JP2004056113A - Cat-PECVD METHOD AND SEMICONDUCTOR DEVICE FORMED USING SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for depositing a film in a large area while the thickness/quality of the film are highly uniform at a high speed with high quality and to provide a semiconductor device formed using the same. <P>SOLUTION: In a Cat-PECVDC (catalytic plasma enhanced chemical vapor deposition) method, a source gas containing at least one of Si and C in a molecular formula and a non-Si non-C gas containing a gas not containing the Si and the C in a molecular formula, heated by a heat catalyst arranged on a gas inlet path are injected from a plurality of gas jet ports, provided at an antenna electrode passing through a hollow part of the electrode installed in a film deposition space and having a hollow structure. The gases, injected into the space and mixed, are decomposed/activated by a plasma generated by the electrode connected to a high-frequency power source, and the film is deposited on a base disposed opposite to the electrode in the space. The semiconductor device is formed by using this method. <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, further relates performed technique 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. 9 shows a PECVD apparatus as Conventional Example 1, and FIG. 10 shows a Cat-CVD apparatus as Conventional Example 2. 9, 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. 10, 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 a case where a Si film is formed using a gas as an example, in the PECVD apparatus shown in FIG. 9, the gas introduced from a gas inlet 501 provided in a shower head 500 is supplied from a gas outlet 502 by a 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]
Further, in the Cat-CVD apparatus shown in FIG. 10, 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 Non-Patent Document 1 and Non-Patent Document 2), however, it is necessary to generate sufficient atomic hydrogen to form a crystalline Si film. However, when a high-speed film formation of a certain degree or more is required, an increase in plasma power is unavoidable, and the above-mentioned problem cannot be avoided.
[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. For this reason, it is also 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 recently been focused (see Non-Patent Documents 3 and 4).
[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 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 order to solve the above-mentioned problems, the present inventors have been studying the integration of the PECVD method and the Cat-CVD method for some time. Cat-PECVD method has been disclosed.
[0014]
FIG. 11 shows a typical device structure. 11, 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 is mixed with the Si-based gas in the plasma space 707 to form a film. 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]
Non-Patent Document 5 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.
[0018]
Non-Patent Document 6 discloses a capacitively coupled RF plasma CVD apparatus in which a thermal catalyst is installed in a plasma space, but it does not separate and introduce a gas, but also introduces a gas. The 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.
[0019]
Patent Literature 4 discloses a catalytic CVD method in which a radiation blocking member through which a gas can pass is provided between a catalyst body and a substrate. However, gas separation is performed so that a raw material gas is not activated by a thermal catalyst body. It is not a method of activating the source gas by plasma. Of course, there is no concept of an antenna electrode.
[0020]
Further, Patent Document 5 discloses a thin film forming apparatus provided with a catalyst electrode between a plasma generation electrode and a gas inlet, but does not separate and introduce a raw material gas, and furthermore, does not emit radiation. Nor does it have a structure. Also, there is no concept of an antenna electrode.
[0021]
Patent Document 6 discloses a catalyst in which a raw material gas is supplied into a container in which a thermal catalyst is disposed, the inside of the container is isolated from a substrate, and a gas is supplied to the substrate by a differential pressure from a gas outlet. Although a CVD apparatus is disclosed, it does not separate and introduce a source gas, and does not relate to a PECVD method. Also, there is no concept of an antenna electrode.
[0022]
Patent Document 7 discloses a method of forming a film by introducing a raw material gas and a heating gas for decomposing the raw material gas, but does not use a shower head and has a radiation blocking structure. It does not have any. Also, there is no concept of an antenna electrode.
[0023]
Further, Patent Document 8 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.
[0024]
Further, Patent Document 9 discloses a method in which a mesh-like activation 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 a radiation blocking structure. Also, there is no concept of an antenna electrode.
[0025]
Further, Patent Document 10 discloses a structure in which one transport pipe has the other transport pipe disposed inside, 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.
[0026]
Patent Document 11 discloses that a hydrogen gas 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 hydrogen gas is activated periodically. Thus, a method of performing film deposition by intermittently and periodically exposing a substrate to plasma 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.
[0027]
Further, Patent Document 12 discloses a method in which a raw material gas is decomposed by the action of a catalyst, and this is plasma-treated to form a film. However, this method does not separate and introduce the raw material gas. It is neither used nor has a radiation blocking structure. Also, there is no concept of an antenna electrode.
[0028]
Further, Patent Document 13 discloses a method of forming a film with an apparatus configuration having a surface reaction mechanism portion installed in the vicinity from a plasma generation unit to a substrate surface, but without thermally decomposing a raw material gas. It does not separate and introduce 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.
[0029]
Patent Document 14 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.
[0030]
Patent Document 15 discloses that SiH is used in a plasma space. ₄ And H ₂ And introduced separately, H ₂ Discloses a method of activating with heat, plasma, or the like in 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.
[0031]
Patent Document 16 discloses an antenna electrode type PECVD apparatus which is excellent in uniform large-area film formation using a ladder-shaped planar coil (ladder) electrode, but heats a gas using a thermal catalyst.・ It does not activate.
[0032]
Patent Document 17 discloses an antenna-electrode-type PECVD apparatus capable of forming a large-area uniform-thickness film by supplying AM-modulated VHF high-frequency (20 to 600 MHz to microwave) to an inductive coupling electrode. However, the method does not use a thermal catalyst to heat and activate the gas.
[0033]
Patent Document 18 discloses a method in which a hardly decomposable gas is heated by a gas heater in advance to improve the decomposability in plasma to obtain a high-quality film. However, the method 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.
[0034]
Patent Document 19 describes a method for realizing high-speed film formation by heating and introducing a reactive gas. However, this method does not use a thermal catalyst, and therefore, a thermal catalyst is installed in an antenna electrode. It 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.
[0035]
Further, Patent Document 20 discloses that a heater capable of independently controlling the temperature of the wire is incorporated into the wire of the ladder-shaped planar coil electrode, and the pressure distribution of the reaction gas in the reaction vessel is controlled to realize uniform and uniform film formation. However, the method does not use a thermal catalyst, and therefore does not install a thermal catalyst in the antenna electrode, or activates (decomposes) only by heating the gas. Absent. Further, the gas is not separated and introduced depending on the gas species.
[0036]
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 and a semiconductor device formed by using the method.
[0037]
[Patent Document 1]
Japanese Patent Application No. 2000-130858
[0038]
[Patent Document 2]
Japanese Patent Application No. 2001-293031
[0039]
[Patent Document 3]
Japanese Patent Application No. 2002-67445
[0040]
[Patent Document 4]
Japanese Patent No. 2692226
[0041]
[Patent Document 5]
JP-A-10-310867
[0042]
[Patent Document 6]
JP-A-11-54441
[0043]
[Patent Document 7]
Patent No. 19952626
[0044]
[Patent Document 8]
Patent No. 194527
[0045]
[Patent Document 9]
Patent No. 1927388
[0046]
[Patent Document 10]
Japanese Patent No. 2557741
[0047]
[Patent Document 11]
Japanese Patent No. 2927944
[0048]
[Patent Document 12]
JP 2000-114256 A
[0049]
[Patent Document 13]
JP 2000-331942 A
[0050]
[Patent Document 14]
JP 2000-323421 A
[0051]
[Patent Document 15]
JP-A-9-137274
[0052]
[Patent Document 16]
Japanese Patent Application Laid-Open No. Hei 4-236781
[0053]
[Patent Document 17]
JP 2001-295052 A
[0054]
[Patent Document 18]
JP-A-7-41950
[0055]
[Patent Document 19]
JP-A-6-283436
[0056]
[Patent Document 20]
JP-A-5-283344
[0057]
[Non-patent document 1]
J. Meier et al, Technical digest of 11th PVSEC (1999) p. 221
[0058]
[Non-patent document 2]
O. Vetter et al, Technical digest of 11th PVSEC (1999) p. 233
[0059]
[Non-Patent Document 3]
H. Matsumura, Jpn. J. Appl. Phys. 37 (1998) p. 3175-3187
[0060]
[Non-patent document 4]
R. E. FIG. I. Schropp et al, Technical digest of 11th PVSEC (1999) p. 929-930
[0061]
[Non-Patent Document 5]
Technical digest of 11th PVSEC (1999) p. 779
[0062]
[Non-Patent Document 6]
Technical digest of 16th EPSEC (2000) p. 421
[0063]
[Means for Solving the Problems]
According to the Cat-PECVD method of the present invention, 1) a raw material gas containing a gas containing at least one of Si and 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 are provided on the antenna electrode in a separated state through the hollow portion of the antenna electrode having a hollow structure installed in the film forming space. The plurality of gas outlets are jetted into the film forming space, and the mixed gas jetted into the film forming space is decomposed and activated by plasma generated by the antenna electrode connected to a high-frequency power supply, A film is deposited on a substrate disposed opposite to the antenna electrode in the film forming space.
[0064]
2) The thermal catalyst is provided in a hollow portion of the antenna electrode.
[0065]
3) In 1), the thermal catalyst is disposed in the hollow portion of the antenna electrode, and the gas outlet of the antenna electrode is configured such that heat radiation from the thermal catalyst does not directly reach the film-forming substrate. May be arranged.
[0066]
4) In any one of 1) to 3), the antenna electrode is shaped like a rod or a U-shape.
[0067]
5) In any one of 1) to 3), a plurality of the antenna electrodes are arranged in parallel to form an array antenna electrode unit.
[0068]
6) In any one of 1) to 3), the source gas and the non-Si non-C gas are ejected from different antenna electrodes.
[0069]
7) In any one of 1) to 3), a gas for doping into the film may be introduced into at least one of the introduction path of the source gas and the introduction path of the non-Si non-C-based gas. Features.
[0070]
Further, the semiconductor device of the present invention is formed by forming a semiconductor film formed by the Cat-PECVD method according to any one of 8) 1) to 7) on a base.
[0071]
9) The semiconductor film is formed by adding H to the non-Si non-C-based gas. ₂ Is a Si-based film formed by the inclusion of
[0072]
10) The Si-based film is a hydrogenated amorphous Si film, and the hydrogen concentration in the Si-based film is 15 atomic% or less.
[0073]
11) In the semiconductor film, the raw material gas contains 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 a Si-C-based film formed by including
[0074]
12) In the semiconductor film, the source gas includes a gas containing Si in a molecular formula, and the non-Si non-C gas includes H. ₂ And a Si—N-based film formed by including a gas containing N in a molecular formula in at least one of the raw material-based gas and the non-Si non-C-based gas.
[0075]
13) The semiconductor film is formed by forming the source gas containing a gas containing Si in a molecular formula and the non-Si non-C gas containing a gas containing O in a molecular formula. It is a -O-based film.
[0076]
14) In the semiconductor film, 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
[0077]
15) In the semiconductor film, the source-based gas contains a gas containing C in a molecular formula, and the non-Si non-C-based gas contains H. ₂ Is a C-based film formed by the inclusion of
[0078]
16) The semiconductor device is a photoelectric conversion device, a photoreceptor device, or a display device.
[0079]
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 position of an antenna electrode. FIG. 2 is a cross-sectional view when a heater is installed on the inner wall of the film forming chamber in FIG. FIG. 3 shows an example in which the antenna electrodes are arranged in an array, and is a cross-sectional view when the film-forming surface of the base is oriented in a direction parallel to the plane of the drawing. Only a part of the unit is shown, and details of the end structure of the antenna electrode are omitted: refer to FIGS. FIG. 4 is a cross-sectional view of the array-shaped antenna electrode as viewed from the center axis direction. FIG. 5 is a sectional view showing a detailed structure of the antenna electrode. FIG. 6 is a perspective view showing a three-dimensional structure of the antenna electrode. FIG. 7 is a cross-sectional view showing the structure of an antenna electrode incorporating a plurality of thermal catalysts.
[0080]
In these figures, reference numeral 101 denotes an inlet of a raw material gas containing a gas containing at least one of Si and C in a molecular formula, and 102 denotes introduction of a non-Si non-C gas consisting of a gas not containing Si and C in a molecular formula. The opening 103 is a thermal catalyst, 104 is a power supply for heating the thermal catalyst 103, 105 is plasma, 106a is an antenna electrode with a built-in thermal catalyst, 106b is an antenna electrode without a built-in thermal catalyst, and 107a and 107b are high frequency. Power supplies, 108a and 108c are phase converters, 108b and 108d are power distributors, 109, 109a and 109b are bases for film formation, 110 is a heater for heating the base, and 111a is provided on the antenna electrode 106a with a built-in thermal catalyst. 111b is a gas outlet provided on the antenna electrode 106b without a built-in thermal catalyst, and 112 is a gas outlet for electrical insulation. An edge member, 113 is a chamber (film forming chamber) constituting a film forming space, 114a and 114b are hollow portions provided inside the antenna electrode, 115 is an inner wall surface heater provided on the inner wall surface of the chamber, and 116 is a thermal contact. This is a medium selection switch.
[0081]
As described above, the Cat-PECVD method of the present invention uses a raw material gas containing a gas containing at least one of Si and C in the molecular formula, and a molecular catalyst heated by the thermal catalyst 103 provided in the gas introduction path. A non-Si non-C-based gas composed of a gas not containing Si and C is separated from each other, and the hollow portions (114b) of the antenna electrodes (106b, 106a) having a hollow structure are installed in the film forming space. , 114a), are ejected from a plurality of gas outlets provided in the antenna electrode into the film forming space, and the gas ejected and mixed into the film forming space is connected to a high frequency power supply (107a, 107b). Is decomposed and activated by the plasma generated by the antenna electrode, and a film is deposited on the base 109 disposed opposite to the antenna electrode in the film forming space. The thermal catalyst 103 is disposed in the hollow portion 114a of the antenna electrode. As will be described later, the gas outlet of the antenna electrode receives heat radiation from the thermal catalyst 103 as a substrate to be formed. It is characterized by being arranged so as not to reach the base 109 directly.
[0082]
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.
[0083]
Hereinafter, each part will be described in detail.
[0084]
<Electrode shape>
First, as the shape of the 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.
[0085]
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 generating electrode, if λ >> L, an electromagnetic wave interference effect does not occur and uniform plasma is generated. Therefore, 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.
[0086]
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.
[0087]
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 the introduction of GaN is progressing, and this technology can also be used in the present Cat-PECVD method.
[0088]
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.
[0089]
<Position where thermal catalyst is installed>
Next, the installation position of the thermal catalyst body 103 is the most preferable, and the most preferable one has a hollow structure as shown in FIGS. 1, 2, 3, 4, 5, 6, and 7. This is a case where the antenna is installed inside (hollow portion) of the antenna electrode. By placing the thermal catalyst inside the antenna electrode, the heated and activated non-Si non-C-based gas enters the plasma space generated outside the antenna without excessively impairing its temperature and activity. Since it is fed, 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.
[0090]
As described above, the installation position of the thermal catalyst body 103 is most preferably inside the hollow antenna electrode. However, even when the thermal catalyst body 103 is installed in the gas path on the upstream side of the hollow antenna, the above-described effects can be obtained. Therefore, if it is particularly difficult to install the thermal catalyst inside the hollow antenna electrode, the thermal catalyst can be installed in the gas path on the upstream side of the hollow antenna. However, in any case, it is still the most desirable to dispose the thermal catalyst in the antenna electrode in order to maximize the effects of the present invention.
[0091]
<Antenna electrode array>
Next, as for the arrangement of the antenna electrodes, the base 109 is a plate or a film having a certain area, such as a substrate of a solar cell or the like, and the film is formed on the surface. As shown in FIG. 3 and FIG. 4, it is desirable that a plurality of the antenna electrodes are arranged in parallel and arranged in an array to form an array antenna electrode unit. Thereby, a film can be formed uniformly and over a large area.
[0092]
<Gas separation introduction method>
Next, a method of separating and introducing a non-Si non-C-based gas and a raw material-based gas is the simplest method, as shown in FIG. 4, when each gas is ejected from a different antenna electrode. At this time, the thermal catalyst 103 is placed inside the antenna electrode 106a into which the non-Si non-C-based gas is introduced. Here, if the distance between the antenna electrodes cannot be sufficiently reduced, and there is a possibility that the mixing of the non-Si non-C-based gas and the raw material-based gas in the plasma may be insufficient, a single antenna electrode may be used. A plurality of independent hollow spaces may be formed so that the non-Si non-C-based gas and the raw material-based gas are simultaneously ejected from one antenna electrode through different hollow spaces (not shown). Also at this time, the thermal catalyst 103 is provided in the introduction path of the non-Si non-C-based gas.
[0093]
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 gas are mixed and introduced, not only the non-Si non-C gas but also the raw material gas is heated by the thermal catalyst disposed in the introduction path. When the temperature of the thermal catalyst 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 produced. This is because it is significantly consumed before reaching the membrane space.
[0094]
<Gas outlet position>
Next, at the gas outlet position, in the case of the antenna electrode 106a in which the thermal catalyst 103 is installed, as shown in FIG. It is arranged so that the radiation does not 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 the case of the antenna electrode 106b in which the thermal catalyst is not installed inside, the gas outlet may be at an arbitrary position.
[0095]
<Arrangement of array antenna electrode unit>
Next, it is desirable that the array-shaped antenna electrode units are 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-shaped antenna electrode unit as described later. Further, for example, when a glass substrate or the like is used as the base 109, 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-shaped antenna electrode unit itself does not occur.
[0096]
As described above, it is desirable that the array-shaped antenna electrode unit is arranged vertically so that its array surface is parallel to the direction of gravity. Of course, the array-shaped antenna electrode unit is arranged so that its array surface is perpendicular to the direction of gravity. The horizontal arrangement is not particularly limited so that the problem of the array-shaped electrodes and the substrate being bent and the problem of falling and adhering of the powder can be almost ignored. Absent.
[0097]
<Substrate arrangement>
Next, it is desirable that the bases 109 are arranged on both sides of the array antenna electrode unit (see FIGS. 1 and 4). This enables simultaneous film formation on both sides of the array-shaped antenna electrode unit, thereby doubling the productivity of the apparatus.
[0098]
<Substrate heater arrangement>
Next, as shown in FIG. 1, it is desirable that the substrate heating heaters 110 be arranged on both sides of the array-shaped antenna electrode unit with the substrate therebetween. That is, it is preferable that a substrate heating heater is disposed on a surface of the substrate opposite to a surface facing the array antenna electrode 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.
[0099]
<Number and arrangement of array antenna electrode units>
Next, it is desirable that a plurality of sets of arrayed antenna electrode units are arranged in parallel in one film forming chamber (FIG. 1 shows an example in which three arrayed antenna electrode units are arranged). By doing so, simultaneous film formation by a plurality of array-shaped antenna electrode units becomes possible. Considering the simultaneous double-sided film formation with one array-shaped antenna electrode unit, for example, two sets of array-shaped antenna electrode units are arranged in parallel. If this is done, simultaneous film formation on four sides is possible. If three sets are arranged in parallel, simultaneous film formation on six sides is shown (FIG. 1 shows this case). By increasing the number of arrayed antenna electrode units in parallel as described above, the 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.
[0100]
<Power supply method>
Next, as a method of feeding power to the antenna electrode 106a or 106b, for example, as shown in FIG. 3, high-frequency power from the high-frequency power supply 107a or 107b may be distributed and transmitted by the power distributor 108b or 108d. Alternatively, a high frequency power supply may be provided for each antenna electrode (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.
[0101]
<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 or 108c. However, as shown in FIG. 3, for example, the feeding points to the adjacent antenna electrodes of the array-shaped antenna electrode unit are located in opposite directions. The same effect can be realized by arranging them, and by using both of them, a more uniform large-area plasma can be generated.
[0102]
<High-frequency power supply method>
Further, as another method for easily realizing film formation of a uniform film thickness and a uniform film quality over a large area, a plurality of high-frequency electric powers having different frequencies are superimposed and supplied to the antenna electrodes 106a and 106b, so that a different space can be obtained. There is a method of superposing a plurality of plasmas having a target density distribution. 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.
[0103]
As another method, there is a method in which high-frequency power of a different frequency is supplied to each adjacent antenna electrode. This may be achieved, for example, by making the frequencies of the high frequency power supplies 107a and 107b different in FIG. With this configuration, the plasma density distribution can be made more uniform by the electromagnetic interaction between the adjacent electrodes and the like, so that a large-area uniform film can be formed on the substrate.
[0104]
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.
[0105]
Furthermore, if high-frequency power is intermittently supplied to the antenna electrodes 106a and 106b by, for example, pulse modulation of plasma, the generation and growth of powder can be suppressed as compared with the case of continuous plasma generation, and the film quality can be reduced. May be effective for improvement.
[0106]
<High frequency power supply frequency>
Next, in the Cat-PECVD method and apparatus of the present invention, the antenna electrodes 106a and 106b for generating plasma are connected to the high-frequency power sources 107a and 107b, and the frequency of the high-frequency power sources 107a and 107b is 13.56 MHz or more. 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).
[0107]
That is, in the conventional flat electrode, as described above, it is possible to realize a large-area film with a uniform film thickness of about 1 m square size and a uniform film quality without relatively difficulty up to about 27 MHz, and more. According to the present invention, even in a high frequency region of 27 MHz or higher, a large area uniform film thickness and a uniform film quality superior to those of the prior art can be obtained. Can be
[0108]
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.
[0109]
Here, the higher the frequency of the high-frequency power sources 107a and 107b, the higher the electron density in the plasma. Therefore, 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.
[0110]
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.
[0111]
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.
[0112]
<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.
[0113]
<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.
[0114]
<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.
[0115]
<Activation amount adjustment method>
Here, H ₂ As a method for 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.
[0116]
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, as shown in FIG. 7, when a plurality of thermal catalysts 103 are provided in one antenna electrode, if these can be heated independently, the thermal catalysts 103 to be heated as necessary are provided. The degree of heating or decomposition / activation of the non-Si / non-C-based gas can be changed in a stepwise manner by determining the number.
[0117]
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.
[0118]
The third method is to design and adjust the diameter of the non-Si non-C-based gas jet port 111a and the diameter of the raw material gas jet port 111b separately, or to adjust the total number of non-Si non-C-based gas jet ports 111a and the raw material gas jet port 111a. The total number of 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 ejection port 111a reduces the amount of heated or decomposed and activated non-Si non-C-based gas ejected 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 the non-Si non-C-based gas that has been heated or decomposed and activated to the plasma space 105.
[0119]
The 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, 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.
[0120]
<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 the catalyst has a catalytic action to promote 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.
[0121]
<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.
[0122]
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. Specifically, as shown in FIG. 2, if a heater is installed on the wall surface of the film forming chamber, the wall surface of the film forming chamber can be heated. 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.
[0123]
<Doping gas introduction method>
Next, when supplying a doping gas, the doping gas can be introduced into at least one of the source gas introduction path and 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.
[0124]
<Electric circuit>
It is desirable to install a pass capacitor (not shown) as 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.
[0125]
<Substrate shape>
As the substrate 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.
[0126]
<Apparatus (see FIG. 8)>
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.
[0127]
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.
[0128]
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.
[0129]
It is preferable that at least one of the plurality of vacuum chambers is a film forming chamber capable of realizing the PECVD method. As a result, 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. Can be raised.
[0130]
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.
[0131]
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.
[0132]
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.
[0133]
<Semiconductor device>
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, and to provide a semiconductor device having such a semiconductor film formed on a substrate. Although it can be provided (here, the effect of high-speed and high-quality film formation is disclosed in Japanese Patent Application Nos. 2001-29331 and 2002-38686 by the present inventors). In particular, the effect is remarkably exerted on a Si-based film or a C-based film.
[0134]
In the first example, the source 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. .
[0135]
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.
[0136]
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.
[0137]
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.
[0138]
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.
[0139]
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.
[0140]
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 high speed and with high uniformity of film thickness and film quality over a large area for the reasons already described above. Can be.
[0141]
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.
[0142]
<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.
[0143]
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. Aside from 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.
[0144]
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.
[0145]
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. A similar effect can be obtained by a device having a display function such as an image sensor or an X-ray panel other than the TFT.
[0146]
<Thin-film Si solar cell>
Hereinafter, a thin-film Si solar cell as a device according to the present invention will be described with reference to FIG. In FIG. 12, 11 is a light-transmitting 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.
[0147]
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.
[0148]
Next, the first transparent conductive film 12 is formed. The material of the transparent conductive film 12 is SnO ₂ , ITO, ZnO, etc., 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. As the film forming method, a known technique such as a CVD method, an evaporation method, an ion plating method, and a sputtering method can be used. 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.
[0149]
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.
[0150]
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.
[0151]
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 a small light absorption loss, and 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.
[0152]
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.
[0153]
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 ~ 1 × 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.
[0154]
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.
[0155]
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.
[0156]
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. 1 × 10 for doping element concentration ¹⁸ ~ 1 × 10 ²¹ / 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 a small light absorption loss, and 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.
[0157]
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 of forming the crystalline silicon film, a conventionally known PECVD method or Cat-CVD method can be used. Since a film can be formed at a high speed and in 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.
[0158]
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.
[0159]
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 ~ 1 × 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.
[0160]
In order to further improve the junction characteristics, a substantially i-type non-single-crystal is used 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). An Si layer may be inserted. At this time, the thickness of the insertion layer is about 0.5 to 50 nm.
[0161]
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.
[0162]
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 a vapor deposition 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. A thickness of about 10 nm may be provided between the two films.
[0163]
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.
[0164]
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. .
[0165]
【The invention's effect】
According to the Cat-PECVD method of claims 1 to 7, a molecular gas heated by a raw material gas containing a gas containing at least one of Si and C in a molecular formula, and a thermal catalyst disposed in a gas introduction path. And a non-Si non-C-based gas composed of a gas not containing Si and C are separated from each other and pass through the hollow portion of the antenna electrode having a hollow structure installed in the film forming space to the antenna electrode. Gases ejected from the plurality of gas ejection ports provided into the film forming space, and mixed and ejected into the film forming space are decomposed and activated by plasma generated by the antenna electrode connected to a high-frequency power supply. Thus, since a film is deposited on the substrate disposed opposite to the antenna electrode in the film forming space, high-speed, high-quality film formation of a Si-based film or a C-based film can be performed with a uniform thickness and uniformity over a large area. film In can be realized.
[0166]
In particular, according to the Cat-PECVD method, a film can be formed uniformly and over a large area.
[0167]
According to the semiconductor device of the eighth to sixteenth aspects, it is possible to achieve high uniformity of film thickness and film quality over a large area, high performance, and rapid manufacturing.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view schematically illustrating an example of an apparatus for realizing a Cat-PECVD method according to the present invention.
FIG. 2 is a cross-sectional view schematically illustrating an example of an apparatus for realizing the Cat-PECVD method according to the present invention (an example in which a heater is installed on a wall surface of a film forming chamber).
FIG. 3 is a diagram schematically illustrating an example of an antenna electrode arrangement for realizing the Cat-PECVD method according to the present invention, and is a cross-sectional view of a film forming surface of a base.
FIG. 4 is a diagram schematically illustrating an example of an antenna electrode arrangement for realizing the Cat-PECVD method according to the present invention, and is a cross-sectional view as viewed from a center axis direction of the antenna electrode.
FIG. 5 is a diagram schematically illustrating an example of an antenna electrode with a built-in thermal catalyst for realizing the Cat-PECVD method according to the present invention, and is a longitudinal sectional view when the central axis direction of the antenna electrode is vertical.
FIG. 6 is a perspective view schematically illustrating an example of an antenna electrode with a built-in thermal catalyst for realizing the Cat-PECVD method according to the present invention.
FIG. 7 is a cross-sectional view schematically illustrating an example of an antenna electrode with a built-in thermal catalyst (two built-in thermal catalysts) realizing the Cat-PECVD method according to the present invention.
FIG. 8 is a configuration diagram schematically illustrating a film processing system according to the present invention.
FIG. 9 is a cross-sectional view schematically illustrating an example of a conventional PECVD apparatus.
FIG. 10 is a cross-sectional view schematically illustrating an example of a conventional Cat-CVD apparatus.
FIG. 11 is a cross-sectional view schematically illustrating an example of a Cat-PECVD apparatus.
FIG. 12 is a sectional view schematically showing an example of a thin film device according to the present invention.
[Explanation of symbols]
101: Raw material gas inlet
102: Non-Si non-C gas inlet
103: thermal catalyst
104: Power supply for heating the thermal catalyst
105: Plasma
106a: antenna electrode with built-in thermal catalyst
106b: Antenna electrode without built-in thermal catalyst
107: High frequency power supply
107a: High frequency power supply (1)
107b: High frequency power supply (2)
108a: phase converter
108b: power distributor
108c: phase converter
108d: power distributor
109: Substrate
109a: Substrate
109b: Substrate
110: Substrate heater
111a: Gas outlet for antenna electrode with built-in thermal catalyst
111b: Gas electrode outlet for antenna electrode without built-in thermal catalyst
112: insulating member
113: Chamber
114a: hollow portion (non-Si non-C gas path)
114b: hollow part (raw material gas path)
115: Inner wall heater

Claims (16)

A raw material gas containing a gas containing at least one of Si and C in a molecular formula, and a non-Si non-gas containing a gas containing neither Si nor C in a molecular formula heated by a thermal catalyst disposed in a gas introduction path. The C-based gas is separated from the film-forming space through a plurality of gas ejection ports provided in the antenna electrode through the hollow portion of the antenna electrode having a hollow structure installed in the film-forming space in a state where they are separated from each other. The gas that has been ejected and mixed into the film-forming space is decomposed and activated by plasma generated by the antenna electrode connected to a high-frequency power supply, and faces the antenna electrode in the film-forming space. A Cat-PECVD method, wherein a film is deposited on a substrate arranged in a vertical direction. The Cat-PECVD method according to claim 1, wherein the thermal catalyst is provided in a hollow portion of the antenna electrode. The thermal catalyst is disposed in a hollow portion of the antenna electrode, and a gas outlet of the antenna electrode is disposed so that heat radiation from the thermal catalyst does not directly reach the film-formed substrate. The Cat-PECVD method according to claim 1, wherein The Cat-PECVD method according to any one of claims 1 to 3, wherein the antenna electrode has a rod shape or a U shape. 4. The Cat-PECVD method according to claim 1, wherein a plurality of the antenna electrodes are arranged in parallel to form an array antenna electrode unit. 5. The Cat-PECVD method according to any one of claims 1 to 3, wherein the raw material gas and the non-Si non-C gas are ejected from different antenna electrodes. 4. A gas for doping the film is introduced into at least one of the introduction path of the source gas and the introduction path of the non-Si non-C-based gas. The described Cat-PECVD method. A semiconductor device comprising a semiconductor film formed by the Cat-PECVD method according to claim 1 on a substrate. The semiconductor film, the semiconductor device according to claim 8, wherein the the non-Si non-C-based gas is a Si-based film formed by the inclusion of H _2. 10. The semiconductor device according to claim 9, wherein the Si-based film is a hydrogenated amorphous Si film, and a hydrogen concentration in the Si-based film is 15 atomic% or less. The semiconductor film is formed by containing a gas containing Si in a molecular formula and a gas containing C in a molecular formula in the raw material gas, and forming H _{2 in the} non-Si non-C-based gas. The semiconductor device according to claim 8, wherein the semiconductor device is a -C-based film. In the semiconductor film, the raw material gas contains a gas containing Si in a molecular formula, the non-Si non-C gas contains H ₂ , and the raw material gas and the non-Si non-C gas 9. The semiconductor device according to claim 8, wherein at least one of the semiconductor devices is a Si-N-based film formed by containing a gas containing N in a molecular formula. The semiconductor film is a Si—O-based film formed by including a gas containing Si in a molecular formula in the source gas and a gas containing O in a molecular formula in the non-Si non-C-based gas. The semiconductor device according to claim 8, wherein In the semiconductor film, the source-based gas includes a gas containing Si and a gas containing Ge in a molecular formula, and the non-Si non-C-based gas contains H ₂ to form a Si-Ge-based gas. The semiconductor device according to claim 8, wherein the semiconductor device is a film. The semiconductor film is a C-based film formed by including a gas containing C in a molecular formula in the raw material-based gas and including H _{2 in the} non-Si non-C-based gas. The semiconductor device according to claim 8, wherein: The semiconductor device according to claim 8, wherein the semiconductor device is a photoelectric conversion device, a photoreceptor device, or a display device.

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