JPH08316150A - Apparatus and method for forming deposit film - Google Patents

Abstract

PURPOSE: To suppress the variation of the characteristics of an electrophotographic photosensitive body and to improve durability against film separation and flaws. CONSTITUTION: In a hollow columnar deposit chamber 1111, a rectangular or columnar substrate 1112 is provided. Raw-material gas, which is introduced into the deposit chamber and contains at least silicon atoms, is decomposed by high-frequency electric power. Noncrystalline material, wherein at least silicon atoms are the parent material, is deposited on the substrate. This is the deposit film forming apparatus for performing these functions. The heating amount of a substrate heating means 1113 for setting the substrate at the intended temperature is set so that the amount is more at any one-end side or both end sides in the longitudinal direction of the substrate and less at the central part. Thus, the temperature gradient is provided in the longitudinal direction of the substrate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deposited film forming apparatus or a deposited film forming method, and means, for example, light (light in a broad sense, such as ultraviolet rays, visible rays, infrared rays, X-rays and γ rays). It is preferably used for an apparatus and a method for continuously and stably forming a light receiving member sensitive to an electromagnetic wave.

[0002]

As a material for forming a photoconductive layer in a solid-state image pickup device, an electrophotographic light-receiving member in the field of image formation, or an original reading a-Si device, SN is highly sensitive.
It has a high ratio [photocurrent (Ip) / (Id)], has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves that it irradiates, has fast photoresponsiveness, and has a desired dark resistance value. In addition, the solid-state image pickup device is required to have no pollution, and the afterimage can be easily processed within a predetermined time. Particularly in the case of the electrophotographic light-receiving member used in an office as an office machine, the above-mentioned pollution-free property at the time of use is an important point.

A material which has been drawing attention from such a viewpoint is amorphous silicon whose dangling bond is modified with a monovalent element such as hydrogen or a halogen atom (hereinafter referred to as “amorphous silicon”).
"A-Si"), for example, JP-A-54-
Japanese Patent No. 86341 describes application to a light receiving member for electrophotography.

Conventionally, as a method of forming a light-receiving member made of a-Si on a cylindrical substrate, a sputtering method, a method of decomposing a raw material gas by heat (thermal CVD method),
Method of decomposing raw material gas by light (optical CVD method), method of decomposing raw material gas by plasma (plasma CVD
Law) and many others are known. Above all, plasma CVD
The method, that is, the method of decomposing the raw material gas by direct current or high frequency, microwave glow discharge, etc. to form a deposited film on the cylindrical substrate is a method of forming a light receiving member for electrophotography,
Currently, it is very practically used.

FIG. 4 is a schematic sectional view of a typical plasma CVD apparatus. In the figure, (4100) shows the entire vacuum reaction vessel, (4111) is a cathode electrode which also serves as a side wall of the vacuum reaction vessel, (4120) is a gate which is the upper wall of the vacuum reaction vessel, and (4121) is a vacuum. It is the bottom wall of the reaction vessel. The cathode electrode (4111) and the upper wall (412)
0) and the bottom wall (4121) respectively refer to the insulator (412).
Insulated in 2).

Reference numeral (4112) is a base member installed in a vacuum reaction vessel, and the base member (4112) is grounded to serve as an anode electrode. In the base (4112),
A substrate heater (4113) is installed to heat the substrate to a predetermined temperature before film formation, to maintain the substrate at a predetermined temperature during film formation, or to anneal the substrate after film formation. Used to do. As shown in FIG. 5 (a), the heating element attached to this base heater is designed so that the temperature of the cylindrical base becomes uniform in the axial direction by winding a sheath heater at even intervals. There is. A specific example of another substrate heater is shown in FIG. 5 (b). In this example, the heating element is wound so as to reciprocate in the axial direction, and in this case as well, it is devised so that the amount of heat generated in the axial direction becomes uniform.

Reference numeral (4114) is a deposited film forming source gas introducing pipe, which is provided with a large number of gas release holes (not shown) for releasing the source gas in the vacuum reaction space. The other end of the introduction pipe (4114) communicates with the deposited film forming raw material gas supply system (4200) through the raw material gas pipe (4116) and the valve (4260).

Reference numeral (4119) is an exhaust pipe for evacuating the inside of the vacuum reaction vessel, and is connected to a vacuum exhaust device (4117) via an exhaust valve (4118). (4
115) is a means for applying a voltage to the cathode electrode (4111). (4124) is a vacuum gauge and 4123 is a leak valve.

The operating method of the deposited film forming apparatus by the plasma CVD method is performed as follows. That is,
After the gas in the vacuum reaction vessel is evacuated through the exhaust pipe (4119), an inert gas such as Ar or He is flown from the gas supply device (4200) at a predetermined flow rate to set a predetermined internal pressure. The heater (4113) heats and holds the substrate (4112) so that it has a uniform predetermined temperature in both the axial direction and the circumferential direction. Next, for example, in the case of forming an a-SiH deposited film through the source gas introduction pipe (4114), a source gas such as silane is introduced into the vacuum reaction vessel, and the source gas is supplied through the source gas introduction pipe (4114). The raw material gas is discharged into the vacuum reaction container through a hole (not shown). Simultaneously with this, a high frequency, for example, is applied between the cathode electrode (4111) and the substrate (anode electrode) (4112) from the voltage applying means (4115) to generate plasma discharge. Thus, the raw material gas in the vacuum reaction vessel is excited and excited to generate seeds, and radical particles such as Si ^* , SiH ^*, etc. ( ^* represents an excited state), electrons, ionic particles, etc. are generated, and these particles or A chemical interaction between these particles and the surface of the substrate forms a deposited film on the surface of the substrate. The raw material gas supply device (4200) has the same configuration as the raw material gas supply device (1200) described later, and thus the description thereof is omitted here.

[0010]

With such a conventional light receiving member forming apparatus, it becomes possible to obtain a light receiving member having practical characteristics and uniformity to some extent.

However, in recent years, the specifications required by the market have become stricter year by year, and further higher image quality, higher speed, higher durability, and higher functionality are desired. In addition, there is a growing demand for differentiating copiers, and higher functionality and higher performance than ever before is required. It is becoming more and more difficult to meet these strict requirements by improving the copying machine itself, or only by improving it.
As a result, electrophotographic photoreceptors are also required to have improved optical characteristics and electrical characteristics more than ever before. For this reason, even in the manufacturing process of the photosensitive layer, strict control is required more than ever before.

A conventionally used so-called coaxial type film forming apparatus in which a cylindrical substrate is installed in the center of a reaction furnace and a cathode electrode is installed coaxially on the outer periphery thereof has a low apparatus cost and a-Si. However, when a deposition condition of an a-Si film is changed for the purpose of further improving the quality by using the apparatus of this type by using the apparatus of this type, it is sure that a part of the cylindrical substrate is obtained. Although it is possible to determine the manufacturing conditions that satisfy the above-mentioned required electrophotographic characteristics, the plasma state is likely to be biased under such manufacturing conditions, and as a side effect, unevenness of the characteristics in the generatrix direction of the electrophotographic photoreceptor is caused. May deteriorate and the quality of the electrophotographic photoreceptor may deteriorate. This characteristic unevenness in the busbar direction occurs relatively frequently particularly when a large amount of hydrogen gas is added to the raw material gas or when the high frequency power is large with respect to the raw material gas flow rate as a manufacturing condition.

Therefore, in the case of an electrophotographic photoconductor manufactured under a manufacturing condition in which a large amount of hydrogen gas is added to a raw material gas or a high frequency power, uneven spectral sensitivity occurs in the generatrix direction.

The unevenness of the residual potential occurs.

Fogging occurs.

Film peeling occurs.

-It is easily scratched. The problem is that it is difficult to obtain a deposited film with a uniform film quality that satisfies the requirements of various optical and electrical characteristics and that has few image defects during image formation by an electrophotographic process in high yield. There are still problems to be solved.

Therefore, while the characteristics of the light receiving member itself are improved, it is necessary to improve the characteristics of the film forming apparatus so as to solve the above problems.

[0019]

The deposited film forming apparatus of the present invention has a hollow columnar deposition chamber provided with an exhaust port on the upper surface and / or the lower surface side for connecting to an exhaust system. A rectangular or columnar substrate is installed so that the length direction of the deposition chamber and the length direction of the deposition surface are substantially parallel, and the source gas containing at least silicon atoms introduced into the deposition chamber is supplied by high frequency power. In a deposited film forming apparatus for decomposing and depositing an amorphous material having at least silicon atoms as a base material on the substrate, the heating value of the substrate heating means for setting the substrate to a desired temperature is It is characterized in that the temperature is set to be large on one end side or both end sides and small on the center side so that a temperature gradient is provided in the length direction of the substrate.

Further, in the deposited film forming method of the present invention, a hollow columnar deposition chamber provided with an exhaust port on the upper surface and / or the lower surface side for connecting to an exhaust system is provided. A rectangular or columnar substrate is installed such that the length directions of the deposition surface and the deposition surface are substantially parallel, and the source gas containing at least silicon atoms introduced into the deposition chamber is decomposed by high frequency power, In a deposited film forming method for depositing an amorphous material containing at least silicon atoms as a base material, the temperature of the base is high at one end side or both end sides in the length direction of the base, and the central portion It is characterized in that the film is formed in such a manner that the temperature is set to a low value and the temperature gradient is given in the length direction of the substrate.

The deposition chamber of the deposited film forming apparatus according to the present invention has a hollow columnar shape (having an upper surface and a lower surface) and is provided with an exhaust port for connecting to an exhaust system on the upper surface and / or the lower surface. It is sufficient if it is hollow, but it is preferable that it has a hollow cylindrical shape in consideration of the conductance of exhaust gas.

Although the substrate arranged in the deposition chamber has a rectangular shape or a columnar shape, it does not have to be a single substrate or a single columnar body (including a hollow columnar body), and a plurality of substrates can be used. The present invention can be applied to a structure in which a plurality of columns are arranged to form a rectangular shape, a plurality of columnar bodies are stacked, a plurality of substrates are attached to a supporting member of the columnar body, and the like.

The use of the present invention is not particularly limited, but since it can be preferably used in the manufacturing apparatus and the manufacturing method of the electrophotographic photosensitive member, the following description will be made on the case of manufacturing the electrophotographic photosensitive member. To explain.

When the present invention is applied to an electrophotographic photosensitive member, the conductive substrate may have a cylindrical shape and a heater for heating the substrate may be installed inside, or silicon. Hydrogen gas is 2 to 8 with respect to gas containing as atoms
It is also possible to use the raw material gas contained twice.

Even if the electrophotographic photosensitive member has a three-layer structure of a lower blocking layer, a photosensitive layer and a surface protection layer, it has a three-layer structure of a charge transport layer, a charge generation layer and a surface protection layer. Is also good.

In a conventional so-called coaxial type film forming apparatus in which a cylindrical substrate is coaxially installed at the center of a cylindrical cathode, a gas pipe is installed parallel to the bus line direction of the cylindrical substrate, and a bus bar is provided. Since the gas is exhausted from one end in the direction, the film forming gas has a form of flowing along the generatrix direction of the cylindrical substrate. In the manufacturing apparatus having such a configuration, it is unavoidable structurally that the composition ratio of the raw material gas deviates in the axial direction of the cylindrical substrate.

For example, when depositing an a-Si film on a cylindrical substrate using such a film forming apparatus, the source gas is discharged from the gas pipe and then flows along the axial direction of the cylindrical substrate to the exhaust port. Go. During this period, the high-frequency power applied gradually decomposes and deposits the gas composition, so that the gas composition becomes non-uniform on the upstream side and the downstream side of the gas flow. When a source gas such as silane is decomposed by high-frequency power, it is separated into silicon and hydrogen, and silicon is deposited on the substrate and hydrogen is exhausted. Therefore, the further downstream the raw material gas is decomposed, the more the proportion of hydrogen gas. Therefore, the film is formed below the cylindrical substrate under the condition that the hydrogen content is larger than the optimum film formation condition.

As described above, in the coaxial type film forming apparatus, the film forming conditions tend to deviate below the cylindrical substrate.
In particular, the amount of hydrogen in the source gas may be larger than that in the center.

Generally, in the a-Si film, when the amount of hydrogen in the raw material gas increases, the hydrogen content in the film tends to increase in proportion to this, and therefore, the electrophotographic photosensitive member manufactured by the conventional apparatus. Regarding, the amount of hydrogen in the film is large in the lower part of the photoconductor and small in the central part. If the amount of hydrogen in the film becomes too large, the band gap of the a-Si film becomes wide and it becomes difficult to absorb short-wave light, so that uneven spectral sensitivity occurs in the electrophotographic photosensitive member. Further, a proper amount of hydrogen atoms terminates the dangling bond and is indispensable for improving the film quality, but excessive hydrogen atoms adversely deteriorate the film quality and the doping efficiency of impurities decreases. This causes uneven residual potential and fogging.

Further, depending on the structure of the film forming apparatus or the film forming conditions, the amount of hydrogen in the raw material gas may become excessive not only in the lower portion but also in the upper portion, resulting in uneven electrophotographic characteristics. found. This is because the ratio of the raw material gas to the high frequency power is relatively small on the upstream side of the flow of the raw material gas, so that the high frequency power tends to be excessive compared to other parts of the cylindrical substrate, and therefore the silane It is thought that the decomposition of the raw material gas such as, and so on, will increase the amount of hydrogen in the discharge space. Further, it is considered that one of the causes of excess hydrogen is that the exhaust speed is reduced because it is on the side opposite to the exhaust port, and gas accumulation is likely to occur.

This problem of axial unevenness becomes more serious as the manufacturing conditions in which the proportion of hydrogen gas added to the raw material gas is high or the higher the high frequency power becomes.

In order to solve this problem, the present inventors first studied to eliminate the non-uniformity of the gas composition. However, in the case of the coaxial type film forming apparatus, in order to eliminate the composition unevenness of the raw material gas, the exhaust method of the film forming apparatus must be changed drastically, which is unsuitable from the viewpoint of industrial investment efficiency. Came to the conclusion.

Therefore, it was examined that the conventional apparatus structure was maintained as it was and the characteristics of the electrophotographic photosensitive member were made uniform although the composition of the raw material gas was not uniform.

As a result, the heating elements of the substrate heater provided inside the cylindrical substrate are distributed so as to increase in the lower portion and / or the upper portion, and the temperature distribution of the cylindrical substrate is substantially lowered in the central portion. It has been found that the above problems can be solved by setting the height to be higher at the lower part and / or the upper part. Further, when the present invention is applied to the conventional film forming apparatus, the effect can be obtained only by changing the substrate heating heater for heating the cylindrical substrate. Therefore, the above-mentioned problems can be solved with a minimum device remodeling cost. Therefore, it has been found that the industrial advantages are great.

Although it is not clear about this mechanism, the present inventors consider as follows.

When, for example, an a-Si deposited film is formed on a substrate by the plasma CVD method, the reaction includes the decomposition process of the source gas in the vapor phase, the transport process of active species from the discharge space to the substrate surface, and the substrate surface. The surface reaction process in 3 can be considered separately. This growth process includes a-S containing hydrogen.
The following is a more detailed description using i as an example. Decomposed species of silane and hydrogen that have been decomposed and transported in plasma adhere to the substrate to form a network of a-Si film, but the growth of a-Si in which the network is not completed three-dimensionally On the other hand, due to desorption of hydrogen atoms, bonding of hydrogen atoms and silicon atoms to dangling bonds, rearrangement of atoms with high energy bond, etc. A reaction (relaxation process) occurs. At this time, if the concentration of hydrogen radicals in the vapor phase becomes high, SiH ₂ in the vapor phase and the substrate surface,
Higher-order hydrogen bonds such as (SiH ₂ ) _n are easily formed, and the amount of hydrogen in the film increases. In addition, when the number of such high-order hydrogen bonds is increased, the number of chain structures is increased, and dangling bonds of silicon atoms are easily generated locally. However, at this time, if the substrate temperature is increased, excessive hydrogen molecules and atoms are released again, the amount of hydrogen in the film is reduced, and low-order hydrogen bonds are easily formed.
-Si bonds are formed, as the deposited film decreases dangling bonds, reduction of the gap level density, phenomena such as Si-H ₂ bond is reduced Si-H bonds as the main is observed. As a result, the characteristics of the electrophotographic photosensitive member are improved by raising the substrate temperature.

By this mechanism, the amount of hydrogen in the film is optimized, the spectral sensitivity unevenness and the film quality, which have been generated by the conventional large amount of hydrogen in the film and the wide band gap, are deteriorated, and the doping efficiency of impurities is decreased. Uneven residual potential that occurs,
It is assumed that the fogging and the like have improved.

Further, it was found that, as an unexpected effect, a secondary effect that film peeling hardly occurs can be obtained. That is, in the conventional apparatus, film peeling occasionally occurred at the end of the cylindrical substrate under the conditions of large amount of hydrogen addition and high RF power, but no film peeling occurred by using the apparatus of the present invention. became.

Regarding the cause of this, in the case of a device that originally uses a very thick deposited film of 30 to 100 μm like an electrophotographic photoreceptor, film peeling is prevented by balancing the film stress between the layers of the deposited film. are doing. However, in the conventional film forming apparatus, since the film structure is different between the central part and the end part of the cylindrical substrate, it is considered that the balance of the film stress is lost and the film is easily peeled off. In the manufacturing apparatus of the present invention, since a uniform film composition is obtained in the entire axial direction of the cylindrical substrate, it can be imagined that such a problem does not occur easily.

The effect of reducing film peeling of the electrophotographic photoconductor is not only that the number of defective photoconductors due to film peeling can be reduced, but also contamination of the deposited film forming apparatus due to film peeling can be prevented. The image defects caused by dust in the film forming furnace of the electrophotographic photosensitive member where the film did not peel off were significantly reduced, and as a result, a large effect was obtained in improving the yield as a whole.

Further, this effect is particularly remarkable in preventing deterioration of image characteristics during repeated use. The surface of the electrophotographic photosensitive member rubs against the transfer paper or the cleaning blade every time it is repeatedly used. Therefore, the spherical protrusions are easily lost. In the manufacturing apparatus of the present invention, since the number of spherical projections is very small in the first place, the number of spherical projections missing due to rubbing is greatly reduced, and the increase in “potches” due to long-term use can be suppressed.

In the above description, it is assumed that the present invention is supposed to improve the characteristics by optimizing the amount of hydrogen in the film, but a gas containing halogen is used as the source gas. Also, since the same characteristic improvement is observed when the present invention is used, it is also assumed that the present invention optimizes the amount of halogen atoms in the film.

(Detailed Description of the Invention) An embodiment of the electrophotographic photosensitive member manufacturing apparatus of the present invention will be described in detail below with reference to the drawings.

FIG. 1 is a schematic block diagram showing an example of an apparatus for manufacturing an electrophotographic photosensitive member by a high frequency plasma CVD (hereinafter referred to as "RF-PCVD") method according to the present invention.

The structure of the apparatus for producing a deposited film by the RF-PCVD method shown in FIG. 1 is as follows. This apparatus is roughly classified into a deposition apparatus (1110), a source gas supply apparatus (1200), and a reaction vessel (111) that also functions as a cathode electrode.
1) It comprises an exhaust device (1117) for reducing the pressure inside. The reaction vessel (1) in the deposition apparatus (1100)
111), the conductive cylindrical substrate (11
12), a substrate heating heater (1113), a source gas introduction pipe (1114) are installed in the inside so as to be parallel to the axial direction of the conductive cylindrical substrate, and a high frequency matching box (1115) is connected. . Exhaust is made from the lower part of the reaction vessel. (1120) is a gate, (1122) is an insulator, (1121) is a bottom plate,
(1119) is an exhaust port.

The substrate heating heater (1113) has a large number of windings of the heating heater at the lower end and a small distribution in the center so that the temperature of the lower part of the conductive cylindrical substrate according to the present invention is higher than that of the center. A heating heater is wrapped around.

The source gas supply device (1200) is made of SiH.
_{4, H 2, CH 4,} NO, cylinder source gas such as B ₂ H _6, GeH ₄ and (1221-1226) valve (123
1-1236, 1241-1246, 1251-125
6) and mass flow controller (1211-12)
16), and each source gas cylinder has a valve (1
It is connected to the gas introduction pipe (1114) in the reaction vessel (1111) via 260).

The deposited film can be formed using this apparatus, for example, as follows.

First, the cylindrical substrate (1112) is installed in the reaction vessel (1111), and the inside of the reaction vessel (1111) is exhausted by the exhaust device (1117). After evacuating the inside of the vacuum reaction vessel, an inert gas such as Ar or He is flown from the gas supply device (1200) at a predetermined flow rate, and after setting a predetermined internal pressure, the substrate heater (1113) is turned on.
Then, the temperature of the cylindrical substrate (1112) is lowered so that it is low at the center and high at both ends. The temperature of the cylindrical substrate is maintained at a desired temperature between 250 ° C. and 400 ° C. at the center and between 280 ° C. and 450 ° C. at both ends.

A raw material gas for forming a deposited film is supplied to a reaction vessel (11
11), the gas cylinder valve (123)
1-1123), leak valve of the reaction vessel (1123)
Check that the outflow valve (1
251 to 1256), inflow valves (1241 to 124)
6) After confirming that the auxiliary valve (1260) is opened, first, the main valve (1118) is opened to exhaust the reaction vessel (1111) and the gas pipe (1116).

Next, the reading of the vacuum gauge (1124) is about 5 × 1.
Auxiliary valve (1260) at 0 ^-6 Torr,
Close the outflow valves (1251-1256).

After that, gas cylinders (1221-122)
From (6), each gas is introduced by opening the valve (1231 to 1236), and the pressure of each gas is adjusted (for example, 2 kg / cm ² ) by the pressure adjuster (1261 to 1266). Next, the inflow valves (1241 to 1246) are gradually opened to allow the respective gases to flow through the mass flow controllers (1211 to 1216).
Introduce inside.

When the cylindrical substrate (1112) reaches a predetermined temperature distribution, the necessary ones of the outflow valves (1251 to 1256) and the auxiliary valve (1260) are gradually opened, and a predetermined amount is supplied from the gas cylinder (1221 to 1226). Of the gas of the reaction vessel (1114) through the gas introduction pipe (1114).
11) Introduced in Next, the mass flow controllers (1211 to 1216) are adjusted so that each raw material gas has a predetermined flow rate. At that time, the reaction vessel (111
While watching the vacuum gauge (1124) so that the pressure in 1) becomes a predetermined pressure of 1 Torr or less, the main valve (111)
8) Adjust the opening. When the internal pressure is stable, RF
A power supply (not shown) is set to a desired power, and the reaction vessel (111) is passed through the high frequency matching box (1115).
RF power is introduced into 1) to generate an RF glow discharge. The source energy introduced into the reaction vessel is decomposed by this discharge energy, and a predetermined deposited film containing silicon as a main component is formed on the cylindrical substrate (1112). After the desired film thickness is formed, the supply of RF power is stopped, the outflow valves (1251 to 1256) are closed to stop the gas from flowing into the reaction vessel (1111), and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, an electrophotographic photosensitive member having a multilayer structure is formed.

Needless to say, all the outflow valves other than the required gas are closed when forming each layer, and each gas is supplied to the reaction vessel (111).
1) In order to avoid remaining in the pipe from the outflow valve (1251 to 1256) to the reaction vessel (1111), the outflow valve (1251 to 1256) is closed, the auxiliary valve (1260) is opened, and the main Valve (11
If necessary, the operation of 18) is fully opened and the system is once evacuated to a high vacuum.

In order to make the film formation uniform, the cylindrical substrate (1112) is rotated at a predetermined speed by a driving device (not shown) during the film formation.

Needless to say, the above-mentioned gas species and valve operation may be changed according to the conditions for forming each layer.

Next, high frequency plasma CVD using a frequency in the VHF band (hereinafter abbreviated as "VHF-PCVD").
A method of manufacturing the electrophotographic light-receiving member formed by the method will be described.

RF-PC in the manufacturing apparatus shown in FIG.
The deposition apparatus (1100) by the VD method is replaced with the deposition apparatus (2100) shown in FIG.
0), it is possible to obtain a photoreceptive member manufacturing apparatus for electrophotography by the VHF-PCVD method.

This apparatus is roughly classified into a reaction vessel (2125) having a vacuum airtight structure and capable of reducing the pressure, a source gas supply apparatus (1200), and an exhaust apparatus (2117) for reducing the pressure inside the reaction vessel. It consists of Inside the reaction vessel (2125), a cylindrical substrate (2112), a substrate heater (2113), a source gas introduction pipe (211)
4), reaction vessel (2125), cathode electrode (211)
1) is installed, and a high frequency matching box (2115) is further connected to the cathode electrode. Further, the inside of the reaction vessel (2125) is connected to an exhaust device (2117, for example, a vacuum pump) through an exhaust pipe (2119).

In order to increase the temperature of the lower part of the conductive cylindrical substrate according to the present invention as compared with the central part, the substrate heating heater (2113) has a large number of windings of the exothermic heater at the lower end and a small number at the central part. Exothermic heaters are wound so as to be distributed.

The source gas supply device (1200) is made of SiH.
₄ , GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH _{3 and} other source gas cylinders (1221 to 1226) and valves (12)
31-1236, 1241-1246, 1251-12
56) and mass flow controller (1211-1)
216), and the cylinder of each source gas is connected to the gas introduction pipe (2114) in the reaction container (2125) via the valve (2260).

Formation of a deposited film by this apparatus by the VHF-PCVD method can be performed as follows.

First, the cylindrical substrate (2112) is installed in the reaction container (2125), and the reaction container (2125) is exhausted through the exhaust pipe (2119) by the exhaust device (2117, for example, a vacuum pump), The pressure inside the reaction vessel (2125) is adjusted to 1 × 10 ⁻⁶ Torr or less. continue,
The substrate heating heater (2113) is turned on to heat the cylindrical substrate (2112) so that the temperature is low at the center and high at both ends. The temperature of the cylindrical substrate is 250 ° C to 4 at the center.
Heat and hold at a desired temperature between 00 ° C and 280 ° C-450 ° C at both ends.

A raw material gas for forming a deposited film is supplied to a reaction vessel (21
25), the gas cylinder valve (123
1 to 1236), confirm that the leak valve (not shown) of the reaction vessel is closed, and check the inflow valve (124
1 to 1246), an outflow valve (1251 to 1256),
After confirming that the auxiliary valve (2260) is opened, first, the main valve (2118) is opened to exhaust the reaction vessel (2125) and the gas pipe.

Next, the reading of the vacuum gauge (2124) is about 5 × 1.
Auxiliary valve (2260) at 0 ^-6 Torr,
Close the outflow valves (1251-1256).

After that, gas cylinders (1221-122)
From 6), each gas is introduced by opening the valve (1231 to 1236), and each gas pressure is adjusted to ² kg / cm ² by the pressure adjuster (1261 to 1266). Next, the inflow valves (1241 to 1246) are gradually opened to introduce the respective gases into the mass flow controllers (1211 to 1216).

After the preparation for film formation is completed as described above, each layer is formed on the cylindrical substrate (2112) as follows.

When the cylindrical substrate (2112) reaches a predetermined temperature, the necessary ones of the outflow valves (1251 to 1256) and the auxiliary valve (2260) are gradually opened, and the gas cylinders (1221 to 1226) are brought to a predetermined temperature. A gas is introduced into the reaction vessel (212) through a gas introduction pipe (2114).
5) Introduced into the discharge space. Next, the mass flow controllers (1211 to 1216) are adjusted so that each raw material gas has a predetermined flow rate. At that time, the opening of the main valve (2118) is adjusted while observing the vacuum gauge (2124) so that the pressure in the discharge space becomes a predetermined pressure of 1 Torr or less.

For forming the a-Si layer, when the pressure is stable, for example, a VHF power source (not shown) having a frequency of 450 MHz is set to a desired power, and the matching box (2) is formed.
115), VHF electric power is introduced into the discharge space to cause glow discharge. Thus, in the discharge space, the introduced source gas is excited by the discharge energy and dissociates, and a predetermined deposited film is formed on the base body (2112).

After the desired film thickness is formed, the supply of VHF electric power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a desired light-receiving layer having a multilayer structure is formed.

Needless to say, all of the outflow valves other than the necessary gas are closed when forming each layer, and each gas is supplied to the reaction vessel (212).
5) In order to avoid remaining in the pipe from the outflow valve (1251 to 1256) to the reaction vessel (2125), the outflow valve (1251 to 1256) is closed, the auxiliary valve (2260) is opened, and the main Valve (21
If necessary, the operation of 18) is fully opened and the system is once evacuated to a high vacuum.

(2123) is a leak valve, (211)
6) is a source gas pipe, (2121) is a bottom plate, (212)
0) is a gate and 2122 is an insulator.

Needless to say, the above-mentioned gas species and valve operation may be changed according to the conditions for forming each layer.

A concrete example of the substrate heater (1113) for giving a temperature gradient to the cylindrical substrate (1112) is shown in FIG.
Shown in FIG. 3 (a) is similar to the substrate heating heater shown in the apparatus diagram of FIG. 1, in which one sheath-shaped heating element is wound around the heater supporting member, and this winding method is used at the bottom of the heater. By making it dense and rough in the center, the amount of heat generated is adjusted to be large in the lower part and small in the center. In FIG. 3 (b), one sheath heater is evenly wound around the whole, and another sheath heater is used to wind only around the lower part so that the heat generation amount of the lower part is increased. In the case of this type of substrate heating heater, each sheath heater has its own temperature controller and power supply, so that the heat generation amount in the upper, middle, and lower parts can be controlled independently, so the temperature of the cylindrical substrate can be controlled more strictly. Is preferred. FIG. 3 (a),
Although the example of (b) is an example of increasing the heat generation amount only in the lower part,
Of course, the effect of the present invention can be obtained even if the upper and lower sides of this structure are reversed and the amount of heat generation only in the upper part is increased. FIG.
In (c), the heating elements are densely wound in the upper and lower portions and coarsely wound in the center, and the heat generation amount is set to be large in the upper and lower portions of the substrate heating heater and small in the central portion. In FIG. 3 (d), three heating elements are used, one is wound around the entire heater, and the other two are wound only above and below respectively, and the central temperature is lowered by adjusting the voltage applied to each heating element. The upper and lower temperatures can be set high. This configuration is desirable in that the temperature difference between the center and the end can be adjusted arbitrarily. In FIG. 3 (e), the heating element is divided into three areas of an upper portion, a central portion, and a lower portion, and one heating element is coarsely and densely wound in each area. In this example, the upper, middle, and lower regions are divided into three regions, but of course, it may be divided into more regions, in which case the temperature can be adjusted more finely. Further, it is of course possible to connect a temperature controller to each area and control the temperature independently.

The substrate temperature near the center of the cylindrical substrate is generally 200 ° C. or higher and 350 ° C. or lower, preferably 230 ° C. or higher and 330 ° C. or lower, and more preferably 250 ° C. or higher and 300 ° C. or lower. Reduce ring bonds,
It is preferable because it is a dense film.

In order to obtain the effects of the present invention, the temperature increase at the upper and / or lower part of the cylindrical substrate can be obtained by increasing the temperature of the central substrate of the cylindrical substrate by about 5 ° C to 100 ° C. . Further, increasing the temperature in the range of 20 ° C. to 50 ° C. is more suitable for obtaining the effect of the present case. In any case, it is desirable that the substrate temperature at the end of the substrate is 450 ° C. or lower. This is because the dehydrogenation reaction proceeds too much when the substrate temperature exceeds 450 ° C.

The effect of the present invention can be obtained regardless of the distribution shape of the temperature distribution at the time of film formation of the cylindrical substrate as long as the temperature is increased in the lower part and / or the upper part with respect to the central part in the axial direction. An example is shown in FIG. 6. In FIG. 6A, the center of the cylindrical substrate is set flat to a predetermined temperature, and the temperature is set to rise in the lower part. In FIG. 6B, the substrate temperature is set to continuously increase from the center to the lower part. In FIG. 6C, the center is set flat to a predetermined temperature, and the lower end is set flat to a temperature higher than the center. Further, as shown by the broken lines in FIGS. 6A to 6C, the temperature of the cylindrical substrate is not limited to the lower part,
Of course, the effect of the present invention can be obtained even if the upper part is also raised,
Since the heating state becomes vertically symmetrical, it may be more effective in suppressing the axial unevenness of the electrophotographic photosensitive member depending on the configuration of the film forming apparatus and the film forming conditions. Furthermore, FIG.
Even if the temperature distribution shown by the solid line in (c) is inverted upside down to raise the temperature only in the upper part from the central part to the lower part, the effect of the present invention can be obtained similarly. The effect of the present invention is shown in FIG.
The effect is sufficiently obtained in any of the temperature distributions (a) to (c). It goes without saying that the effect of the present case can be obtained similarly even if it is an intermediate pattern between the patterns of FIGS. 6A, 6B, and 6C.

When actually applied to a manufacturing apparatus, it is desirable from the standpoint of capital investment to set the heater for heating the substrate and set it in the pattern of FIG. 6 (a) or 6 (b), which is easy to adjust. .

The heating element constituting the substrate heating heater may be of a vacuum type, and more specifically, an electric resistance heating element such as a sheath heater, a plate heater, a ceramic heater or a carbon heater, a liquid, a gas or the like may be used. Examples of the heating medium include a heating element by a heat exchange means. Further, a heat-radiating lamp heating element such as a halogen lamp or an infrared lamp can also be preferably used as the substrate heating heater of the present invention, but in this case, a lamp having a larger electric power at the end of the heater than the centrally installed lamp is used. It is necessary to install it so that a temperature gradient is formed. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used.

The substrate used in the present invention includes:
It may be electrically conductive or electrically insulating. As the conductive substrate, Al, Cr, Mo, Au, In, Nb, Te,
Examples thereof include metals such as V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. Further, at least the surface of the electrically insulating substrate such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide or the like, which is a synthetic resin film or sheet, glass or ceramic, on which the light receiving layer is formed, is formed. A conductively treated substrate can also be used.

The substrate used in the present invention may be in the form of a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface, and the thickness of the substrate may be the same as that of a desired electrophotographic light-receiving member. The thickness is determined as appropriate so that it can be formed, but when flexibility as a light receiving member for electrophotography is required, it can be made as thin as possible within a range in which the function as a substrate can be sufficiently exerted. However, the substrate is usually 10 in terms of manufacturing and handling, mechanical strength and the like.
It is considered to be μm or more.

In particular, when image recording is performed using coherent light such as laser light, in order to more effectively eliminate image defects due to so-called interference fringe patterns that appear in visible images, unevenness is formed on the surface of the substrate. May be provided. The unevenness provided on the surface of the substrate is described in JP-A-60-168156, JP-A-60-178457, and JP-A-60-22585.
It is prepared by a known method described in Japanese Patent Publication No. 4 or the like.

Further, as another method for more effectively eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, the surface of the substrate is provided with a concavo-convex shape by a plurality of spherical trace depressions. Good. That is, the surface of the substrate has irregularities smaller than the resolving power required for the electrophotographic light-receiving member, and the irregularities are due to a plurality of spherical trace depressions. The unevenness due to the plurality of spherical trace depressions provided on the surface of the substrate is formed by the known method described in JP-A-61-231561.

The charge injection blocking layer of an electrophotographic photosensitive member suitable for production by the production apparatus of the present invention is a photoconductive layer from the substrate side when the photoreceptive layer is subjected to a constant polarity charging treatment on its free surface. It has a function of preventing charges from being injected into the layer side, and has a so-called polarity dependence, which does not exhibit such a function when subjected to a charging treatment of the opposite polarity. In order to impart such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer. Atoms for controlling conductivity contained in the layer may be evenly distributed in the layer or may be unevenly distributed in the layer thickness direction. There may be a portion contained in the state of being. When the distribution concentration is non-uniform, it is preferable that the distribution concentration is large so that it is distributed on the substrate side.

However, in any case, it is desirable that the content be evenly distributed in the in-plane direction parallel to the surface of the substrate in order to make the characteristics uniform in the in-plane direction.

The atoms contained in the charge injection blocking layer for controlling the conductivity include so-called impurities in the field of semiconductors, and the atoms belonging to Group IIIb of the periodic table (hereinafter, referred to as “III”) which give p-type conduction characteristics. Or an atom belonging to Group Vb of the periodic table (hereinafter abbreviated as “Group Vb atom”) that imparts n-type conductivity. Specific examples of the group IIIb atom include B (boron), Al (aluminum), Ga (gallium), In (indium), and Ta (thallium), and B, Al, and Ga are particularly preferable. is there. Specific examples of the group Vb atom include P (phosphorus), As (arsenic), and Sb.
(Antimony), Bi (bismuth), etc., especially P,
As is preferred.

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

Further, the charge injection blocking layer has carbon atoms,
By containing at least one of a nitrogen atom and an oxygen atom, it is possible to further improve the adhesion with another layer provided in direct contact with the charge injection blocking layer.

The carbon atoms, nitrogen atoms or oxygen atoms contained in the layer may be evenly distributed in the layer, or even though they are contained in the layer thickness direction. There may be a portion containing the non-uniformly distributed state. However, in any case, it is desirable that the content be evenly distributed in the in-plane direction parallel to the surface of the substrate in order to make the characteristics uniform in the in-plane direction.

The content of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in the entire region of the charge injection blocking layer is appropriately determined so that the object of the present invention can be effectively achieved. In the case of one kind, as the amount thereof, in the case of two or more kinds, as the sum thereof, preferably 1 × 10 ⁻³ to 50
Atomic%, more preferably 5 × 10 ⁻³ to 30 at%, optimally 1 × 10 ⁻² to 10 at%.

Further, hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer compensate for dangling bonds existing in the layer and are effective in improving the film quality. The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the charge injection blocking layer is preferably 1 to 50 atom%,
It is more preferably 5 to 40 atomic%, and most preferably 10 to 30 atomic%.

The thickness of the charge injection blocking layer is preferably 0.1 to 5 μm, and most preferably 1 to 4 μm from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.

In order to form the charge injection blocking layer having the characteristics capable of achieving the object of the present invention, 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 are set. Is required to be set appropriately.

The flow rate of the diluting gas H ₂ and / or He is appropriately selected according to the layer design, but H ₂ is usually added to the Si supply gas in the range of 1 to 20.
It is desirable to control in the range of double, preferably 3 to 15 times, and optimally 5 to 10 times.

Similarly, the gas pressure in the reaction vessel is appropriately selected in the optimum range according to the layer design.
0 ^{−4 to} 10 Torr, preferably 5 × 10 ^{−4 to} 5 Torr
r, optimally 1 × 10 ^{−3 to} 1 Torr is preferable.

Similarly, the discharge power is appropriately selected in an optimum range according to the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 0.5 to 7 times (0.5).
W / cc to 7 W / cc), preferably 1 to 6 times (1 W /
cc-6W / cc), optimally 1.5-5 times (1.5W
/ Cc to 5 W / cc) is desirable.

It is necessary that the photoconductive layer of the electrophotographic photosensitive member suitable for production by the production apparatus of the present invention contains a hydrogen atom and / or a halogen atom. This is because it is required to compensate dangling bonds and improve the layer quality, especially the photoconductivity and the charge retention property. Therefore, the content of hydrogen atoms or halogen atoms, or the amount of the sum of hydrogen atoms and halogen atoms is 10 to 30 atom%, more preferably 15 to 25 atom% with respect to the sum of silicon atoms and hydrogen atoms and / or halogen atoms. Is desirable.

The substances that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ and Si.
Silicon hydrides (silanes) in a gas state such as ₃ H ₈ and Si ₄ H ₁₀ or capable of being gasified are mentioned as being effectively used, and further, they are easy to handle during layer formation and have good Si supply efficiency. In view of the above points, SiH ₄ and Si ₂ H ₆ are preferable. Then, structurally introducing hydrogen atoms into the photoconductive layer to be formed, and in order to further facilitate the control of the introduction ratio of hydrogen atoms, in order to obtain the film characteristics to achieve the object of the present invention, these It is necessary to form a layer by mixing a desired amount of a gas of a silicon compound containing H ₂ or a hydrogen atom with the above gas. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio.

Further, as a raw material gas for supplying a halogen atom used in the present invention, for example, a halogenated gas, a halide, an interhalogen compound containing a halogen, a silane derivative substituted with a halogen, or the like is gasified or gasified. The halogen compound to be obtained is preferable. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains silicon atoms and a halogen atom as constituent elements, can also be cited as an effective one. Halogen compounds that can be preferably used in the present invention include fluorine gas (F ₂ ) and Br.
F, ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ ,
Interhalogen compounds such as IF ₇ can be mentioned. As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom, specifically, silicon fluoride such as SiF ₄ and Si ₂ F ₆ can be mentioned as a preferable example.

Hydrogen atoms contained in the photoconductive layer or /
In order to control the amount of halogen atoms and halogen atoms, for example, the temperature of the substrate, the amount of raw material used to contain hydrogen atoms and / or halogen atoms introduced into the reaction vessel, the discharge power, etc. may be controlled. . In the present invention, it is preferable that the photoconductive layer contains an atom for controlling conductivity, if necessary. Atoms that control conductivity may be contained in the photoconductive layer in a uniformly distributed state.
Alternatively, there may be a portion containing a non-uniform distribution in the layer thickness direction.

Examples of the atoms that control the conductivity include so-called impurities in the semiconductor field.
Atoms belonging to Group IIIb of the periodic table giving p-type conduction characteristics (hereinafter abbreviated as “Group IIIb atoms”) or atoms belonging to Group Vb of the periodic table giving n-type conduction characteristics (hereinafter “Group Vb atoms”). It is abbreviated as ")" can be used.

Specific examples of the group IIIb atom include boron (B), aluminum (Al), gallium (Ga),
There are indium (In), thallium (Tl) and the like, and B, Al and Ga are particularly preferable. As the group Vb atom,
Specifically, phosphorus (P), arsenic (As), antimony (S)
b), bismuth (Bi), etc., and P and As are particularly preferable.

The content of atoms controlling the conductivity contained in the photoconductive layer is preferably 1 × 10 ^-2 to 1 × 10.
⁴ atomic ppm, more preferably 5 × 10 ^{-2 to} 5 × 10 ³
Atomic ppm, optimally 1 × 10 ^-1 to 1 × 10 ³ atom pp
m is desirable.

Atoms that control conductivity, eg, III
To structurally introduce a group b atom or a group Vb atom, a raw material for introducing a group IIIb atom or a raw material for introducing a group Vb atom in a gas state is placed in a reaction vessel during layer formation. Then, it may be introduced together with another gas for forming the photoconductive layer. As the raw material for introducing the group 111b atoms or the raw material for introducing the group Vb atoms, those which are gaseous at room temperature and atmospheric pressure or which can be easily gasified under at least the layer forming conditions are adopted. Is desirable.

As a raw material for introducing such a group IIIb atom, specifically, for introducing a boron atom, B ₂ H
_{6, B 4 H 10, B} 5 H 9, B 5 H 11, B 6 H 10, B 6 H
₁₂ , borohydride such as B ₆ H ₁₄ , BF ₃ , BCl ₃ , BB
Examples thereof include boron halides such as r ₃ . Besides this, Al
Cl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ ,
TlCl _{3 and the} like can also be mentioned.

As a raw material for introducing a group Vb atom, PH ₃ , P for introducing a phosphorus atom is effectively used.
₂ H ₄ etc. Phosphorus hydride, PH ₄ I, PF ₃ , PF ₅ , PC
Examples thereof include phosphorus halides such as l ₃ , PCl ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , A
sCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , Sb
F ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ ,
BiCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a Group Vb atom. In addition, these raw material substances for atom introduction for controlling conductivity may be diluted with H ₂ and / or He as necessary and used.

In the present invention, the layer thickness of the photoconductive layer is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economical effects, and is preferably 20 to 50.
μm, more preferably 23 to 45 μm, most preferably 25 to
The thickness is preferably 40 μm.

In order to achieve the object of the present invention and form a photoconductive layer having desired film characteristics, the mixing ratio of the gas for supplying Si and the diluting gas, the gas pressure in the reaction vessel, the discharge power and the substrate It is necessary to set the temperature appropriately. The flow rate of H ₂ and / or He used as a diluent gas is appropriately selected in accordance with the layer design, but H ₂ and / or He is usually used as the gas for Si supply,
-20 times, preferably 4-15 times, and optimally 5-10 times.

Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, but the optimum range is usually 1 × 1.
0 ^{−4 to} 10 Torr, preferably 5 × 10 ^{−4 to} 5 Torr
r, optimally 1 × 10 ^{−3 to} 1 Torr is preferable.

Similarly, the discharge power is appropriately selected in accordance with the layer design, and the optimum range is selected, but the discharge power with respect to the flow rate of the gas for supplying Si is normally 0.5 to 7 times (0.5).
W / cc to 7 W / cc), preferably 1 to 6 times (1 W /
cc-6W / cc), optimally 1.5-5 times (1.5W
/ Cc to 5 W / cc) is desirable.

In the present invention, the above-mentioned ranges are mentioned as the desirable numerical ranges of the substrate temperature and the gas pressure for forming the photoconductive layer, but the conditions are not usually independently determined separately, and are desired. It is desirable to determine the optimum value on the basis of mutual and organic relationships so as to form a light receiving member having the above characteristics.

In the electrophotographic photosensitive member suitable for manufacturing by the manufacturing apparatus of the present invention, it is preferable that an amorphous silicon type surface layer is further formed on the photoconductive layer. This surface layer has a free surface and is provided mainly for achieving the object of the present invention in moisture resistance, continuous repeated use characteristics, electric pressure resistance, use environment characteristics, and durability. Further, in the present invention, since each of the amorphous materials forming the photoconductive layer forming the light receiving layer and the surface layer has a common constituent element of a silicon atom, a chemical element is formed at the stacking interface. The stability is fully ensured.

The surface layer may be made of any material as long as it is an amorphous silicon type material. For example, the surface layer contains a hydrogen atom (H) and / or a halogen atom (X),
Further, amorphous silicon containing carbon atoms (hereinafter referred to as “a-SiC: H, X”), hydrogen atoms (H)
Amorphous silicon containing a halogen atom (X) and / or an oxygen atom (hereinafter referred to as “a-Si”).
O: H, X ”), hydrogen atom (H) and / or halogen atom (X), and further nitrogen atom containing amorphous silicon (hereinafter“ a-SiN: H, X ”).
Amorphous silicon (hereinafter referred to as “a-SiCON: H, X”) containing a hydrogen atom (H) and / or a halogen atom (X), and further containing at least one of a carbon atom, an oxygen atom and a nitrogen atom. And the like) are preferably used.

The material of the surface layer used in the present invention may be any amorphous material containing silicon, but a compound with a silicon atom containing at least one element selected from carbon, nitrogen and oxygen is preferable. , Especially a
A material containing -SiC as a main component is preferable.

When the surface layer is composed mainly of a-SiC, the amount of carbon is preferably in the range of 30% to 90% with respect to the sum of silicon atoms and carbon atoms.

Further, in the present invention, it is required that the surface layer contains hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, especially photoconductivity. This is to improve the characteristics and the charge retention characteristics. The hydrogen content is usually 30 to 70 atom%, preferably 35 to 65 atom%, and most preferably 40 to 60 atom% with respect to the total amount of the constituent atoms.
Further, the content of fluorine atoms is usually 0.01.
-15 atom%, preferably 0.1-10 atom%, optimally 0.6-4 atom% is desirable.

Used in the formation of the surface layer of the present invention
As a substance that can be a gas for supplying silicon (Si),
SiH_Four, Si₂H₆, Si₃H₈, Si_FourH_TenEtc.
Gas or gasifiable silicon hydrides (silanes)
Are listed as being used effectively.
Si is easy to handle and has good Si supply efficiency.
H _Four, Si₂H₆Are preferred. Well
In addition, if necessary, the raw material gas for supplying these Si
H₂Dilute with gas such as He, Ar, Ne, etc.
May be.

As a substance which can be a gas for supplying carbon,
A hydrocarbon in a gas state such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ and C ₄ H ₁₀ or a gasifiable hydrocarbon can be effectively used, and further, it is easy to handle at the time of forming a layer, Si
CH ₄ and C ₂ H ₆ are preferable as they are preferable in terms of supply efficiency. In addition, these raw material gases for supplying C may be diluted with a gas such as H ₂ , He, Ar, or Ne as needed before use.

Examples of substances that can be used as a gas for supplying nitrogen or oxygen include NH ₃ , NO, N ₂ O, NO ₂ , O ₂ and C.
A compound in a gas state such as O, CO ₂ , N ₂ or the like which can be gasified is mentioned as being effectively used. In addition, these raw material gases for supplying nitrogen and oxygen may be diluted with a gas such as H ₂ , He, Ar, and Ne as needed before use.

Further, in order to make it easier to control the introduction ratio of hydrogen atoms introduced into the surface layer to be formed, hydrogen gas or a silicon compound gas containing hydrogen atoms may be added to these gases. It is preferable to form a layer by mixing a desired amount. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio.

As a raw material gas for supplying halogen atoms, a gaseous or gasifiable halogen compound such as a halogen gas, a halide, an interhalogen compound containing halogen, or a silane derivative substituted with halogen is preferably used. . Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains silicon atoms and a halogen atom as constituent elements, can also be cited as an effective one. Specific examples of the halogen compound that can be preferably used in the present invention include fluorine gas (F ₂ ), BrF, ClF, ClF ₃ and Br.
Interhalogen compounds such as F ₃ , BrF ₅ , IF ₃ and IF ₇ can be mentioned. As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom, specifically, silicon fluoride such as SiF ₄ and Si ₂ F ₆ can be mentioned as a preferable example.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer, for example, the temperature of the substrate, the reaction vessel of the raw material used for containing hydrogen atoms and / or halogen atoms The amount to be introduced into the inside, the discharge power, etc. may be controlled.

The carbon atom and / or the oxygen atom and / or the nitrogen atom may be uniformly contained in the surface layer, or may be nonuniform so that the content changes in the layer thickness direction of the surface layer. There may be a part that has an analysis.

The thickness of the surface layer in the present invention is usually 0.01 to 3 μm, preferably 0.05 to 2 μm, and most preferably 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 characteristics such as increase in residual potential are deteriorated.

The gas pressure in the reaction vessel was also designed to be a layer.
Therefore, the optimum range is appropriately selected, but in the normal case, it is preferable.
It is 1 × 10^-Four10 Torr, more preferably 5 ×
10 ^-Four~ 5 Torr, optimally 1 x 10^-3~ 1 Torr
Is preferred.

Similarly, the discharge power is appropriately selected in accordance with the layer design, and the optimum range is selected. The discharge power with respect to the flow rate of the gas for supplying Si is normally 0.5 to 7 times (0.5).
W / cc to 7 W / cc), preferably 1 to 6 times (1 W /
cc-6W / cc), optimally 1.5-5 times (1.5W
/ Cc to 5 W / cc) is desirable.

The electrophotographic photosensitive member manufactured by the apparatus of the present invention can be used not only in electrophotographic copying machines, but also in electrophotographic applications such as laser beam printers, CRT printers, LED printers, liquid crystal printers and laser plate making machines. It can also be used widely.

[0130]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. [Embodiment 1] An apparatus for producing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
A blocking type electrophotographic photosensitive member was formed on an aluminum cylinder obtained by mirror-finishing a cylindrical substrate having a length of 8 mm, a length of 358 mm, and a wall thickness of 5 mm under the conditions shown in Table 1 below.

[0131]

[Table 1] In this embodiment, the substrate heating heater of FIG. 3 (a) is used by adjusting the winding method, and the temperature of the central portion of the cylindrical substrate is set to 2
The temperature of the lower part of the cylindrical substrate is set to 60 ° C., and the temperature of the lower part of the cylindrical substrate is + 5 ° C., + 10 ° C., + 20 ° C., + 30 ° C., + 40 ° C.
A total of 6 types of photoconductors were prepared at + 50 ° C. The temperature distribution of the cylindrical substrate was set to have the pattern shown in FIG.

The produced light receiving member was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing),
The charging ability unevenness, sensitivity unevenness, color reproducibility unevenness, ghost, fog and forced jam test were evaluated by the following methods.

(Electrical charge unevenness) The electrophotographic photosensitive member is installed in an electrophotographic apparatus, corona charging is performed by applying a high voltage of +6 kV to the charger, and the surface potential of the dark portion of the electrophotographic photosensitive member is set at the developing position. taking measurement. Five points are measured in the axial direction of the electrophotographic photoreceptor, and the potential unevenness at this time is evaluated.

(Sensitivity unevenness) The electrophotographic photosensitive member is charged to a constant dark part surface potential. Immediately thereafter, a halogen lamp light excluding light in the wavelength range of 600 nm or more is irradiated using a filter, and the light amount is adjusted so that the surface potential of the bright portion of the electrophotographic photosensitive member becomes a predetermined value. The amount of light required at this time is converted from the lighting voltage of the halogen lamp light source. According to this procedure, 5-point sensitivity is measured in the axial direction of the electrophotographic photosensitive member, and the sensitivity unevenness at this time is evaluated.

Each of the charging unevenness and the sensitivity unevenness was evaluated by dividing it into ⊚: very good ∘: good Δ: no practical problem x: practical problem

(Color Reproducibility) Black with a density of 0.3 and a density of 0.4
Of red and blue of 0.4 density are printed on the upper and lower 5 places on the platen, and the electrophotographic device is set so that the black printed image becomes 0.6 on the copy image. Conditioned and imaged. At this time, the image densities of red and blue prints were measured and evaluated at 5 points in the axial direction of the electrophotographic photoreceptor. However, the image density is measured by an image densitometer: Macbeth
Performed using RD914.

Regarding color reproducibility: ⊚ ... The image density corresponding to the red and blue prints on the copy image was high at any location in the axial direction of the electrophotographic photoconductor, and was easy to read.

∘: There was a part where the density of the image corresponding to the printing of red and blue was slightly low on the copy image, but there was no problem in reading.

Δ: On the copy image, the density of the image corresponding to the red and blue prints was low, and there were some parts that were difficult to read.

X: The density of the image corresponding to the red and blue prints was low on the copy image, and there were unreadable portions. It was divided into and evaluated.

(Ghost) A ghost test chart (part number: FY9-9040) manufactured by Canon Inc. was used to measure reflection density of 1.
1. Place a black circle with a diameter of 5 mm on the image edge of the platen, and place a Canon halftone chart (part number: FY9-9042) on top of it. The difference between the reflection density of 5 mm in the ghost chart and the reflection density of the halftone portion was measured. According to this procedure, ghosts are measured and evaluated at five locations in the axial direction of the electrophotographic photosensitive member.

The ghosts were evaluated by dividing them into ⊚: particularly good ∘: good Δ: no problem in practical use ×: problem in practical use

(Fog) A solid white original is copied with an appropriate exposure amount and the density unevenness of the obtained image is measured. By this procedure, 5-point fog is measured and evaluated in the axial direction of the electrophotographic photosensitive member.

Regarding fogging, ⊚: no fogging was observed at all, which is very good.

◯: Fogging is slightly observed, but it is good.

Δ: Fog is slightly large, but it is at a conventional level.

X: There are many fogs and there is a problem in practical use. It was divided into and evaluated.

(Forced Jam Test) The device was installed in an electrophotographic apparatus, and a paper jam condition was forcibly generated during paper passing. This operation was repeated 10 times, and it was checked on the image whether the photoreceptor was scratched.

With regard to the forced jam test, ⊚: very good without scratches.

B: The photoconductor was slightly scratched, but it did not appear in the image and was good.

Δ: The photoreceptor was considerably scratched, but it did not appear in the image, and there was no problem in practical use.

X: There are scratches on the image, which is a problem in practical use. It was divided into and evaluated. [Comparative Example 1] RF-shown in FIG. 2 in which the substrate heating heater shown in FIG.
Using an apparatus for manufacturing a photoreceptive member for electrophotography by the PCVD method, a substrate was placed on a cylindrical aluminum substrate having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was mirror-finished, under the conditions shown in Table 1. A blocking electrophotographic photoreceptor was formed on the substrate.

In this comparative example, the one in which the substrate heater is wound as shown in FIG. 5A is used, and the temperature of the entire cylindrical substrate is set to 2
The temperature was uniformly set at 90 ° C., and a total of one type of photoconductor was prepared.
The temperature distribution of the cylindrical substrate is flat.

The produced light receiving member was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing),
The charging ability unevenness, the sensitivity unevenness, the color reproducibility unevenness, the ghost, the fog, and the forced jam test were evaluated in the same manner as in Example 1.

Table 2 shows the evaluation results of the electrophotographic photosensitive members prepared in Example 1 and Comparative Example 1.

[0156]

[Table 2] As is clear from Table 2, when the electrophotographic photosensitive member was produced, the temperature of the substrate at both ends was set to 5 ° C. to 5 °
It was found that the photosensitive member raised by 0 ° C. has improved the charging ability unevenness, the sensitivity unevenness, the blue reproducibility unevenness, the ghost, and the fog unevenness, and is not easily scratched even in the forced jam test, and that a dense film can be formed. did. Also, especially from 20 ℃ to 40
This effect was remarkable when set to ° C. [Embodiment 2] An apparatus for producing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
A blocking type electrophotographic photosensitive member was formed on an aluminum cylinder obtained by mirror-finishing a cylindrical substrate having a length of 8 mm, a length of 358 mm and a wall thickness of 5 mm under the conditions shown in Table 3.

[0157]

[Table 3] In this embodiment, the pattern of FIG. 6C is used for the substrate heater, and the hydrogen content of the photoconductive layer is 1 to 1 with respect to SiH ₄ .
A total of 6 types of samples were prepared by changing to 0 times.

The temperature of the cylindrical substrate is 260 at the center.
A heater was used which was set to 0 ° C. and the temperature of both ends of the cylindrical substrate was + 20 ° C. compared to the center.

The produced light receiving member was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing),
The charging ability unevenness, the sensitivity unevenness, the color reproducibility unevenness, the ghost, the fog, and the forced jam test were evaluated in the same manner as in Example 1. [Comparative Example 2] An apparatus for producing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
A blocking type electrophotographic photosensitive member was formed on an aluminum cylinder obtained by mirror-finishing a cylindrical substrate having a length of 8 mm, a length of 358 mm and a wall thickness of 5 mm under the conditions shown in Table 3.

In this embodiment, the amount of hydrogen in the photoconductive layer is set to SiH.
_A total of 6 types of samples were prepared by changing the value from ₄ to 1 to 10.

The cylindrical substrate was set to be uniform at 260 ° C. using the heater shown in FIG. 5 (a).

The produced light receiving member was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing),
The charging ability unevenness, the sensitivity unevenness, the color reproducibility unevenness, the ghost, the fog, and the forced jam test were evaluated in the same manner as in Example 1.

The results of Example 2 and Comparative Example 2 are summarized in Table 4.
Shown in In a deposited film forming apparatus using a conventional substrate heater, when the amount of hydrogen in the raw material gas is more than double the amount of SiH ₄ , the axial unevenness tends to worsen.
In the deposited film forming apparatus of the present invention, even if the amount of hydrogen increased up to 8 times, it did not deteriorate, and it became clear that the latitude at the time of manufacturing the electrophotographic photosensitive member was dramatically improved.

[0164]

[Table 4] [Embodiment 3] A substrate having a diameter of 10 is used by using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
A blocking type electrophotographic photosensitive member was formed on an aluminum cylinder obtained by mirror-finishing a cylindrical substrate having a length of 8 mm, a length of 358 mm, and a wall thickness of 5 mm under the conditions shown in Table 1.

In this example, the substrate heating heater shown in FIGS. 3 (a) and 3 (b) was used in an adjusted manner, and the temperature of the central portion of the cylindrical substrate was set to 260.degree. The temperature at the lower end is + 30 ° C. compared to the center, and the temperature distribution of the cylindrical substrate is as shown in FIG. 6 (a) using the heater of FIG. 3 (a).
The pattern of (b) was changed to the pattern of FIG. 6 (c) using the heater of FIG. 3 (b), and three types of photoreceptors were prepared in total.

The produced electrophotographic photosensitive member was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing), and charging performance unevenness, sensitivity unevenness, color reproducibility unevenness, ghost, fog and forced jam tests were carried out in Examples. When evaluated by the same method as in Example 1, the same results as the evaluation results at + 30 ° C. in Example 1 were obtained, and the effect of the present invention is shown in FIG.
It has been clarified that any of the patterns (a), (b), and (c) can be obtained. [Embodiment 4] Using a manufacturing apparatus for an electrophotographic light-receiving member by the RF-PCVD method shown in FIG.
A 1-inch Si wafer was attached to the inside and the bottom to form a substrate, and an amorphous silicon deposited film was formed under the following conditions.

[0167]

Table 5 SiH ₄ 100 sccm H ₂ 500 sccm Power 300 W Internal pressure 0.5 Torr Film thickness 1 μm In this example, the one in which the substrate heating heater of FIG. Temperature 2
The temperature of the lower part of the cylindrical substrate is set to 90 ° C., and the temperature of the lower part of the cylindrical substrate is + 5 ° C., + 10 ° C., + 20 ° C., + 30 ° C., + 40 ° C.
A total of 6 types of samples were prepared at + 50 ° C. The temperature distribution of the cylindrical substrate was set to be the pattern of FIG. 6 (b).

The hydrogen content of the produced sample was measured by infrared absorption spectral distribution, and when the hydrogen content in the central part was 1, the variation in the hydrogen content in the upper and lower parts was evaluated.

A: The distribution is small within ± 10%.

◯: The distribution is slightly small within ± 20%.

Δ: Standard within ± 30%.

X: The distribution is large at ± 30% or more. [Comparative Example 3] Using a manufacturing apparatus of a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4, on a cylindrical substrate,
An amorphous silicon deposited film was formed under the conditions shown in Table 5 by attaching a 1-inch Si wafer to the lower part of the middle as a base.

In this comparative example, the method of winding the substrate heater shown in FIG. 5B was used, and the temperature of the entire cylindrical substrate was set to 2
The temperature was set to 90 ° C. uniformly and a total of one type of sample was prepared. The temperature distribution of the cylindrical substrate is flat.

The upper, middle and lower parts of the produced a-Si film were subjected to infrared absorption spectroscopy in the same manner as in Example 4 to measure the amount of hydrogen in the film. The amount of hydrogen in the upper and lower parts was evaluated when the amount of hydrogen in the center was 1.

The results of Example 4 and Comparative Example 3 are summarized in Table 6.
Shown in It has been clarified that the variation of the hydrogen content in the film in the axial direction of the cylindrical substrate can be suppressed by using the deposited film forming apparatus of the present invention.

[0176]

[Table 6] [Embodiment 5] Using a manufacturing apparatus for an electrophotographic light-receiving member by the RF-PCVD method shown in FIG.
An amorphous silicon deposited film was formed under the conditions shown in Table 7 by attaching a 1-inch Si wafer to the lower part of the middle as a base.

[0177]

[Table 7] SiH ₄ 100 sccm H ₂ (change) Power 400 W Internal pressure 0.3 Torr Film thickness 1 μm In this example, the amount of hydrogen in the photoconductive layer was 1 relative to SiH ₄ .
Six kinds of samples were prepared by changing the amount up to 10 times.

The temperature of the cylindrical substrate is 260 at the center.
A heater was used which was set to 0 ° C. and the temperature of both ends of the cylindrical substrate was + 20 ° C. compared to the center.

The upper, middle and lower parts of the produced a-Si film were subjected to infrared absorption spectroscopy in the same manner as in Example 4 to measure the amount of hydrogen in the film. The amount of hydrogen in the upper and lower parts was evaluated when the amount of hydrogen in the center was 1. [Comparative Example 4] Using a manufacturing apparatus for a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
An amorphous silicon deposited film was formed under the conditions shown in Table 7 by attaching a 1-inch Si wafer to the lower part of the middle as a base.

In this example, the amount of hydrogen in the photoconductive layer was set to SiH.
_A total of 6 types of samples were prepared by changing the value from ₄ to 1 to 10.

The cylindrical substrate was set to be uniform at 260 ° C. using the heater shown in FIG. 5 (a).

The upper, middle and lower parts of the produced a-Si film were subjected to infrared absorption spectroscopy in the same manner as in Example 4 to measure the amount of hydrogen in the film. The amount of hydrogen in the upper and lower parts was evaluated when the amount of hydrogen in the center was 1.

The results of Example 5 and Comparative Example 4 are summarized in Table 8.
Shown in In a conventional deposited film forming apparatus using a substrate heater, when the amount of hydrogen in the source gas is more than double the amount of SiH ₄ , the unevenness of the amount of hydrogen in the film tends to worsen. In the film forming apparatus, it became clear that even if the amount of hydrogen increased up to 10 times, it did not deteriorate and the uniformity of the a-Si film was dramatically improved.

[0184]

[Table 8] [Embodiment 6] A substrate having a diameter of 1 is used by using an apparatus for producing a photoreceptive member for electrophotography by the VHF-PCVD method shown in FIG.
A blocking type electrophotographic photoreceptor was formed on an aluminum cylinder obtained by mirror-finishing a cylindrical substrate having a length of 08 mm, a length of 358 mm and a wall thickness of 5 mm under the conditions shown in Table 9.

[0185]

[Table 9] In this embodiment, the substrate heater of FIG. 3 (a) is wound upside down, and the temperature is adjusted so that the temperature in the central part to the lower part is 260 ° C. and the temperature in the upper part is + 30 ° C. higher than that. To create a photoconductor. The temperature distribution of the cylindrical substrate was such that the pattern of the solid line in FIG. 6 (b) was upside down.

The produced light receiving member is set in an electrophotographic apparatus (NP6150 manufactured by Canon is modified for testing),
When the charging ability unevenness, the sensitivity unevenness, the color reproducibility unevenness, the ghost, the fog and the forced jam test were evaluated by the same method as in Example 1, the same good results as in Example 1 were obtained, and the deposited film formation of the present invention was obtained. The apparatus has also been found to be effective in the VHF plasma CVD method. [Embodiment 7] A substrate having a diameter of 10 is used by using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
A function-separated electrophotographic photosensitive member was formed on an aluminum cylinder obtained by mirror-finishing a cylindrical substrate having a length of 8 mm, a length of 358 mm, and a wall thickness of 5 mm under the conditions shown in Table 10.

[0187]

[Table 10] In the present embodiment, the one in which the winding method of the substrate heating heater of FIG. 3D is adjusted is used, and the temperature of the central portion of the cylindrical substrate is set to 2
A photoconductor was prepared by setting the temperature to 70 ° C. so that the temperature at both ends of the cylindrical substrate was + 50 ° C. as compared with the temperature at the center. The temperature distribution of the cylindrical substrate was set to have the pattern shown in FIG. 6 (c).

The produced light receiving member is set in an electrophotographic apparatus (NP6150 manufactured by Canon is modified for testing),
When the charging ability unevenness, the sensitivity unevenness, the color reproducibility unevenness, the ghost, the fog and the forced jam test were evaluated by the same method as in Example 1, the same good results as in Example 1 were obtained, and the deposited film formation of the present invention was obtained. The apparatus has also been found to be optimal in the production of function-separated type electrophotographic photoreceptors. [Embodiment 8] A substrate having a diameter of 1 is used by using the electrophotographic light-receiving member producing apparatus by the VHF-PCVD method shown in FIG.
On an aluminum cylinder, which is mirror-finished on a cylindrical substrate having a length of 08 mm, a length of 358 mm, and a wall thickness of 5 mm, Table 11
A function-separated type electrophotographic photosensitive member was formed on the substrate under the conditions shown in.

[0189]

[Table 11] In the present embodiment, the one in which the winding method of the substrate heater of FIG. 3 (e) is adjusted is used, and the temperature of the central portion of the cylindrical substrate is set to 2
A photoconductor was prepared by setting the temperature to 70 ° C. so that the temperature at both ends of the cylindrical substrate was + 50 ° C. as compared with the temperature at the center. The temperature distribution of the cylindrical substrate was set to have the pattern shown in FIG. 6 (c).

The produced light receiving member was set in an electrophotographic apparatus (Canon NP6150 was modified for testing),
When the charging ability unevenness, the sensitivity unevenness, the color reproducibility unevenness, the ghost, the fog and the forced jam test were evaluated by the same method as in Example 1, the same good results as in Example 1 were obtained, and the deposited film formation of the present invention was obtained. The apparatus has also been found to be optimal in the production of function-separated type electrophotographic photoreceptors.

[0191]

As described above, according to the present invention, in a deposited film forming apparatus for depositing at least an amorphous material containing silicon atoms as a base material on a rectangular or columnar substrate, The temperature is set to be high at one end side or both end sides in the length direction of the substrate and low at the center, and film formation is performed with a temperature gradient in the length direction of the substrate. By doing, the properties of the deposited film are improved,
For example, when this deposited film is used for an electrophotographic photosensitive member, unevenness in characteristics such as unevenness of spectral sensitivity, unevenness of residual potential, and fog can be suppressed, and durability against film peeling and scratches is improved.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram for explaining a configuration of a preferred embodiment of an electrophotographic photosensitive member manufacturing apparatus according to the present invention using an RF plasma CVD method.

FIG. 2 is a schematic configuration diagram for explaining a configuration of a preferred embodiment of an electrophotographic photosensitive member manufacturing apparatus according to the present invention using a VHF plasma CVD method.

3 (a) to 3 (e) are schematic explanatory views schematically showing a specific example of a substrate heating heater used in the electrophotographic photosensitive member manufacturing apparatus according to the present invention.

FIG. 4 is a schematic configuration diagram for explaining a configuration of a conventional apparatus for manufacturing an electrophotographic photosensitive member, which uses an RF plasma CVD method.

5 (a) and 5 (b) are schematic explanatory views schematically showing a specific example of a substrate heating heater used in a conventional electrophotographic photosensitive member manufacturing apparatus.

6 (a) to 6 (c) are graphs schematically showing the distribution pattern of the heating temperature of the substrate in the axial direction, which is carried out in the electrophotographic photosensitive member manufacturing apparatus of the present invention.

[Explanation of symbols]

 1100, 2100 Deposition device 1111, 2111 Reaction vessel 1112, 2112 Cylindrical substrate 1113, 2113 Substrate heating heater 1114, 2114 Raw material gas introduction pipe 1115, 2115 Matching box 1116, 2116 Raw material gas pipe 1117, 2117 Exhaust pump 1118, 2118 Main exhaust Valves 1119 and 2119 Exhaust ports 1120 and 2120 Gate valves 1121 and 12121 Bottom plates 1122 and 2122 Insulators 1123 and 2123 Leak valves 1124 and 2124 Vacuum gauges 2125 Cathode electrodes 1200 Raw material gas supply devices 1211 to 1216 Mass flow controllers 1221 to 1226 Raw material gas cylinders 1231 to 1231 1236 Raw material gas cylinder valve 1241-1246 Gas inflow valve 1251-1256 gas Outflow valve 1261-1266 Pressure regulator 1260, 2260 Auxiliary valve

Claims (11)

[Claims] 1. A hollow columnar deposition chamber provided with an exhaust port for connecting to an exhaust system on the upper surface and / or the lower surface side, and the length direction of the hollow columnar deposition chamber and the length direction of the deposition surface are substantially the same. A rectangular or columnar substrate is installed so as to be parallel, the source gas containing at least silicon atoms introduced into the deposition chamber is decomposed by high frequency power, and at least silicon atoms are used as a base material on the substrate. In a deposited film forming apparatus for depositing an amorphous material, the amount of heat generated by a substrate heating means for setting the substrate at a desired temperature is at either one end side or both end sides in the length direction of the substrate. An apparatus for forming a deposited film, characterized in that a large amount is set and a small number is set in the central portion, and a temperature gradient is provided in the length direction of the substrate. 2. The substrate heating means is composed of a sheath heater, and the sheath heater is densely present at either one end side or both end sides in the length direction of the substrate and is roughly present at the central portion. The deposition film forming apparatus according to claim 1, wherein the deposition film forming apparatus is set to: 3. The substrate heating means is divided into three regions for heating at least one end, the center, and the opposite end of the substrate, and the heat generation amount of each region can be independently controlled. The deposited film forming apparatus according to claim 1 or 2, wherein 4. The deposited film forming apparatus according to claim 1, wherein the substrate is a conductive cylindrical substrate. 5. A cathode electrode is concentrically provided outside the cylindrical substrate, and a source gas supply means is installed parallel to the axial direction of the cylindrical substrate.
The deposited film forming apparatus as described in 1. 6. The substrate heating means is installed inside the cylindrical substrate.
The deposited film forming apparatus as described in 1. 7. The deposited film is formed using a source gas containing hydrogen gas in an amount of 2 to 8 times the source gas containing silicon as a constituent atom. The deposited film forming apparatus according to claim 1. 8. The high frequency power is 0.5 W / cc to 7 with respect to the source gas containing silicon atoms among the source gases.
The deposited film forming apparatus according to any one of claims 1 to 7, wherein the deposited film is formed within a range of W / cc. 9. The substrate is a conductive cylindrical substrate,
The deposited film deposited on the cylindrical substrate is composed of three layers of a lower blocking layer, a photosensitive layer and a surface protective layer, and the cylindrical substrate on which the deposited film is formed is used as an electrophotographic photoreceptor. The deposited film forming apparatus according to any one of claims 4 to 8. 10. The substrate is a conductive cylindrical substrate, and the deposited film deposited on the cylindrical substrate is a charge transport layer,
9. A cylindrical substrate having a charge generating layer and a surface protective layer and having a deposited film formed thereon is used as an electrophotographic photosensitive member. Deposited film forming device. 11. A hollow columnar deposition chamber provided with an exhaust port for connecting to an exhaust system on the upper surface and / or the lower surface side, and the length direction of the hollow columnar deposition chamber and the length direction of the deposition surface are substantially the same. A rectangular or columnar substrate is installed so as to be parallel, the source gas containing at least silicon atoms introduced into the deposition chamber is decomposed by high frequency power, and at least silicon atoms are used as a base material on the substrate. In the deposited film forming method for depositing an amorphous material, the temperature of the base is set to be high at one end side or both end sides in the length direction of the base and set to be low at the central part,
A method for forming a deposited film, characterized in that the film is formed with a temperature gradient in the length direction of the substrate.