JPS642191B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical field to which the invention pertains] The present invention relates to deposited films on a substrate, particularly functional films, particularly semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, imaging devices, photovoltaic devices, etc. This invention relates to an apparatus using plasma CVD method which is most suitable for forming non-monocrystalline deposited films such as amorphous or polycrystalline. [Description of the Prior Art] Conventionally, element members used in semiconductor devices, photoreceptor devices for electrophotography, line sensors for image input, image pickup tube devices, photovoltaic devices, etc. have been made of amorphous silicon, such as hydrogen atoms or and amorphous silicon (hereinafter referred to as "a-Si(H,X)") films containing halogen atoms have been proposed, and some of them have been put into practical use. Then, such a-Si(H,
In addition to X) films, several methods of forming a-Si (H, ,
There are optical CVD methods, among others, plasma CVD method has been put into practical use as the most suitable method and is generally widely used. By the way, the plasma CVD method uses high frequency or microwave energy to excite the deposited film-forming gas near the substrate surface to species (convert into radicals).
In this method, a chemical interaction is caused to occur, and a film is deposited on the surface of the substrate.As an apparatus for this purpose, for example, the apparatus shown in FIG. 2 has been proposed. In FIG. 2, 201 indicates the entire reaction vessel, 202 indicates the side wall, and 203 indicates the bottom wall. 204 is a multi-perforated inner wall, 205 is an exhaust pipe, 20
6 is an exhaust valve, 207 is a gas introduction pipe, 208 is a valve provided on the gas introduction pipe, 209 is a cylindrical base, 210 is a cylinder for holding the base, 211 is a heater, 212 is a support leg, 213 is a high frequency or microwave 214 is a high frequency or microwave, 215 is a waveguide, 216 is a dielectric window, A is a reaction chamber, and B is a gas chamber. Formation of a deposited film using such a conventional deposited film forming apparatus is performed as follows. That is, the gas in the reaction chamber A of the reaction container 201 is evacuated through the exhaust pipe 205, and the cylindrical substrate 209 is heated and maintained at a predetermined temperature by the heater 211. Next, in the case of forming, for example, an a-Si (H, It is discharged into the reaction chamber A from a large number of holes in the multi-perforated inner wall 204 of the chamber B. At the same time, from the generation source 213, for example, microwave 2
14, and the microwave 214 is transmitted to the waveguide 2
15 and is introduced into the reaction chamber A through the dielectric window 216. In this way, the raw material gas in the reaction chamber A is excited and activated (excited speciation) by the microwave energy, and becomes radical particles, electrons, and ions such as Si ^* , SiH ^*, etc. (* indicates an excited state). Particles and the like are generated and react with each other to form a deposited film on the surface of the base 209. Although the above-mentioned conventional deposition film forming apparatus using the plasma CVD method is generally widely adopted as an optimal one, there are several problems. That is, since the waveguide and, in many cases, the substrate holding means are also fixed, the high frequency or microwave electric field radiated into the reaction chamber is stronger on the side of the dielectric window provided at the end of the waveguide. As the electric field progresses in the opposite direction, it becomes weaker and the intensity distribution of the electric field depends on the wavelength of the applied radio frequency or microwave. The gas is excited at a density that follows the intensity distribution of the electric field and becomes excited species, and the thickness of the film deposited on the substrate surface naturally becomes thicker in areas where the electric field is stronger, while it becomes thicker in areas where the electric field is weaker. Become thin. This non-uniformity in film thickness is due to
This is even more noticeable when the length of the substrate is longer than the radio frequency or microwave wavelength. Also,
Such a difference in electric field strength distribution has an adverse effect on not only the thickness of the deposited film but also the density, hardness, composition, etc. of the film being non-uniform. deposited film,
In particular, there is a problem in that it is difficult to consistently obtain a deposited film with a large area. In particular, it has been proposed to simultaneously form deposited films on a plurality of substrates in order to improve the utilization efficiency of raw material gas and reduce the cost of products, but in such a case, the above-mentioned problems become even more serious. Furthermore, during the process of forming a deposited film, the deposited film already formed on the surface of the substrate is bombarded by ions generated in the plasma, which adversely affects the properties of the deposited film thus formed. In other words, the impact of the ions causes structural defects in the deposited film, such as breaking bonds between atoms in the deposited film, or ions being implanted and remaining in the deposited film.As a result, optical and Electrical or photoconductive properties may deteriorate or change over time. Furthermore, the high frequency or microwave radiated through the waveguide is affected by the substrate placed in the reaction vessel, the gas introduction pipe, the shape of the reaction vessel, the arrangement of the exhaust pipe, etc. It becomes difficult to form a stable electric field, adjust impedance matching, and form a uniform electric field intensity distribution, and there are also problems such as plasma generation in unnecessary areas or abnormal discharge. Separately, the various devices mentioned above have become diversified, and element materials for these devices are needed, that is, devices that satisfy all the requirements such as various characteristics, are suitable for the target object and use, and in some cases have a large area. It has become a social demand to constantly supply stable deposited film products at low cost, and there is a strong desire to develop an apparatus that satisfies this demand. [Object of the invention] The present invention provides photovoltaic elements, semiconductor devices,
The purpose is to solve the above-mentioned problems and meet the above-mentioned requirements regarding conventional devices for forming deposited films used in image input line sensors, imaging devices, electrophotographic photoreceptor devices, etc. It is. That is, the main object of the present invention is to produce a deposited film that is uniform in thickness and quality and has excellent optical, electrical, and photoconductive properties by plasma CVD. An object of the present invention is to provide a film forming apparatus. Another object of the present invention is to improve the utilization efficiency of raw material gases, to improve the productivity and mass production of films, and to use plasma that makes it possible to increase the area of films.
An object of the present invention is to provide a deposited film forming apparatus using a CVD method. Yet another object of the present invention is to provide plasma CVD in which the deposited film formed on the substrate is not directly affected by plasma during the deposited film formation process.
An object of the present invention is to provide a deposited film forming apparatus using a method. [Structure and Effects of the Invention] As a result of intensive research in order to overcome the above-mentioned problems with the conventional plasma CVD deposited film forming apparatus and achieve the above-mentioned purpose, the present inventor has developed a high-frequency or micro- A waveguide is connected to the wave generation source, an electromagnetic horn is connected to the waveguide immediately before the reaction vessel, and the electromagnetic horn is connected to the substrate support surface of the cylindrical substrate support means disposed inside the reaction vessel. A plurality of electromagnetic horns are introduced into the reaction vessel in parallel, and the tip of the electromagnetic horn is made of a metal plate or metal mesh having a large number of holes large enough to prevent the passage of high frequency waves or microwaves,
When raw material gas is introduced into the terminal end of the electromagnetic horn to generate plasma, no plasma is emitted through the holes in the metal plate or the metal mesh, and only the excited and specified raw material gas is dispersed and released into the reaction vessel. The present invention has been completed by solving the above-mentioned problems and obtaining knowledge that can achieve the above-mentioned objects. That is, the deposited film forming apparatus using the plasma CVD method of the present invention includes a reaction vessel for forming a deposited film on a substrate, a means for introducing a raw material gas for forming the deposited film into the reaction vessel, and a means for introducing the raw material gas for forming the deposited film into the reaction vessel. A waveguide is connected to the high frequency or microwave generation source, and the device is composed of a high frequency or microwave generating means for exciting and specifying the reaction vessel, and a means for evacuating the inside of the reaction vessel. An electromagnetic horn is connected to the waveguide, and a plurality of electromagnetic horns are connected to the waveguide.
The cylindrical substrate support means arranged in the reaction vessel extends into the reaction vessel parallel to the substrate support surface, and the terminal end of the electromagnetic horn has a dielectric material and a high frequency wave or a microwave to an extent that does not pass therethrough. It has a space separated by a metal plate or metal mesh having a large number of holes with a size of The main feature is that the reaction mixture is dispersed and released into the reaction vessel through a large number of holes in the metal plate or metal mesh. In the deposited film forming apparatus using the plasma CVD method of the present invention, the plasma remains in the space provided at the end of the electromagnetic horn, and only the excited species are emitted through the hole in the metal plate or metal mesh at the tip of the electromagnetic horn. be done. In other words, there is no plasma near the surface of the substrate placed in the reaction vessel, only excited species exist, and the substrate surface is not adversely affected by the plasma, and the length of the substrate is Even if the wavelength is longer than the wavelength of the wave, the quality, thickness and electrical
This allows efficient mass production of deposited films with stable optical and photoconductive properties. Furthermore, by providing a plurality of electromagnetic horns with such a configuration and different raw material gases introduced into each electromagnetic horn, different excited species are emitted from the tip of each electromagnetic horn, and the plurality of excited species are brought into the vicinity of the substrate surface. can be mixed to form a deposited film. In such a case, the emission of each excited species can be controlled independently. Furthermore, it is possible to simultaneously form deposited films on a plurality of substrates within the same apparatus, and it is possible to provide deposited film products at low cost. The raw material gas used to form the deposited film by the apparatus of the present invention is one that is excited and speciated by high frequency or microwave energy, and undergoes chemical interaction to form the desired deposited film on the substrate surface. For example, when forming an a-Si (H, Gaseous substances such as silanes and halogenated silanes, or easily gasified substances can be used. These source gases may be used alone or in combination of two or more. Further, these raw material gases may be used after being diluted with an inert gas such as He or Ar. Furthermore, the a-Si (H, can be mixed with the raw material gas and/or the diluent gas and introduced into the reaction chamber. The substrate may be electrically conductive, semiconductive, or electrically insulating; specific examples include metal, ceramics, glass, and the like. The substrate temperature during the film forming operation is not particularly limited, but
The temperature is generally in the range of 450°C, preferably 50 to 350°C. In addition, when forming a deposited film, the pressure inside the reaction chamber is increased by 5x before introducing the raw material gas.
10 ^-6 Torr or less, preferably 1 x 10 ^-6 Torr or less, and when introducing the raw material gas, the pressure inside the reaction chamber is 1 x 10 ^-2 to 1 Torr, preferably 5 x 10 ^-2 to 1 Torr.
It is desirable to do so. Note that in forming a deposited film using the apparatus of the present invention, as described above, the raw material gas is normally introduced into the reaction chamber without prior treatment (excited speciation), where it is excited and speciated using radio frequency or microwave energy. This is done by causing chemical interaction, but when using two or more raw material gases,
It is also possible to make one of them into excited species in advance and then introduce it into the reaction chamber. Hereinafter, the apparatus for forming a deposited film using the plasma CVD method of the present invention will be explained in more detail with reference to the embodiment shown in FIG. 1, but the apparatus of the present invention is not limited thereto. FIG. 1A is a schematic diagram of the entire deposited film forming apparatus using the plasma CVD method of the present invention, FIG. 1B is a schematic diagram showing its cross section, and FIG. 1C is a
FIG. 2 is a schematic diagram of an electromagnetic horn as a waveguide constituting the device of the present invention. In the figure, 101 is a high frequency or microwave generation source, to which a waveguide 102 is connected.
103 is an electromagnetic horn connected to the waveguide 102, 104 is a reaction vessel, and a cylindrical substrate support means 105 is disposed within the reaction vessel.
The substrate supporting means 105 is placed in the reaction vessel 104 with a cylindrical substrate mounted thereon or one or more flat substrates placed thereon. The electromagnetic horn 103 is connected to the waveguide 102 immediately in front of the reaction vessel 104 and extends into the reaction vessel 104 parallel to the substrate support surface of the substrate support means 105 . The opening of the electromagnetic horn 103 has the same length as the length of the cylindrical base support means 105 in the longitudinal direction. At the terminal end of the electromagnetic horn 103, as shown in FIG. 1C,
A space is provided that is separated by a dielectric 106 and a metal plate 107 having a large number of holes 108 that are large enough not to transmit high frequencies or microwaves. 109 is a raw material gas introduction pipe, one end of which is connected to the dielectric material 106.
and a metal plate 107 having a large number of holes 108, and the other end communicates with a raw material gas supply source (not shown) via a valve (not shown). The raw material gas supplied from the raw material gas supply source is introduced into the space via the raw material gas introduction pipe 109, and is excited and specified by the plasma generated in the space. In order to efficiently generate plasma within this time and space, it is desirable that the distance between the dielectric 106 and the metal plate 107 having a large number of holes be 10 mm or more. Further, as the dielectric material 106,
It is desirable to use a highly heat-resistant material with a high dielectric constant, low dielectric loss, and ceramics such as silicone resin, Teflon resin, and alumina. In this example device, an example is shown in which a metal plate 107 having a large number of holes 108 is used, but a metal mesh may also be used. The only thing that can pass through the holes in the metal plate or the metal mesh is the source gas that has been excited and specified in the space, but not the plasma, so only the excited species can react through the many holes in the metal plate or the metal mesh. It is dispersed and released towards the substrate surface within the space. Furthermore, in the apparatus of the present invention, a plurality of electromagnetic horns 103 having such a configuration are installed, and different raw material gases are introduced into the terminal end of each electromagnetic horn 103 and passed through the holes of the respective metal plates or metal mesh. By dispersing and releasing different excited species into a reaction vessel, the plurality of excited species come into contact near the substrate surface and cause a chemical reaction to form a deposited film on the substrate surface. In addition, in the example apparatus shown in FIG. 1, an example is shown in which the number of electromagnetic horns is two, but the number of electromagnetic horns is determined as appropriate depending on the deposited film to be formed. . Further, it goes without saying that the raw material gas introduced into each electromagnetic horn may be a mixed gas obtained by mixing two or more kinds of raw material gases. Reference numeral 110 denotes exhaust pipes provided at both ends of the reaction container to evacuate the inside of the reaction container, one end of which opens into the reaction container, and the other end of which is connected to an exhaust device through a valve (not shown). (not shown). A heating heater (not shown) is provided inside the cylindrical substrate support means 105 to heat the substrate to a predetermined temperature before film formation, to maintain the substrate at a predetermined temperature during film formation, or to heat the substrate to a predetermined temperature during film formation. Used for post-film annealing. Furthermore, the cylindrical substrate support means 105 is mechanically connected to a driving means (not shown) that provides rotation, and the cylindrical substrate support means is rotated by the driving means during film formation. In the example apparatus shown in FIG. 1, an example is described in which four cylindrical substrate support means 105 are installed in the reaction vessel, but the number of cylindrical substrate support means is the same as the number of electromagnetic horns. The number is determined as appropriate and may be the same as or different from the number of electromagnetic horns. The plasma of the present invention configured as described above
In the deposited film forming apparatus using the CVD method, during the deposition operation, the raw material gas introduced into the space provided at the end of the electromagnetic horn 103 is excited and speciesized by the plasma generated in the space, and 1
Only the excited species are efficiently released from the metal plate or metal mesh 107 having a large number of holes at the tip of the reaction vessel 104 toward the surface of the substrate attached to the cylindrical substrate support means 105 in the reaction vessel 104. . Different excited species are emitted from the plurality of electromagnetic horns, and two or more excited species come into contact near the surface of the substrate to cause a reaction and form a deposited film. At this time, since the cylindrical substrate support means is rotated, the density distribution of excited species near the substrate surface becomes uniform, and furthermore, since plasma that has a negative effect on the deposited film does not exist near the substrate surface, the deposited film is deposited on the substrate surface. The resulting film is uniform and homogeneous, and a deposited film product of desired quality and rich in various properties can be obtained. [Example] Next, the operation of the apparatus for forming a deposited film using the plasma CVD method of the present invention will be explained using examples, but the following examples are not intended to limit the operation of the apparatus. Example 1 Using the apparatus shown in FIG. 1, an electrophotographic light-receiving layer made of a-Si:H:F was formed on a cylindrical Al substrate in the following manner. That is, first, four cylindrical substrate support means 105 each having a cylindrical Al substrate mounted thereon are installed in the reaction vessel 104, an exhaust valve (not shown) is opened, and the inside of the reaction vessel is discharged from the exhaust pipe 109. Evacuate and
The inside of the reaction vessel was kept at a vacuum level of 10 ⁻⁵ Torr. At the same time, the four cylindrical substrate support means 105 were rotated by a driving means (not shown), and the substrate temperature was maintained at 300° C. by a heating heater (not shown). Two types of raw material gases are introduced into the space provided at the end of each electromagnetic horn 103 through the gas introduction pipe 109, and then introduced into the reaction vessel 104 through the metal plate 107 having a large number of holes. did. After adjusting the exhaust valve (not shown) to set the internal pressure of the reaction vessel to 0.01 Torr, 2.45 GHz microwaves are emitted to generate plasma in each electromagnetic horn 103, and each excited species is extracted from each source gas. was generated. These excited species form a large number of pores 108
A deposited film consisting of a-Si:H:F was formed on the surface of the Al substrate, which was introduced into the reaction vessel 104 through the metal plate 107 having a ion beam and reacted with each excited species. Similar operations were repeated to form a three-layer photoreceptive layer on the Al substrate. The conditions for forming each layer are shown in Table 1 below. After forming the three layers, the heating heater and rotation were stopped, and after cooling to a predetermined temperature, the exhaust valve was opened to return the inside of the reaction vessel to atmospheric pressure, and the four Al substrates on which the deposited films were formed were removed. They were taken out of the system and evaluated for their properties as electrophotographic photoreceptors.
Images were evaluated using a photocopy machine. The evaluation results are shown in Figure 4. As a result of the evaluation, a uniform and homogeneous film was deposited over the entire surface of the substrate, and the deposited film had good charging ability and sensitivity. Moreover, the obtained image had few image defects over the entire surface.
Furthermore, all of the photoreceptive layers on the four Al substrates showed comparable characteristics.

[Table] Comparative Example 1 Using the apparatus shown in FIG. 2, an electrophotographic light-receiving layer made of a-Si:H:F was formed on a cylindrical Al substrate in the following manner. That is, first, a cylindrical substrate is attached to the cylindrical substrate support means 210.
Place the one equipped with the Al substrate in the reaction vessel,
The exhaust valve 206 was opened and the inside of the reaction vessel was evacuated through the exhaust pipe 205 to bring the inside of the reaction vessel to a degree of vacuum of 10 ⁻⁶ Torr. At the same time, while rotating the cylindrical substrate support means 210 by a driving means (not shown), the substrate temperature is raised to 300° C. by the heating heater 211.
It was heated and maintained at . Two types of raw material gases are introduced into the gas chamber B through the gas introduction pipe 207, and the raw material gases are released into the reaction chamber A from a large number of holes in the multi-perforated inner wall 204 of the gas chamber B. Ta. Exhaust valve 206
After adjusting the internal pressure of the reaction vessel 201 to 0.01Toorr, the microwave generation source 213 generates 2.45GHz.
The microwave 214 passed through the waveguide 215 and was introduced into the reaction chamber A through the dielectric window 216, generating plasma in the reaction chamber A. Radical particles, electrons, ion particles, etc. generated in the plasma at this time reacted with each other to form a deposited film of a-Si:H:F on the cylindrical substrate 209. Similar operations were repeated to form a three-layer photoreceptive layer on the Al substrate. The conditions for forming each layer are shown in Table 2 below. After completing the three-layer film formation, the heating heater and rotation were stopped, and after cooling to a predetermined temperature, the exhaust valve was opened to return the inside of the reaction vessel to atmospheric pressure, and the Al substrate on which the deposited film was formed was removed from the system. Each sample was taken out and its properties as an electrophotographic photoreceptor were evaluated, and the images were evaluated using a photocopying machine. 5th evaluation result
As shown in the figure. As is clear from FIG. 5, the film thickness became thicker as it approached the dielectric window 216 into which non-uniform microwaves were introduced. Further, the properties as an electrophotographic photoreceptor were also non-uniform.

[Table] Represents the
Example 2 Using the apparatus shown in FIG. 1, a photoconductive thin film made of a-Si:H:F was formed on a glass substrate in the following manner. That is, first, four cylindrical base support means 10
A cylindrical Al substrate having three 7059 glass substrates manufactured by Corning Co. as shown in FIG. In addition, in FIG. 3, 301 is a cylindrical base;
2 is a claw for fixing the glass substrate, 303-1, 303
-2 and 303-3 indicate glass substrates, respectively. Next, an exhaust valve (not shown) was opened to evacuate the inside of the reaction container through the exhaust pipe 109, and the inside of the reaction container was brought to a vacuum level of 10 ^-6 Torr. At the same time, the four cylindrical substrate support means 105 were rotated by a driving means (not shown), and the substrate temperature was maintained at 300° C. by a heating heater (not shown). Two types of raw material gases are introduced into the space provided at the end of each electromagnetic horn 103 through the gas introduction pipe 109, and then introduced into the reaction vessel 104 through the metal plate 107 having a large number of holes. did. After adjusting the exhaust valve (not shown) to set the internal pressure of the reaction vessel to 0.01 Torr, 2.45 GHz microwaves are emitted to generate plasma in each electromagnetic horn 103 and release each excited species from each source gas. was generated. These excited species form a large number of pores 108
The excited species were introduced into the reaction vessel 104 through the metal plate 107 having an a-Si:H:F layer, and each excited species reacted to form a deposited film of a-Si:H:F on the surface of the glass substrate. Table 3 shows the film forming conditions at this time. After completing the film formation, the heating heater and rotation were stopped, and after cooling to a predetermined temperature, the exhaust valve was opened to return the inside of the reaction vessel to atmospheric pressure. After that, the four Al substrates on which the deposited films were formed were taken out of the system, and each
Remove the glass substrate mounted on the Al substrate,
After measuring the thickness of each deposited film, a comb-shaped electrode was formed on the deposited film by Al vapor deposition. Then, after measuring the dark conductivity (σd) by applying a DC voltage of 10 V in a dark place, the He-
The photoconductivity (σp) was measured by irradiating light with a wavelength of 6328 Å using a Ne laser. The results are shown in FIG. As is clear from FIG. 6, the film thickness was uniform and good photoconductive properties were obtained over the entire cylindrical substrate.

[Table] Comparative Example 2 Using the apparatus shown in FIG. 2, a photoconductive thin film made of a-Si:H:F was formed on a glass substrate in the following manner. That is, first, the base support means 210 is manufactured by Corning Corporation.
After mounting the cylindrical Al substrate with the 7059 glass substrate mounted as shown in FIG. 3 and placing it in the reaction vessel 201, open the exhaust valve 206 and exhaust the
The inside of the reaction vessel 201 was made to have a degree of vacuum of 10 ^-6 Torr. At the same time, the cylindrical substrate support means 210 was rotated by a driving means (not shown), and the substrate temperature was maintained at 300° C. by the heating heater 211. Two types of raw material gases were introduced into the gas chamber B through the gas introduction pipe 207, and the raw material gases were released into the reaction chamber A from a large number of holes in the multi-perforated inner wall 204 of the gas chamber B. . Exhaust valve 206
After adjusting the internal pressure of the reaction vessel 201 to 0.01 Torr, a microwave generator of 2.45 GHz is applied from the microwave source 213.
The microwave 214 passed through the waveguide 215 and was introduced into the reaction chamber A through the dielectric window 216, generating plasma in the reaction chamber A. Radical particles, electrons, ion particles, etc. generated in the plasma at this time react with each other to form a deposited film of a-Si:H:F on the cylindrical base 209 and the glass substrate attached to the cylindrical base. It was done. Table 4 shows the film forming conditions at this time. After completing the film formation, the heating heater and rotation were stopped, and after cooling to a predetermined temperature, the exhaust valve was opened to return the inside of the reaction vessel to atmospheric pressure. After that, the Al substrate on which the deposited film was formed was taken out of the system, the glass substrate mounted on the Al substrate was removed, and the thickness of each deposited film was measured, and then a comb-shaped electrode was formed by vapor deposition of Al. Formed on a deposited film. Then, after measuring the dark conductivity (σd) by applying a 10V DC voltage in a dark place, the
The photoconductivity (σp) was measured by irradiating light with a wavelength of 6328 Å using a Ne laser. The results are shown in FIG. As is clear from FIG. 7, the film thickness was non-uniform, and the closer it was to the dielectric window 216 into which microwaves were introduced, the thicker the film was.
Furthermore, the photoconductive properties are non-uniform and are inferior to the photoconductive properties of the deposited film obtained in Example 1 in any region on the glass substrate.

【table】 [Brief explanation of drawings]

FIG. 1A is a schematic diagram of the entire apparatus showing a typical example of a deposited film forming apparatus using the plasma CVD method of the present invention, FIG. 1B is a schematic diagram showing its cross section, and FIG. 1C is a schematic diagram of the apparatus according to the present invention. This is a schematic diagram of the waveguide and electromagnetic horn that form part of the device. FIG. 2 is a cross-sectional view schematically showing an example of a deposited film forming apparatus using a conventional plasma CVD method. FIG. 3 is a perspective view schematically showing a state in which a glass substrate is attached to a cylindrical base. 4 to 7 are diagrams showing the film thickness and photoconductive properties of deposited films obtained in Example 1, Comparative Example 1, Example 2, and Comparative Example 2 of the present invention, respectively. In FIGS. 1A to C, 101...high frequency or microwave generation source, 102... waveguide, 10
3... Electromagnetic horn, 104... Reaction container, 105
... Cylindrical base support means, 106 ... Dielectric material,
107...Metal plate with many holes, 108...
Excited species discharge hole, 109... Raw material gas introduction pipe, 11
0...Exhaust pipe. Regarding FIG. 2, 201...reaction vessel, 202
... Side wall, 203 ... Bottom wall, 204 ... Multi-perforated inner wall, 205 ... Exhaust pipe, 206 ... Exhaust valve,
207...Gas introduction pipe, 208...Valve, 20
9... Cylindrical base, 210... Base holding cylinder,
211...Heater, 212...Shinan leg, 213
...High frequency or microwave source, 214...
High frequency or microwave, 215...Waveguide, 2
16...Dielectric window. Regarding FIG. 3, 301... cylindrical substrate, 30
2...Glass substrate fixing claw, 303-1, 30
3-2, 303-3...Glass substrate.

Claims (1)

[Scope of Claims] 1. A reaction vessel for forming a deposited film on a substrate, means for introducing a raw material gas for forming the deposited film into the reaction vessel, and a high frequency wave for exciting and specifying the raw material gas. or a plasma comprising a microwave generating means and a means for evacuating the inside of the reaction vessel.
This is a deposited film forming apparatus using the CVD method, in which a waveguide is connected to a high frequency or microwave generation source, and an electromagnetic horn is connected to the waveguide immediately before the reaction vessel, and a plurality of the electromagnetic horns are connected to the The electromagnetic horn extends into the reaction container parallel to the substrate support surface of the cylindrical substrate support means disposed in the reaction container, and the end of the electromagnetic horn is provided with a dielectric material and a material that does not transmit high frequencies or microwaves. It has a space separated by a metal plate or metal mesh having many holes of the same size, and plasma is generated in the space, and only the excited species of the raw material gas introduced into the space is generated. A deposited film forming apparatus using a plasma CVD method, characterized in that the film is dispersed and discharged into a reaction vessel through a large number of holes or a metal mesh in the metal plate. 2. A deposited film forming apparatus using a plasma CVD method according to claim 1, wherein a plurality of cylindrical substrate supporting means are arranged in a reaction container. 3. The deposited film forming apparatus using the plasma CVD method according to claim 1, wherein the opening of the electromagnetic horn is equal to the longitudinal length of the cylindrical substrate support means. 4. A deposited film forming apparatus using a plasma CVD method as set forth in claim 1, which comprises means for rotating a cylindrical substrate support means disposed within a reaction vessel. 5. The deposited film forming apparatus using the plasma CVD method according to claim 1, wherein the distance between the dielectric material and the metal plate or metal mesh having a large number of holes is 10 mm or more. 6. The plasma according to claim 1, wherein the source gas introduced into the space formed by the dielectric and the metal plate or metal mesh having a large number of holes is different depending on each electromagnetic horn.
Deposited film forming equipment using CVD method.