF ₃ / H ₂ (dilution: 1000pp
m) gas, CH ₄ gas in the deposition chamber 419, valves 481, 471, 470, 482, 472, 483,
473, 484 and 474 were operated and introduced through the gas introduction pipe 469. At this time, the H ₂ gas flow rate is 60 scm,
SiH ₄ / H ₂ (dilution degree: 1000 ppm) gas flow rate 0.4 sccm, BF ₃ / H ₂ (dilution degree: 1000 pp
m) Gas flow rate is 8 sccm, CH ₄ gas flow rate is 0.3 s
Mass flow controller 476, so that it becomes ccm,
Adjusted by 477, 478, 479, the deposition chamber 41
The conductance valve opening (not shown) was adjusted so that the pressure inside 9 was 1.7 Torr. The power of the RF power source 423 is set to 0.07 W / cm ³ , RF power is introduced into the plasma forming cup 421 to cause glow discharge, and formation of the RF p-type layer on the p / i buffer layer is started. RF when the RF p-type layer having a layer thickness of 10 nm is formed
The power was turned off, the glow discharge was stopped, and the formation of the RF p-type layer 205 was completed. Valves 472, 482, 473, 48
3, 474 and 484 are closed to close the p-type layer deposition chamber 41.
The inflow of SiH ₄ / H ₂ gas, BF ₃ / H ₂ gas, and CH ₄ gas into the chamber 9 was stopped, and the p-type layer deposition chamber 419 was held for 3 minutes.
After continuously flowing H ₂ gas into the inside, valves 471, 48
1, 470 were closed to stop the inflow of H ₂ and the inside of the p-type layer deposition chamber 419 and the gas pipe were evacuated to 1 × 10 ⁻⁵ Torr.

Next, in order to perform the hydrogen plasma treatment containing a trace amount of group V element of the present invention, the transfer chamber 402 and the deposition chamber 417 are passed through the transfer chamber 403 which has been evacuated in advance by a vacuum exhaust pump (not shown).
The gate valves 408 and 407 were opened and conveyed. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 410 and heated, and the inside of the deposition chamber 417 was evacuated by a vacuum exhaust pump (not shown) to a pressure of about 1 × 10 ⁻⁵ Torr.

Next, a hydrogen group containing minute amount of group V element of the present invention
Zuma treatment was performed under the conditions shown in Table 2 (1). Trace amount of the present invention
To perform the hydrogen plasma treatment containing a group V element, a group V element
PF as contained gas₃/ H₂(Dilution: 1%) Gas, Siri
SiH as gas containing carbon atoms_FourGas, H₂Gas deposition
Introduced into the chamber 417 through a gas introduction pipe 429,
H₂Valve 4 so that the gas flow rate is 1100 sccm
41, 431, 430 open, mass flow controller
-Adjusted with 436. Group V element-containing gas PF ₃Gas
All H₂Valve 4 to be 0.4% to the gas flow rate
Open 43 and 433 with the mass flow controller 439
It was adjusted. Silicon atom-containing gas is SiH_FourIs all H₂Moth
Valve 443, so that the flow rate becomes 0.03%.
Open 433 and adjust with the mass flow controller 438
It was Pressure in the deposition chamber 417 is 0.013 Tor
Adjust with a conductance valve (not shown) so that it becomes r
It was Heat the substrate so that the temperature of the substrate 490 becomes 250 ° C.
Where the heater 410 is set and the substrate temperature is stable
Then, the VHF power of the VHF power source (not shown) is 0.07 W / c.
m³, VHF power is introduced, and plasma formation power is set.
A glow discharge is caused to occur in the lamp 420 for 4 minutes of the present invention.
A hydrogen plasma treatment containing a trace amount of Group V element was performed. afterwards
Turn off VHF power to stop glow discharge and deposit chamber
-PF into 417₃/ H₂, SiH_FourStop gas inflow
To the deposition chamber 417 for 4 minutes.₂Flushing gas
After continuing, H₂The gas flow was stopped and the deposition chamber 4
1 × 10 inside 17 and gas pipe^-FiveVacuum up to Torr
Exhausted.

To form the RFn-type layer made of μc-Si, H ₂ gas was introduced into the deposition chamber 417 through the gas introduction pipe 429, and the H ₂ gas flow rate was 200 sccm.
The valves 441, 431, and 430 were opened so as to be set, and the mass flow controller 436 adjusted. The conductance valve (not shown) was used to adjust the pressure in the deposition chamber 417 to 1.1 Torr. The substrate heating heater 410 is set so that the temperature of the substrate 490 becomes 250 ° C., and when the substrate temperature becomes stable, SiH ₄ gas,
PF ₃ / H ₂ (dilution: 1%) gas is deposited in chamber 41
The valves 443, 433, 444, and 434 were operated into the chamber 7 and introduced through the gas introduction pipe 429. At this time, SiH
₄ gas flow rate is 1.5 sccm, H ₂ gas flow rate is 280 sc
cm, PF ₃ / H ₂ (dilution degree: 1%) gas flow rate is 25 sc
Mass flow controllers 438, 4 to be cm
The pressure inside the deposition chamber 417 was adjusted to 1.1 Torr. RF power supply 42
2 was set to 0.04 W / cm ³ , RF power was introduced into the plasma-forming cup 420 to cause glow discharge, and formation of the RFn-type layer on the RFp-type layer was started. When the RFn-type layer was formed, the RF power supply was turned off to stop the glow discharge, and the formation of the RFn-type layer 206 was completed. SiH ₄ gas into the deposition chamber 417, PF ₃
/ H ₂ stop the flow of gas, 2 minutes, after which continued to flow H ₂ gas into the deposition chamber, the flow of H ₂ is also stopped, and vacuum evacuating the deposition chamber and the gas in the pipe up to 1 × 10 ^-5 Torr.

Next, an n / i buffer layer 252 made of a-SiC was formed by the RFPCVD method. First, the transfer chamber 403 and the i-type layer deposition chamber 4 which have been evacuated by a vacuum exhaust pump (not shown) in advance.
The gate valve 407 was opened into the substrate 18 and the substrate 490 was transported. The back surface of the substrate 490 is brought into close contact with the substrate heating heater 411 to heat it, and the pressure inside the i-type layer deposition chamber 418 is adjusted to about 1 × 10 ⁻⁵ Torr by a vacuum exhaust pump (not shown).
It was evacuated until.

To prepare the n / i buffer layer 252, the substrate heating heater 411 is set so that the temperature of the substrate 490 becomes 250 ° C., and when the substrate is sufficiently heated, the valves 464, 454, 450, 463. , 453,
465 and 455 were gradually opened, and Si ₂ H ₆ gas, H ₂ gas, and CH ₄ gas were caused to flow into the i-type layer deposition chamber 418 through the gas introduction pipe 449. At this time, the Si ₂ H ₆ gas flow rate was 0.4 sccm, and the H ₂ gas flow rate was 90 sccc.
The mass flow controllers 459, 458, and 460 adjusted the flow rates of m and CH ₄ gas to be 0.2 sccm.

The pressure in the i-type layer deposition chamber 418 is
Conductance bar not shown so as to be 1.0 Torr
The opening of the lube was adjusted. Next, set the RF power source 424 to 0.0
6 W / cm³To the bias rod 428,
By causing a low discharge and opening the shutter 427
Starting the fabrication of the n / i buffer layer on the RF n-type layer,
When an n / i buffer layer having a thickness of 10 nm was prepared, R
Stop the F glow discharge, turn off the output of the RF power source 424, n
/ I buffer layer 252 was completed. Valve 46
4, 454, 465, 455 are closed and the i-type layer deposition cha is
Si into the chamber 418₂H₆Gas, CH_FourThe inflow of gas
Stop and hold for 2 minutes in the i-type layer deposition chamber 418₂gas
And then the valves 453 and 450 are closed and the i-type
1 × 10 in the layer deposition chamber 418 and the gas pipe
^-FiveEvacuated to Torr. Next, R consisting of a-Si
The Fi type layer 207 was formed by the RFPCVD method. R
To prepare the Fi type layer, the temperature of the substrate 490 is 200 ° C.
Set the substrate heating heater 411 so that
Is heated sufficiently, valves 464, 454, 45
0, 463, 453 gradually open, Si₂H₆Gas, H
₂Gas is introduced into the i-type layer deposition chamber through the gas introduction pipe 449.
-It was made to flow into 418. At this time, Si ₂H₆Gas flow rate
2 sccm, H₂So that the gas flow rate is 85 sccm
Adjust with each mass flow controller 459, 458
did. The pressure inside the i-type layer deposition chamber 418 is 0.6.
The conductance valve (not shown) is set to Torr.
The opening was adjusted. Next, set the RF power source 424 to 0.07 W /
cm³To the bias rod 428, the glow is released.
N / i by generating electricity and opening the shutter 427
Starting the preparation of the RFi type layer on the buffer layer 252,
When an i-type layer with a thickness of 110 nm was produced, RF glow emission was performed.
Turn off the power, turn off the output of the RF power supply 424, and turn on the RFi type layer 2
The production of 07 was completed. Close valves 464, 454,
Si into i-type layer deposition chamber 418₂H₆Gas inflow
Stop for 2 minutes into the i-type layer deposition chamber 418₂Moth
After continuing to flow the gas, the valves 453 and 450 are closed and i
1 × 1 inside the mold layer deposition chamber 418 and inside the gas pipe
0^-FiveEvacuated to Torr.

Next, a p / i buffer composed of a-SiC
The layer 262 was formed by the RFPCVD method. p / i
The temperature of the substrate 490 is required to form the stuffer layer 262.
Set the heater 411 for heating the substrate to 200 ° C.
Then, when the substrate is sufficiently heated, the valves 464 and 45 are
4, 450, 463, 453, 465, 455 gradually
Open, Si₂H₆Gas, H₂Gas, CH_FourGas introduction
Flow into i-type layer deposition chamber 418 through pipe 449
Let At this time, Si₂H₆Gas flow rate is 0.4 sccm,
H₂Gas flow rate is 65 sccm, CH_FourGas flow rate is 0.3s
Each mass flow controller 4 to be ccm
It was adjusted at 59, 458 and 460. i-type layer deposition chamber
-The pressure inside 418 is not adjusted so that it becomes 1.1 Torr.
The conductance valve opening shown was adjusted. Then R
F power supply 424 0.06 W / cm ³Set to bias
Apply to bar 428 to cause glow discharge, shutter
By opening 427, p / i buffer is placed on the RFi type layer.
Starting the layer preparation, a p / i buffer layer with a layer thickness of 15 nm
The RF power source 4
The output of 24 is cut off to prepare the p / i buffer layer 262.
finished. Close valves 464, 454, 465, 455
Si into the i-type layer deposition chamber 418 ₂H₆gas,
CH_FourStop the flow of gas for 2 minutes i-type layer deposition chamber
H into 418₂After continuing to flow the gas, the valve 453,
450 is closed and inside the i-type layer deposition chamber 418 and
1 x 10 inside the piping^-FiveEvacuated to Torr.

Next, the RF p-type layer 208 made of a-SiC
In order to form the substrate, the gate valve 408 is opened into the transfer chamber 404 and the p-type layer deposition chamber 419 which have been evacuated by a vacuum exhaust pump (not shown) in advance, and the substrate 490 is transferred. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 412 and heated, and the inside of the p-type layer deposition chamber 419 was evacuated to a pressure of about 1 × 10 ⁻⁵ Torr by a vacuum exhaust pump (not shown).

The heater 412 for heating the substrate was set so that the temperature of the substrate 490 became 170 ° C., and when the substrate temperature became stable, H ₂ gas, SiH ₄ / H ₂ (dilution degree: 100
0ppm) gas, BF ₃ / H ₂ (dilution: 1000pp
m) gas, CH ₄ gas in the deposition chamber 419, valves 481, 471, 470, 482, 472, 483,
473, 484 and 474 were operated and introduced through the gas introduction pipe 469. At this time, the H ₂ gas flow rate is 70 scm,
SiH ₄ / H ₂ (dilution degree: 1000 ppm) gas flow rate 0.4 sccm, BF ₃ / H ₂ (dilution degree: 1000 pp
m) Gas flow rate is 7 sccm, CH ₄ gas flow rate is 0.3 s
Mass flow controller 476, so that it becomes ccm,
Adjusted by 477, 478, 479, the deposition chamber 41
The conductance valve opening (not shown) was adjusted so that the pressure inside 9 was 1.7 Torr. The power of the RF power source 423 was set to 0.07 W / cm ³ , RF power was introduced into the plasma forming cup 421 to cause glow discharge, and formation of the RF p-type layer on the p / i buffer layer 262 was started. When the RFp type layer having a layer thickness of 10 nm is formed, the RF power is turned off to stop the glow discharge, and the RFp type layer 20 is formed.
The formation of No. 8 is completed. Valves 472, 482, 473, 4
83, 474, 484 closed and p-type layer deposition chamber 4
SiH ₄ / H ₂ gas, BF ₃ / H ₂ gas, CH ₄ into 19
The gas flow is stopped and the p-type layer deposition chamber 41 is held for 2 minutes.
After continuously flowing H ₂ gas into the valve 9, the valves 471, 48
1, 470 are closed to stop the inflow of H ₂ and the inside of the p-type layer deposition chamber 419 and the gas pipe is 1 × 10 ⁻⁵ Torr.
It was evacuated to.

Next, the gate valve 409 is opened into the unload chamber 405 which has been evacuated by a vacuum exhaust pump (not shown) in advance, the substrate 490 is transferred, and the leak valve (not shown) is opened to open the unload chamber 40.
Leaked 5. Next, ITO having a layer thickness of 70 nm was vacuum-deposited on the RF p-type layer 208 as a transparent conductive layer 212 by a vacuum vapor deposition method.

Next, a mask having comb-shaped holes is placed on the transparent conductive layer 212, and Cr (40 nm) / Ag (1000 n
m) / Cr (40 nm) comb-shaped collector electrode 213
Was vacuum deposited by the vacuum deposition method. This completes the production of the solar cell. This solar cell will be called (SC Ex 2),
Hydrogen plasma treatment conditions containing a trace amount of Group V element of the present invention, R
Table 2 shows the formation conditions of the Fn type layer, the n / i buffer layer, the MWi type layer, the p / i buffer layer, the RFi type layer, and the RFp type layer.
It shows in (1) -2 (2).

Comparative Example 2 A solar cell (SC ratio 2) was manufactured under the same conditions as in Example 2 except that the hydrogen plasma treatment containing a trace amount of Group V element of the present invention was not performed. Six solar cells (SC Ex 2) and (SC ratio 2) were produced, and the initial photoelectric conversion efficiency (photovoltaic power / incident optical power), vibration deterioration, light deterioration, and high temperature and high humidity when bias voltage was applied. Vibration deterioration and light deterioration in the environment were measured.

The initial photoelectric conversion efficiency can be obtained by placing the manufactured solar cell under AM1.5 (100 mW / cm ² ) light irradiation and measuring the VI characteristic. As a result of the measurement, with respect to (SC ratio 2), the fill factor (FF) of the initial photoelectric conversion efficiency of (SC Ex 2), the series resistance (R)
s) and characteristic unevenness are as follows. Fill factor Series Resistance characteristic unevenness (SC Ex 2) 1.18 times 0.88 times 0.81 times For the measurement of vibration deterioration, the solar cell whose initial photoelectric conversion efficiency was measured in advance had a humidity of 56% and a temperature of 28 ° C. Installed in a dark place of the
AM1.5 (100 mW / cm ² ) after adding for 0 hours
It was determined by the rate of decrease in photoelectric conversion efficiency under irradiation (photoelectric conversion efficiency after vibration deterioration test / initial photoelectric conversion efficiency).

Photodegradation was measured by setting a solar cell whose initial photoelectric conversion efficiency had been measured in advance in an environment of a humidity of 56% and a temperature of 28 ° C., and applying AM1.5 (100 mW / cm ² ) light for 550 hours. AM1.5 (100mW / c after irradiation)
m ² ) The decrease rate of the photoelectric conversion efficiency under irradiation (photoelectric conversion efficiency after photodegradation test / initial photoelectric conversion efficiency) was used. As a result of the measurement, the reduction rate of the photoelectric conversion efficiency after the photodegradation and the reduction rate of the photoelectric conversion efficiency after the vibration degradation of (SC ratio 2) to (SC ex 2) were as follows.

[0133] We measured vibration deterioration and light deterioration under high temperature and high humidity environment with bias applied. Two solar cells whose initial photoelectric conversion efficiency was measured in advance were placed in a dark place with a humidity of 91% and a temperature of 82 ° C., and 0.71 V was applied as a forward bias voltage. The above vibration was applied to one of the solar cells to measure the vibration deterioration, and AM1.
The light deterioration was measured by irradiating light of No. 5. As a result of the measurement, the reduction rate of the photoelectric conversion efficiency after the vibration deterioration and the reduction rate of the photoelectric conversion efficiency after the light deterioration of (SC ratio 2) were as follows with respect to (SC ex. 2).

[0134] The state of delamination was observed using an optical microscope. Delamination was not observed in (SC Ex. 2), but slight delamination was observed in (SC ratio 2). As described above, the solar cell of the present invention (SC Ex 2) has a fill factor, series resistance, characteristic unevenness, photodegradation characteristic, adhesiveness in the photoelectric conversion efficiency of the solar cell that is higher than that of the conventional solar cell (SC ratio 2). It was found that it has more excellent durability characteristics.

(Example 3) The triple type solar cell of FIG. 2 was produced using the deposition apparatus shown in FIG. A reflective layer 301 and a reflective enhancement layer 30 prepared by the same method as in Example 1.
The base chamber 490 where the 2 is formed is the load chamber 40
1 was placed on the substrate transfer rail 413, and the inside of the load chamber 401 was evacuated to a pressure of about 1 × 10 ⁻⁵ Torr by a vacuum exhaust pump (not shown).

Next, the gate valve 406 was opened to carry into the transfer chamber 402 and the deposition chamber 417 which had been evacuated by a vacuum exhaust pump (not shown) in advance. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 410 and heated, and the inside of the deposition chamber 417 was evacuated by a vacuum exhaust pump (not shown) to a pressure of about 1 × 10 ⁻⁵ Torr.

After the preparation for film formation is completed as described above, R consisting of μc-Si is prepared by the same method as in Example 1.
The Fn type layer 303 was formed. Next, the gate valve 40 is introduced into the transfer chamber 403 and the deposition chamber 418 which have been evacuated by a vacuum exhaust pump (not shown) in advance.
7 was opened and conveyed. The back surface of the substrate 490 is brought into close contact with the heater 411 for heating the substrate to heat it, and the deposition chamber 418
The inside pressure is about 1 × 10 ^-5 by a vacuum exhaust pump (not shown).
It was evacuated to Torr.

Then, by the same method as in the first embodiment, aS
n / i buffer layer 351 made of i, MWi type layer 304 made of a-SiGe, p / i buffer layer 361 made of a-Si, and RF p type layer 305 made of a-SiC.
Were sequentially formed by the RFPCVD method and the MWPCVD method. Next, in order to perform the hydrogen plasma treatment containing a trace amount of Group V element of the present invention, the substrate 4 was processed by the same method as in Example 1.
90 was transported into the deposition chamber 418.

Next, a hydrogen group containing minute amount of group V element of the present invention
Zuma treatment was performed under the conditions shown in Table 3 (1). Trace amount of the present invention
To perform the hydrogen plasma treatment containing a group V element, a group V element
PH as contained gas₃/ H₂(Dilution: 10%) Gas, shi
SiCl as gas containing recon atom₂H₂/ He (dilution
Degree: 1%) Gas, H₂Gas into the deposition chamber 418
It is introduced through the gas introduction pipe 449, and H₂Gas flow rate 120
Valves 463, 453, 450 so that it becomes 0 sccm
Was opened and adjusted with the mass flow controller 458.
Group V element-containing gas PH₃Gas is all H₂For gas flow rate
Open the valves 468 and 466 so that the ratio becomes 2.0%.
It adjusted with the flow controller 467. Silicon atom
Contained gas is SiCl₂H₂/ He (dilution: 1%) is the total
H₂SiCl for gas flow rate₂H₂Gas ratio is 0.0
Open the valve (not shown) so that it reaches 2%.
Adjusted with the low controller. Deposition chamber 418
Set the internal pressure to 0.008 Torr (not shown).
Adjusted with the inductance valve. The temperature of the substrate 490 is 3
Set the substrate heating heater 411 to be 00 ° C
However, when the substrate temperature is stable, the MW power supply (not shown)
Electric power 0.12W / cm ³To the waveguide 426 and
I-type layer deposition chamber through microwave introduction window 425
-Introducing MW power into 418 to cause glow discharge,
By opening the shutter 427, a minute amount of the present invention for 4 minutes
A hydrogen plasma treatment containing a Group V element was performed. Then MW
Turn off the power, stop the glow discharge, and set the deposition chamber 41.
PH into 8₃/ H₂Gas, SiCl₂H₂/ He gas flow
Turn off the gas for 4 minutes into the deposition chamber 418.₂gas
After continuing to flow, H₂Stop the gas inflow,
1 × 10 inside the bar 418 and gas pipe^-FiveTorr
It was evacuated.

Then, in the same manner as in Example 1, μc-
RF n-type layer 306 made of Si, n / made of a-Si
i buffer layer 352, MWi type layer 307 made of a-SiGe, p / i buffer layer 36 made of a-Si
2. The RF p-type layer 308 made of a-SiC is RFPCV
The layers were sequentially formed by the D method and the MWPCVD method. Next, Table 3 (2) shows the hydrogen plasma treatment containing a trace amount of Group V element of the present invention.
It went on condition of. To carry out the hydrogen plasma treatment containing a trace amount of Group V element of the present invention, PH _{3 is used} as a Group V element containing gas.
/ H ₂ (dilution: 10%) gas, SiH ₄ gas as a silicon atom-containing gas, and H ₂ gas are introduced into the deposition chamber 417 through a gas introduction pipe 429, and the H ₂ gas flow rate is 1
Valves 441, 431, 4 to 300 sccm
30 was opened, and it adjusted with the mass flow controller 436. The mass flow controller 439 is opened by opening the valves 444 and 434 so that the group V element-containing gas PH ₃ gas may change from 2.5% to 0.2% with respect to the total H ₂ gas flow rate.
I adjusted it with. For the silicon atom-containing gas, the valves 443 and 433 are opened so that the SiH ₄ gas is 0.04% of the total H ₂ gas flow rate, and the mass flow controller 438 is used.
I adjusted it with. The pressure in the deposition chamber 417 is 0.8T
The conductance valve (not shown) was used to adjust the value to orr. The substrate heating heater 410 is set so that the temperature of the substrate 490 becomes 250 ° C., and when the substrate temperature is stable, the power of the RF power source 424 is set to 0.05 W / cm ³ , the RF power is introduced, and plasma is supplied. Forming cup 42
Glow discharge is generated in 0 and the trace amount V of the present invention is used for 3 minutes.
A hydrogen plasma treatment containing a group element was performed. After that, the RF power supply is turned off, the glow discharge is stopped, the flow of PH ₃ / H ₂ gas and SiH ₄ gas into the deposition chamber 417 is stopped, and H ₂ gas is continuously flowed into the deposition chamber 417 for 3 minutes. The inflow of H ₂ gas was also stopped, and the inside of the deposition chamber 417 and the inside of the gas pipe were evacuated to 1 × 10 ⁻⁵ Torr.

Then, in the same manner as in Example 1, μc-
RF n-type layer 309 made of Si, n made of a-SiC
/ I buffer layer 353, RFi type layer 310 made of a-Si, p / i buffer layer 36 made of a-SiC
3, RFpV layer 311 made of a-SiC
The layers were sequentially formed by the D method. Next, on the RF p-type layer 311, as a transparent conductive layer 312, ITO having a layer thickness of 70 nm was vacuum deposited by a vacuum deposition method.

Next, a mask having comb-shaped holes is placed on the transparent conductive layer 312, and Cr (40 nm) / Ag (1000 n
m) / Cr (40 nm) comb-shaped collector electrode 313
Was vacuum deposited by the vacuum deposition method. This completes the production of the solar cell. We will call this solar cell (SC Ex 3),
Hydrogen plasma treatment conditions containing a trace amount of Group V element of the present invention, R
Table 3 shows the formation conditions of the Fn type layer, the n / i buffer layer, the MWi type layer, the p / i buffer layer, the RFi type layer, and the RFp type layer.
It shows in (1) -3 (3).

Comparative Example 3 A solar cell (SC ratio 3) was produced under the same conditions as in Example 3 except that the trace amount Group V element-containing hydrogen plasma treatment of the present invention was not performed. Six solar cells (SC Ex 3) and (SC ratio 3) each were produced, and the initial photoelectric conversion efficiency (photovoltaic power / incident optical power), vibration deterioration, light deterioration, high temperature and high humidity environment when bias voltage was applied. The vibration deterioration, the light deterioration, and the reverse bias voltage application characteristics were measured.

The initial photoelectric conversion efficiency can be obtained by placing the manufactured solar cell under AM1.5 (100 mW / cm ² ) light irradiation and measuring the VI characteristic. As a result of the measurement, the fill factor (FF) of the initial photoelectric conversion efficiency and the series resistance (Rs) of (SC Ex 3) against (SC ratio 3)
And the characteristic unevenness was as follows. Fill factor Series Resistance Characteristic unevenness (SC ratio 3) 1.19 times 0.88 times 0.80 times The vibration deterioration was measured with a solar cell whose initial photoelectric conversion efficiency was measured in advance at a humidity of 56% and a temperature of 27 ° C. Installed in a dark place of the
AM1.5 (100 mW / cm ² ) after adding for 0 hours
It was determined by the rate of decrease in photoelectric conversion efficiency under irradiation (photoelectric conversion efficiency after vibration deterioration test / initial photoelectric conversion efficiency).

Photodegradation was measured by setting a solar cell whose initial photoelectric conversion efficiency had been measured in advance in an environment of a humidity of 56% and a temperature of 27 ° C., and AM1.5 (100 mW / cm ² ) light for 550 hours. AM1.5 (100mW / c after irradiation)
m ² ) The decrease rate of the photoelectric conversion efficiency under irradiation (photoelectric conversion efficiency after photodegradation test / initial photoelectric conversion efficiency) was used. As a result of the measurement, the reduction rate of the photoelectric conversion efficiency after the photodegradation and the reduction rate of the photoelectric conversion efficiency after the vibration degradation of (SC ratio 3) to (SC ex 3) were as follows.

[0146] We measured vibration deterioration and light deterioration under high temperature and high humidity environment with bias applied. Two solar cells whose initial photoelectric conversion efficiency was measured in advance were placed in a dark place with a humidity of 92% and a temperature of 80 ° C., and 0.71 V was applied as a forward bias voltage. The above vibration was applied to one solar cell to measure vibration deterioration, and AM1.5 was applied to the other solar cell.
Then, the light deterioration was measured.

As a result of the measurement, for (SC Ex 3), (S
The reduction rate of the photoelectric conversion efficiency after vibration deterioration of C ratio 3) and the reduction rate of the photoelectric conversion efficiency after light deterioration were as follows. For the measurement of the reverse bias voltage application characteristic, the solar cell whose initial photoelectric conversion efficiency was measured in advance had a humidity of 54% and a temperature of 8%.
Install in a dark place at 1 ℃, reverse bias voltage 5.0V,
After applying for 100 hours, AM1.5 (100 mW / cm
² ) The photoelectric conversion efficiency under irradiation was measured, and the reduction rate (photoelectric conversion efficiency after application of reverse bias voltage / initial photoelectric conversion efficiency) was used.

As a result of the measurement, for (SC Ex 3), (S
The reduction rate of the C ratio 3) after applying the reverse bias voltage was as follows. (SC ratio 3) 0.84 times The state of layer delamination was observed using an optical microscope. Delamination was not observed in (SC Ex 3), but slight delamination was observed in (SC ratio 3).

As described above, the solar cell of the present invention (SC Ex 3) has a curvilinear factor in photoelectric conversion efficiency of the solar cell, series resistance, characteristic unevenness, and photodegradation characteristics, which are higher than those of the conventional solar cell (SC ratio 3). It was found that the adhesiveness, the durability, and the reverse bias voltage application characteristic were more excellent. (Example 4) Similar to Example 3, the hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 4 (1) using the deposition apparatus shown in FIG. The triple solar cell shown in FIG. 2 was manufactured. Table 4 (1) shows the conditions for hydrogen plasma treatment containing a trace amount of Group V element, and Table 4 (2) shows the conditions for producing a triple solar cell.

The triple solar cell thus produced was evaluated in the same manner as in Example 3. The results are shown in Table 4 (3).
The hydrogen flow rate of the hydrogen plasma treatment containing a trace amount of Group V element of the present invention is 1 to the fill factor in the photoelectric conversion efficiency of the solar cell, the characteristic unevenness, the photodegradation characteristic, the series resistance characteristic, the durability, and the reverse bias voltage application characteristic. 2000 sccm was found to be a suitable flow rate.

(Embodiment 5) Similar to Embodiment 3, the hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 5 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3. Table 5 (1) shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
Table 5 (2) shows the conditions for producing the triple solar cell.

In the same manner as in Example 3, the produced triple type solar cells were evaluated for the price. The results are shown in Table 5 (3).
Even if the input power of the hydrogen plasma treatment containing a trace amount of group V element of the present invention is changed from the RF power supply of Example 4 to the VHF power supply, the fill factor in the photoelectric conversion efficiency of the solar cell, characteristic unevenness, photodegradation characteristics, series resistance characteristics , Durability, reverse bias voltage application characteristics, hydrogen flow rate is 1 ~ 2000scc
It has been found that m is a suitable flow rate.

Example 6 As in Example 3, the hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 6 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3. Table 6 (1) shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
Table 6 (2) shows the conditions for producing the triple solar cell.

The triple solar cell thus prepared was evaluated in the same manner as in Example 3. The results are shown in Table 6 (3).
The amount of the Group V element-containing gas added to the hydrogen gas in the trace amount Group V element-containing hydrogen plasma treatment of the present invention is determined by the fill factor in the photoelectric conversion efficiency of the solar cell, characteristic unevenness, photodegradation characteristics, and series resistance. It has been found that the preferable range of the characteristics, durability, and reverse bias voltage application characteristic is 0.05% to 3%.

(Embodiment 7) Similar to Embodiment 3, hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 7 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3. Table 7 (1) shows the treatment conditions for hydrogen plasma containing a group V element.
Table 7 (2) shows the conditions for manufacturing the ripple-type solar cell.

The triple solar cell thus produced was evaluated in the same manner as in Example 3. The results are shown in Table 7 (3).
The addition amount of the group V element-containing gas added to the hydrogen gas of the hydrogen plasma treatment containing a minute amount of group V element of the present invention is the same as that of the solar cell even when the input power is changed from the RF power supply of Example 6 to the VHF power supply. It was found that in the photoelectric conversion efficiency, the fill factor, the characteristic unevenness, the photodegradation characteristic, the series resistance characteristic, the durability, and the reverse bias voltage application characteristic are preferably in the range of 0.05% to 3%.

(Embodiment 8) Similar to Embodiment 3, hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 8 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3. Table 8 (1) shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
Table 8 (2) shows conditions for producing the triple solar cell.

The triple solar cell thus prepared was evaluated in the same manner as in Example 3. The results are shown in Table 8 (3).
The addition amount of the group V element-containing gas added to the hydrogen gas of the hydrogen plasma treatment containing a small amount of group V element of the present invention is the same as that of the solar cell even when the input power is changed from the RF power source of Example 6 to the MW power source. It was found that the preferable range of the fill factor, unevenness of characteristics, photodegradation characteristics, series resistance characteristics, durability, and reverse bias voltage application characteristics in the photoelectric conversion efficiency is 0.05% to 3%.

(Embodiment 9) As in Embodiment 3, the hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 9 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3. Table 9 (1) shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
Table 9 (2) shows the conditions for producing the triple solar cell.

The triple solar cell thus produced was evaluated in the same manner as in Example 3. The results are shown in Table 9 (3).
The addition amount of the silicon atom-containing gas added to the hydrogen gas in the hydrogen plasma treatment containing a trace amount of Group V element of the present invention depends on the fill factor in the photoelectric conversion efficiency of the solar cell, characteristic unevenness, photodegradation characteristic, series resistance characteristic, In terms of durability and reverse bias voltage application characteristics, it was found that the preferable range is 0.001% to 0.1%.

(Embodiment 10) Similar to Embodiment 3, hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 10 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3.
Table 10 shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
In (1), Table 10 shows the production conditions of the triple solar cell.
It shows in (2).

The produced ripple-type solar cell was evaluated in the same manner as in Example 3. The results are shown in Table 10 (3). The amount of the silicon atom-containing gas added to the hydrogen gas in the hydrogen plasma treatment containing a trace amount of Group V element of the present invention is
Even when the applied power was changed from the RF power supply of Example 9 to the VHF power supply, the fill factor, characteristic unevenness, photodegradation characteristics, series resistance characteristics, durability, and reverse bias voltage application characteristics of the photoelectric conversion efficiency of the solar cell were 0. 001% to 0.1%
Was found to be the preferred range.

(Embodiment 11) Similar to Embodiment 3, hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 11 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3.
Table 11 shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
In (1), Table 11 shows the manufacturing conditions of the ripple-type solar cell.
It shows in (2).

The triple solar cell thus produced was evaluated in the same manner as in Example 3. The results are shown in Table 11 (3). The amount of the silicon atom-containing gas added to the hydrogen gas in the hydrogen plasma treatment containing a trace amount of Group V element of the present invention is
Even when the applied power was changed from the RF power supply of Example 9 to the MW power supply, the fill factor, characteristic unevenness, photodegradation characteristics, series resistance characteristics, durability, and reverse bias voltage application characteristics of the photoelectric conversion efficiency of the solar cell were 0. 001% to 0.1%
Was found to be the preferred range.

(Embodiment 12) As in Embodiment 3, using the deposition apparatus shown in FIG. 3, hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 12 (1). The triple type solar cell of FIG. 2 was produced in the same manner as in 3.
Table 12 shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
Table 1 shows the manufacturing conditions of the triple type solar cell in (1).
It shows in (2).

The triple solar cell thus prepared was evaluated in the same manner as in Example 3. The results are shown in Table 12 (3). The pressure of the hydrogen plasma treatment containing a trace amount of Group V element of the present invention is, when an RF power source is used for input power, a fill factor, a characteristic unevenness, a photodegradation characteristic, a series resistance characteristic, a durability in a photoelectric conversion efficiency of a solar cell, It was found that in the reverse bias voltage application characteristic, 0.05 Torr to 10 Torr is a preferable range.

(Embodiment 13) As in Embodiment 3, using the deposition apparatus shown in FIG. 3, the trace amount group V element-containing hydrogen plasma treatment of the present invention was performed twice under the conditions of Table 13 (1). The triple type solar cell of FIG. 2 was produced in the same manner as in 3.
Table 13 shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
Table 1 shows the manufacturing conditions of the triple type solar cell in (1).
It shows in (2).

The produced ripple-type solar cell was evaluated in the same manner as in Example 3. The results are shown in Table 13 (3). The pressure of the hydrogen plasma treatment containing a trace amount of group V element of the present invention is, when a VHF power source is used for input power, a fill factor, a characteristic unevenness, a photodegradation characteristic, a series resistance characteristic, a durability in a photoelectric conversion efficiency of a solar cell, It was found that in the reverse bias voltage application characteristic, 0.0001 Torr to 1 Torr is a preferable range.

(Embodiment 14) Similar to Embodiment 3, hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 14 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3.
Table 14 shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
In (1), Table 14 shows the manufacturing conditions of the triple solar cell.
It shows in (2).

The triple solar cell thus produced was evaluated in the same manner as in Example 3. The results are shown in Table 14 (3). The pressure of the trace amount group V element-containing hydrogen plasma treatment of the present invention is, when an MW power source is used for input power, a fill factor in photoelectric conversion efficiency of a solar cell, characteristic unevenness, photodegradation characteristic, series resistance characteristic, durability, Reverse bias voltage application characteristics from 0.0001 Torr to 0.01 To
It has been found that rr is in the preferred range.

(Example 15) [0171] Similar to Example 3, hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice using the deposition apparatus shown in Fig. 3 under the conditions of Table 15 (1). The triple type solar cell of FIG. 2 was produced in the same manner as in 3.
Table 15 shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
Table 15 shows the manufacturing conditions of the triple type solar cell in (1).
It shows in (2).

The triple solar cell thus prepared was evaluated in the same manner as in Example 3. The results are shown in Table 15 (3). The input power density (electric energy) of the hydrogen plasma treatment containing a trace amount of Group V element of the present invention is a fill factor in the photoelectric conversion efficiency of the solar cell when an RF power source is used for the input power,
0.01W / cm ^{3 in} characteristic unevenness, photodegradation characteristics, series resistance characteristics, durability, reverse bias voltage application characteristics
Therefore, it was found that 1.0 W / cm ³ is a preferable range.

(Example 16) Similar to Example 3, hydrogen plasma treatment containing a trace amount of group V element of the present invention was performed twice under the conditions of Table 16 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3.
Table 16 shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
Table 1 shows the manufacturing conditions of the triple solar cell in (1).
It shows in (2).

The triple solar cell thus prepared was evaluated in the same manner as in Example 3. The results are shown in Table 16 (3). The input power density (power amount) of the hydrogen plasma treatment containing a trace amount of Group V element of the present invention is a fill factor, a characteristic unevenness, a photodegradation characteristic, a series in the photoelectric conversion efficiency of a solar cell when a VHF power source is used for the input power. 0.01W / in resistance characteristics, durability, reverse bias voltage application characteristics
It has been found that a preferable range is from cm ³ to 1.0 W / cm ³ .

(Embodiment 17) Similar to Embodiment 3, hydrogen plasma treatment containing a trace amount of group V element of the present invention was performed twice under the conditions of Table 17 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3.
Table 17 shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
Table 17 shows the manufacturing conditions of the triple solar cell in (1).
It shows in (2).

The triple solar cell thus prepared was evaluated in the same manner as in Example 3. The results are shown in Table 17 (3). The input power density (electric energy) of the hydrogen plasma treatment containing a trace amount of Group V element of the present invention is a fill factor in the photoelectric conversion efficiency of the solar cell when an MW power supply is used for the input power,
It was found that 0.1 W / cm ³ to 10 W / cm ³ are preferable ranges in terms of characteristic unevenness, photodegradation characteristics, series resistance characteristics, and durability.

(Embodiment 18) Similar to Embodiment 3, hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 18 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3.
Table 18 shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
In (1), Table 18 shows the manufacturing conditions of the triple solar cell.
It shows in (2).

The triple solar cell thus prepared was evaluated in the same manner as in Example 3. The results are shown in Table 18 (3). The substrate temperature of the hydrogen plasma treatment containing a trace amount of Group V element of the present invention is, when an RF power source is used for input power, a fill factor, a characteristic unevenness, a photodegradation characteristic, a series resistance characteristic, a durability in the photoelectric conversion efficiency of the solar cell. It was found that 100 ° C. to 400 ° C. is a preferable range in the reverse bias voltage application characteristic.

(Example 19) Similar to Example 3, the hydrogen plasma treatment containing a trace amount of Group V element of the present invention was performed twice under the conditions of Table 19 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3.
Table 19 shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
In (1), Table 19 shows the manufacturing conditions of the triple solar cell.
It shows in (2).

The triple solar cell thus prepared was evaluated in the same manner as in Example 3. The results are shown in Table 19 (3). The substrate temperature of the hydrogen plasma treatment containing a trace amount of group V element of the present invention is, when a VHF power source is used for input power, a fill factor in photoelectric conversion efficiency of a solar cell, characteristic unevenness, photodegradation characteristic, series resistance characteristic, durability. It was found that 50 ° C. to 300 ° C. is a preferable range in the reverse bias voltage application characteristic.

(Embodiment 20) Similar to Embodiment 3, hydrogen plasma treatment containing a trace amount of group V element of the present invention was performed twice under the conditions of Table 20 (1) using the deposition apparatus shown in FIG. The triple type solar cell of FIG. 2 was produced in the same manner as in 3.
Table 20 shows the hydrogen plasma treatment conditions containing a trace amount of Group V element.
Table 1 shows the manufacturing conditions of the triple solar cell in (1).
It shows in (2).

The triple solar cell thus produced was evaluated in the same manner as in Example 3. The results are shown in Table 20 (3). The substrate temperature of the hydrogen plasma treatment containing a trace amount of Group V element of the present invention is, when an MW power source is used for input power, a fill factor, a characteristic unevenness, a photodegradation characteristic, a series resistance characteristic in the photoelectric conversion efficiency of a solar cell, Durability from 50 ℃ to 3
It was found that 00 ° C was the preferred range.

(Example 21) The triple type solar cell of FIG. 2 was produced using the deposition apparatus shown in FIG. A reflective layer 301 and a reflective enhancement layer 3 prepared by the same method as in Example 1.
02 is formed on the substrate 490 and the load chamber 4
No. 01 was placed on the substrate transfer rail 413, and the inside of the load chamber 401 was evacuated to a pressure of about 1 × 10 ⁻⁵ Torr by a vacuum exhaust pump (not shown).

Next, the gate valve 406 was opened to carry the wafer into the transfer chamber 402 and the deposition chamber 417 which had been evacuated by a vacuum exhaust pump (not shown) in advance. The back surface of the substrate 490 was brought into close contact with the substrate heating heater 410 and heated, and the inside of the deposition chamber 417 was evacuated by a vacuum exhaust pump (not shown) to a pressure of about 1 × 10 ⁻⁵ Torr.

Next, a hydrogen plasma treatment containing a small amount of silane-based gas was performed under the conditions shown in Table 21 (1). SiH ₄ / H ₂ (dilution: 1000 ppm) gas as a silicon atom-containing gas is used to perform the hydrogen plasma treatment containing a small amount of silane-based gas.
H ₂ gas is introduced into the deposition chamber 417 through a gas introduction pipe 429.
And the valves 441, 431 and 430 were opened so that the H ₂ gas flow rate was 1100 sccm, and the mass flow controller 436 adjusted. The silicon atom-containing gas was adjusted by the mass flow controller 437 by opening the valves 442 and 432 so that the ratio of SiH ₄ gas to the total H ₂ gas flow rate was 0.03%. The pressure in the deposition chamber 417 was adjusted to 0.8 Torr by a conductance valve (not shown). The substrate heating heater 410 is set so that the temperature of the substrate 490 becomes 360 ° C., and when the substrate temperature becomes stable, the RF power source 422 is set.
Was set to 0.05 W / cm ³ , RF power was introduced, glow discharge was generated in the plasma forming cup 420, and hydrogen plasma treatment containing a small amount of silane-based gas was performed for 3 minutes. Then turn off the RF power to stop glow discharge,
After stopping the inflow of SiH ₄ / H ₂ gas into the deposition chamber 417 and continuing to flow the H ₂ gas into the deposition chamber 417 for 5 minutes, the inflow of H ₂ gas is also stopped and the inside of the deposition chamber 417 and the gas pipe are stopped. Was evacuated to 1 × 10 ⁻⁵ Torr.

After the preparation for film formation is completed as described above, R consisting of μc-Si is prepared by the same method as in Example 2.
The Fn type layer 303 was formed. Next, a hydrogen plasma treatment containing a trace amount of silane-based gas was performed under the conditions shown in Table 21 (2). Next, in the same manner as in Example 2, n / i made of a-SiC
The buffer layer 351 was formed by the RFPCVD method.

Next, a hydrogen plasma treatment containing a small amount of silane-based gas was performed under the conditions shown in Table 21 (3). Next, the MWi-type layer 304 made of a-SiGe was formed by the MWPCVD method in the same manner as in Example 2. Next, a hydrogen plasma treatment containing a trace amount of silane-based gas was performed under the conditions shown in Table 21 (4).
Next, by the same method as in Example 2, p made of a-SiC was used.
The / i buffer layer 361 was formed by the RFPCVD method.

Next, a hydrogen plasma treatment containing a small amount of silane-based gas was performed under the conditions shown in Table 21 (5). Next, the RF p-type layer 305 made of a-SiC is subjected to R by the same method as in the second embodiment.
It was formed by the FPCVD method. Next, the trace amount V of the present invention
The group element-containing hydrogen plasma treatment was performed under the conditions shown in Table 21 (6).

Then, in the same manner as in Example 2, μc-S
The RF n-type layer 306 made of i was formed by the RFPCVD method. Next, a hydrogen plasma treatment containing a trace amount of silane-based gas was performed under the conditions shown in Table 21 (7). Next, in the same manner as in Example 2, the n / i buffer layer 35 made of a-SiC was formed.
2 was formed by the RFPCVD method.

Next, a hydrogen plasma treatment containing a trace amount of silane-based gas was performed under the conditions shown in Table 21 (8). Next, the MWi type layer 307 made of a-SiGe was formed by the MWPCVD method in the same manner as in Example 2. Next, a hydrogen plasma treatment containing a trace amount of silane-based gas was performed under the conditions shown in Table 21 (9).
Next, by the same method as in Example 2, p made of a-SiC was used.
The / i buffer layer 362 was formed by the RFPCVD method.

Next, a hydrogen plasma treatment containing a small amount of silane-based gas was performed under the conditions shown in Table 21 (10). Next, in the same manner as in Example 2, the RF p-type layer 30 made of a-SiC was used.
8 was formed. Next, the trace amount group V element-containing hydrogen plasma treatment of the present invention was performed under the conditions shown in Table 21 (11).

Then, in the same manner as in Example 2, μc-
An RFn type layer 309 made of Si was formed. Next, a slight amount of silane-based gas-containing hydrogen plasma treatment was performed under the conditions shown in Table 21 (12). Then, in the same manner as in Example 2, aS
RFPCVD of n / i buffer layer 353 made of iC
Formed by the method. Next, a slight amount of silane-based gas-containing hydrogen plasma treatment was performed under the conditions shown in Table 21 (13). Next, the RFi type layer 310 made of a-Si was formed by the RFPCVD method in the same manner as in Example 2.

Then, a hydrogen plasma treatment containing a trace amount of silane-based gas was performed under the conditions shown in Table 21 (14). Next, the p / i buffer layer 363 made of a-SiC was formed by the RFPCVD method in the same manner as in Example 2. Next, hydrogen plasma treatment containing a trace amount of silane-based gas was performed under the conditions shown in Table 21 (15). Then, in the same manner as in Example 2, a
The RFp type layer 311 made of —SiC was formed by the RFPCVD method.

Next, on the RF p-type layer 311, as the transparent conductive layer 312, ITO having a layer thickness of 70 nm was vacuum-deposited by a vacuum deposition method. Next, a mask with comb-shaped holes is placed on the transparent conductive layer 312, and Cr (40 nm) / Ag (1000 n
m) / Cr (40 nm) comb-shaped collector electrode 313
Was vacuum deposited by the vacuum deposition method.

With the above, the production of the solar cell was completed. This solar cell will be referred to as (SC Ex. 21), and the conditions of the trace amount group V element-containing hydrogen plasma treatment and the trace amount silane-based gas-containing hydrogen plasma treatment of the present invention, RFn type layer, n / i buffer layer, MWi type layer. , P / i buffer layer, RFi type layer,
The conditions for forming the RF p-type layer are shown in Tables 21 (1) to 21 (16).

Comparative Example 21 A solar cell (SC ratio 21) was used under the same conditions as in Example 21 except that the trace amount group V element-containing hydrogen plasma treatment and the trace amount silane gas-containing hydrogen plasma treatment of the present invention were not performed. It was made. Solar cell (SC Ex 21)
And (SC ratio 21) were produced by 7 pieces respectively, and initial photoelectric conversion efficiency (photovoltaic power / incident optical power), vibration deterioration, light deterioration, vibration deterioration in high temperature and high humidity environment when bias voltage was applied, light deterioration, And the reverse bias voltage application characteristics were measured.

The initial photoelectric conversion efficiency can be obtained by placing the manufactured solar cell under AM1.5 (100 mW / cm ² ) light irradiation and measuring the VI characteristic. As a result of the measurement, the fill factor (FF) of the initial photoelectric conversion efficiency and the series resistance (R
s) and characteristic unevenness are as follows. Fill factor Series Resistance Characteristic unevenness (SC Ex. 21) 1.20 times 0.85 times 0.80 times The vibration deterioration was measured by using a solar cell whose initial photoelectric conversion efficiency was measured in advance at a humidity of 58% and a temperature of 26 ° C. Installed in a dark place at a vibration frequency of 60 Hz and an amplitude of 0.1 mm.
AM1.5 (100 mW / cm ² ) after adding for 0 hours
It was determined by the rate of decrease in photoelectric conversion efficiency under irradiation (photoelectric conversion efficiency after vibration deterioration test / initial photoelectric conversion efficiency). Photodegradation was measured by installing a solar cell whose initial photoelectric conversion efficiency had been measured in advance in an environment with a humidity of 58% and a temperature of 26 ° C.
Reduction rate of photoelectric conversion efficiency under AM1.5 (100 mW / cm ² ) irradiation after irradiation with 1.5 (100 mW / cm ² ) light for 560 hours (photoelectric conversion efficiency after light deterioration test / initial photoelectric conversion efficiency) ).

As a result of the measurement, for (SC Ex 21), (S
The rate of decrease in photoelectric conversion efficiency after photodegradation and the rate of decrease in photoelectric conversion efficiency after vibration degradation of C ratio 21) were as follows. We measured vibration deterioration and light deterioration under high temperature and high humidity environment with bias applied. Two solar cells whose initial photoelectric conversion efficiencies were measured in advance were placed in a dark place with a humidity of 94% and a temperature of 84 ° C., and 0.71 V was applied as a forward bias voltage. The above vibration was applied to one solar cell and vibration deterioration was measured, and AM1.5 was applied to the other solar cell.
Then, the light deterioration was measured.

As a result of the measurement, (SC Ex 21),
The rate of decrease in photoelectric conversion efficiency after vibration deterioration (SC ratio 21) and the rate of decrease in photoelectric conversion efficiency after light deterioration were as follows. For the measurement of the reverse bias voltage application characteristic, a solar cell whose initial photoelectric conversion efficiency was measured in advance had a humidity of 53% and a temperature of 8%.
Installed in a dark place at 2 ℃, reverse bias voltage 5.0V,
After applying for 100 hours, AM1.5 (100 mW / cm
² ) The photoelectric conversion efficiency under irradiation was measured, and the reduction rate (photoelectric conversion efficiency after application of reverse bias voltage / initial photoelectric conversion efficiency) was used.

As a result of the measurement, (SC Ex 21),
The rate of decrease (SC ratio 21) after application of the reverse bias voltage was as follows. (SC ratio 21) 0.82 times The state of layer delamination was observed using an optical microscope. No layer peeling was observed in (SC Ex 21), but (SC ratio 21)
A slight delamination was observed in. As described above, the solar cell of the present invention (SC Ex 21) is the same as the conventional solar cell (SC ratio 2).
Fill factor in the photoelectric conversion efficiency of the solar cell than 1),
It was found that the series resistance, unevenness in characteristics, photodegradation characteristics, adhesion, durability, and reverse bias voltage application characteristics were further excellent.

In the above embodiments, the n-type layer, n /
The solar cell in which the i-buffer layer, the i-type layer, the p / i buffer layer, and the p-type layer are stacked in this order has been described. The p-type layer, the p / i buffer layer, the i-type layer, and the n / i buffer layer are formed on the substrate. The same hydrogen plasma treatment was also performed on the solar cell in which the n-type layer was laminated in this order to manufacture the solar cell. When the same evaluation as in the above-mentioned example was performed, the solar cell in which the space between the p-type layer and the n-type layer was plasma-treated with the hydrogen gas containing the silicon atom-containing gas and the group V element-containing gas of the periodic table showed photoelectric conversion. Fill factor in efficiency, characteristic unevenness, photodegradation characteristics,
It was confirmed that it has excellent series resistance characteristics, durability, and reverse bias voltage application characteristics. In addition, near the interface between the substrate and the p-type layer, further near the interface between the n / i buffer layer and the n-type layer, or near the interface between the n / i buffer layer and the i-type layer, the p / i buffer layer and the i-type The above characteristics are further improved by plasma-treating the vicinity of the interface between the layers and the vicinity of the interface between the p / i buffer layer and the p-type layer with hydrogen gas containing a silicon atom-containing gas that does not substantially deposit. I understand.

[0202]

[Table 1 (1)]

[0203]

[Table 1 (2)]

[0204]

[Table 2 (1)]

[0205]

[Table 2 (2)]

[0206]

[Table 3 (1)]

[0207]

[Table 3 (2)]

[0208]

[Table 3 (3)]

[0209]

[Table 4 (1)]

[0210]

[Table 4 (2)]

[0211]

[Table 4 (3)]

[0212]

[Table 5 (1)]

[0213]

[Table 5 (2)]

[0214]

[Table 5 (3)]

[0215]

[Table 6 (1)]

[0216]

[Table 6 (2)]

[0217]

[Table 6 (3)]

[0218]

[Table 7 (1)]

[0219]

[Table 7 (2)]

[0220]

[Table 7 (3)]

[0221]

[Table 8 (1)]

[0222]

[Table 8 (2)]

[0223]

[Table 8 (3)]

[0224]

[Table 9 (1)]

[0225]

[Table 9 (2)]

[0226]

[Table 9 (3)]

[0227]

[Table 10 (1)]

[0228]

[Table 10 (2)]

[0229]

[Table 10 (3)]

[0230]

[Table 11 (1)]

[0231]

[Table 11 (2)]

[0232]

[Table 11 (3)]

[0233]

[Table 12 (1)]

[0234]

[Table 12 (2)]

[0235]

[Table 12 (3)]

[0236]

[Table 13 (1)]

[0237]

[Table 13 (2)]

[0238]

[Table 13 (3)]

[0239]

[Table 14 (1)]

[0240]

[Table 14 (2)]

[0241]

[Table 14 (3)]

[0242]

[Table 15 (1)]

[0243]

[Table 15 (2)]

[0244]

[Table 15 (3)]

[0245]

[Table 16 (1)]

[0246]

[Table 16 (2)]

[0247]

[Table 16 (3)]

[0248]

[Table 17 (1)]

[0249]

[Table 17 (2)]

[0250]

[Table 17 (3)]

[0251]

[Table 18 (1)]

[0252]

[Table 18 (2)]

[0253]

[Table 18 (3)]

[0254]

[Table 19 (1)]

[0255]

[Table 19 (2)]

[0256]

[Table 19 (3)]

[0257]

[Table 20 (1)]

[0258]

[Table 20 (2)]

[0259]

[Table 20 (3)]

[0260]

[Table 21 (1)]

[0261]

[Table 21 (2)]

[0262]

[Table 21 (3)]

[0263]

[Table 21 (4)]

[0264]

[Table 21 (5)]

[0265]

[Table 21 (6)]

[0266]

[Table 21 (7)]

[0267]

[Table 21 (8)]

[0268]

[Table 21 (9)]

[0269]

[Table 21 (10)]

[0270]

[Table 21 (11)]

[0271]

[Table 21 (12)]

[0272]

[Table 21 (13)]

[0273]

[Table 21 (14)]

[0274]

[Table 21 (15)]

[0275]

[Table 21 (16)]

[0276]

According to the present invention, impurities (for example, oxygen, nitrogen, carbon, iron, chromium) which become defect levels when adsorbed on the wall surface of a deposition chamber or contained in a semiconductor layer which is usually contained in a hydrogen plasma treatment are obtained according to the present invention. , Nickel, aluminum, etc.) can be solved. In addition, stable hydrogen plasma treatment can be performed. As a result, 1) it is possible to provide a photovoltaic element in which the semiconductor layer is not substantially peeled off when the photovoltaic element is placed in high temperature and high humidity.

2) When a pin structure is formed on a flexible substrate, it is possible to provide a photovoltaic element in which the pin semiconductor layer is less likely to peel off even if the substrate is bent. 3) It is possible to provide a photovoltaic element in which an increase in the defect level near the interface between the substrate and the semiconductor layer is suppressed by irradiation with light for a long time. 4) It is possible to provide a photovoltaic element in which the substrate and the semiconductor layer are not peeled off even when irradiated with light under high temperature and high humidity and in which characteristic deterioration such as increase in series resistance is suppressed.

5) It is possible to provide a photovoltaic element with little deterioration in characteristics even when used at a high temperature. 6) It is possible to provide a photovoltaic element that is not easily broken when a reverse bias is applied to the photovoltaic element. 7) It is possible to provide a photovoltaic element having a small series resistance even in the initial stage of forming the photovoltaic element.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view of a photovoltaic element to which the method for forming a photovoltaic element of the present invention is applied.

FIG. 2 is a schematic explanatory view of another photovoltaic element to which the method for forming a photovoltaic element of the present invention is applied.

FIG. 3 is a schematic explanatory diagram of a photovoltaic device forming apparatus suitable for the method for forming a photovoltaic device of the present invention.

[Explanation of symbols]

200,300 support, 201,301 reflective layer (or transparent conductive layer), 202,302 reflection increasing layer (or antireflection layer), 203,303 first n-type layer (or p-type layer), 204,304 First i-type layer, 205,305 First p-type layer (or n-type layer), 212,312 Transparent conductive layer (or conductive layer), 213,313 Current collecting electrode, 251,351 First n / i buffer layer, 261,361 i-th p / i buffer layer, 206,306 second n-type layer (or p-type layer), 207,307 second i-type layer, 208,308 second p-type layer Layer (or n-type layer), 252,352 second n / i buffer layer, 262,362 second p / i buffer layer, 309 third n (or p-type layer), 311 third p-type Layer (or n-type layer), 310 3 i-type layer, 353 third n / i buffer layer, 363 third p / i buffer layer, 400 forming apparatus, 401 load chamber, 402, 403, 404 transfer chamber, 405 unload chamber, 406 , 407, 408, 409 Gate valve, 410, 411, 412 Substrate heating heater, 413 Substrate transport rail, 417 n-type layer (or p-type layer) deposition chamber, 418 i-type layer deposition chamber, 419 p-type layer ( Or n-type layer) deposition chamber, 420,421 plasma forming cup, 422,423,424 power supply, 425 microwave introduction window, 426 waveguide, 427 shutter, 428 bias rod, 429,449,469 gas introduction tube , 430, 431, 432, 433, 434, 441, 4
42,443,444,450,451,452,4
53, 454, 455, 461, 462, 463, 4
64, 465, 468, 466, 470, 471, 47
2,473,474, 481,482, 483,48
4 valves, 436, 437, 438, 439, 456, 457, 4
58, 459, 460, 467, 476, 477, 4
78,479 Mass flow controller, 490 Substrate holder.

Claims (5)

[Claims] 1. A non-single-crystal n-type layer (or p-type layer) containing a silicon atom, a non-single-crystal i-type n / i buffer layer (or p / i buffer layer), and a non-single crystal on a substrate. i
Type layer, non-single crystal i-type p / i buffer layer (or n /
i buffer layer) and non-single crystal p-type layer (or n-type layer)
In a method for forming a photovoltaic device in which at least two or more pin structures formed by laminating a silicon atom are laminated, a silicon atom-containing gas that does not substantially deposit near an interface where the p-type layer and the n-type layer are in contact with each other. A method of forming a photovoltaic element, which comprises performing a plasma treatment with hydrogen gas containing a group V element-containing gas of a periodic table. 2. A plasma treatment is carried out in the vicinity of the interface between the substrate and the n-type layer (or in the vicinity of the interface between the substrate and the p-type layer) with hydrogen gas containing a silicon atom-containing gas that is not substantially deposited. The method for forming a photovoltaic element according to claim 1, wherein 3. An interface near the interface between the n / i buffer layer and the n-type layer, an interface near the interface between the n / i buffer layer and the i-type layer, and an interface between the p / i buffer layer and the i-type layer. In the vicinity, and the p / i buffer layer and the p
The method for forming a photovoltaic element according to claim 1 or 2, wherein the vicinity of the interface in contact with the mold layer is plasma-treated with hydrogen gas containing a silicon atom-containing gas that is not substantially deposited. 4. The silicon atom-containing gas is Si
_{H 4, Si 2 H 6,} SiF 4, SiFH 3, SiF 2 H 2, S
_{iF 3 H, SiCl 2 H 2} , SiCl 3 H, of the SiCl _4, claim, characterized in that it comprises at least one 1
4. The method for forming a photovoltaic element according to any one of 3 above. 5. The method for forming a photovoltaic element according to claim 1, wherein the content of the silicon atom-containing gas with respect to the hydrogen gas is 0.1% or less. .