JP2004031701A - Cat-pecvd method, film formed using the same, thin film device equipped with the film, and film processing system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a Cat-plasma enhanced chemical vapor deposition (PECVD) method through which a film having high uniformity in film thickness and film quality can be formed with high productivity, and to provide a film formed through the above method, a thin film device using the film, and a film processing system. <P>SOLUTION: This Cat-PECVD method a method in which is material gases containing Si and/or C in their molecular formulas, and non-Si/non-C gases which are heated by a thermal catalyst and contain no Si/no C in their molecular formulas, are jetted out into a film forming space from a plurality of gas exhaust nozzles provided to the hollow parts of a firs and a second gas introduction tubes, passing through the hollow parts of the first and second gas introduction tubes each equipped with a hollow structure as the material gases pass through the first gas introduction tube serving also as an antenna electrode and the non-Si/non-C gases pass through the second gas introduction tube. The gases jetted into the film forming space and mixed together are made to deposit the film on a substrate by the use of plasma produced by the first gas introduction tube connected to a high-frequency power supply. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a plasma enhanced chemical vapor deposition (PECVD) method, which is a chemical vapor deposition (CVD) method using plasma as a means for decomposing and activating a film forming gas, and a method for decomposing and activating a film forming gas. Cat-CVD (Catalytic Chemical Vapor Deposition: Catalytic CVD) method (HW-CVD (Hot-wire CVD) method is the same principle) that is a CVD method using a thermal catalyst as a conversion means. The present invention relates to a Cat-PECVD method which is a CVD method, a film formed by using the method, and a thin film device formed by using the film. High quality In, yet it can be a film with a uniform thickness and homogeneous quality over a large area, to a technique for further perform a film with very high productivity.
[0002]
[Prior art and its problems]
High-quality, high-speed film forming technology is indispensable for high performance and low cost of various thin-film devices. In particular, thin-film Si-based solar cells, which are representative of photoelectric conversion devices, have high-quality, high-speed Si-based films. In addition to film formation, large area film formation and high productivity are also required.
[0003]
The PECVD method and the Cat-CVD method are widely known as low-temperature film forming methods for Si-based thin films, and both are actively researching and developing mainly for the formation of hydrogenated amorphous silicon films and crystalline silicon films. Has been made.
[0004]
FIG. 8 shows a PECVD apparatus as Conventional Example 1, and FIG. 9 shows a Cat-CVD apparatus as Conventional Example 2. 8, 500 is a shower head, 501 is a gas inlet, 502 is a gas outlet, 503 is a plasma space, 504 is a plasma generation electrode, 505 is a high-frequency power source, 505 is a base, 507 is a base heater, and 508 is a base heater. A gas pump vacuum pump 509 is an insulating member for electrical insulation. 9, 600 is a shower head, 601 is a gas inlet, 602 is a gas outlet, 603 is an active gas space, 604 is a thermal catalyst, 605 is a power supply for heating the thermal catalyst, 606 is a base, 607 Denotes a substrate heating heater, and 608 denotes a gas exhaust vacuum pump.
[0005]
Where SiH ₄ Gas and H ₂ Taking the case where a Si film is formed using a gas as an example, in the PECVD apparatus shown in FIG. 8, the gas introduced from the gas introduction port 501 provided in the shower head 500 is plasma It is guided to the space 503 and excited and activated in the plasma space 503 to generate a deposited species, which is deposited on the opposed substrate 506 to form a Si film. Here, the plasma is generated by using a high frequency power supply 505.
[0006]
In the Cat-CVD apparatus shown in FIG. 9, the gas introduced from the gas inlet 601 provided in the shower head 600 is guided from the gas outlet 602 to the film forming space and installed in the film forming space. The active catalyst 604 is activated to form an active gas space 603 to generate deposition species, which are deposited on the opposing substrate 606 to form a Si film. Here, heating of the thermal catalyst 604 is realized by using a heating power supply 605.
[0007]
However, these conventional techniques have the following problems. That is, in the PECVD method, in order to realize high-speed film formation, the plasma power is increased and the SiH ₄ Gas or H ₂ Although it is necessary to promote the decomposition of gas, this increase in plasma power is nothing less than increasing the electron temperature Te in the plasma (the plasma potential Vp increases in proportion to Te). Increases the ion bombardment on the film formation surface, ₂ This leads to the promotion of the production of higher order silanes (eventually the promotion of the production of powder) due to the increase in the production rate of molecules, and it is inevitable to introduce elements that go against the improvement of quality.
[0008]
Here, if the plasma excitation frequency is set to the VHF band or higher instead of increasing the plasma power, the ion bombardment is reduced due to the reduction of the plasma potential Vp, and a high quality film of a hydrogenated amorphous silicon film or a crystalline silicon film can be formed. Is effective (see J. Meier et al, Technical digest of 11th PVSEC (1999) p. 221, O. Vetterl et al, Technical digest of 11th PVSEC (1999), p. 233, etc.) In order to form a film, it is necessary to generate sufficient atomic hydrogen. For this reason, no matter how the VHF band frequency is used, if a high-speed film formation of a certain degree or more is required, an increase in plasma power cannot be avoided. I ca n’t avoid the above-mentioned problems. Was Tsu.
[0009]
Therefore, as a measure for increasing the atomic hydrogen density without increasing the plasma power, the hydrogen dilution rate is increased, that is, the gas flow ratio H is increased. ₂ / SiH ₄ It is conceivable that the SiH ₄ Since the partial pressure of the gas is lowered, and if the gas is left as it is in a direction opposite to the high-speed film formation, the plasma power is eventually increased to increase the SiH. ₄ The decomposition must be promoted, and the above-mentioned problem cannot be avoided.
[0010]
In addition, as a measure that can reduce ion bombardment even when the plasma power is increased, it is conceivable to increase the film forming pressure. However, the increase in the film forming pressure on the other hand causes the acceleration of the higher silane generation reaction due to the increase in the gas molecule density. As a result, it has been difficult for this method to eliminate factors that reduce film quality such as powder generation.
[0011]
On the other hand, in the Cat-CVD method, since the plasma is not used, the above-described problem of ion bombardment does not exist in principle, powder generation is extremely small, and generation of atomic hydrogen is greatly promoted. High-quality Si films can be formed relatively easily at high speed, and furthermore, there is no principle restriction on the enlargement of the area. Therefore, attention has been paid to recent years (H. Matsumura, Jpn. J. Appl. Phys. 37 ( 1998) 3175-3187, RE I. I. Sroppp et al, Technical digest of 11th PVSEC (1999) p.
[0012]
However, at present, the problem of substrate temperature rise due to radiation from the thermal catalyst is inevitable, and it is not always easy to stably form a high-quality film. Also, SiH ₄ Since the gas is directly decomposed by the thermal catalyst, generation of atomic Si is inevitable. This atomic Si is not preferable for forming a high quality Si film, and the atomic Si becomes H or H in a gas phase. ₂ SiH or SiH produced by reaction with ₂ Such radicals are similarly unfavorable for the formation of a high-quality Si film, so that it is very difficult to form a high-quality crystalline Si film at a high speed.
[0013]
In view of the above problems, the present inventors have been studying the integration of the PECVD method and the Cat-CVD method for some time, and have already reported Japanese Patent Application Nos. 2000-130858, 2001-29331, and 2002. No. 67445 discloses a Cat-PECVD method of a cathode type with a built-in thermal catalyst.
[0014]
FIG. 10 shows a typical device structure. In FIG. 10, 700 is a shower head, 701 is a source gas inlet, 702 is a non-Si non-C gas inlet, 703 is a source gas inlet, 704 is a non-Si non-C gas inlet, and 705 is heat. A catalyst body, 706 is a heating power supply, 707 is a plasma space, 708 is a plasma generation electrode, 709 is a high-frequency power supply, 710 is a source gas outlet, 711 is a non-Si / non-C gas outlet, and 712 is a product. A base for the film, 713 is a heater for heating the base, 714 is a vacuum pump for gas exhaust, and 715 is a radiation blocking member.
[0015]
This Cat-PECVD method uses a Si-based source gas and H ₂ Separately introduce gas and introduce H ₂ The gas is heated and activated by the thermal catalyst 705 provided in the gas introduction path, and forms a film by being mixed with the Si-based gas in the plasma space 707. Even with this, a high-quality crystalline Si film having high crystallinity can be easily obtained. This is because the use of a thermal catalyst in this method ₂ The amount of decomposition and activation of ₄ Can be freely controlled independently of the amount of decomposition and activation of ₄ Is activated only by plasma, so that undesired radical generation by the thermal catalyst 705 can be avoided, and a radiation blocking member 715 can be provided, so that radiation that directly reaches the base 712 from the thermal catalyst 705 can be prevented. It can be shut off to avoid an undesired rise in the film forming surface temperature, and furthermore, the gas heating effect as a secondary effect using the thermal catalyst 705 suppresses the higher silane generation reaction in the gas phase ( SiH ₂ Since the higher silane generation reaction due to the molecule insertion reaction is an exothermic reaction, an increase in gas temperature due to gas heating has an effect of applying a brake to the higher silane generation reaction). Further, by using the shower head 700 and using a non-plate-like electrode (for example, an antenna electrode) instead of the conventional plate-like electrode as the plasma generation electrode 708, a high-frequency power supply of 27 MHz or more can be used. It had the ability to achieve uniform film thickness and uniform film quality in a large area. Further, as a more specific form in this case, a method in which a non-planar electrode also serves as a shower head has been partially disclosed. As described above, a satisfactory uniform film thickness distribution (within ± 15% as a guide) and a homogeneous film quality distribution (for example, within ± 15% as a crystallization rate distribution and within ± 10% as an efficiency characteristic distribution) in a 1 m square size are obtained. High-speed, high-quality film-forming conditions could be obtained.
[0016]
However, even in the prior art by the present inventors exhibiting these remarkable effects, the technique of the system in which the non-plate-shaped electrode also serves as a shower head has room for further improvement, and in particular, breakthrough in high productivity of the apparatus. Technology development was desired.
[0017]
In order to solve these problems, the present inventors have developed an antenna electrode type Cat-PECVD method disclosed in Japanese Patent Application No. 2002-155737-155544. In other words, a completely new film forming technique in which a thermal catalyst is incorporated in a hollow portion of an antenna electrode having a hollow structure was invented. As a result, uniform large-area plasma can be generated even at a high frequency using the VHF band, and at the same time, even under high-speed film forming conditions, for example, high-quality hydrogenated amorphous silicon film or crystalline It has become possible to form silicon films. By arranging a plurality of antenna electrodes arranged in parallel in the film-forming chamber in parallel, a plurality of antenna electrodes can be simultaneously formed on a plurality of substrates, thereby realizing a highly productive film processing system. I was able to.
[0018]
However, in the antenna electrode having the built-in thermal catalyst, the high-frequency power in the VHF band is supplied to generate a plasma at the antenna electrode, and is supplied to heat the thermal catalyst inside the antenna electrode. The problem still remains that plasma generation may not always be stable due to interaction with electric power. Further, there has been a problem that an antenna electrode having a built-in thermal catalyst may be deformed by heating due to radiant heat from the thermal catalyst.
[0019]
In addition, Technical digest of 11th PVSEC (1999) p779 discloses a plasma CVD apparatus in which a thermal catalyst is disposed immediately after a hydrogen gas introduction port. Although the introduction ports of the hydrogen gas and the silane gas are different, the hydrogen gas and the silane gas do not pass through the shower electrode, and it is difficult to obtain a uniform film thickness distribution and film quality distribution over a large area. Also, since the thermal catalyst is not isolated from the film forming space by the shower electrode, it is impossible to reduce the contact reaction with the silane gas, and it is not preferable in high-quality film forming to use atomic Si or gas phase reaction with the atomic Si. SiH and SiH which are undesirable in the same high quality film formation ₂ Is inevitable. Further, the concept of the radiation blocking structure and the concept of VHF band generation of the plasma generation frequency is not shown, and it is difficult to achieve high quality. In addition, it does not use an antenna electrode which is a core of the present invention described later.
[0020]
In addition, Technical Digest of 16th EPSEC (2000) p421 discloses a capacitively coupled RF plasma CVD apparatus in which a thermal catalyst is installed in a plasma space. Also, the introduced gas does not pass through the shower electrode. Further, since the thermal catalyst is installed in the plasma space, it is impossible to block radiation to the base. Also, there is no concept of an antenna electrode.
[0021]
Further, Japanese Patent No. 2692226 discloses a catalytic CVD method in which a radiation blocking member through which a gas can pass is provided between a catalyst and a substrate. However, a gas is used so that a raw material gas is not activated by a thermal catalyst. It does not separate and introduce, nor does it activate the source gas by plasma. Of course, there is no concept of an antenna electrode.
[0022]
Japanese Patent Application Laid-Open No. 10-310867 discloses a thin film forming apparatus having a catalyst electrode between a plasma generating electrode and a gas inlet, but does not separate and introduce a raw material gas. Nor does it have a radiation blocking structure. Also, there is no concept of an antenna electrode.
[0023]
In Japanese Patent Application Laid-Open No. 11-54441, a raw material gas is supplied into a container in which a thermal catalyst is disposed, and the inside of the container is isolated from the substrate. Although a catalytic CVD device to be supplied is disclosed, it does not relate to separating and introducing a raw material gas, and does not relate to a PECVD method. Also, there is no concept of an antenna electrode.
[0024]
Also, Japanese Patent No. 19952626 discloses a method of forming a film by introducing a raw material gas and a heating gas for decomposing the raw material gas. Neither does it have a blocking structure. Also, there is no concept of an antenna electrode.
[0025]
Further, Japanese Patent No. 19945527 discloses a method of forming a film by thermally decomposing a raw material gas. However, the method is not a method of not thermally decomposing a raw material gas and does not have a radiation blocking structure. Further, neither a plasma nor a shower head is used. Of course, there is no concept of an antenna electrode.
[0026]
Further, Japanese Patent No. 1927388 discloses a method in which a mesh-like activating means made of tungsten is provided in a film forming space to activate a gas containing hydrogen to deposit a film. It is not a method of separating and introducing without performing, and does not have a radiation blocking structure. Also, there is no concept of an antenna electrode.
[0027]
Also, Japanese Patent No. 2574741 discloses a structure in which one transport pipe has the other inside it, ₄ And H ₂ Is disclosed, but it does not use a shower head, nor does it have a radiation blocking structure. Also, there is no concept of an antenna electrode.
[0028]
Also, Japanese Patent No. 2927944 discloses that a hydrogen region is activated in a space different from a film formation space, mixed with a source gas and brought into contact with the source gas to form a plasma region, and the activation of the hydrogen gas is periodically performed. Although a method of depositing a film by intermittently and periodically exposing the substrate to the plasma is disclosed, it does not use a shower head and does not have a radiation blocking structure. Also, there is no concept of an antenna electrode.
[0029]
Japanese Patent Application Laid-Open No. 2000-114256 discloses a method of forming a film by decomposing a raw material gas by acting a catalyst and subjecting the raw material gas to plasma treatment, but this method does not separate and introduce the raw material gas. Further, neither a shower head nor a device having a radiation blocking structure is used. Also, there is no concept of an antenna electrode.
[0030]
Japanese Patent Application Laid-Open No. 2000-331942 discloses a method in which a film is formed by an apparatus having a surface reaction mechanism provided near the plasma generation unit to the substrate surface. It does not separate and introduce without decomposition and does not use a shower head. Further, since the thermal catalyst is between the plasma and the substrate, it is impossible to block radiation to the substrate. Also, there is no concept of an antenna electrode.
[0031]
Japanese Patent Application Laid-Open No. 2000-323421 discloses that SiH ₄ And H ₂ And SiH ₄ The gas is activated by plasma to irradiate the substrate with ions and radicals, ₂ A method of irradiating a substrate with a gas activated by a heated catalyst provided in a gas inlet is disclosed. However, the method does not use a shower head and does not have a radiation blocking structure. Also, there is no concept of an antenna electrode.
[0032]
Also, Japanese Patent Application Laid-Open No. Hei 9-137274 discloses that SiH ₄ And H ₂ And introduced separately, H ₂ Discloses a method of activating with heat or plasma during the introduction process, but does not use a shower head and does not have a radiation blocking structure. Also, there is no concept of an antenna electrode.
[0033]
Japanese Patent Application Laid-Open No. Hei 4-236781 discloses an antenna electrode type PECVD apparatus which is excellent in forming a large area and uniform film using a ladder-shaped flat coil (ladder) electrode. It does not heat and activate the gas.
[0034]
Japanese Patent Application Laid-Open No. 2001-295052 discloses an antenna-electrode-type PECVD capable of forming a large-area uniform film thickness by supplying AM-modulated VHF high-frequency (20 to 600 MHz to microwave) to an inductive coupling electrode. Although an apparatus is disclosed, it does not use a thermal catalyst to heat and activate a gas.
[0035]
Japanese Patent Application Laid-Open No. 7-41950 discloses a method in which a hardly decomposable gas is heated in advance by a gas heating heater to improve the decomposability in plasma to obtain a high quality film. It does not use a catalyst, and thus does not provide a thermal catalyst in the antenna electrode, and does not lead to activation (decomposition) only by heating the gas. Also, SiH ₄ And H ₂ And introduced separately, H ₂ It does not heat and activate only the thermal catalyst.
[0036]
Japanese Patent Application Laid-Open No. 6-283436 describes a method for realizing high-speed film formation by heating and introducing a reactive gas. However, a method using a thermal catalyst is not used. It does not provide a catalyst body, nor does it lead to activation (decomposition) only by heating the gas. Also, SiH ₄ And H ₂ And introduced separately, H ₂ It does not heat and activate only the thermal catalyst.
[0037]
Japanese Patent Application Laid-Open No. 5-283344 discloses that a heater capable of independently controlling the temperature of a wire is incorporated into the wire of a ladder-like planar coil electrode to control the pressure distribution of a reaction gas in a reaction vessel to obtain a uniform and homogeneous material. Although a method of realizing film formation is described, it does not use a thermal catalyst, and therefore does not install a thermal catalyst in an antenna electrode, and is activated (decomposed) only by heating a gas. It does not even lead to. Further, the gas is not separated and introduced depending on the gas species.
[0038]
The present invention has been made in view of such a background, and is intended to form a Si-based film or a C-based film with high speed and high quality and with a uniform film thickness and uniform film quality over a large area. It is another object of the present invention to provide a Cat-PECVD method capable of achieving extremely high productivity, a film formed using the Cat-PECVD method, and a device manufactured using the film.
[0039]
[Means for Solving the Problems]
According to the Cat-PECVD method of the present invention, a raw material gas containing a gas containing Si and / or C in a molecular formula and a molecular formula heated by a thermal catalyst disposed in a gas introduction path do not contain Si and C. These gas introduction pipes pass through the hollow portions of the first and second gas introduction pipes having a hollow structure installed in the film forming space in a state in which the non-Si non-C-based gas is separated from each other. When the raw material-based gas is ejected from the plurality of gas outlets provided to the film forming space through the first gas introduction pipe also serving as an antenna electrode, the non-Si non-C-based gas is supplied to the second gas introduction pipe. The mixed gas of the raw material gas and the non-Si non-C-based gas jetted into the film formation space through the gas introduction tube, respectively, was connected to the first gas introduction tube. High frequency power from high frequency power supply Is decomposed and activated by the plasma generated by, characterized in that layer on the first and second oppositely disposed substrates gas inlet tube in the casting space is deposited.
[0040]
Further, the second gas introduction pipe is made of a nonmetallic material.
[0041]
In addition, the first gas introduction tube also serving as the antenna electrode is rod-shaped or U-shaped, the thermal catalyst is installed in a hollow portion of the second gas introduction tube, A plurality of introduction pipes are arranged in parallel to form an arrayed gas introduction pipe unit, the base is arranged on both sides of the arrayed gas introduction pipe unit, and the arrayed gas introduction pipe unit of the base is A substrate heating heater is disposed on a surface opposite to the surface facing the substrate, a plurality of the array-like gas introduction pipe units are present in one film forming chamber, and each unit has a parallel array surface. And an apparatus configuration capable of performing simultaneous double-sided film formation by the respective array-like gas introduction pipe units, and the source gas introduction path and / or the non-Si non-C A gas introduction path, introducing a gas for doping in the membrane, respectively characterized.
[0042]
Further, the film of the present invention is characterized by being formed by the above-mentioned Cat-PECVD method. In particular, in this film, the raw material gas contains a gas containing Si in a molecular formula but does not contain a gas containing C in a molecular formula, and the non-Si non-C-based gas contains H ₂ Is contained, the Si-based film is a hydrogenated amorphous Si film, the hydrogen concentration in the film is 15 atomic% or less, and the Si-based film is crystalline Si. A hydrogen concentration of 10 atomic% or less in the film, the source gas includes a gas containing Si in a molecular formula and a gas containing C in a molecular formula, and the non-Si non-C-based gas contains H ₂ Is contained, and the source gas contains a gas containing Si in a molecular formula, and the non-Si non-C gas contains H ₂ And a Si-N-based film formed by including a gas containing N in a molecular formula in at least one of a raw material gas or a non-Si / non-C-based gas. Contains a gas containing Si, the non-Si non-C-based gas is a Si—O-based film formed by including a gas containing O in a molecular formula, and the raw material-based gas contains Si in a molecular formula. And a gas containing Ge. The non-Si non-C-based gas contains H ₂ Is contained, and the source gas contains a gas containing C in a molecular formula, and the non-Si non-C gas contains H. ₂ Is a C-based film formed by the inclusion of
[0043]
Further, a thin film device according to the present invention includes the above film. In particular, the thin film device is a photoelectric conversion device, a photoreceptor device, or a display device, and the base is a flat plate, a cylinder, or a film.
[0044]
Further, the present invention is characterized in that it is a film processing system in which a plurality of processing chambers including at least one apparatus for realizing the Cat-PECVD method are connected.
[0045]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings schematically illustrating the embodiments. FIG. 1 is an overall view showing an example of an apparatus for realizing the Cat-PECVD method of the present invention. In the case where the film-forming surface of a flat substrate is oriented in a direction perpendicular to the paper, a thermal catalyst is incorporated. It is sectional drawing in the 2nd gas introduction pipe position. FIG. 2 shows an example in which the gas introduction pipes are arranged in an array, and is a cross-sectional view when the film forming surface of the substrate is oriented in a direction parallel to the plane of the drawing. Only a part of the introduction pipe unit is shown, and the details of the end structure of the first gas introduction pipe made of a metal material also serving as an antenna electrode are omitted: see FIGS. FIG. 3 is a cross-sectional view of the array-like gas introduction pipe viewed from the central axis direction. FIG. 4 is a cross-sectional view showing a detailed structure of a first gas introduction pipe made of a metal material that also functions as an antenna electrode without incorporating a thermal catalyst. FIG. 5 is a perspective view showing a three-dimensional structure of a second gas introduction pipe containing a thermal catalyst.
[0046]
In these figures, 101 is an inlet for a raw material gas containing a gas containing Si and / or C in the molecular formula, 102 is an inlet for a non-Si non-C gas consisting of a gas not containing Si and C in the molecular formula, 103 is a thermal catalyst, 104 is a power supply for heating the thermal catalyst 103, 105 is plasma, 106a is a first gas introduction pipe made of a metal material which does not incorporate the thermal catalyst and also serves as an antenna electrode, and 106b is a thermal catalyst , A high-frequency power supply, 108a a phase converter, 108b a power distributor, 109, 109a and 109b are substrates for film formation, 110 is a heater for heating the substrate, and 111a is a heater for heating the substrate. A gas outlet provided in the first gas introduction tube 106a which also functions as an antenna electrode without incorporating a thermal catalyst, and 111b is a gas outlet provided in the second gas introduction tube 106b which incorporates a thermal catalyst. Outlet, 112 a chamber insulating member for electrically insulating and 113 constituting the deposition space (film deposition chamber), 114a and 114b is a hollow portion of the gas inlet tube.
[0047]
As described above, in the Cat-PECVD method of the present invention, the raw material gas containing the gas containing Si and / or C in the molecular formula, and the Si in the molecular formula heated by the thermal catalyst disposed in the gas introduction path. The non-Si non-C-based gas composed of a gas not containing C passes through the hollow portions of the first and second gas introduction pipes having a hollow structure installed in the film forming space in a state where they are separated from each other. When being ejected from the plurality of gas ejection ports provided in these gas introduction pipes into the film forming space, the raw material gas passes through the first gas introduction pipe made of a metal material, and the non-Si non-C-based gas passes through the first gas introduction pipe. The mixed gas of the raw material gas and the non-Si non-C-based gas ejected to the film formation space through the second gas introduction pipe, respectively, is injected to the film formation space. Connected to the gas inlet pipe Is decomposed and activated by plasma generated by high-frequency power from the high-frequency power supply, and a film is deposited on a substrate disposed in the film-forming space so as to face the first and second gas introduction pipes. It is characterized by.
[0048]
Although not shown, the chamber 113 is evacuated by a vacuum pump. At this time, it is desirable to use a dry pump such as a turbo-molecular pump in order to suppress impurities from being exhausted from the exhaust system into the film formed on the substrate. At this time, the ultimate vacuum degree is at least 1 × 10 ^-3 Pa or less and 1 × 10 ^-4 It is more desirable to set it to Pa or less. The pressure during film formation is in the range of about 10 to 1000 Pa. The temperature of the substrate 109 by the substrate heating heater 110 is set to a temperature of 100 to 400 ° C, preferably 150 to 350 ° C.
[0049]
Hereinafter, each part will be described in detail.
= Separation of the first gas introduction pipe and the second gas introduction pipe =
First, the purpose of separating the first gas introduction pipe and the second gas introduction pipe is to separate the antenna electrode having a built-in thermal catalyst, as already described in the section of “Prior art and its problems”. When used, it is to solve the problem that the plasma generation may not always be stabilized due to the interaction between the high-frequency power for plasma generation and the power for heating the thermal catalyst. This can be realized by making the first gas introduction tube function as an antenna electrode and incorporating a thermal catalyst in the second gas introduction tube as in the present invention. As a result, uniform plasma generation can be stably and easily realized, and a uniform film thickness and uniform film quality can be formed in a large area.
= Material of the second gas inlet tube =
Further, the second gas introduction pipe of the present invention is desirably made of a nonmetallic material. As the nonmetallic material, a ceramic material such as glass, quartz, alumina, or SiC can be used. This solves the problem that the antenna electrode may be heated and deformed by radiant heat from the thermal catalyst, which has been a problem when using an antenna electrode made of a metal material having a built-in thermal catalyst.
= Gas inlet tube shape =
First, as the shape of the first gas introduction tube made of a metal material also serving as an antenna electrode, a shape such as a rod shape or a U shape can be selected. Specifically, the rod-shaped thing is the simplest thing, for example, is disclosed in JP-A-1-47875, JP-A-1-230782, and JP-A-2001-274101. The U-shape is disclosed in JP-A-4-21781.
[0050]
Here, the reason why the antenna type electrode is used instead of the conventional flat type electrode is as follows. Generally, the relationship between the frequency f of the high frequency power supply and the wavelength λ is given by λ = v / f in the plasma. Here, v is the propagation speed of the electromagnetic wave in the plasma, which is smaller than the speed c (light speed) of the electromagnetic wave in vacuum, so that λ is at most c / f or less. On the other hand, assuming that the length L of one side of the square electrode is a typical characteristic length as the size of the plasma generation electrode, if λ≫L, an electromagnetic wave interference effect does not occur and uniform plasma is generated. In addition, it is possible to form a film having a uniform thickness and a uniform film quality. For example, when f = 13.5 MHz, λ is about 22 m at the maximum, and it can be seen that the interference effect is not a problem with a 1 m square size plasma generating electrode.
[0051]
However, when the frequency f of the high frequency power supply is increased and λ / 4 becomes a value of about L or less, the interference effect cannot be ignored. For example, when f = 60 MHz, λ / 4 is 1.25 m at the maximum, and an interference effect occurs in a simple plate-shaped plasma generating electrode of 1 m square size, and a uniform electromagnetic field distribution, that is, uniform plasma generation is performed. Can not be expected.
[0052]
For this reason, in the case of forming a large-area film having a size of about 1 m square or more in a region where the frequency of the high-frequency power supply is equal to or higher than the VHF band, an antenna-type electrode is used instead of a flat-type plasma generation electrode, and a phase control technique described later is used. The development of technology for making the plasma generation uniform by introducing GaN is progressing, and this technology can also be used in the present Cat-PECVD method.
[0053]
The cross-sectional shape parallel to the direction perpendicular to the long axis direction of the antenna electrode may be generally a circle or a square. However, when more uniform film forming characteristics are particularly required, a more uniform plasma generation can be obtained. Is preferably a square that can realize the following.
= Installation position of thermal catalyst =
Next, although the installation position of the thermal catalyst body 103 is most desirable, the inside of the second gas introduction pipe having a hollow structure as shown in FIGS. (Hollow part). The non-Si non-C-based gas heated and activated by the thermal catalyst placed inside the second gas introduction pipe can be used without excessively impairing its temperature and activity. Is fed into the plasma space generated by the first gas inlet tube also serving as an antenna electrode, and its effect on film formation can be sufficiently maintained. For example, H ₂ Using SiH as the raw material gas ₄ , A low hydrogen dilution rate (low H ₂ / SiH ₄ Ratio) or low-frequency high-frequency power conditions make it easier to form a crystalline Si film, and also make it easier to form a hydrogenated amorphous Si film with a low hydrogen concentration in the film, which was also difficult without using a thermal catalyst. The effect of becoming dull is obtained.
[0054]
As described above, the installation position of the thermal catalyst body 103 is most desirably inside the second gas introduction pipe. However, even when the heat catalyst body 103 is installed in the gas path on the upstream side of the second gas introduction pipe, If it is particularly difficult to install the thermal catalyst inside the second gas introduction pipe, the thermal catalyst may be placed in the gas upstream of the second gas introduction pipe. It can also be installed on the route. However, in any case, it is still the most desirable to install the thermal catalyst inside the second gas introduction pipe in order to maximize the effects of the present invention.
= Array of gas introduction tubes =
Next, as for the method of arranging the gas introduction pipes, the base 109 is a plate or a film having a certain area, such as a substrate of a solar cell, for example. As shown in FIG. 2 and FIG. 3, it is preferable that a plurality of the introduction pipes are arranged in parallel and arranged in an array to form an arrayed gas introduction pipe unit. As a result, the first gas inlet tube also serving as an antenna electrode functions as an array-shaped antenna electrode unit, so that uniform and large-area plasma generation and film formation can be performed.
= Gas separation introduction method =
Next, a method for separating and introducing a raw material gas and a non-Si non-C-based gas will be described. As shown in FIGS. The gas is spouted independently from the second gas introduction pipes. At this time, the thermal catalyst 103 is desirably installed inside the second gas introduction pipe 106b into which the non-Si non-C-based gas is introduced.
[0055]
Here, the reason why the raw material gas and the non-Si non-C-based gas are separately introduced is that it is desired to heat only the non-Si non-C-based gas with the thermal catalyst. That is, if the raw material gas and the non-Si non-C-based gas are mixed and introduced, not only the non-Si non-C-based gas but also the raw-material gas is supplied by the thermal catalyst disposed in the gas introduction path. If the thermal catalyst temperature is equal to or higher than the decomposition temperature of the raw material gas, the raw material gas is decomposed and activated to form a film on the gas introduction path, and the raw material gas is heated. This is because it is significantly consumed before reaching the film forming space.
= Gas outlet position =
Next, at the gas outlet position, in the case of the second gas introduction pipe 106b in which the thermal catalyst 103 is installed, as shown in FIG. It is desirable that the heat radiation from 103 is arranged so as not to directly reach the film-forming substrate 109a or 109b. As a result, an undesired increase in the film forming surface temperature due to the radiation generated from the thermal catalyst can be avoided, and stable control of the film quality can be realized. In addition, in the case of the first gas introduction pipe 106a also serving as an antenna electrode in which the thermal catalyst is not installed, the gas ejection port may be at an arbitrary position.
= Arrangement of array antenna electrode unit =
Next, it is desirable that the array-shaped gas introduction tube unit is arranged vertically so that the array surface is parallel to the direction of gravity. By doing so, it is possible to very effectively prevent the powder from dropping and adhering to the base 109 during film formation on both sides of the array-like gas introduction tube unit as described later. In the case where a glass substrate or the like is used as the base 109, for example, the glass substrate can be transported in a vertical type, so that there is an advantage that handling becomes extremely easy without causing a problem of bending of the glass substrate. Of course, in this case, there is an advantage that the problem of bending of the array-like gas introduction pipe unit itself does not occur.
[0056]
As described above, it is desirable that the array-like gas introduction pipe unit is arranged vertically so that its array surface is parallel to the direction of gravity. The horizontal arrangement is not particularly limited so as to be perpendicular to the substrate, and the latter horizontal arrangement is adopted if the problem of the array electrode and the base body bending and the problem of powder drop adhesion can be almost ignored. No problem.
= Substrate arrangement =
Next, it is desirable that the bases 109 are arranged on both sides of the array-like gas introduction tube unit (see FIGS. 1 and 3). This enables simultaneous film formation on both sides of the array-shaped antenna electrode unit, thereby doubling the productivity of the apparatus.
= Substrate heater arrangement =
Next, as shown in FIG. 1, the substrate heater 110 is desirably disposed on both sides of the array-like gas introduction tube unit with the substrate interposed therebetween. That is, it is desirable that a substrate heater be disposed on the surface of the substrate opposite to the surface facing the array-like gas introduction pipe unit. This makes it possible to control the substrate deposition surface temperature during film deposition, and it becomes easier to realize high quality film deposition.
= Number and arrangement of array gas introduction pipe units =
Next, it is desirable that a plurality of sets of arrayed gas introduction pipe units are arranged in parallel in one film forming chamber (FIG. 2 shows an example in which three arrayed gas introduction pipe units are arranged). By doing so, simultaneous film formation by a plurality of array-like gas introduction pipe units becomes possible. Considering the simultaneous double-sided film formation with one array-like gas introduction pipe unit, for example, an array-like gas introduction pipe unit becomes 2 Simultaneous film formation on four sides is possible if the groups are arranged in parallel, and simultaneous film formation on six sides when three sets are arranged in parallel (FIG. 2 shows this case). ... If the number of arrayed gas introduction pipe units is increased in parallel, productivity as a film forming apparatus can be increased to several times or more at once. This is impossible with a conventional parallel plate type PECVD apparatus.
= Power supply method =
Next, as a method of supplying power to the first gas introduction tube 106a also serving as an antenna electrode, for example, as shown in FIG. 2, high-frequency power from a high-frequency power supply 107 is distributed by a power distributor 108b and transmitted. Alternatively, a high-frequency power supply may be provided for each of the first gas introduction pipes also serving as antenna electrodes (not shown). Here, the number of high-frequency power sources and the number of distributions do not necessarily have to match, and it is usually effective to reduce the equipment cost by realizing more power distribution with a smaller number of high-frequency power sources. If one high-frequency power supply cannot distribute and supply all necessary high-frequency power, a plurality of high-frequency power supplies can be prepared and distributed and supplied as needed.
= Phase control =
Next, in order to prevent non-uniform distribution of plasma due to unnecessary interference effects (strengthening and weakening), it is desirable that the phase of the high-frequency power is different at least between adjacent electrodes. This can be realized by using the phase converter 108a, but the same can be achieved by arranging the power supply points to the adjacent first gas introduction pipes in the array-like gas introduction pipe unit so as to be located in opposite directions to each other. (Not shown), and by using both of them, a more uniform large-area plasma can be generated.
= High frequency power supply method =
Further, as another method for making it easier to form a film having a uniform thickness and a uniform film quality over a large area, a plurality of high-frequency powers having different frequencies are superposed and supplied to the first gas introduction pipe 106a also serving as an antenna electrode. Then, there is a method of superimposing a plurality of plasmas having different spatial density distributions. As a result, the plasma density distribution can be made more uniform, so that a large-area uniform film can be formed on the substrate.
[0057]
As another method, there is a method of supplying high-frequency power of a different frequency to each of the first gas introduction pipes serving also as adjacent antenna electrodes (not shown). With this configuration, the plasma density distribution can be made more uniform by the electromagnetic interaction between the first gas introduction pipes which also serve as adjacent antenna electrodes, so that a large area and uniform film formation can be formed on the substrate. Can be performed.
[0058]
Still another method is to temporally fluctuate and modulate the high-frequency power frequency, temporally fluctuate the spatial density distribution of the plasma, and average the time, resulting in a uniform film formation. There is.
[0059]
Furthermore, if high-frequency power is intermittently supplied to the first gas introduction pipe 106a also serving as an antenna electrode, for example, by pulse-modulating plasma, the generation and growth of powder can be reduced as compared with the case of continuous plasma generation. In some cases, it can be suppressed and is effective for improving the film quality.
= High frequency power supply frequency =
Next, in the Cat-PECVD method and apparatus of the present invention, the first gas introduction pipe 106a also serving as an antenna electrode for generating plasma is connected to the high frequency power supply 107, and the frequency of the high frequency power supply 107 is 13.56 MHz or higher. In particular, the effect of the present invention, that is, the effect on large-area uniform film thickness / homogeneous film formation is remarkably exhibited in a high-frequency region of 27 MHz or more (so-called VHF band or more).
[0060]
That is, as described above, in the conventional flat electrode, a large-area film having a uniform film thickness of about 1 m square size and uniform film quality can be realized without relatively difficulty up to about 27 MHz. According to the present invention, even in a high-frequency region of 27 MHz or more, a large-area uniform film thickness / homogeneous film forming characteristic far superior to the conventional technology can be obtained.
[0061]
As the high frequency frequency of the VHF band, an arbitrary value can be selected as a continuous amount, and it is desirable to select an optimum frequency according to the electrode size and shape, but usually 40 MHz, 60 MHz is often used industrially. , 80 MHz, 100 MHz, etc. are sufficient.
[0062]
Here, the higher the frequency of the high-frequency power supply 107, the higher the electron density in the plasma, so that the decomposition activation rate of the raw material gas increases and the film forming speed increases. Further, as a non-Si non-C-based gas, H ₂ When a gas is used, the generation rate of atomic hydrogen is also increased, so that the crystallization promoting effect can be more remarkably obtained. Therefore, a crystalline Si film can be obtained even under high-speed film forming conditions.
[0063]
Further, in the present invention, the activation of the non-Si non-C-based gas can be further promoted by using the thermal catalyst, so that H ₂ When a gas is used, the effect of promoting crystallization is further increased in addition to the above-described effect of VHF itself, and a high-quality crystalline Si film can be obtained even under higher-speed film forming conditions. In particular, when forming a hydrogenated amorphous Si film, a film having a lower hydrogen concentration can be formed, and a hydrogenated amorphous Si film having more excellent light stability than that obtained by a conventional PECVD method alone can be obtained.
[0064]
Note that the frequency of the high-frequency power supply does not need to be limited to the VHF band up to about 100 MHz, and can be used up to the higher frequency UHF band and frequencies in the microwave range.
= Thermal catalyst =
Next, at least the surface of the thermal catalyst body 103 is made of a metal material in order to make the thermal catalyst body 103 function as a thermal catalyst body by applying an electric current thereto and heating and increasing the temperature by the Joule heat, but this metal material is more preferable. Is desirably made of a metal material containing at least one of Ta, W, Re, Os, Ir, Nb, Mo, Ru, and Pt as a main component. In addition, as the thermal catalyst 103, a wire material of the above-described metal material is usually used in many cases. However, it is not particularly limited to the wire shape, and a plate shape or a mesh shape may be used. it can. If the metal material as the thermal catalyst material contains impurities that are not preferable for film formation, before using the thermal catalyst 103 for film formation, a temperature higher than the heating temperature during film formation is required in advance. Preheating for several minutes or more is effective in reducing impurities.
= Power supply for heating the thermal catalyst =
As the power supply 104 for heating the thermal catalyst 103, it is usually convenient to use a DC power supply, but there is no problem even if an AC power supply with a low frequency that does not generate plasma is used. When a DC power supply is used, DC power may be intermittently supplied to the thermal catalyst 103 in order to control the degree of heating or decomposition / activation of the non-Si non-C-based gas as described later.
= Activation of non-Si non-C based gas =
Next, the non-Si non-C-based gas is heated by the thermal catalyst 103 and guided to the plasma space 105. A part of the non-Si non-C-based gas is decomposed and activated by the thermal catalyst 103, and the degree thereof is reduced to the temperature of the thermal catalyst. Proportional. For example, H ₂ The generation of atomic hydrogen by the decomposition reaction becomes remarkable when the temperature of the thermal catalyst exceeds about 1000 ° C. depending on the pressure of the gas. This atomic hydrogen acts very effectively to promote crystallization of the Si film as described above. Even when the temperature of the thermal catalyst is about 1000 ° C. or less, the generation of atomic hydrogen is not so remarkable, and the temperature condition in which the crystallization promoting effect is not so expected, the secondary effect of using the thermal catalyst is also provided. Because the gas heating effect as described above suppresses the reaction of generating higher order silane, it is still effective for forming a high quality hydrogenated amorphous silicon film. However, it is desirable that the temperature of the thermal catalyst be at least 100 ° C. or more, more preferably 200 ° C. or more, in order to obtain the above effect. By setting the temperature to 200 ° C. or higher, the effect of gas heating can be more remarkably obtained. Note that the maximum temperature of the thermal catalyst is set to 2000 ° C. or lower, more preferably 1900 ° C. or lower. If the temperature exceeds 1900 ° C., problems such as degassing of impurities from the catalyst body and peripheral members and evaporation of the material itself of the catalyst body begin to occur. If the temperature exceeds 2000 ° C., the degassing and evaporation become remarkable.
= Activation amount adjustment method =
Here, H ₂ As a method of realizing a method other than controlling the degree of heating or decomposition / activation of a non-Si non-C-based gas represented by the above-mentioned method using the temperature of the thermal catalyst, there is the following method.
[0065]
The first method is to control the surface area of the thermal catalyst 103. According to this, the degree of heating or decomposition / activation of the non-Si non-C-based gas can be controlled without lowering the temperature of the thermal catalyst body 103 while maintaining it at a certain temperature or higher. For example, in the case where a linear catalyst is used as the thermal catalyst 103, the surface area of the thermal catalyst 103 can be controlled by selecting the length and diameter of the thermal catalyst 103 and the number of the thermal catalyst 103 provided in one antenna electrode. . In particular, when a plurality of thermal catalysts 103 are installed in one antenna electrode (not shown), if these can be heated independently, the number of thermal catalysts to be heated can be determined as necessary. Thus, the degree of heating or decomposition / activation of the non-Si non-C-based gas can be changed stepwise.
[0066]
The second method is to heat the thermal catalyst 103 intermittently or periodically. Specifically, if the power of the heating power supply 104 is provided intermittently, for example, in a pulsed manner, or if a low-frequency AC power supply is used, the heating of the thermal catalyst 103 can be performed periodically. This makes it possible to continuously control the reaction time between the non-Si non-C-based gas and the thermal catalyst 103 per unit time, so that the degree of heating or decomposition / activation of the non-Si non-C-based gas is continuously controlled. Can be.
[0067]
The third method is to separately design and adjust the diameter of the source gas outlet 111a and the diameter of the non-Si non-C gas outlet 111b, or to adjust the total number of the source gas outlets 111a and the non-Si non-C The total number of system gas outlets 111b is designed and adjusted separately. The reduction in the diameter or the total number of ports in the non-Si non-C based gas outlet 111b reduces the amount of non-Si non-C based gas heated or decomposed and activated into the plasma space 105, and the non-Si non-C Increasing the diameter or increasing the total number of ports in the system gas outlet 111b can increase the amount of non-Si non-C-based gas that has been heated or decomposed and activated to the plasma space 105.
[0068]
A fourth method is to add a non-Si non-C-based gas introduction path (not shown) in which a thermal catalyst is not provided in the gas introduction path (not shown), and to adjust the flow rate of the non-Si non-C-based gas passing through the thermal catalyst 103. The purpose is to enable independent control of the flow rate of the non-Si non-C-based gas that does not pass through the thermal catalyst. That is, there are a plurality of introduction paths of the non-Si non-C-based gas, and at least one non-Si non-C-based gas is introduced into the plasma space without being heated by the thermal catalyst. As a result, the heated or decomposed / activated non-Si non-C-based gas and the non-Si non-C-based gas that are not heated can be mixed at an arbitrary gas flow ratio, and are released into the plasma space 105. The density of the heated or decomposed / activated non-Si non-C-based gas can be continuously changed. Here, the non-Si non-C-based gas introduction path which is not heated may be merged with the raw material-based gas introduction path, and the introduction structure becomes simpler if merged in this way.
= Gas path material =
Next, at least a part of the surface of at least one of the inner wall of the gas pipe and the inner wall of the hollow antenna electrode in the non-Si non-C-based gas introduction path is made of a material containing at least one of Ni, Pd, and Pt. Is desirable. These metal elements are, for example, H ₂ Since there is a catalytic action that promotes the dissociation of gas molecules, the probability that the decomposed and activated non-Si non-C-based gas is recombined and deactivated on the surface of the member can be reduced.
= Gas heating =
Next, it is desirable that a thermal catalyst be provided (not shown) also in the raw material gas introduction path in order to promote the gas heating effect. However, the temperature of the thermal catalyst is controlled to be lower than the temperature at which the raw material gas is decomposed so that the raw material gas is not decomposed by the thermal catalyst. For example, SiH is used as a source gas. ₄ Is used, the temperature is set to 500 ° C. or lower, preferably 400 ° C. or lower.
[0069]
As another method of promoting the gas heating effect, there is a method of installing a heater on the wall surface of the film forming chamber. That is, in the conventional method in which the inner wall surface of the film forming chamber is not particularly heated, a higher silane generation reaction (exothermic reaction) easily occurs on the inner wall surface of the film forming chamber having a low temperature, and this is an important factor of the deterioration of the film quality. In contrast to the cause of powder generation, this method actively heats the inner wall of the film-forming chamber, which suppresses the exothermic reaction of higher silane generation and reduces the amount of powder generated. it can. Here, when the raw material gas contains a gas containing Si in a molecular formula, the temperature of the heater is set to 500 ° C. or lower, preferably 400 ° C. or lower. Thereby, the thermal CVD reaction (film formation reaction) on the heater surface is sufficiently suppressed, so that the waste of the source gas in this portion can be suppressed.
= Doping gas introduction method =
Next, when supplying a doping gas, the doping gas can be introduced into the source gas introduction path and / or the non-Si non-C-based gas introduction path. At this time, the p-type doping gas contains B ₂ H ₆ Etc., and the n-type doping gas is PH ₃ Etc. can be used.
= Electric circuit =
It is desirable to provide a pass capacitor (not shown) as a high-frequency blocking means in the circuit of the catalyst body heating power supply 104. Thus, the entry of high-frequency components from the high-frequency power supply can be prevented, and stable film formation can be realized more reliably.
= Substrate shape =
As the base 109, for example, in the case of a device such as a solar cell, a plate-shaped substrate such as a glass substrate, or a film-shaped substrate such as a metal material or a resin material can be used. In this case, a non-flat plate such as a cylinder can be used.
= Membrane =
According to the Cat-PECVD method of the present invention, it is possible to form a high-speed, high-quality film with high uniformity in both film thickness and film quality over a large area. Are disclosed in Japanese Patent Application Nos. 2001-29331 and 2002-38686 filed by the present inventors), and specifically, the effect is remarkably exerted particularly on a Si-based film or a C-based film described below. .
[0070]
In the first example, the raw material gas contains a gas containing Si in the molecular formula, but does not contain a gas containing C in the molecular formula, and the non-Si non-C-based gas contains H. ₂ Is a Si-based film formed by including Si. Specifically, for example, the raw material gas is SiH ₄ And H for non-Si non-C-based gas ₂ Is used, a high-quality hydrogenated amorphous silicon film or a high-quality crystalline silicon film can be formed at a high speed and with a high uniformity of film thickness and film quality over a large area for the above-mentioned reason. .
[0071]
According to the method of the present invention, the hydrogen concentration in the hydrogenated amorphous silicon film can be set to 15 atomic% or less. More preferably, it can be set to 10 atomic% or less, further preferably 5 atomic% or less, whereby the problem of photodeterioration of the hydrogenated amorphous silicon film, which has been a long-standing problem, can be significantly reduced. When used for a battery, high stabilization efficiency can be obtained.
[0072]
Further, according to the method of the present invention, the hydrogen concentration in the crystalline silicon film can be set to 10 atomic% or less. More preferably, it can be set to 5 atomic% or less, further preferably 3.5 atomic% or less, whereby the deterioration with time of the characteristics due to the post-oxidation phenomenon at the crystal grain boundary described in the section of the embodiment of the solar cell described later. Can be reduced. That is, by setting the hydrogen content in the film to 5 atomic% or less, the temporal deterioration rate can be reduced to about several percent or less, and by setting the hydrogen concentration in the film to 3.5 atomic% or less, the temporal deterioration rate can be made almost zero.
[0073]
In the second example, the source gas contains a gas containing Si in the molecular formula and a gas containing C in the molecular formula, and the non-Si non-C-based gas contains H ₂ Is a Si-C-based film formed by including the above. Specifically, for example, the raw material gas is SiH ₄ And CH ₄ And H for non-Si non-C-based gas ₂ Is used to form a high-quality hydrogenated amorphous silicon carbide film or a high-quality crystalline silicon carbide film at a high speed and with high uniformity of film thickness and film quality over a large area for the reasons already described above. Can be.
[0074]
In the third example, the source gas contains a gas containing Si in a molecular formula, and the non-Si non-C gas contains H. ₂ , And the gas containing N in the molecular formula is a Si—N-based film formed by being included in at least one of a source gas or a non-Si non-C-based gas. Specifically, for example, the raw material gas is SiH ₄ And H for non-Si non-C-based gas ₂ With NH as a gas containing N ₃ Is used to form a high-quality hydrogenated amorphous silicon nitride film or a high-quality crystalline silicon nitride film at a high speed and with a high uniformity of film thickness and film quality over a large area for the reasons described above. Can be.
[0075]
The fourth example is a Si—O-based film formed by including a gas containing Si in the molecular formula in the raw material-based gas and a gas containing O in the molecular formula in the non-Si non-C-based gas. . Specifically, for example, the raw material gas is SiH ₄ And if necessary H ₂ For non-Si non-C based gas ₂ If He or Ar is used, a high-quality amorphous silicon oxide film or a high-quality crystalline silicon oxide film can be formed at a high speed over a large area with high uniformity of film thickness and film quality for the above-mentioned reason. Can be formed.
[0076]
In the fifth example, the source gas contains a gas containing Si in a molecular formula and a gas containing Ge, and the non-Si non-C gas contains H ₂ Is a Si-Ge-based film formed by including Si. Specifically, for example, the raw material gas is SiH ₄ And GeH ₄ And H for non-Si non-C-based gas ₂ Is used to form a high-quality hydrogenated amorphous silicon germanium film or a high-quality crystalline silicon germanium film at a high speed and with high uniformity of film thickness and film quality over a large area for the reasons already described above. Can be.
[0077]
In the sixth example, the source gas contains a gas containing C in the molecular formula, and the non-Si non-C-based gas contains H. ₂ Is a C-based film formed by the inclusion of Specifically, for example, CH- ₄ And a small amount of O if necessary ₂ And H for non-Si non-C-based gas ₂ By using, a high-quality amorphous carbon film or a high-quality crystalline carbon film can be formed at a high speed over a large area with high uniformity of film thickness and film quality for the above-mentioned reason. Specifically, a film such as a diamond film or a diamond-like carbon film can be formed.
= Thin film device =
Next, when the film formed by the Cat-PECVD method of the present invention is used for a thin film device, the following thin film device can be manufactured at high performance and at low cost.
[0078]
A first example of a thin film device is a photoelectric conversion device. If a film formed by the Cat-PECVD method of the present invention is used for a photoactive layer, high-performance characteristics can be realized at high speed, that is, at low cost. In particular, in the case of a solar cell, which is a representative example of a photoelectric conversion device, the high-speed, high-quality, large-area film forming characteristics of the Cat-PECVD method of the present invention are sufficiently exhibited to produce a high-efficiency and low-cost thin-film solar cell. be able to. Other than the solar cell, a similar effect can be obtained with a device having a photoelectric conversion function such as a photodiode, an image sensor, or an X-ray panel.
[0079]
The second example of the device is a photoreceptor device. If a film formed by the Cat-PECVD method of the present invention is used for the photoreceptive layer, high-performance characteristics can be realized at high speed, that is, at low cost. In particular, when used for a silicon-based film in a photosensitive drum, a relatively thick silicon-based film ranging from several μm to several tens μm can be formed with high quality in a short time, which is very effective in reducing the manufacturing cost.
[0080]
The third example of a device is a display device. If a film formed by the Cat-PECVD method of the present invention is used as a driving film, high-performance characteristics can be realized at high speed, that is, at low cost. In particular, when it is used for an amorphous silicon film or a polycrystalline silicon film in a TFT, which is a representative example of a large-area device next to a solar cell, it is very effective in reducing the manufacturing cost for the same reason as described for the solar cell. Similar effects can be obtained with devices having a display function such as an image sensor and an X-ray panel other than the TFT.
= Apparatus (see FIG. 6) =
The film processing system for realizing the Cat-PECVD method of the present invention is a film processing system including a plurality of vacuum chambers having at least one film forming chamber capable of realizing the above-described method.
[0081]
Here, the plurality of vacuum chambers include at least a p-type film forming film forming chamber, an i-type film forming film forming chamber, and an n-type film forming film forming chamber. The chamber is desirably a film forming chamber capable of realizing the Cat-PECVD method of the present invention.
[0082]
It is preferable that at least one of the plurality of vacuum chambers is a film forming chamber capable of realizing the Cat-CVD method. This enables, for example, a high-speed and high-quality hydrogenated amorphous silicon film to be formed by a Cat-CVD method. For example, a hydrogenated amorphous silicon film can be used as a photoactive layer of a top cell of a tandem solar cell. For example, the degree of freedom in combination when forming a multilayer film can be increased. It is known that a hydrogenated amorphous silicon film formed by the Cat-CVD method can have a lower hydrogen concentration than that formed by the PECVD method, and it is possible to realize a smaller optical bandgap characteristic which is more excellent in light absorption characteristics. it can. Further, there is an advantage that the photodegradation characteristic, which has been a long-standing problem of the hydrogenated amorphous silicon film, can be suppressed to a low level.
[0083]
It is preferable that at least one of the plurality of vacuum chambers is a film forming chamber capable of realizing the PECVD method. This increases the degree of freedom of combination when forming a multilayer film, for example, film deposition on a film surface that is weak to the reduction action of atomic hydrogen such as an oxide transparent conductive film can be realized under conditions where this reduction action is suppressed as much as possible. be able to.
[0084]
Further, it is desirable that the plurality of vacuum chambers include at least a front chamber for the purpose of not opening the film forming chamber to the atmosphere. Further, if the plurality of vacuum chambers include at least a front chamber and a rear chamber, productivity is improved. More desirable above. Also, it is desirable that the plurality of vacuum chambers include at least a heating chamber in order to improve productivity.
[0085]
In the method of arranging the plurality of vacuum chambers, the plurality of vacuum chambers can be connected and arranged in a linear manner continuously, or the plurality of vacuum chambers are arranged in a star shape so as to be connected to at least one existing core chamber. You can also.
[0086]
Here, it is desirable that the film forming chamber is of a vertical type in which a substrate such as a glass substrate is processed in a vertical type. By using the vertical type, it is less susceptible to the drop adhesion of foreign matter such as powder, which is a problem in the horizontal deposition method, and the uneven temperature on the base film formation surface due to the warpage of the substrate, which is a problem in the horizontal deposition method. Distribution is less likely to occur. However, as long as these problems do not actually cause a problem, a horizontal type may be used.
= Thin-film Si solar cell =
Hereinafter, a thin-film Si solar cell will be described as an embodiment of the device according to the present invention with reference to FIG. In FIG. 10, 11 is a translucent substrate, 12 is a first transparent conductive film, 13 is a semiconductor multilayer film, 13a is a first semiconductor bonding layer, 13b is a second semiconductor bonding layer, and 14 is a second transparent conductive layer. A conductive film, 15a is a metal film serving as a first extraction electrode, and 15b is a metal film serving as a second extraction electrode.
[0087]
First, the translucent substrate 11 is prepared. As the translucent substrate 11, a plate material or a film material made of glass, plastic, resin, or the like can be used.
[0088]
Next, the first transparent conductive film 12 is formed. The material of the transparent conductive film 12 is SnO ₂ Well-known materials such as ITO, ITO, and ZnO can be used. However, when a subsequent Si film is formed, SiH ₄ And H ₂ Therefore, it is desirable to form a ZnO film having excellent reduction resistance at least as a final surface, since it will be exposed to a hydrogen gas atmosphere caused by the use of GaN. Known techniques such as a CVD method, a vapor deposition method, an ion plating method, and a sputtering method can be used as a film forming method. The thickness of the first transparent conductive film 12 is adjusted in the range of about 60 to 500 nm in consideration of the antireflection effect and the reduction in resistance.
[0089]
Next, the semiconductor multilayer film 13 is formed. Here, a tandem type in which semiconductor films are stacked in a pinpin (or nipnip) configuration will be described as an example, but a single junction in which a semiconductor film is stacked in a pin (or nip) configuration is not limited to the tandem type. The contents described in the present embodiment can of course be applied to a triple junction type in which a semiconductor film is stacked in a pinpinpin (or nipnipnip) configuration or a multi-junction type element structure of a triple junction type or higher.
[0090]
First, a first semiconductor bonding layer 13a including a hydrogenated amorphous silicon film in a photoactive layer is formed. Specifically, it is preferable to have a p-type layer (n-type layer) / photoactive layer / n-type layer (p-type layer) structure (not shown), and the photoactive layer is i-type. The above notation indicates the order of film formation, meaning lower layer / upper layer.
[0091]
Here, as the p-type layer (n-type layer), a crystalline silicon film including a hydrogenated amorphous silicon film or a microcrystalline silicon film can be used. The film thickness is adjusted in the range of about 2 to 100 nm depending on the material. 1 × 10 for doping element concentration ¹⁸ ~ 1 × 10 ²¹ / Cm ³ As a degree, substantially p ⁺ Type (n ⁺ Type). The SiH used for film formation ₄ , H ₂ And the doping gas B ₂ H ₆ (PH ₃ )) Plus CH ₄ If an appropriate amount of gas containing C (carbon) such as _x C _1-x A film is obtained, which is very effective for forming a window layer with small light absorption loss, and is also effective for reducing a dark current component for improving an open circuit voltage. A similar effect can be obtained by mixing an appropriate amount of a gas containing O (oxygen) or a gas containing N (nitrogen) in addition to C. Here, as a method for forming the silicon film, a conventionally known PECVD method or Cat-CVD method can be used, but the method of the present invention can be used as a matter of course.
[0092]
Next, a hydrogenated amorphous silicon film is used for the photoactive layer, and the film thickness is adjusted in the range of about 0.1 to 0.5 μm. The conductivity type is basically i-type, but for the purpose of fine adjustment of the internal electric field strength distribution, n ⁻ Type (p ⁻ (Actually, even a non-doped film usually shows a slight n-type characteristic). Here, as a method for forming the hydrogenated amorphous silicon film, a conventionally known PECVD method or Cat-CVD method can be used. However, if the method of the present invention is used, a high-quality hydrogenated amorphous silicon film can be obtained. Since the film can be formed at a high speed with a large area and with high productivity, it is particularly effective for manufacturing a high-efficiency and low-cost thin-film Si solar cell. Further, according to the present invention, the hydrogen concentration in the film can be reduced to 15 atomic% or less, but more preferably 10 atomic% or less, more preferably 5 atomic% or less, which is difficult to realize by the conventional PECVD method. Since a film is obtained, the degree of photodegradation, which has been a problem of hydrogenated amorphous silicon films for many years, can be reduced.
[0093]
Finally, as the n-type layer (p-type layer), a crystalline silicon film including a hydrogenated amorphous silicon film and a microcrystalline silicon film can be used. The thickness is adjusted in the range of about 2 to 100 nm depending on the material. 1 × 10 for doping element concentration ¹⁸ -10 ²¹ / Cm ³ The degree is substantially n ⁺ Type (p ⁺ Type). The SiH used for film formation ₄ , H ₂ And the doping gas PH ₃ (B ₂ H ₆ )) Plus CH ₄ If an appropriate amount of gas containing C (carbon) such as _x C _1-x A film can be obtained, and a film with little light absorption loss can be formed, and it is also effective in reducing a dark current component for improving an open circuit voltage. A similar effect can be obtained by mixing an appropriate amount of a gas containing O (oxygen) or a gas containing N (nitrogen) in addition to C. Here, as a method for forming the silicon film, a conventionally known PECVD method or Cat-CVD method can be used, but the method of the present invention can be used as a matter of course.
[0094]
In order to further improve the junction characteristics, an i-type non-conductive layer is formed between the p-type layer (n-type layer) and the photoactive layer or between the photoactive layer and the n-type layer (p-type layer). Single-crystal Si layer or non-single-crystal Si _x C _1-x Layers may be inserted. At this time, the thickness of the insertion layer is about 0.5 to 50 nm.
[0095]
Next, a second semiconductor bonding layer 13b including a crystalline silicon film in the photoactive layer is formed. Specifically, it is desirable to use a p-type layer (n-type layer) / photoactive layer / n-type layer (p-type layer) (not shown), and the photoactive layer is preferably i-type.
[0096]
Here, as the p-type layer (n-type layer), a crystalline silicon film including a hydrogenated amorphous silicon film or a microcrystalline silicon film can be used. The thickness is adjusted in the range of about 2 to 100 nm depending on the material. Doping element concentration is 1 × 1E18 to 1E21 / cm ³ As a degree, substantially p ⁺ Type (n ⁺ Type). Note that the SiH used for film formation is ₄ , H ₂ And the doping gas B ₂ H ₆ (PH ₃ )) Plus CH ₄ If an appropriate amount of gas containing C (carbon) such as _x C _1-x A film is obtained, which is very effective for forming a window layer with small light absorption loss, and is also effective for reducing a dark current component for improving an open circuit voltage. A similar effect can be obtained by mixing an appropriate amount of a gas containing O (oxygen) or a gas containing N (nitrogen) in addition to C. Here, as a method for forming the silicon film, a conventionally known PECVD method or Cat-CVD method can be used, but the method of the present invention can be used as a matter of course.
[0097]
Next, a crystalline silicon film typified by a microcrystalline silicon film is used for the photoactive layer, and the thickness is adjusted in a range of about 1 to 3 μm. The conductivity type is basically i-type, but for the purpose of fine adjustment of the internal electric field strength distribution, n ⁻ Type (p ⁻ Type). At this time, as the film structure, the surface shape after film formation is suitable for optical confinement as an aggregate of (110) -oriented columnar crystal grains generated as a result of preferential growth of the (110) plane among the crystal planes. It is desirable to have a self-generated uneven structure. Here, as a method for forming the crystalline silicon film, a conventionally known PECVD method or Cat-CVD method can be used. However, by using the method of the present invention, a high-quality crystalline silicon film can be formed. Since a film can be formed at a high speed and with a large area and with high productivity, it is particularly effective for manufacturing a high-efficiency and low-cost thin-film Si solar cell. Further, according to the present invention, a crystalline silicon film having a hydrogen concentration in the film of 10 atomic% or less can be obtained, but a film having a low hydrogen concentration of 5 atomic% or less, still more preferably 3.5 atomic% or less can be obtained. Obtainable.
[0098]
Here, in the case of a crystalline silicon film, most of the hydrogen is present in the crystal grain boundary portion, and the bonding state of the hydrogen with Si and the density thereof are determined by the quality of the crystal grain boundary (the carrier reclamation at the crystal grain boundary). (Proportional to the reciprocal of the binding rate). That is, SiH is a state in which two H atoms and two other Si atoms are bonded to one Si atom existing at the crystal grain boundary. ₂ The higher the bond density, the more the so-called post-oxidation phenomenon (when the film is exposed to the ₂ , CO ₂ , H ₂ Oxygen-containing gas components such as O diffuse, adsorb, and oxidize at the crystal grain boundaries in the film, causing a change in the bonding state of the crystal grain boundaries.) Of the film quality with the passage of time (that is, deterioration of the characteristics with the passage of time). However, as the hydrogen concentration in the film decreases, the SiH ₂ Since the bond density is also reduced, it is possible to reduce the deterioration with time due to the post-oxidation. Specifically, when the hydrogen concentration in the film is 5 atomic% or less, the temporal deterioration rate can be suppressed to about several percent or less, and when the hydrogen concentration in the film is 3.5 atomic% or less, the temporal deterioration rate becomes almost zero. can do. As a result, a more efficient solar cell can be manufactured.
[0099]
Finally, as the n-type layer (p-type layer), a crystalline silicon film including a hydrogenated amorphous silicon film and a microcrystalline silicon film can be used. The thickness is adjusted in the range of about 2 to 100 nm depending on the material. 1 × 10 for doping element concentration ¹⁸ -10 ²¹ / Cm ³ The degree is substantially n ⁺ Type (p ⁺ Type). The SiH used for film formation ₄ , H ₂ And the doping gas PH ₃ (B ₂ H ₆ )) Plus CH ₄ If an appropriate amount of gas containing C (carbon) such as _x C _1-x A film can be obtained, and a film with little light absorption loss can be formed, and it is also effective in reducing a dark current component for improving an open circuit voltage. A similar effect can be obtained by mixing an appropriate amount of a gas containing O (oxygen) or a gas containing N (nitrogen) in addition to C. Here, as a method for forming the silicon film, a conventionally known PECVD method or Cat-CVD method can be used, but the method of the present invention can be used as a matter of course.
[0100]
In order to further improve the junction characteristics, substantially i-type non-single-crystal Si is provided between the p-type layer (n-type layer) and the photoactive layer or between the photoactive layer and the n-type layer (p-type layer). Layers may be inserted. At this time, the thickness of the insertion layer is about 0.5 to 50 nm.
[0101]
Next, a second transparent conductive film 14 is formed. As a transparent conductive film material, SnO as a metal oxide material is used. ₂ , ITO, ZnO and the like can be used. Known techniques such as a CVD method, an evaporation method, an ion plating method, a sputtering method, and a sol-gel method can be used as a film forming method. The second transparent conductive film 14 can be omitted when high efficiency is not particularly required.
[0102]
Finally, a metal film 15a and a metal film 15b to be the extraction electrodes 1 and 2 are formed. As the metal material, it is desirable to use Al, Ag, or the like, which has excellent conductivity and light reflection properties. As the film forming method, known techniques such as an evaporation method, a sputtering method, an ion plating method, and a screen printing method can be used. The electrode pattern can be formed into a desired pattern by using a masking method, a lift-off method, or the like. At this time, the film thickness is about 0.1 μm or more. When the adhesive strength between the metal film 15a and the second transparent conductive film 14 or between the metal film 15b and the first transparent conductive film 12 is low, a thin metal film such as Ti which is easily oxidized has a thickness of 1 to 4. It is preferable to intervene between the two films at about 10 nm.
[0103]
When a light confinement structure is introduced for the purpose of further improving the conversion efficiency, the structure described in Japanese Patent Application No. 2002-78196 can be employed. That is, the maximum height Rmax of the unevenness at the interface between the first transparent conductive film and the semiconductor multilayer film is smaller than the maximum height Rmax of the unevenness at the interface between the second transparent conductive film and the metal film. (At this time, the maximum height Rmax of the unevenness at the interface between the first transparent conductive film and the semiconductor multilayer film is preferably 0.08 μm or less, and the second transparent conductive film and the metal The maximum height Rmax of the unevenness at the interface with the film is preferably 0.05 μm or more), and the maximum height Rmax of the unevenness at the interface between the semiconductor multilayer film and the second transparent conductive film is the first height. The maximum height Rmax of the unevenness at the interface between the transparent conductive film and the semiconductor multilayer film is smaller than the maximum height Rmax of the unevenness at the interface between the second transparent conductive film and the metal film. Or a light-transmitting structure The structure in which the interface between the conductive substrate and the first transparent conductive film has a concavo-convex structure can form an effective light confinement structure, so that the photocurrent density increases. And higher conversion efficiency can be realized.
[0104]
As described above, according to the present invention, a high-quality Si thin film can be formed at high speed and in a large area with high productivity, so that a high-efficiency and low-cost thin-film Si solar cell can be manufactured. .
[0105]
【The invention's effect】
According to the Cat-PECVD method of claims 1 to 9, a raw material gas containing a gas containing Si and / or C in a molecular formula, and Si in a molecular formula heated by a thermal catalyst disposed in a gas introduction path. And a non-Si non-C-based gas composed of a gas not containing C pass through the hollow portions of the first and second gas introduction pipes having a hollow structure installed in the film forming space in a state where they are separated from each other. When the raw material gas is ejected from the plurality of gas outlets provided in these gas introduction pipes into the film forming space, the raw material gas passes through the first gas introduction pipe also serving as an antenna electrode and passes through the first non-Si non-C gas. Is ejected into the film formation space through the second gas introduction pipe, and the mixed gas of the raw material gas and the non-Si non-C gas ejected into the film formation space is mixed with the first gas introduction gas. High frequency power supply connected to pipe Is decomposed and activated by the plasma generated by the high-frequency power, and a film is deposited on the substrate disposed in the film formation space so as to face the first and second gas introduction pipes. Interaction between high-frequency power and power for heating the thermal catalyst can be eliminated, making it easier to achieve uniform plasma generation, making it possible to form a uniform film and a uniform film quality over a large area. it can.
[0106]
In particular, in the Cat-PECVD method according to the second aspect, since the second gas introduction pipe is made of a nonmetallic material, it is possible to suppress the gas introduction pipe from being heated and deformed by radiant heat of the thermal catalyst.
[0107]
Further, according to the film of claims 10 to 18 and the thin film device of claims 19 to 21, the uniformity of film thickness and film quality over a large area is high, and high-performance and rapid production is possible. Can be.
[0108]
According to the film processing system of claim 22, it is possible to manufacture a thin film device with high productivity.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view illustrating an apparatus structure for realizing a Cat-PECVD method according to the present invention.
FIG. 2 is a diagram schematically illustrating an example of an arrangement of gas introduction pipes for realizing the Cat-PECVD method according to the present invention, and is a cross-sectional view of a film forming surface of a substrate.
FIG. 3 is a diagram schematically illustrating an example of an arrangement of gas introduction pipes for realizing the Cat-PECVD method according to the present invention, and is a cross-sectional view as viewed from a central axis direction of the gas introduction pipe.
FIG. 4 is a diagram schematically illustrating an example of a first gas introduction pipe that does not incorporate a thermal catalyst for realizing the Cat-PECVD method according to the present invention, where the central axis direction of the gas introduction pipe is vertical. FIG.
FIG. 5 is a perspective view schematically illustrating a second gas introduction pipe example made of a metal material that also functions as an antenna electrode without incorporating a thermal catalyst for realizing the Cat-PECVD method according to the present invention.
FIG. 6 is a configuration diagram schematically illustrating a film processing system according to the present invention.
FIG. 7 is a cross-sectional view schematically illustrating an example of a conventional PECVD apparatus.
FIG. 8 is a cross-sectional view schematically illustrating an example of a conventional Cat-CVD apparatus.
FIG. 9 is a cross-sectional view schematically illustrating an example of a Cat-PECVD apparatus.
FIG. 10 is a sectional view schematically showing an example of a thin film device according to the present invention.
[Explanation of symbols]
11: Translucent substrate
12: first transparent conductive film
13: Semiconductor multilayer film
13a: first semiconductor bonding layer
13b: second semiconductor bonding layer
14: second light-transmitting conductive film
15a: Extraction electrode 1
15b: extraction electrode 2
101: Source gas supply port
102: Non-Si non-C-based gas supply port
103: thermal catalyst
104: Power supply for heating the thermal catalyst
105: Plasma
106a: 1st gas introduction pipe (also serves as antenna electrode)
106b: 2nd gas introduction pipe
107: High frequency power supply
108a: phase converter
108b: power distributor
109: Substrate
110: Substrate heater
111a: gas ejection port of first gas introduction pipe
111b: Gas ejection from the second gas introduction pipe
112: insulating member
113: Chamber
114a: hollow portion (non-Si non-C gas path)
114b: hollow portion (source gas path)

Claims (22)

A non-Si non-C-based gas composed of a raw material gas containing a gas containing Si and / or C in a molecular formula, and a gas not containing Si and C in a molecular formula heated by a thermal catalyst disposed in a gas introduction path Are separated from each other, pass through the hollow portions of the first and second gas introduction pipes having a hollow structure installed in the film forming space, and a plurality of gas ejection ports provided in the gas introduction pipes When the raw material-based gas is ejected from the film forming space through the first gas introduction pipe also serving as an antenna electrode, the non-Si non-C-based gas passes through the second gas introduction pipe, thereby forming the film-forming gas. The mixed gas of the raw material gas and the non-Si non-C gas ejected into the space and ejected into the film forming space is generated by high-frequency power from a high-frequency power supply connected to the first gas introduction pipe. By the plasma Cat-PECVD method characterized by the membrane is deposited on the first and second oppositely disposed substrates gas introduction pipe is decomposed and activated, in the film forming space Te. The Cat-PECVD method according to claim 1, wherein the second gas introduction pipe is made of a non-metallic material. 2. The Cat-PECVD method according to claim 1, wherein the first gas introduction tube serving also as the antenna electrode has a rod shape or a U shape. 3. The Cat-PECVD method according to claim 1, wherein the thermal catalyst is provided in a hollow portion of the second gas introduction pipe. 2. The Cat-PECVD method according to claim 1, wherein a plurality of the gas introduction pipes are arranged in parallel to form an array gas introduction pipe unit. 3. The Cat-PECVD method according to claim 5, wherein the bases are arranged on both sides of the array-like gas introduction pipe unit. The Cat-PECVD method according to claim 5, wherein a substrate heating heater is disposed on a surface of the substrate opposite to a surface facing the arrayed gas introduction pipe unit. A plurality of the arrayed gas introduction pipe units are present in one film forming chamber, and each unit is arranged so that each array surface is parallel. The Cat-PECVD method according to claim 5, wherein the apparatus has a device configuration capable of forming a film. 2. The Cat-PECVD method according to claim 1, wherein a gas for doping the film is introduced into the source gas introduction path and / or the non-Si non-C gas introduction path. 3. A film formed by the Cat-PECVD method according to claim 1. The film is formed by including a gas containing Si in the molecular formula but not a gas containing C in the molecular formula in the raw material gas, and containing H _{2 in the} non-Si non-C-based gas. The film according to claim 10, wherein the film is a Si-based film. The film according to claim 11, wherein the Si-based film is a hydrogenated amorphous Si film, and a hydrogen concentration in the film is 15 atomic% or less. The film according to claim 11, wherein the Si-based film is a crystalline Si film, and a hydrogen concentration in the film is 10 atomic% or less. In the film, the source-based gas includes a gas including Si in a molecular formula and a gas including C in a molecular formula, and the non-Si non-C-based gas includes H ₂ to form a Si—C-based gas. The film according to claim 10, which is a film. The membrane, wherein the raw material based gas includes a gas containing Si in the molecular formula, wherein the non-Si non-C-based gas include H _2, at least one of the raw material based gas or non-Si · non-C-based gas The film according to claim 10, wherein the film is a Si-N-based film formed by including a gas containing N in a molecular formula. The film is a Si-O-based film formed by including a gas including Si in a molecular formula in the source-based gas and including a gas including O in a molecular formula in the non-Si non-C-based gas. The film according to claim 10, wherein: The film is a Si-Ge based film formed by including a gas containing Si in a molecular formula and a gas containing Ge in the raw material gas, and containing H _{2 in the} non-Si non-C based gas. The membrane according to claim 10, wherein: The film is a C-based film formed by containing a gas containing C in a molecular formula in the raw material-based gas and containing H _{2 in the} non-Si non-C-based gas. Item 11. The film according to Item 10. A thin-film device comprising the film according to claim 10. 20. The thin film device according to claim 19, wherein the thin film device is a photoelectric conversion device, a photoreceptor device, or a display device. 20. The thin film device according to claim 19, wherein the substrate according to claim 1 has a shape of a flat plate, a cylinder, or a film. A film processing system comprising a plurality of processing chambers including at least one apparatus for realizing the Cat-PECVD method according to claim 1.

Images