JP3441876B2 - Method for manufacturing light receiving member - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device such as a functionally deposited film, especially a photoconductor for electrophotography, a photovoltaic device, a line sensor for image input, an image pickup device, and a TFT, which are formed by a plasma CVD method. Can be used suitably,
The present invention relates to an improved deposited film forming method for continuously forming a crystalline or non-single crystalline semiconductor. In particular, the present invention relates to a manufacturing method in a continuous production apparatus for forming a large-area deposited film such as an electrophotographic photosensitive member.

[0002]

Description of the Related Art Conventionally, semiconductor devices, electrophotographic photoconductors, image input line sensors, image pickup devices,
Photovoltaic device, other various electronic elements,
As an element member used for an optical element or the like, a non-crystalline material such as amorphous silicon, for example, amorphous silicon compensated with hydrogen or / and halogen (eg, fluorine, chlorine, etc. [hereinafter, abbreviated as A-Si (H, X)]) is used. Single crystalline deposited films or crystalline deposited films such as diamond thin films have been proposed, some of which have been put to practical use. Then, such a deposited film is decomposed into a raw material gas by a plasma CVD method, that is, a glow discharge by a direct current, a high frequency, or a microwave, and the deposited film is formed of a support such as glass, quartz, a heat resistant synthetic resin film, stainless steel, or aluminum. It is formed by the method of forming on the above, and various apparatuses for it are proposed.

For example, FIG. 1 is a schematic configuration diagram showing an example of a continuous production apparatus for electrophotographic photoreceptors by a high frequency plasma CVD method (hereinafter abbreviated as "PCVD").
The structure of the production apparatus shown in FIG. 1 is as follows. This device is roughly classified into a support charging container (1100), a support heating device (1200), a reaction device (1300), a support cooling and discharging device (1400), and a dedicated transfer device that can move between these containers. It is composed of a device (1900). Vacuum container (1101, 1201, 1301) of each device
a to c, 1401, and 1901), exhaust means (1501 to 1507) for evacuating the inside of the container, exhaust valve (1
Opening / closing gates (1801 to 1807) that can be connected to each vacuum container are installed. The support charging container (1101) is provided with a leak valve (1701) for returning the inside of the container to the atmosphere. The support heating container (1201) has an auxiliary valve (1702) for introducing gas used for heating, and the support cooling and discharge container (1401) has a leak valve (for returning the inside of the container to the atmosphere). 1705) is provided. The reaction vessel (1301a-c) is provided with a reaction gas outflow valve (1703).
a to c, 1704) and a high frequency matching box (not shown) are connected. The transfer-dedicated vacuum container includes an exhaust valve (1607) for creating a vacuum inside the container, an exhaust valve (1608) for creating a vacuum between the gates, and a leak valve (1706) for returning the space between the gates to the atmosphere. A support chucking (1951) and a moving rail (1952) are provided. The number of the support input container (1101), the heating container (1201), the reaction containers (1301a to 1301c), the cooling and taking out container (1401) is selected so that there is no waste depending on the processing time. It Further, a plurality of vacuum containers (1901) dedicated to transfer can be provided so that a plurality of supports can be transferred at the same time.
The transfer device (1900) may be a linear movement type or a movement in the circumferential direction.

In such a continuous production apparatus, the operation is performed as follows, for example.

A support is put into a support feeding container (1101), and the inside of the container is gradually evacuated from atmospheric pressure to a predetermined vacuum degree. When a predetermined degree of vacuum is reached, a vacuum container (1901) dedicated to transportation is used, and a vacuum support heating container (12) is used.
01) to transfer the heating gas to the auxiliary valve (1702)
From above to a predetermined pressure, and heated to a predetermined temperature using a heater (not shown) installed in the container. The heated support is a vacuum container (190
1) and transferred into a vacuum reaction container (1301a-c). A deposited film is formed by a predetermined means in the reaction container, and then the film is transferred to a vacuum cooling and discharge container (1401) and cooled to a predetermined temperature, and then a leak gas is leaked from a leak valve (1705). Flow until atmospheric pressure, then discharge.

Each vacuum container (1101, 1201, 130)
1 a to c, 1401) and dedicated to carrying the vacuum container (1901)
In order to transfer the support between the
0) moves onto the vacuum container to be taken out, and the gate (180
7) The gate (1801-1806) of the vacuum container for taking out
One of the above). After that, exhaust means (150
7) A vacuum is applied between the gates by the exhaust valve (1608). When the inside of the vacuum container (1901) is not at a predetermined degree of vacuum, the exhaust valve (1607) evacuates. When the degree of vacuum between the gates reaches a predetermined level, both gates are opened to transfer the support. After delivery,
Both gates are closed and the gate-to-gate leak valve (170
The gas for leak is made to flow from 6), and atmospheric pressure is applied between the gates. After that, the gate (1807) of the vacuum container (1901) dedicated to transfer is cut off, and the transfer device (1900) moves to the next step. The transfer of the support is performed using chucking (1951). All of these steps are performed by automatic control.

The reaction vessel will be described in more detail with reference to the schematic configuration diagram of the reaction apparatus shown in FIG.
100), a source gas supply device (2200), an opening / closing gate (2120), and an exhaust device (not shown) for reducing the pressure inside the reaction vessel (2111). A support (2112), a heater for heating the support (2113), a reaction vessel (2111) in the deposition apparatus (2100),
A raw material gas introduction pipe (2114) is installed, and a high frequency matching box (2115) is further connected.

The source gas supply device (2200) is made of SiH.
₄ , GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH _{3 and} other source gas cylinders (2212-1226) and valves (22)
31-2236, 2241-2246, 2251-22
56) and a mass flow controller (2211-2)
216), and the cylinder of each source gas is connected to the gas introduction pipe (2114) in the reaction vessel (2111) via the valve (2260).

Formation of a deposited film using such a deposited film forming apparatus is performed, for example, as follows.

First, a support (2112) heated to a predetermined temperature is opened / closed in a reaction container (2111) which is evacuated to a vacuum by an evacuation means (not shown) by a vacuum container (not shown) dedicated to transportation. Input through the gate (2120),
The support (2113) is heated by the heater (2113) for heating the support.
The temperature of 12) is controlled to a predetermined temperature.

A raw material gas for forming a deposited film is supplied to a reaction vessel (21
11), the gas cylinder valve (223
1 to 2236), the leak valve of the reaction vessel (2123)
Make sure that the inlet valve (22
41 to 2246), the outflow valve (2251 to 225)
6) After confirming that the auxiliary valve (2260) is opened, first, the main valve (2118) is opened to exhaust the reaction vessel (2111) and the gas pipe (2116).

Next, the reading of the vacuum gauge (2124) is about 5 × 1.
Auxiliary valve (2260) at 0 ^-6 Torr,
Close the outflow valves (2251-2256).

After that, the gas cylinders (2221-222)
From (6), each gas is introduced by opening the valves (2231-2236), and the pressure of each gas is adjusted to ² kg / cm ² by the pressure adjuster (2261-2266).

Next, the inflow valves (2241-2246)
Is gradually opened and each gas is introduced into the mass flow controller (2211 to 2216).

After the preparation for film formation is completed as described above, each layer is formed by the following procedure.

When the support (2112) reaches a predetermined temperature, the necessary ones of the outflow valves (2251-2256) and the auxiliary valve (2260) are gradually opened,
A predetermined gas is introduced from the gas cylinders (2212-1226) into the reaction container (2111) through the gas introduction pipe (2114). Next, mass flow controller (2211
.About.2216) so that each raw material gas is adjusted to have a predetermined flow rate. At that time, a vacuum gauge (2) is used so that the pressure inside the reaction vessel (2111) becomes a predetermined pressure of 1 Torr or less.
The opening of the main valve (2118) is adjusted with reference to the output of 124). When the internal pressure is stable, frequency 1
A high frequency power supply (not shown) of 3.56 MHz is set to a desired power, and high frequency power is introduced into the reaction vessel (2111) through the high frequency matching box (2115) to cause glow discharge. The source gas introduced into the reaction vessel is decomposed by this discharge energy, and the support (2
112) where a predetermined deposited film containing silicon as a main component is formed. After the desired film thickness is formed, the supply of the high frequency power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction container, 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 can be formed.

Needless to say, all the outflow valves other than the necessary gas are closed when forming the respective layers, and the respective gases are supplied to the reaction vessel (211).
1) In order to avoid remaining in the pipe from the outflow valve (2251 to 2256) to the reaction vessel (2111), the outflow valve (2251 to 2256) is closed, the auxiliary valve (2260) is opened, and the main valve is further opened. Valve (21
If necessary, the operation of 18) is fully opened and the system is once evacuated to a high vacuum. During this period, all is performed by automatic control.

When a deposited film having a large area such as that of an electrophotographic photosensitive member is formed in this way, it is necessary to make the film thickness and film quality uniform, and various apparatus configurations have been proposed for that purpose.

For example, according to Japanese Patent Laid-Open No. 58-101420, a support is used as a discharge electrode and a DC bias is applied between a pair of electrodes so as to cancel a self-potential. A method for obtaining a deposited film with uniform and good properties of is described.

Further, in Japanese Examined Patent Publication No. 4-350171, a continuously movable strip-shaped member is arranged so as to form an outer wall with respect to a support and a discharge space, a DC bias is applied, and the strip-shaped member itself is heated. A method for obtaining a uniform deposited film with less loss is described. However, these methods are used at the time of forming a deposited film, and there is no description that they play an auxiliary role at the time of heating.

[0022]

However, although the electrophotographic photosensitive member produced by the conventional apparatus has been improved in yield in terms of uniform film thickness and film quality, it has a characteristic of continuous production. The reality is that there is room for further improvement in terms of stabilization.

Under such circumstances, although the film thickness and film quality can be made uniform to some extent by the above-mentioned conventional technique with respect to the above problems, it is still sufficient to further improve the stability of production. Absent. In particular, as a challenge to further improve the image quality of amorphous silicon-based photoconductors, it is necessary to obtain a uniform film and to perform stable production without causing characteristic changes due to changes in film thickness over time in continuous production. Is mentioned.

For that purpose, it is necessary to establish the stability of the discharge in the reaction space, and at the same time, it is necessary to further improve the conditions for obtaining a uniform deposited film. Especially when it is necessary to heat the support for forming the deposited film as in the case of the amorphous silicon photosensitive member, maintaining the support with a uniform temperature distribution greatly affects the properties of the deposited film. Therefore, more stable temperature distribution becomes an important factor.

[0025]

SUMMARY OF THE INVENTION The main object of the present invention is to provide a continuous production method of a photoreceptive member by a plasma CVD method, which can stabilize the temperature distribution of a support and can constantly form a deposited film having a uniform film thickness and film quality. To provide.

Another object of the present invention is to improve various physical properties of a film to be formed, film formation speed, reproducibility, film productivity, and dramatically improve the yield in mass production. Another object of the present invention is to provide a method for continuously producing a deposited film by a plasma CVD method that enables the above.

[0027]

Means and Actions for Solving the Problems The present inventors have
Overcoming the above-mentioned problems in the conventional deposited film forming method,
As a result of intensive studies to achieve the above-mentioned object of the present invention, it was found that the stability of the characteristics depends largely on the temperature of the support.

Particularly in the case of a continuous production apparatus in which the heating step and the film forming step are separated from each other, it is important that the heating step proceeds smoothly because the heating step is common to all the film forming steps. The temperature distribution needs to be constant every time.

Since the support moves in a vacuum by mechanical transportation, if there is uneven temperature distribution during transportation, the low temperature portion and the high temperature portion cancel each other out, resulting in a distribution different from that during heating. From this fact, as a means for effectively obtaining the uniformity of the temperature distribution of the support, by providing an auxiliary member that makes the temperature distribution more uniform in the heating container, it is possible to make the temperature distribution uniform in the heating step. The temperature distribution can be stabilized more than ever, and the rate of temperature rise is also increased. As a result, even in continuous production equipment, the temperature change during vacuum transfer is suppressed, and the quality and thickness of the deposited film are always uniform. Was completed. Further, by setting the distance between the auxiliary member in the heating container and the support within a certain range, the effect in the continuous production apparatus was further improved.

That is, by keeping the distance within a specific range, it is possible to eliminate the change with time in the film quality and film thickness of the deposited light receiving member, and it is possible to dramatically improve the productivity in continuous production. I found it possible.

The present invention has been completed based on various findings, and at the time of manufacturing a light receiving member, at least a support heating container and a reaction container for forming a deposited film, and these
It consists of a vacuum container dedicated to transportation that can be moved between containers.
The container has a connectable open / close gate,
Between the reactor and reaction vessel and the vacuum vessel dedicated to the transfer
In order to make uniform the heat distribution in the support heating container, using a continuous production device equipped with movable body
After raising the temperature of the support body by providing a heating auxiliary member having no opening in the longitudinal direction facing the support body, the support body is placed in front of the support body.
The film is transferred into the reaction vessel and deposited by plasma CVD.
Is a new technology that is characterized by

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to the drawings.

FIG. 3 is a sectional view schematically showing the arrangement of the support and the heating auxiliary member in the heating container in the apparatus for manufacturing a light receiving member by the plasma CVD method of the present invention. In the figure, 3111 is a heating container, 3112 is a support, 3113 is a heater for heating the support, 3114 is a gas introduction pipe, 31
15 is an auxiliary member for heating mounted in the heating container, 311
6 is a gas introduction pipe, 3117 is a leak valve, 3118 is an exhaust valve, 3119 is a vacuum gauge, 3120 is a gate valve, 3121 is a base stand, 3122 is an insulating ring, 31
Reference numerals 24 denote exhaust pipes, respectively.

In the conventional apparatus, the support was simply placed and heated in the atmosphere of the heating gas. However, in such a state, there is a problem that the temperature distribution will affect the electrophotographic characteristics if further improvement of the characteristics is required for the electrophotographic photosensitive member. To solve these problems,
Although the amount of gas and the internal pressure were changed and the continuous production was dealt with, and some improvements were made, productivity and other problems are still insufficient.

The present invention comprises a support charging container, a support heating container, a reaction container for forming a deposited film , a support cooling and discharging container, and a vacuum container dedicated to the transfer which is movable between these containers. , Each container is provided with a connectable opening / closing gate, and is dedicated to the support heating container and the reaction container and the transport .
In a continuous production apparatus in which a support can be moved in and out of a vacuum container, a heating auxiliary member, which is installed in the support heating container and has no opening in the longitudinal direction facing the support, must be provided. As a result, the temperature distribution on the surface of the support can be made uniform and the rate of temperature rise can be increased, and the quality and thickness of the deposited film that is constantly deposited can be made uniform.

The heat buffering auxiliary member used in the present invention may be made of any material as long as it has a good thermal conductivity, but especially Al, Cr, Mo, Au, In, N.
Examples thereof include metals such as b, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof, such as stainless steel. In addition, polyester, polyethylene, polycarbonate,
Films or sheets of synthetic resins such as cellulose acetate, polypropylene, polyvinyl chloride, polystyrene and polyamide, glass, ceramics and alumina are suitable for the present invention.

The length in the longitudinal direction of the heating auxiliary material used in the present invention may be stored in the heating container, but the length in the longitudinal direction of the support is L, and the length in the longitudinal direction of the heating auxiliary member is Y. In this case, Y is preferably 0.83L ≦ Y ≦ 1.80L, and optimally L ≦ Y ≦ 1.40L.

The distance between the heating assisting member and the support used in the present invention is preferably 1.1≤W / S≤3, where S is the outer diameter of the support and W is the outer diameter of the heating assisting member. 0,
Optimally, it is preferable that 1.2 ≦ W / S ≦ 2.5.

The heating gas used in the present invention may be any gas as long as it is suitable for heating, but an inert gas such as Ar, He, Ne, Xe, or N.
₂ , H _2, etc. are also effective in the present invention.

The support used in the present invention may be conductive or electrically insulating.

As the conductive support, Al, Cr, M
o, Au, In, Nb, Te, V, Ti, Pt, Pd,
Metals such as Fe, and alloys of these, such as stainless steel, may be mentioned. Also, polyester, polyethylene,
A support in which at least the surface of the electrically insulating support, such as a film or sheet of synthetic resin such as polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, or polyamide, glass, or ceramic, on which the light receiving layer is formed, is subjected to a conductive treatment. Can also be used.

The shape of the support used in the present invention may be a cylindrical or plate-like endless belt having a smooth surface or an uneven surface, and the thickness of the support may be a desired value for an electrophotographic photoreceptor. It is appropriately determined so that it can be formed, but when flexibility as an electrophotographic photoreceptor is required, it can be made as thin as possible within a range in which the function as a support can be sufficiently exhibited. However, the support is usually 10 μm in terms of manufacturing and handling, mechanical strength and the like.
That is all.

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, the surface of the support is You may provide unevenness. The unevenness provided on the surface of the support is disclosed in JP-A-60-168156.
No. 60-178457, No. 60-225.
It is created by a known method described in Japanese Patent Publication No. 854.

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 support is provided with a concavo-convex shape by a plurality of spherical trace depressions. May be. That is, the surface of the support has irregularities that are smaller than the resolving power required for the electrophotographic photoreceptor, 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 support is prepared by the known method described in JP-A-61-231561.

In order to form a deposited film by the glow discharge method using the apparatus of the present invention, basically, a source gas for supplying Si capable of supplying silicon atoms (Si) and hydrogen atoms (H) are used. A raw material gas for H supply that can be supplied and / or a raw material gas for X supply that can supply a halogen atom (X) are introduced into the reaction vessel in a desired gas state, and glow discharge is performed in the reaction vessel. The layer made of a-Si: H, X may be formed on a predetermined support which has been raised and installed at a predetermined position in advance.

The substances which can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ and Si ₃
Gaseous or gasifiable silicon hydrides (silanes) such as H ₈ and Si ₄ H ₁₀ are mentioned as being effectively used. Further, they are easy to handle during layer formation, have good Si supply efficiency, etc. In this respect, SiH ₄ and Si ₂ H ₆ are preferable.

Then, hydrogen atoms are introduced into the structure of the structure in the deposited film to be formed so that the introduction ratio of hydrogen atoms can be controlled more easily to obtain film characteristics that achieve the object of the present invention. Therefore, it is advisable to form a layer by mixing a required amount of H ₂ and / or He or a silicon compound gas containing a hydrogen atom with these gases. 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, a gaseous or gasifiable halogen compound such as a halogen gas, a halide, an interhalogen compound, a halogen-substituted silane derivative and the like is effective. Are preferred. 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 and ClF.
Examples thereof include interhalogen compounds such as ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ . Specific examples of a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom, include SiF ₄ and Si ₂
Silicon fluoride such as F ₆ can be mentioned as a preferable example.

The amount of hydrogen atoms and / or halogen atoms contained in the deposited film can be controlled by, for example, the temperature of the support, the reaction of the raw material used to contain the hydrogen atoms and / or halogen atoms. The amount introduced into the container, the discharge power, etc. may be controlled.

The present invention can be effectively applied even under the following conditions. That is, it is preferable that the deposited film in the present invention contains, if necessary, atoms that control the electrical conductivity of the carrier. Atoms that control the electric conductivity of the carrier may be contained in the deposited film in a uniformly distributed state, or may be contained in a non-uniformly distributed state in the layer thickness direction. May be.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors,
An atom belonging to Group IIIb of the periodic table giving the p-type conductivity (hereinafter abbreviated as “Group IIIb atom”) or an atom belonging to Group Vb of the periodic table giving the n-type conductivity (hereinafter “Vb”). (Abbreviated as "group atom") 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 deposited film 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 atomic ppm
Is desirable.

Atoms that control conductivity, eg, III
To introduce a group b atom or a group Vb atom into the structure, a raw material for introducing a group IIIb atom or a raw material for introducing a group Vb atom is reacted in a gas state during layer formation. It may be introduced into the container together with another gas for forming a deposited film. As a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom, a gaseous substance at room temperature and normal pressure, or at least a substance that can be easily gasified under the layer forming condition is 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 . In addition to this, Al
Cl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ ,
TlCl _{3 and the} like can also be mentioned.

Effectively used as a raw material for introducing a group Vb atom is PH ₃ , P for introducing a phosphorus atom.
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 ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF
₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , B
iCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a Group Vb atom.

Further, these raw material substances for introducing atoms for controlling the conductivity may be diluted with H ₂ and / or He as necessary and used.

In order to achieve the object of the present invention and form a deposited film 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 support The temperature may be set appropriately.

The flow rate of H ₂ and / or He used as the diluent gas is appropriately selected in accordance with the layer design, but H ₂ and / or He is usually added to the Si supply gas in the range of 3 to 3. 20 times, preferably 4 to 15
It is desirable to control in the range of double, 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 according to the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 2 to 7 times, preferably 2.5 to 6 times. Optimally, it is desirable to set the range of 3 to 5 times.

Further, the temperature of the support is appropriately selected in accordance with the layer design, and is usually 200 to
The temperature is preferably 350 ° C.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the temperature of the support and the gas pressure for forming the deposited film, but these conditions are not usually independently determined separately. It is desirable to determine the optimum value on the basis of mutual and organic relationships so as to form an electrophotographic photoreceptor having desired characteristics.

Hereinafter, the apparatus of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. [Heating Experimental Example 1] A support heating container shown in FIG. 2 using an Al holder (length 1000 mm) on which a mirror-finished Al cylinder (support) having a length of 358 mm and an outer diameter φ108 mm is mounted. Then, the temperature distributions in the longitudinal direction and the circumferential direction were measured under the conditions shown in Table 1 using a plurality of heat-buffering auxiliary members having the same length as the support shown in FIG. The results are shown in Table 2. Ar was used as the heating gas.

As a method of evaluating the temperature distribution, the evaluation was performed according to the following criteria. (Evaluation of Temperature Distribution in Longitudinal Direction) Temperature unevenness is 10 ° C. or less, which is particularly excellent ... ◎ Temperature unevenness is 10 ° C. to 20 ° C., which is excellent. However, there is no problem in practical use. △ (Evaluation of temperature distribution in the circumferential direction) Temperature unevenness is 5 ° C or less, which is particularly excellent ◎ ◎ Temperature unevenness is 5 ° C to 10 ° C, which is good. Yes ... Temperature unevenness is 10 ° C. or more, but there is no problem in practical use .... △ The above three-level evaluation was performed.

[0066]

[Table 1] [Experimental Heating Example 2] Heating was performed under the same support heating container and heating conditions as in Experimental Heating Example 1 except that the thermal buffering auxiliary member was not used. After that, evaluation was performed in the same manner as in heating experiment example 1. The results are also shown in Table 2. Similarly, FIG. 9 shows the result of comparing the heating rate until reaching the target temperature with the heating experimental example 1. In the figure, white circles indicate heating experiment example 1, and black circles indicate heating experiment example 2.

[0067]

[Table 2] It is apparent from Table 2 and FIG. 9 that the cylindrical heat buffering auxiliary member has the best results both in the longitudinal direction and in the circumferential direction. In addition, the rate of temperature rise was also increased due to the presence of the heat buffering auxiliary member. [Experimental Heating Example 3] The same support heating container as in Experimental Example 1 was used, and the type 1 thermal buffering auxiliary member shown in FIG. 4 was used as the thermal buffering auxiliary member. At that time, the flow rate of Ar and the internal pressure were changed under the conditions shown in Table 3 to measure the temperature distribution in the longitudinal direction and the circumferential direction. The results are shown in Table 4.

[0068]

[Table 3]

[0069]

[Table 4] From Table 4, it is clear that Ar is 1000 sccm to 2000 s
Good results were shown when the internal pressure was 0.50 torr in the range of ccm. [Experimental heating example 4] When the length in the longitudinal direction of the thermal buffering auxiliary member was changed using the thermal buffering auxiliary member of Type 1 in the same support heating container as in heating experimental example 1, the temperature in the longitudinal direction was changed. The distribution was measured. The results are shown in Table 6. At this time, heating was performed under the conditions shown in Table 5.

[0070]

[Table 5]

[0071]

[Table 6] From Table 6, it is clear that good results were obtained in the range of 716 to 1000. [Experimental heating example 5] Heating was performed under the conditions shown in Table 5 using the same support, apparatus and heat buffering auxiliary member as in experimental heating example 3. At this time, the temperature distributions in the longitudinal direction and the circumferential direction when different materials were used for the heat buffering auxiliary member were measured. The results are shown in Table 7.

[0072]

[Table 7] As is clear from Table 7, good temperature distribution results were obtained regardless of the material used. [Example 1] A on which a cylinder (support) made of Al having a length of 358 mm and an outer diameter of 108 mm and having a mirror-finished surface was placed
Using a holder made of 1 (length 1000 mm), the temperature rising rate of the support was measured when the distance between the support and the thermal buffering auxiliary member was changed in the apparatus shown in FIG. The result is shown in FIG. (The interval is represented by W / S when the outer diameter of the support = S and the outer diameter of the heat buffering auxiliary member = W, and the numbers attached to the symbols in the figure are the ratios). Good results are shown in the range of 2 ≦ W / S ≦ 2.5. [Example 2] In the continuous production apparatus shown in Fig. 1 using the same support as in Example 1 and equipped with a support heating container, heating was performed using a heat buffering auxiliary member in the support heating container, and thereafter. The film was transported to a reaction container and 10 continuous films were formed under the conditions shown in Table 8. However, the heat buffering auxiliary member is made of stainless steel and has W / S
= 1.5 and set in the heating container.

The electrophotographic photosensitive member thus produced was evaluated for electrophotographic characteristics as follows.

The electrophotographic photosensitive member thus prepared was put in a copying machine NP6060 manufactured by Canon Inc., which had been modified so that the process speed could be arbitrarily changed in the range of 200 to 800 mm / sec for an experiment, and the charging device was set to 5 to 8 kV. The voltage was applied to perform corona charging, an image was formed on a transfer paper by a normal copying process, and the image quality was evaluated by the following procedure. The electrophotographic photosensitive member manufactured under the same manufacturing conditions as described above was evaluated, and the evaluation results are shown in Table 9.

Evaluation of Image Defect The image sample showing the largest number of image defects was selected and evaluated among the image samples obtained when a full-face halftone original and a character original were copied on the original table while changing the process speed. As an evaluation method, the image sample was observed with a magnifying glass and evaluated by the state of white spots within the same area. ◎… Good. ○: There are some white spots. △… There are slight white dots on the entire surface, but there is no problem in recognizing the characters. ×: Some characters are difficult to read because there are many white dots.

Evaluation of Electrophotographic Characteristics (Charging Ability) The surface potential of the photoconductor obtained at the developing position when the same charging voltage is applied at a normal process speed is evaluated by a relative value as the charging ability. However, the charging ability of the electrophotographic photosensitive member obtained in Comparative Example 1 is 100%.

Electrophotographic characteristics (potential unevenness in the busbar direction) The unevenness was measured by measuring the charging potential at five points in the busbar direction of the electrophotographic photosensitive member. The unevenness is less than 5 V, which is very good .... ○ The unevenness is 5 V or more and less than 30 V, which is good. Δ The unevenness is 30 V or more ... × Electrophotographic characteristics (circumferential potential unevenness) Electrophotography When a constant current value is applied in the circumferential direction of the photoconductor, the potential is measured in the circumferential direction at a certain point, and it is defined as the circumferential potential unevenness, and it is measured at five points in the busbar direction, and the maximum value is the circumferential potential. It was evaluated as unevenness. Mura is less than 5 V Very good ... O Mura is 5 V or more and less than 30 V, good ... Δ Mura is 30 V or more ... × (Comparative Example 1) In a support heating container The electrophotographic characteristics of the electrophotographic photosensitive member produced under the same conditions and conditions as in Example 2 except that the auxiliary member for heat buffering property was not used are also shown in Table 9 as Comparative Example 1. .

[0078]

[Table 8]

[0079]

[Table 9] As is clear from Table 9, stable and good results were obtained in the electrophotographic photosensitive member produced using the heat buffering auxiliary member. Also, an unexpected effect was an improvement in charging ability. [Example 3] μwPC shown in FIGS. 5 and 6 as a film forming apparatus
Heating was performed under the conditions shown in Table 10 using the same support as in Example 1 and the thermal buffering auxiliary member set to W / S = 1.5, except that the heating container and reaction container of the VD apparatus were used. Then, under the conditions shown in Table 11, the charge injection blocking layer, the charge transport layer,
An electrophotographic photosensitive member comprising a charge generation layer and a surface layer is prepared,
When the same evaluation as in Example 2 was performed, similarly good results were obtained.

[0080]

[Table 10]

[0081]

[Table 11] Example 4 VHFP shown in FIGS. 7 and 8 as a film forming apparatus
Heating was performed under the conditions shown in Table 12 using the same support as in Example 1 except that the heating vessel and reaction vessel of the CVD apparatus were used and the thermal buffering auxiliary member set to W / S = 1.5. After that, under the conditions shown in Table 13, an electrophotographic photosensitive member was prepared,
When the same evaluation as in Example 2 was performed, similarly good results were obtained.

[0082]

[Table 12]

[0083]

[Table 13]

[0084]

According to the present invention, the temperature distribution of the support can be made uniform by using the heat buffering auxiliary member, and the time required for raising the temperature of the support can be shortened, thereby improving the production tact and saving energy. At the same time, it is possible to suppress the change in film thickness over time in continuous production, and to dramatically improve the yield.

[Brief description of drawings]

FIG. 1 is a support charging container, a support heating container, a reaction container,
It is a schematic explanatory view of a continuous production apparatus having a support cooling and discharge container and a vacuum container dedicated to transportation that is movable between these containers.

FIG. 2 is a schematic explanatory view showing a cylindrical heating container that also serves as an electrode, a counter electrode including a support, a gas introduction branch pipe, and the like in the deposited film forming apparatus by the plasma CVD method of the present invention.

FIG. 3 is a cross-sectional view schematically showing a support heating container provided with the heat buffering auxiliary member of the present invention.

FIG. 4 is a view showing heat cushioning auxiliary members having different shapes in heating experiment example 1.

FIG. 5 is a diagram showing a heating container according to a third embodiment.

FIG. 6 is a diagram showing a reaction container in Example 3.

FIG. 7 is a diagram showing a heating container according to a fourth embodiment.

FIG. 8 is a diagram showing a reaction container in Example 4.

FIG. 9 is a diagram showing a comparison of temperature rises in heating experiment examples 1 and 2.

FIG. 10 is a diagram showing a temperature rise in Example 1.

[Explanation of symbols]

1100/1101 Support feeding device / Support feeding container 1200/1201 Support heating device / Support heating container 1300 / 1301a to c Reactor / Reaction container 1400/1401 Cooling and discharging device / Cooling and discharging container 1501 to 1507 Exhaust Means (vacuum pump) 1601 to 1608 Exhaust valve 1701, 1705, 1706 Leak valve 1702 Heating gas auxiliary valve 1703a to c, 1704 Gas outflow valve 1801 to 1807 Open / close gate 1900/1901 Transport device / Vehicle dedicated to transport 1951 Transport chat King 1952 Transfer rail 2100 Deposition device 2111 Reaction vessel 3111 Heating vessels 2112, 3112 Supports 2113, 3113 Heating heaters 2114, 3114 Raw gas introduction pipe 2115 Matching boxes 2116, 3116 Raw gas pipes 2117, 3117 Reaction vessel leak valve 2118 , 3118 Main exhaust valve 2119, 3119 Vacuum gauge 2200 Source gas supply device 2211 to 2216 Mass flow controller 2221 to 2226 Source gas cylinder 2231 to 2236 Source gas cylinder valve 2241 2246 gas inlet valve 2251 to 2256 gas outflow valves 2261 to 2266 pressure regulators 3115 thermal buffer auxiliary member 3120 gate valve 3121 baseplate 3122 insulation ring 3124 exhaust pipe 501-1 / 501-2,611-1 / 611-2 heating Vessel / reaction vessel 502-2 μW introduction window 503-2 μW introduction pipe 504-1, 504-2, 612-1, 612-2 Exhaust port 505-1, 505-2, 617-1, 617-2 Support 506-2 Discharge space 507-1, 507-2 Heating heater 508-1, 508-2 Rotating shaft 509-1, 509-2 Rotating motor 510-2 DC power supply 512-1, 512-2 Raw material gas introduction pipe 613-1, 613-2 Heating heaters 614-1, 614-2 Raw material gas introduction pipe 615-2 VHF introduction rod 616-2 Matching box

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A 64-56874 (JP, A) JP-A 6-324505 (JP, A) JP-A 8-27578 (JP, A) JP-A 4- 212167 (JP, A) JP 64-8275 (JP, A) JP 60-11850 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 5/08

Claims (4)

(57) [Claims] 1. Forming at least a support heating vessel and a deposited film
And a support- use vacuum container for transporting the containers, each container being provided with an opening / closing gate which can be connected to the support heating container and the reaction container. using a continuous production apparatus which enables out movement of the support with the vacuum chamber of the transport dedicated to the support heating vessel
After increasing the temperature of the opposite longitudinally provided thermal buffer auxiliary member without opening the support to the support, before the support
A method of manufacturing a light-receiving member, which comprises transporting the material into a reaction container and forming a deposited film by a plasma CVD method. 2. A method according to claim 1, wherein the performing by arranged with a distance from the support of the heat shock auxiliary member and the support member and the similar cross-sectional shape. Wherein said heat shock auxiliary member with its outer diameter is W, the outer diameter of the support when the S, to claim 1 or 2, characterized in that it satisfies the following expression The method described. 1.1 ≦ W / S ≦ 3.0 4. The method according to claim 3 , wherein when the outer diameter of the heat-absorbing auxiliary member is W and the outer diameter of the support is S, the following equation is satisfied. 1.2 ≦ W / S ≦ 2.5