JPH11135444A - Method and device for forming deposit film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a deposit film by which a light- receiving part for electrophotography having good image quality can be manufactured and a device therefor, by preventing the abnormal growth of the deposit film and reducing the occurrence of spherical projections. SOLUTION: In a method for forming a deposit film in which a base body for forming the deposit film is arranged in a hermetically closed reaction chamber, a raw material gas is introduced into the reaction chamber, and high-frequency power is applied to the eaction chamber by means of introducing means for introducing high frequency power to generate glow discharge in the reaction chamber, the introducing means for high frequency power has at least an electrode 101 for introducing high-frequency power and an insulating body 102 for covering the electrode 101 to separate the surface of the electrode from a glow discharge region, and the electrode has plurality of gas discharge holes 101' through which gas is blown to the inner surface of the insulating body 102, and the deposit film is formed while the gas is being discharged from the gas discharge holes 101'.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deposited film, especially a functional deposited film, particularly a semiconductor device, a light receiving member for electrophotography,
The present invention relates to a method and an apparatus for forming a deposited film for forming a semiconductor film, which are suitably used for an image input line sensor, an imaging device, a photovoltaic device, and the like.

[0002]

2. Description of the Related Art In the field of image formation, a photoconductive material for forming a light receiving layer in a light receiving member has high sensitivity.
It has a high SN ratio [photocurrent (Ip) / dark current (Id)], has an absorption spectrum suitable for the spectral characteristics of the radiated electromagnetic wave, has a fast photoresponse, has a desired dark resistance value, and is used. Are required to be harmless to the human body. In particular, in the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used in an office as an office machine, the above-described non-polluting property during use is important.

Non-single-crystal silicon, in particular, amorphous silicon (a-
A light receiving member for electrophotography using Si) (hereinafter referred to as a
-Si electrophotographic light-receiving member). For example, JP-A-54-86341 discloses that a
A technique relating to a light receiving member for electrophotography using -Si for a photoconductive layer and having excellent moisture resistance, durability, and electric properties is described. Also, JP-A-62-168161 discloses that
As the surface layer, silicon atoms and carbon atoms and 41 to 70a
A technique using an amorphous material containing atomic% of hydrogen atoms as a constituent element is described. With these technologies, electrical, optical, photoconductive properties and environmental properties of use,
A that can improve the durability and further improve the image quality;
An electrophotographic light-receiving member made of -Si has been put to practical use.

[0004] By the way, the production of a light-receiving member for electrophotography requires advanced technology. In particular, in the case of an a-Si electrophotographic light-receiving member, a large area and a large film thickness are required as compared with other devices. It is an important matter how to prevent abnormal growth of the film, which is generated by using foreign matter as a nucleus during the deposition of the Si film.

[0005] For these reasons, various proposals have been made on how to manufacture industrially stable and high-quality a-Si electrophotographic light-receiving members. In particular, with regard to the electrophotographic light-receiving member, the generation of spherical projections which cause image defects called “white spots” in which fine white spots occur on a copy image is a problem.
It is considered that most of the causes of the generation of such spherical projections are that, during the formation of the deposited film, fragments generated by peeling of the film generated inside the deposited film forming apparatus adhere to the surface of the base and cause abnormal growth of the film.

[0006] For example, Japanese Patent Application Laid-Open No. 4-183871 discloses a technique in which a microwave introducing means is composed of two different regions in a deposited film forming apparatus. According to the publication, the permittivity (ε) at the frequency of microwave using the surface of the microwave introducing means which is in contact with the plasma.
And the dielectric contact (tan δ) of 2 × 10 ⁻² or less, stabilization of discharge and prevention of peeling of the deposited film can be achieved. As a result, the uniformity of the deposited film can be improved and the image can be improved. It is said that the occurrence of defects can be suppressed. In addition, as an optimal method, a technique of coating an alumina ceramic with a microwave introducing means by a plasma spraying method is mentioned. With such a technique, it has become possible to form a high-quality deposited film with few spherical protrusions.

[0007]

However, in recent years,
Electrophotographic apparatuses are required to have higher image quality, higher speed, and higher durability than ever before. Furthermore, in order to reduce service costs, it is necessary to reduce the number of maintenance operations by improving the reliability of each component. Under such circumstances, the light receiving member for electrophotography can be used repeatedly for a longer time than before without maintenance by a service person in various environments. Under such circumstances, there is room for improvement in the conventional electrophotographic light receiving member.

For example, in a light receiving member for electrophotography manufactured using a conventional film forming apparatus having a high frequency introducing means, a minute "white spot" may be generated depending on image forming conditions.

Further, industrially, when productivity is considered, speeding up the formation of a deposited film is an important technical problem. To speed up the deposition film formation, it is general to increase the source gas and the introduced power. However, in a conventional film forming apparatus having a high-frequency introduction means, the insulator covering the electrodes and the electrodes simultaneously forms the introduced power. As the temperature increases, the temperature rises, and problems such as peeling of a film deposited on the insulator and breakage of the insulator due to a thermal gradient occur, and the intended purpose may not be sufficiently achieved.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a deposited film capable of producing an electrophotographic light-receiving member having excellent image quality by suppressing abnormal growth of the deposited film and reducing the occurrence of spherical projections. And to provide a device.

It is another object of the present invention to provide a method and an apparatus for forming a deposited film which can efficiently produce a desired electrophotographic light-receiving member even when the deposited film is formed at a high speed.

[0012]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems in the prior art and achieves the above object.

The present invention provides a method and an apparatus for forming a deposited film having the following configuration.

The method for forming a deposited film according to the present invention includes the following two embodiments.

One embodiment of the method for forming a deposited film of the present invention is as follows.
A substrate for film formation is arranged in a reaction vessel capable of vacuum sealing, a source gas is introduced into the reaction vessel, and high-frequency power is introduced through high-frequency power introduction means, and a glow discharge is caused in the reaction vessel. In the method of forming a deposited film on the substrate by causing the high-frequency power introduction means, at least an electrode for introducing the high-frequency power, and a device for separating the surface of the electrode from the glow discharge region. An insulator covering the electrode, wherein the electrode is formed with a plurality of gas emission holes for blowing gas to the inner surface of the insulator, and blowing out the gas from the emission hole to form the deposition film. It is a method of forming a deposited film, characterized by performing the formation.

Another aspect of the method for forming a deposited film of the present invention is to dispose a substrate for film formation in a vacuum-tight reaction vessel, introduce a source gas into the reaction vessel, Applying a high frequency to the arranged high-frequency introducing means to generate a glow discharge of the introduced source gas to form a deposited film on the substrate; An electrode serving as a tubular gas introduction tube having a gas release hole and an insulator arranged to provide a gap between the gas introduction tube and an insulator for separating the glow discharge from the electrode;
The formation of the deposited film is a method of forming a deposited film performed while discharging a gas for cooling the insulator from the gas discharge holes toward the insulator.

The deposited film forming apparatus of the present invention includes the following two embodiments.

One embodiment of the deposited film forming apparatus of the present invention is as follows.
A vacuum-tight sealable reaction vessel, a substrate holding means for disposing a film-forming substrate in the reaction vessel, a source gas introduction means for introducing a source gas into the reaction vessel, and a high-frequency power supply in the reaction vessel. And a high-frequency power introduction unit for introducing a high-frequency power, the high-frequency power introduction unit is configured to separate at least the electrode for introducing the high-frequency power and the surface of the electrode from the glow discharge region. And an insulator covering the electrode, wherein the electrode is provided with a plurality of gas emission holes for blowing gas to the inner surface of the insulator.

Another aspect of the deposited film forming apparatus of the present invention is a vacuum-tightly sealed reaction vessel, substrate holding means for arranging a film-forming substrate in the reaction vessel, and a raw material gas in the reaction vessel. And a high-frequency power introduction means for introducing high-frequency power into the reaction vessel, the high-frequency power introduction means having a hollow portion, and communicating with the hollow portion. And an insulator provided around the electrode to isolate the electrode from the inside of the reaction vessel and to face the gas release hole. It is a deposited film forming apparatus.

The present invention has been made by the present inventors through experiments to solve the above-mentioned problems, and as a result, the following findings have been obtained, and the present invention has been completed based on the findings. .

That is, as described above, one of the factors that affect the yield of the electrophotographic light-receiving member is the occurrence of spherical projections. As a means for preventing the occurrence of the spherical projection, a high-frequency electrode or the like of the high-frequency power introducing means used for film formation as described above is coated with alumina ceramic or the like by a plasma spraying method or the like. Since the ceramics have a higher surface energy than metals, the adhesion to the deposited film increases,
It is effective as a means for preventing film peeling. From such circumstances, the present inventors have studied a method of providing a cover formed of a ceramic material on the surface of the electrode. However, when such a cover is used, an effective effect can be obtained under certain conditions. However, when the introduced power is increased for the high-speed formation of the deposited film as described above, the effect from the cover surface is increased. It has been found that minute peeling of the film may occur, which may be a factor of the generation of a projection such as a sphere. Furthermore, it has been found that the cover itself may be damaged during formation of the deposited film when the introduced power is excessive.

According to the knowledge of the present inventor, such a problem is caused by the fact that, with the introduction of high frequency power, the temperature of the electrode and the electrode cover becomes high and the surface of the electrode cover reaches a certain temperature or higher. It is presumed that a remarkable change occurs in the film deposited on the surface of the electrode cover, and minute film peeling occurs.

Under these circumstances, a study was made to provide a hollow structure for the electrode of the high-frequency power introducing means and to provide a cooling mechanism.
As a result, although a certain effect was obtained, it was not sufficient. Also, to improve the cooling effect,
Although it is conceivable that the electrode and the electrode cover have a close contact structure, it is practically difficult to eliminate the gap between the electrode and the cover. For example, if thermal expansion occurs in the electrode,
It is necessary to provide a certain gap due to the difference in the coefficient of thermal expansion between the ceramic material and the electrode. Also, with respect to mechanical fitting, ceramic materials have lower toughness than metals, and unless some gap is provided, it often leads to breakage. Therefore, it is a design principle to set an appropriate gap between the electrode and the cover made of the ceramic material.

Further, the present inventor has found that, in the course of the experiment leading to the present invention, temperature unevenness tends to occur in the electrodes as the introduced power increases. The mechanism of this phenomenon is not clear at present, but is presumed to be closely related to the transmission of electromagnetic waves. In particular, it has been found that the temperature of the tip of the electrode tends to rise more easily than other portions, and even if the electrode is cooled uniformly, a temperature gradient occurs.

For the reasons described above, the mechanism of the high-frequency power introducing means having the ceramic material on the electrode is
It has been found that it is difficult to achieve a high level of both suppression of "white spots" and high-speed film formation that is industrially rich.

The present invention has been completed based on the above findings. That is, the high-frequency power introducing means used in the present invention blows gas from the inner electrode to the inner surface of the insulator (electrode cover) covering the electrode for separating the surface of the electrode from the glow discharge region, and effectively discharges the electrode. It has a configuration for cooling the cover. Therefore, it is possible to control the surface temperature of the electrode cover, and it is possible to solve the above-mentioned problem due to an increase in the introduced power.

Further, by changing the way of blowing out the gas emitted from the internal electrode, and particularly by arranging the gas discharging holes so as to blow a large amount of gas to a portion where the temperature is considered to be significantly increased, The effect of reducing the temperature gradient on the cover surface can be obtained.

In the high-frequency power introducing means of the present invention, any internal electrode may be used as long as it can efficiently transmit high-frequency waves into the reaction vessel. What is obtained is preferred. For example, metals such as Al, Ti, Cr, Fe, Ni and Co,
Alternatively, an alloy of these metals such as stainless steel may be used. In addition, since high-frequency waves must be able to be efficiently transmitted into the reaction vessel and a means for releasing gas from the inside (that is, a gas discharge hole) is used, a hollow shape, that is, a so-called pipe shape may be used. desirable.

With respect to the gas discharge holes, it is necessary to consider the shape, size, ratio of the discharge holes to the surface area (opening ratio), and the like. In order to substantially achieve the effects of the present invention, the shape of the gas discharge hole may be circular or slit-shaped, but the area per discharge hole may reduce the high-frequency transmission efficiency. It is preferable that the amount does not decrease. Similarly, the aperture ratio of the emission hole is also
It is preferable that the high-frequency transmission efficiency does not decrease.

The flow rate of the gas discharged from the electrode and the shape and distribution of the gas discharge holes of the electrode are appropriately determined according to the conditions for forming the deposited film. In addition, in the present invention, the surface temperature of the electrode cover during the formation of the deposited film is 200 ° C. to 50 ° C.
Preferably it is in the range of 0 ° C.

The size of the electrode is not particularly limited.
However, a plurality of conductive substrates (for example, having a cylindrical shape)
Are arranged on the same circumference, and the electrodes are arranged in the arrangement circle of the cylindrical conductive substrate, the size of the electrodes (that is, the diameter of the cylindrical or cylindrical high-frequency power introducing means as a whole) is For the diameter of the circle where these substrates are located,
A size having a diameter of about 4 to 25% is preferable.

In the present invention, the gas released from the electrode does not adversely affect the deposited film even when it enters the film formation space.
In addition, an inert gas is preferable from the viewpoint of not disturbing the plasma. Specifically, He, Ar, Ne, Xe
And a mixed gas thereof. Further, H ₂ gas is also effective for the present invention. However, in the case of H ₂ gas, which contributes to the reaction of the source gas, it is necessary to consider the prescription (concentration, flow rate, etc.) of the source gas when introducing the source gas into the film formation space in consideration of these points. It is necessary to adjust the introduction amount.

In the present invention, the insulator material serving as the base material of the electrode cover includes alumina ceramics, aluminum nitride, boron nitride, zircon, cordierite, zircon cordierite, silicon oxide, beryllium oxide, mica-based ceramics, and quartz glass. And Pyrex glass can be used. The shape of the electrode cover is desirably a cylindrical shape (or a cylindrical shape) from the viewpoint of workability, ease of forming the electrode, and the like.

Further, at least the surface of the electrode cover in contact with the discharge space can be provided with irregularities mainly for the purpose of preventing the peeling of the deposited film. In this case, the size of the unevenness is preferably in a range of 5 μm or more and 200 μm or less in ten-point average roughness (Rz) with 2.5 mm as a reference length. The means for providing irregularities on the surface is not particularly limited, but for example, a blasting process of spraying a projectile such as an abrasive is preferable.

The size of the electrode cover is not particularly limited. However, when a plurality of conductive bases (particularly, cylindrical conductive bases) are arranged on the same circumference, and the electrodes are installed within the circle where the conductive bases are arranged, the size of the cylindrical insulator (ie, The diameter of the cylindrical or columnar high-frequency power introducing means is preferably about 4 to 25% of the diameter of the circumference on which these bases are arranged. The thickness of the cylindrical electrode cover is not particularly limited, but is preferably about 0.5 to 20 mm from the viewpoint of processing and mechanical strength.

Distance (gap) between internal electrode and electrode cover
If is too small, the difference in the coefficient of thermal expansion between the internal electrode and the electrode cover (for example, a ceramic material) causes a breakage, and if it is too large, it also affects a sufficient cooling effect and high-frequency transmission. Although the design differs depending on the material of the electrode and the electrode cover, the distance is preferably in the range of 0.5 to 5 mm.

In the present invention, the source gas is decomposed by applying high-frequency power to the high-frequency power introduction means. The frequency of the high-frequency power that can be used in the present invention is not particularly limited.
If the value is less than z, the discharge may be unstable depending on the conditions, and the conditions for forming the deposited film may be limited. When the frequency is higher than 450 MHz, the transmission characteristics of high-frequency power tend to deteriorate, and in some cases, it is difficult to generate glow discharge itself. Therefore, the frequency range of 50 MHz to 450 MHz is optimal. Although any high-frequency waveform may be used, a sine wave, a rectangular wave, or the like is preferable.

Hereinafter, the deposited film forming apparatus of the present invention will be described in more detail with reference to the drawings.

FIG. 1 is a schematic view of a cross section in the generatrix direction (drawing direction) of an example of the high-frequency power introducing means of the present invention. In FIG. 1, 101 is a high-frequency power introduction electrode, and 102 is an electrode cover formed of an insulator. The outside of the electrode cover 102 is a glow discharge region, and the inside is a region separated from the glow discharge region. High frequency power introduction electrode 1
Reference numeral 01 denotes a pipe shape as shown in FIG. 1, in which a plurality of gas discharge holes 101 ′ are arranged, and gas is introduced into the high-frequency power introduction electrode 101 from a gas supply means (not shown). ′, Gas is released to the inner surface of the electrode cover 102. The gas supply means and the high-frequency power introduction electrode 10
The first connection part (not shown) is formed of an insulator so that high-frequency transmission is transmitted only inside the reaction vessel. The high frequency power is supplied from the high frequency power source 103 to the matching box 1.
It is adjusted at 04 and applied to the high-frequency power introduction electrode 101 via the high-frequency transmission circuit and the high-frequency introduction terminal (not shown).

Next, a case where a light receiving member is manufactured by the method of forming a deposited film of the present invention will be described with reference to the drawings.

FIG. 2A is a schematic cross-sectional view of one example of the deposited film forming apparatus of the present invention having an electrode (high-frequency power introduction electrode) having a plurality of gas discharge holes (101 ') shown in FIG. FIG. FIG. 2B is a diagram schematically showing a cross section of the deposited film forming apparatus as shown in FIG.

The high frequency power introducing means in the deposition film forming apparatus has the structure shown in FIG.
As shown in FIG. 2A and FIG. 2B, an electrode 201 provided with a plurality of gas emission holes (101 ′, see FIG. 1) in a uniformly distributed state is covered with an electrode cover 202. is there. A gas supply pipe from a gas supply system for the electrode is connected to the electrode 201 so that a gas (inert gas or hydrogen gas) can be introduced into the electrode.

When a light receiving member is manufactured using the deposited film forming apparatus, the film is formed, for example, as follows.

First, a plurality of preliminarily degreased and cleaned cylindrical substrates 205 are placed in a reaction container 200 on a cylindrical substrate holder 212 having a substrate heating heater 208 therein. The inside of the reaction vessel 200 is evacuated by a vacuum pump (for example). Subsequently, the temperature of each cylindrical substrate 205 is controlled to a predetermined temperature by the heater 208.

When the temperature of the cylindrical substrate 205 reaches a desired temperature, a source gas for film formation is supplied from a source gas supply system via the gas introduction pipe 206 to the film forming space of the reaction vessel 200 surrounded by the cylindrical substrate 205. Supply within. At this time, care should be taken not to cause extreme pressure fluctuation such as gas projection. Next, when the flow rate of the raw material gas reaches a predetermined flow rate, the exhaust valve (not shown) is adjusted while looking at the vacuum gauge (not shown),
Obtain the desired internal pressure. Next, a gas (an inert gas or a hydrogen gas) is introduced into the electrode 201 from another gas supply system (a gas supply system into the electrode 201), and the electrode is passed through a plurality of gas discharge holes of the electrode. The gas (inert gas or hydrogen gas) is released to the inner surface of the cover 202.

When the internal pressure of the reaction vessel 200 is stabilized, the high frequency power supply 203 is set to a desired power. The high frequency power is supplied to the electrode 201 through the matching box 204.
To be applied. At this time, the source gas introduced into the film forming space surrounded by the cylindrical substrate 205 in the reaction vessel 200 is decomposed by the discharge energy, and the respective cylindrical substrates 2 are decomposed.
A predetermined deposited film is to be formed on the substrate 05. During the formation of the deposited film, each of the cylindrical substrates 205 is rotated by the rotation of the substrate holder 212 via the rotation shaft 209 by the rotation force of the motor 211 using the transmission mechanism 210 constituting the rotation mechanism. A deposited film is uniformly formed on the surface of the cylindrical substrate 205. After the desired film thickness is formed, the supply of high frequency power is stopped,
The flow of gas into 00 is stopped, and the formation of the deposited film as the light receiving layer (photoconductive layer) is completed.

When a deposited film composed of a plurality of layers is formed on a cylindrical substrate due to the desired properties of the deposited film, the above operation is repeated to form a light receiving layer having a desired layer structure. can do. Thereby, a plurality of light receiving members can be obtained. As such a light receiving member, for example, a member having a configuration as shown in FIG. 3 can be mentioned.

In FIG. 3, reference numeral 300 denotes a light receiving member;
Reference numeral 1 denotes a substrate, 302 denotes a charge injection blocking layer, 303 denotes a photoconductive layer, 304 denotes a surface layer, and 305 denotes a light receiving layer.

Hereinafter, as an example of producing a light receiving member according to the present invention, a case of producing a light receiving member having the structure shown in FIG. 3 will be described.

Light receiving layer 305 (particularly photoconductive layer 303)
As a material gas for the formation, for example, when an amorphous silicon film is formed, SiH ₄ , Si ₂ H ₆ , Si ₃ H
₈ , Silicon hydride (silanes) in a gas state such as Si ₄ H ₁₀ or capable of being gasified is effectively used as a Si supply gas. In addition to silicon hydride, a silicon compound containing a fluorine atom, a so-called silane derivative substituted with a fluorine atom, specifically, for example, silicon fluoride such as SiF ₄ or Si ₂ F _6, or SiH ₃ F , SiH ₂ F ₂ , SiHF ₃
A gaseous or gasifiable substance such as fluorine-substituted silicon hydride is also effective as the Si supply gas of the present invention. In addition, these raw material gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, or Ne as necessary, and used.

In addition to the above gases, a gas for supplying atoms belonging to Group IIIb of the Periodic Table or a gas for supplying atoms belonging to Group Vb of the Periodic Table can be used as a so-called dopant source, if necessary. For example, boron atom (B)
When used, boron hydrides such as B ₂ H ₆ and B ₄ H ₁₀ and boron halides such as BF ₃ and BCl ₃ can be used. When a phosphorus atom is used, PH ₃ , P ₂ H ₄
Such as hydrogenated phosphorus, PH ₄ I, PF ₃ , PCl ₃ , PBr ₃ ,
Phosphorous halides such as PI ₃ can be used.

Further, at least one selected from a carbon atom, an oxygen atom and a nitrogen atom can be contained in the layer. In this case, examples of the substance that can serve as a carbon atom (C) supply gas include gaseous hydrocarbons such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ , and C ₄ H ₁₀ or hydrocarbons that can be gasified.

Among these hydrocarbons, CH ₄ and C ₂ H are preferred in terms of ease of handling at the time of forming a layer and high C supply efficiency.
₆ is particularly preferred. Further, the raw material gas for supplying C may be used after being diluted with a gas such as H ₂ , He, Ar, or Ne if necessary.

Examples of the substance that can be a gas for supplying oxygen atoms (O) include oxygen (O ₂ ), ozone (O ₃ ), and carbon dioxide (CO ₂ ). Examples of the substance that can serve as a nitrogen atom (N) supply gas include nitrogen gas (N ₂ ), ammonia (NH ₃ ), and hydrazine (H ₂ ) having N as a constituent atom or N and H as constituent atoms. NN
H ₂ ), hydrogen azide (HN ₃ ), ammonium azide (N
Nitrogen compounds such as gaseous or gasifiable nitrogen, such as H ₄ N ₃ ), nitrides and azides.

As a source gas capable of simultaneously supplying oxygen atoms (O) and nitrogen atoms (N), nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ), dinitrogen monoxide (N ₂ O) , Nitrous oxide (N ₂ O ₃ ), nitrous oxide (N ₂ O ₄ ), nitrous oxide (N ₂ O ₅ ), nitric oxide (N
O ₃ ).

The above-mentioned raw material gas may be diluted with H ₂ and / or He, if necessary.

When the light receiving member 300 is for electrophotography, the layer thickness of the light receiving layer 305 (particularly, the photoconductive layer 303) is appropriately determined from the viewpoint of obtaining desired electrophotographic characteristics and economic effects. It is determined as desired, and preferably 15 to 50 μm, more preferably 20 to 45 μm, and most preferably 25 to 40 μm.

Light receiving layer (photoconductive layer) having desired characteristics
It is necessary to appropriately set the mixing ratio of the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power, and the temperature of the substrate in order to form.

The optimum flow rate of the H ₂ gas used as the diluent gas is appropriately selected according to the layer design.
H ₂ gas to the flow rate of the Si supply gas, usually 1
It is desirable to perform control to change within a range of ２０20 times, preferably 2１５15 times, and optimally 3〜１０10 times.

The gas pressure (internal pressure) in the reaction vessel at the time of film formation is 100 mTorr to obtain a desired deposited film.
It is desirably r or less. The preferred range is
3 to 100 mTorr, and a more preferable range is 10 to 100 mTorr.
８０80 mTorr.

Similarly, the optimum range of the discharge power is appropriately selected depending on the layer design and the form of the deposition apparatus. However, in order to obtain a sufficient deposition rate and film characteristics, the discharge power with respect to the flow rate of the Si supply gas is required. It is desirable to set the discharge power in the range of 1 to 20 times, preferably 2 to 10 times, and optimally 3 to 5 times in normal cases.

The temperature of the substrate 301 at the time of film formation is appropriately selected in an optimal range according to the layer design, but is usually preferably 200 to 350 ° C., more preferably 2 to 350 ° C.
It is desirable that the temperature is 30 to 330 ° C, most preferably 250 to 310 ° C.

In the present invention, the film forming conditions for forming a desired photoreceptive layer (photoconductive layer) include those described above. However, these conditions are not usually determined independently and separately. Instead, it is desirable to determine the optimum value based on mutual and organic relationships to form a light receiving member having desired properties.

The substrate 301 used may be either conductive or electrically insulating. As such a substrate,
Al, Cr, Mo, Au, In, Nb, Te, V, T
Examples include metals such as i, Pt, Pd, and Fe, and alloys thereof, for example, stainless steel. In addition, at least the surface of the electrically insulating substrate such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, or a synthetic resin such as polyamide, on the side on which at least the light receiving layer is formed, of an electrically insulating substrate such as glass or ceramics. A substrate subjected to a conductive treatment can also be used.

The shape of the substrate 301 can be a cylindrical or plate-like endless belt having a smooth surface or an uneven surface. The thickness is appropriately determined so that the electrophotographic light-receiving member 300 as shown in FIG. 3 can be manufactured. For example, when flexibility as the electrophotographic light receiving member 300 is required, it can be made as thin as possible within a range where the function as the base 301 can be sufficiently exhibited. However, in any case, the substrate is usually 10 μm or more in terms of production, handling, mechanical strength and the like.

In particular, when performing image recording using coherent light such as laser light, in order to more effectively eliminate image defects caused by a so-called interference fringe pattern appearing in a visible image, the surface of the substrate is made uneven. May be provided.

As another method for more effectively eliminating image defects due to interference fringe patterns when coherent light such as laser light is used, a concave and convex shape formed by a plurality of spherical trace depressions is provided on the surface of a substrate. Is also good. That is, the surface of the substrate has irregularities smaller than the resolution required for the electrophotographic light-receiving member, and the irregularities are caused by a plurality of spherical trace depressions. The unevenness due to the plurality of spherical trace depressions provided on the surface of the base can be produced by a known method described in JP-A-61-231561.

As shown in FIG. 3, the light receiving member for electrophotography manufactured according to the present invention has a function of preventing charge injection from the substrate side between the substrate 301 and the photoconductive layer 303. It is more effective to provide the charge injection blocking layer 302. That is, the charge injection blocking layer 302 has a function of preventing charges from being injected from the substrate 301 side to the photoconductive layer 303 side when the photoreceptive layer 305 receives a charging treatment of a fixed polarity on its free surface. However, such a function is not exhibited when it is subjected to charging treatment of the opposite polarity, that is, it has a so-called polarity dependency. In order to provide such a function, the charge injection blocking layer 302 contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer 303. The atoms for controlling the conductivity contained in the charge injection blocking layer 302 may be distributed evenly and uniformly in the layer, or may be contained evenly in the direction of the thickness of the layer. Some portions may be contained in a state of being uniformly distributed. When the distribution concentration is non-uniform, it is preferable that the compound be contained so as to be distributed more on the substrate side. However, in any case, it is necessary to uniformly contain the particles in a direction in a plane parallel to the surface of the substrate in a uniform distribution from the viewpoint of making the characteristics uniform in the plane direction.

As the atoms for controlling the conductivity contained in the charge injection blocking layer 302, there can be mentioned so-called impurities in the field of semiconductors, and atoms belonging to Group IIIb of the periodic table giving p-type conduction characteristics (hereinafter referred to as atoms). An atom belonging to Group IIIb of the Periodic Table that gives n-type conduction characteristics (hereinafter abbreviated as a "Group Vb atom") or an atom belonging to Group Vb of the periodic table that provides n-type conductivity can be used.

As the Group IIIb atom, specifically,
There are B (boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium) and the like, and B, Al and Ga are particularly preferable. Specific examples of group Vb atoms include P (phosphorus), As (arsenic), and Sb.
(Antimony), Bi (bismuth) and the like, and P and As are particularly preferable.

The content of atoms for controlling conductivity contained in the charge injection blocking layer 302 is appropriately determined as desired so that the object of the present invention can be effectively achieved. 1 × 10 ⁴ atomic ppm, more preferably 50 to 5 × 10 ³ atomic ppm, optimally 1 × 10 ²
Desirably, it is set to １1 × 10 ³ atomic ppm.

Further, the charge injection blocking layer 302 contains at least one of carbon atoms, nitrogen atoms, and oxygen atoms, so that the charge injection blocking layer 302 is in direct contact with another layer provided in direct contact with the charge injection blocking layer. Can be further improved. In this case, at least one of the carbon atom, the nitrogen atom and the oxygen atom may be uniformly distributed in the layer, or may be uniformly distributed in the thickness direction of the layer, but not uniformly. Some portions may be contained in a state of being uniformly distributed. However, in any case, it is necessary to be uniformly contained in an in-plane direction parallel to the surface of the substrate in order to make the characteristics uniform in the in-plane direction.

The charge injection blocking layer 30 of the present invention
The hydrogen atoms contained in 2 compensate for dangling bonds existing in the layer, and are effective in improving the film quality.

The thickness of the charge injection blocking layer 302 is preferably from 0.1 to 5 μm, more preferably from 0.3 to 5 μm, from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
It is desirable that the thickness be 4 μm, most preferably 0.5 to 3 μm.

The charge injection blocking layer 302 comprises a photoconductive layer 303
Can be formed in the same manner as the above-mentioned method.

That is, in order to form the charge injection blocking layer 302 having desired characteristics, similarly to the case of forming the photoconductive layer 303, the mixing ratio of the gas for supplying Si and the diluent gas, It is necessary to appropriately set the gas pressure, the discharge power, and the temperature of the substrate.

[0077] the flow rate of a diluent gas H ₂ and / or He may be appropriately selected within an optimum range in accordance with the layer design, the H ₂ and / or He to the Si-feeding gas,
In the normal case, it is desirable to control to a range of 1 to 20 times, preferably 3 to 15 times, and optimally 5 to 10 times.

The gas pressure (internal pressure) in the reaction vessel at the time of film formation is 100 mTorr to obtain a desired deposited film.
It is desirable to be r or less. A preferred range is 3 to 100 mTorr, and a more preferred range is 10 to 80 mTorr.

Similarly, the optimum range of the discharge power is appropriately selected depending on the layer design and the form of the deposition apparatus. However, the discharge power with respect to the flow rate of the gas for supplying Si is usually 1 to 2 times.
It is desirable to set the range to 0 times, preferably 2 to 10 times, and optimally 3 to 5 times.

Further, the temperature of the substrate is appropriately selected in an optimum range according to the layer design, but is usually preferably 200 to 350 ° C., and more preferably 230 to 330 ° C.
° C, optimally 250-310 ° C.

The above-mentioned film forming conditions for forming the charge injection blocking layer 302 are mentioned above. However, these conditions are not usually determined separately and independently. It is desirable to determine the optimum value of the formation factor of each layer based on mutual and organic relations to be formed.

In the light receiving member 300 for electrophotography,
Base 301 and photoconductive layer 303 or charge injection blocking layer 3
For the purpose of further improving the adhesiveness between Si and N ₂ , for example, Si ₃ N ₄ , SiO ₂ , SiO or a silicon atom is used as a base, and a hydrogen atom and / or a halogen atom, a carbon atom and / or an oxygen atom are used. An adhesion layer formed of an amorphous material containing atoms and / or nitrogen atoms may be provided. Further, a light absorbing layer for preventing the generation of interference fringe patterns due to the reflected light from the base may be provided.

In the light receiving member 300 for electrophotography,
It is preferable to provide a surface layer 304 made of an amorphous silicon material on the photoconductive layer 303.

The constituent material of the surface layer 304 may be any material as long as it is an amorphous silicon-based material. For example, amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing a carbon atom (hereinafter referred to as “a-SiC: H, X”), a hydrogen atom (H) and / or Or amorphous silicon containing a halogen atom (X) and further containing an oxygen atom (hereinafter referred to as “a-SiO: H, X”), a hydrogen atom (H) and / or a halogen atom (X). , An amorphous silicon further containing a nitrogen atom (hereinafter referred to as “a-SiN: H, X”), a hydrogen atom (H) and / or a halogen atom (X), and further containing a carbon atom, an oxygen atom, and a nitrogen atom. A material such as amorphous silicon containing at least one atom (hereinafter referred to as “a-SiCON: H, X”) is preferably used.

In addition, amorphous carbon-based materials can also be used. As a specific example, amorphous carbon “aC: H, X” containing a hydrogen atom (H) and / or a halogen atom (X) can be used. Can be mentioned.

The surface layer 304 is formed by a vacuum deposition film forming method by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics. However, the surface layer 304 and the photoconductive layer are formed in view of productivity of the light receiving member. Preferably, an equivalent deposition method is used.

The substance which can be a silicon (Si) supply gas used in forming the surface layer 304 includes S
Silicon hydrides (silanes) in a gas state such as iH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ or the like, which can be gasified, are preferable. Among these, SiH ₄ and Si ₂ H ₆ are particularly preferable in terms of ease of handling at the time of forming the layer and good Si supply efficiency. These source gases for supplying Si may be used by diluting them with a gas such as H ₂ , He, Ar, or Ne as necessary.

Examples of substances that can serve as a carbon supply gas include:
_{CH 4, C 2 H 6,} C 3 H 8, C 4 gaseous state, such as H _10, or a hydrocarbon which can be gasified are exemplified as preferable. Of these, CH ₄ and C ₂ H ₆ are particularly preferable in terms of ease of handling at the time of forming the layer and good C supply efficiency.
The raw material gas for supplying C may be H ₂ , H
It may be used after being diluted with a gas such as e, Ar, or Ne.

The thickness of the surface layer 304 is preferably 0.01 to 3 μm, more preferably 0.05 to 2 μm,
Optimally, the thickness is desirably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to abrasion or the like during use of the light receiving member, and if it exceeds 3 μm, the electrophotographic properties such as an increase in residual potential are reduced.

Hereinafter, the effects of the present invention will be described with reference to the following experimental examples, but the present invention is not limited thereto.

[0091]

EXPERIMENTAL EXAMPLE 1 Using the deposition film forming apparatus shown in FIG. 2, only Ar gas was introduced into the film formation space through the gas introduction pipe 206,
Plasma was generated under the conditions shown in Table 1, and the surface temperature of the electrode cover 202 during plasma generation 60 minutes later was measured with an infrared radiation thermometer. At this time, He gas was introduced into the electrode 201 and blown out to the inner surface of the electrode cover 202. In this experimental example, a SUS306 pipe-shaped (18 mm outside diameter, 10 mm inside diameter) material was used as an electrode. In addition, a total of 40 gas discharge holes were arranged, each having four circular holes having a diameter of 1.5 mm arranged in a line of 4 in the generatrix direction of the electrode. The electrode cover is made of a ceramic material (outer diameter 26m
m, an inner diameter of 20 mm). The measurement results are shown in FIG.

[0092]

Comparative Experimental Example 1 In this comparative experimental example, FIG.
(A) and the deposited film forming apparatus shown in FIG. 4 (B)) were used. The deposited film forming apparatus replaces the electrode (having a configuration provided with a plurality of gas discharge holes) in the apparatus shown in FIG. 2 with an electrode having no gas discharge holes (high-frequency power introduction electrode) and changes the gas supply system. The configuration is the same as that of the apparatus shown in FIG. The high-frequency power supply means in the deposition film forming apparatus shown in FIG. 4 has a configuration in which a solid electrode 401 having no gas discharge holes is covered with an electrode cover 402.

As in Experimental Example 1, the source gas introduction pipe 406
, Only Ar gas was introduced into the film forming space through the above, plasma was generated under the conditions shown in Table 1, and the surface temperature of the electrode cover 402 during plasma generation 60 minutes later was measured with an infrared radiation thermometer. In this comparative example, a solid material of SUS306 (18 mm in outer diameter) was used for the electrode 401. As the electrode cover 402, a pipe-shaped one made of the same ceramic material (outer diameter 26 mm, inner diameter 20 mm) as in Experimental Example 1 was used. FIG. 5 shows the measurement results.

As is clear from the results shown in FIG. 5, according to the apparatus of the present invention, the surface temperature of the electrode cover during plasma generation can be maintained at a lower temperature than that of the conventional apparatus.

[0095]

[Experimental Example 2] As shown in the surface temperature measurement results of Comparative Experimental Example 1, the temperature rise was large at the lower part of the electrode cover (the tip part in the introduction direction). In this experimental example, as shown in FIG. 6, the distribution state of the gas emission holes of the electrode of the device shown in FIG. 2 was increased in the tip direction as shown in FIG. Then, plasma generation and gas release from the electrode were performed, and the temperature of the electrode cover surface was measured similarly. The gas discharge holes are 10 circular holes having a diameter of 1.5 mm at the distal end 1/3 in the generatrix direction of the electrode and 2/2 at the inlet side.
Five of the three were arranged in quadratic arrangement, and a total of 60 were arranged.

FIG. 7 shows the measurement results. As shown in FIG. 7, it was found that the electrode cover surface temperature became more uniform by distributing a large number of gas emission holes in a portion where the temperature rise was large (here, the electrode tip) as in this experimental example. .

[0097]

Experimental Example 3 A deposited film was formed under the conditions shown in Table 2 using the high-frequency power introducing electrode shown in FIG. 6 in the apparatus shown in FIG. At this time, SiH ₄ was used as a source gas,
In the same manner as in Experimental Example 2, a deposited film was formed for a certain period of time while spraying He gas from the electrode onto the inner surface of the electrode cover, and the state of the deposited film attached to the electrode cover surface was examined.

[0098]

COMPARATIVE EXPERIMENT 2 A deposited film was formed using the deposited film forming apparatus shown in FIG. After forming the deposited film for the same time as in Experimental Example 3, the state of the deposited film adhered to the surface of the electrode cover was similarly examined.

FIG. 8 shows the results of Experimental Example 3 and Comparative Experimental Example 2.
Is shown as a graph.

As shown in FIG. 8, in Experimental Example 3 of the present invention, it was found that the degree of peeling of the deposited film from the electrode cover was improved.

The present invention will be described in more detail with reference to the following examples. The present invention is not limited by these examples.

[0102]

Embodiment 1 Outer diameter 108 mm, length 358 mm, wall thickness 5
An aluminum cylinder having a diameter of 2 mm was mirror-finished and degreased and washed. Six cylindrical substrates were placed in a reaction vessel 200 of the apparatus shown in FIG. 2 as shown in FIG. Then, the frequency of the high-frequency power was set to 105 MHz by the film forming method using the apparatus shown in FIG.
The light receiving member for electrophotography (hereinafter referred to as a drum) having the layer structure shown in FIG.

In this embodiment, the electrode 201 is S
US306 pipe shape (outside diameter 18mm, inside diameter 10mm)
Material used. As gas discharge holes, ten circular holes each having a diameter of 1.5 mm were arranged in four equal lines in the generatrix direction of the electrodes, and a total of 40 gas holes were arranged. For the electrode cover 202, an alumina ceramic (Al ₂ O ₃ ) material processed into a pipe shape with an outer diameter of 26 mm and an inner diameter of 20 mm was used. The surface of the electrode cover (plasma region side) is blasted to have a ten-point average roughness (Rz) in a range of 30 μm or more and 100 μm or less with a reference length of 2.5 mm. He gas was introduced at 1000 sccm and released to the inner surface of the electrode cover.

The "layer thickness" in Table 3 is a rough guide for designing a light receiving member for electrophotography.

[0105]

[Evaluation] The drum thus manufactured was set in an electrophotographic apparatus (NP6060 manufactured by Canon Inc. modified for this test), and the electrophotographic characteristics (state of occurrence of image defects) were evaluated by the following method.

The produced electrophotographic photosensitive member was set on an electrophotographic apparatus (NP6060 manufactured by Canon Inc. modified for this test), and a halftone chart (part number FY9-9042) manufactured by Canon was placed on a document table. The number of white spots having a diameter of 0.5 mm or less within the same area of the copied image obtained at the time of copying was counted. Table 4 shows the obtained results based on the following criteria.

Regarding image defects, ◎: 0 to 2 pieces, not disturbed at all ○: 3 to 5 pieces, not disturbed Δ: 6 to 10 pieces, slightly disturbed ×: 11 or more And if you are worried

[0108]

Comparative Example 1 Using the conventional deposited film forming apparatus shown in FIG.
A drum was prepared under the same conditions as in Example 1. In this comparative example, SUS was used as the electrode 401 of the high-frequency power introduction unit.
A 306 (18 mm outer diameter) solid material was used. The same ceramic material as in Example 1 was used for the electrode cover 402.

The prepared drum was evaluated in the same manner as in Example 1, and the results are shown in Table 4.

As is apparent from the results shown in Table 4, it is understood that the drum of the example of the present invention is superior to the drum of the comparative example in image defects.

[0111]

Example 2 A drum was manufactured under the same conditions as in Example 1 except that the high frequency power introducing means shown in FIG. 6 was used. In this embodiment, a SUS306 pipe-shaped (18 mm outside diameter, 10 mm inside diameter) material is used as the electrode 601, and the gas discharge hole is a circular hole having a diameter of 1.5 mm at one third of the tip side in the generatrix direction of the electrode. Ten pieces and five pieces on the introduction part side 2/3 were each arranged in 4 equal arrangements, and a total of 60 pieces were arranged.

For the electrode cover 602, the same alumina ceramic material as in Example 1 was used.

The prepared drum (electrophotographic photoreceptor) was set in an electrophotographic apparatus (NP6060 manufactured by Canon Inc. modified for this test), and the evaluation of electrophotographic characteristics (charging ability unevenness) was made as follows. Made by the way.

Evaluation of charging ability unevenness: The produced electrophotographic photosensitive member was set in an electrophotographic apparatus (NP6060 manufactured by Canon Inc. modified for this test), and the charging potential was measured in the longitudinal direction of the electrophotographic photosensitive member. . The results obtained are those in which the variation of the charging potential from the average potential is within 3%.
% Are shown in Table 5, and those exceeding 5% are indicated by Δ. In addition, evaluation of image defects was performed in the same manner as in Example 1. Table 5 shows the obtained results.

[0115]

Comparative Example 2 The same evaluation as in Example 2 was performed for the drum prepared in Comparative Example 1.

Table 5 shows the results.

The same evaluation as in Example 2 was performed on the drum prepared in Example 1. Table 5 shows the obtained results.
Shown in

As is clear from the results shown in Table 5, it is understood that the drum of the example of the present invention is particularly excellent in image defects and uneven charging ability.

[0119]

Third Embodiment Under the same conditions as in the second embodiment, the frequency of the high-frequency power is changed to 50 MHz, 80 MHz, 105 MHz and 20 MHz.
The drum was changed to 0 MHz and 450 MHz, and a drum having the layer configuration shown in FIG. 3 was manufactured. In the same manner as in Examples 1 and 2, image defects and charging ability unevenness were evaluated. Table 6 shows the obtained evaluation results.

In Table 6, each evaluation item is shown as a relative evaluation where the case where the frequency of the high frequency power is 105 MHz is 1. As is clear from Table 6, a drum having good characteristics in both spherical projections and unevenness was obtained at any frequency.

[0121]

Embodiment 4 In this embodiment, the gas released from the electrode is H
A drum having the layer configuration shown in FIG. 3 was prepared under the same conditions as in Example 2 except that No. ₂ was used.

The prepared drum was evaluated for image defects and uneven charging ability in the same manner as in Examples 1 and 2. Table 7 shows the obtained results.

Further, in this embodiment, the evaluation of the blank memory was performed by the following method.

Evaluation of blank memory: obtained when an intermediate chart (part number FY9-9042) manufactured by Canon Inc. was copied on a manuscript table with an electrophotographic apparatus NP6060 (modified for testing) manufactured by Canon Inc. The difference in reflection density between the part slightly thinned in the generatrix direction and the normal part due to blank exposure of the image was measured. Table 7 shows the obtained results based on the following criteria.

Regarding the blank memory, ◎: particularly good ○: good △: no problem in practical use ×: some problem in practical use The drum prepared in Example 2 was also used. Example 4
The blank memory was evaluated in the same manner as described above. Table 7 shows the obtained evaluation results.

As shown in Table 7, this embodiment (Embodiment 4)
In, good results were obtained for all items.
In particular, in comparison with Example 2, the result that the blank memory was improved by using hydrogen as the gas released from the electrode was obtained.

[0127]

[Table 1]

[0128]

[Table 2]

[0129]

[Table 3]

[0130]

[Table 4]

[0131]

[Table 5]

[0132]

[Table 6]

[0133]

[Table 7]

[0134]

According to the present invention, the high-frequency power introducing means has at least an electrode for introducing high-frequency power, and an insulator covering the electrode for separating a surface of the electrode from the glow discharge region. A plurality of gas emission holes for blowing gas to the inner surface of the insulator; and forming a deposition film while blowing gas from the emission holes, thereby forming a deposition film of the insulator. By suppressing the rise in surface temperature during the formation and reducing the peeling of the film from the insulator surface, a light-receiving member with few image defects can be efficiently obtained even under high-speed film formation conditions. Further, by appropriately arranging the distribution of the gas emission holes of the internal electrodes, it is possible to obtain a good light receiving member which suppresses the temperature distribution on the insulator surface and simultaneously suppresses the unevenness of the charging ability.
This is presumed to suppress the adverse effects (temperature unevenness, impurity contamination) on the deposited film due to the temperature distribution (partial temperature rise) of the insulator, which is assumed to have conventionally occurred.

Further, by using hydrogen gas as the gas released from the internal electrodes, the effect of improving the blank memory can be obtained. Although the mechanism of this phenomenon is unknown at present, it is necessary to pass hydrogen gas inside a conductor to which a high frequency is applied or to pass through a pipe heated to a certain temperature or higher. Is activated and introduced into (leaked into) the plasma space, thereby contributing to the formation of a deposited film.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a high-frequency power introduction unit of a deposited film forming apparatus according to the present invention.

FIG. 2 is a schematic view showing one example of a deposited film forming apparatus of the present invention.

FIG. 3 is a schematic cross-sectional view illustrating a layer configuration of a light receiving member for electrophotography.

FIG. 4 is a schematic view showing an example of a conventional deposited film forming apparatus.

FIG. 5 shows the results of measuring the surface temperature of the electrode cover in Experimental Example 1 and Comparative Experimental Example 1.

FIG. 6 is a schematic view showing an example of a high-frequency power introducing means of the deposited film forming apparatus of the present invention.

FIG. 7 shows a measurement result of the surface temperature of the electrode cover in Experimental Example 2.

FIG. 8 is a graph showing the relationship between the deposition film formation time and the peeling of the electrode cover surface in Experimental Example 3 and Comparative Experimental Example 2.

[Explanation of symbols]

101, 201, 401, 601 Electrode 101 'Gas emission hole 102, 202, 402, 602 Electrode cover (insulator) 103, 203, 403, 603 Power supply 104, 204, 404, 604 Matching box 200, 400 Reaction vessel 205, 405 Cylindrical substrate 206, 406 Gas inlet tube 207, 407 Exhaust port 208, 408 Heater 209, 409 Rotating shaft 210, 410 Rotating gear 211, 411 Rotating motor 212, 412 Holder 300 Light receiving member 301 Substrate 302 Charge injection blocking layer 303 photosensitive layer 304 surface layer 305 light receiving layer

Claims (30)

[Claims] 1. A glow discharge device comprising: a substrate for film formation arranged in a reaction vessel capable of being vacuum-sealed; a source gas being introduced into the reaction vessel and high-frequency power being introduced through high-frequency power introduction means; In the reaction vessel to form a deposited film on the substrate, wherein the high-frequency power introducing means comprises: an electrode for introducing at least the high-frequency power; An insulator covering the electrode for separation, and the electrode is formed with a plurality of gas discharge holes for blowing gas to the inner surface of the insulator, and the gas is blown out from the discharge hole. A method of forming a deposited film while performing the formation of the deposited film. 2. The method according to claim 1, wherein the base material of the insulator is a ceramic material. 3. The frequency of the high-frequency power is 50 MHz or more.
3. The method according to claim 1, wherein the frequency range is 450 MHz. 4. The method according to claim 1, wherein the plurality of emission holes are uniformly distributed in the electrode. 5. The deposition film forming method according to claim 1, wherein the plurality of emission holes are distributed more in the direction of the tip of the electrode. 6. The method according to claim 1, wherein the gas emitted from the plurality of emission holes is an inert gas. 7. The method according to claim 1, wherein the gas emitted from the plurality of emission holes is a hydrogen gas. 8. The method according to claim 1, wherein the base comprises a plurality of bases, and the bases are arranged in a circle around the high-frequency power supply means. 9. The method according to claim 1, wherein the base has a cylindrical shape. 10. The distance between said insulator and said electrode is 0.5.
The method for forming a deposited film according to any one of claims 1 to 9, which has an interval of 5 mm to 5 mm. 11. The method according to claim 1, wherein the surface of the insulator has a ten-point average roughness Rz of 5 μm to 200 μm with a reference length of 2.5 mm. 12. The insulator has a thickness of 0.5 mm to 20 mm.
The deposited film forming method according to any one of claims 1 to 11, wherein 13. The electrode according to claim 1, wherein the electrode has a hollow shape.
13. The method for forming a deposited film according to any one of claims 12 to 12. 14. The method according to claim 8, wherein the high-frequency power introducing means has a diameter of 4% to 25% with respect to a diameter of a circle on which the base is arranged. 15. Vacuum tightness includes disposing a film-forming substrate in a reaction vessel, introducing a raw material gas into the reaction vessel, and applying high-frequency waves to high-frequency introduction means disposed in the reaction vessel. Applying a glow discharge of the introduced source gas to form a deposited film on the substrate, wherein the high-frequency introduction means is a tubular gas introduction tube having a gas discharge hole for gas release around the tube; An electrode that functions as an electrode and an insulator that is arranged with a gap between the gas introduction tube and an insulator for isolating the glow discharge from the electrode. A method for forming a deposited film, which is performed while discharging a gas for cooling the insulator toward a body. 16. A reaction container capable of vacuum sealing, substrate holding means for disposing a film formation substrate in the reaction container, source gas introducing means for introducing a source gas into the reaction container, and In a deposition film forming apparatus having a high-frequency power introduction unit for introducing high-frequency power into a container, the high-frequency power introduction unit includes at least an electrode for introducing the high-frequency power, and a glow discharge An insulator covering the electrode to separate it from the region,
The electrode has a plurality of gas emission holes for spraying a gas on the inner surface of the insulator, and has a hollow portion which functions as a passage for supplying the gas and communicates with the gas emission holes. Characteristic deposited film forming equipment. 17. The deposited film forming apparatus according to claim 16, wherein a base material of said insulator is a ceramic material. 18. The high-frequency power introducing means according to claim 50, wherein:
18. The deposited film forming apparatus according to claim 16, wherein a frequency in a range of z to 450 MHz can be generated. 19. The deposition film forming apparatus according to claim 16, wherein said plurality of emission holes are uniformly distributed in said electrode. 20. The deposited film forming apparatus according to claim 16, wherein the plurality of emission holes are distributed in a large amount in the direction of the tip of the electrode. 21. The deposited film forming apparatus according to claim 16, wherein the gas supplied to the hollow portion is an inert gas. 22. The deposition film forming apparatus according to claim 16, wherein the gas supplied to the hollow portion is a hydrogen gas. 23. The deposited film forming apparatus according to claim 16, wherein said substrate comprises a plurality of substrates, and said substrates are arranged in a circle around said high-frequency power supply means. 24. The substrate having a cylindrical shape.
24. The deposited film forming apparatus according to any one of claims to 23. 25. A gap between the insulator and the electrode is 0.5
The deposited film forming apparatus according to any one of claims 16 to 24, having a gap of 5 mm to 5 mm. 26. The deposited film forming apparatus according to claim 16, wherein the surface of the insulator has a ten-point average roughness Rz of 5 μm to 200 μm with a reference length of 2.5 mm. 27. The insulator has a thickness of 0.5 mm to 20 mm.
The deposited film forming apparatus according to any one of claims 16 to 26, wherein the thickness is mm. 28. The electrode according to claim 1, wherein the electrode has a hollow shape.
28. The deposited film forming apparatus according to any one of 6 to 27. 29. The deposited film forming apparatus according to claim 23, wherein said high frequency introducing means has a diameter of 4% to 25% with respect to a diameter of a circle on which said base is arranged. 30. A reaction vessel capable of vacuum sealing, a substrate holding means for arranging a film-forming substrate in the reaction vessel, a source gas introduction means for introducing a source gas into the reaction vessel, A high-frequency power introduction unit for introducing high-frequency power into the reaction vessel, the high-frequency power introduction unit has a hollow portion, and an electrode having a gas discharge hole disposed in communication with the hollow portion; A deposition film forming apparatus provided around the electrode, having an insulator provided to isolate the electrode from the inside of the reaction vessel and to face the gas discharge hole.