JP3496903B2 - 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 functional deposited film on a support, particularly an electrophotographic photosensitive member, a photovoltaic device, an image input line sensor, an imaging device, a semiconductor such as a TFT, etc., by a plasma CVD method. can be suitably used as a device, crystalline, or those related to the non-single-crystalline semiconductor improved deposited film forming how to continuously form. In particular, about the way of continuously producing a light-receiving member having a large area, such as the electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Conventionally, amorphous silicon has been used as an element member for semiconductor devices, electrophotographic photoconductors, image input line sensors, image pickup devices, photovoltaic devices, other various electronic elements, optical elements, etc.
For example, amorphous silicon compensated with hydrogen or / and halogen (eg, fluorine, chlorine, etc.) [hereinafter referred to as AS
abbreviated as i (H, X)] or a crystalline deposited film such as a diamond thin film, some of which have been put to practical use. Then, such a deposited film is formed by the plasma CVD method, that is,
The raw material gas is decomposed by glow discharge by direct current, high frequency, or microwave to form a deposited film on a support such as glass, quartz, heat-resistant synthetic resin film, stainless steel, or aluminum. Various proposals have been made.

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 (2100), a support heating device (2200), a reaction device (2300), a support cooling and discharging device (2400), and a transfer-only container movable between these containers. The device (2900). Vacuum container (2101, 2201, 2301) of each device
a to c, 2401, 2901), exhaust means (2501 to 2507) for making the inside of the container a vacuum, exhaust valve (2
601-2607), each vacuum container is provided with an openable / closable gate (2801-2807) which can be connected. Further, the support feeding container (2101) is provided with a leak valve (2701) for returning the inside of the container to the atmosphere. The support heating container (2201) has an auxiliary valve (2702) for introducing a gas used for heating, and the support cooling and discharge container (2401) has a leak valve (for returning the inside of the container to the atmosphere). 2705) is provided. The reaction vessel (2301a-c) is provided with a reaction gas outflow valve (2703).
a to c, 2704) A high frequency matching box (not shown) is connected. The transfer-dedicated vacuum container includes an exhaust valve (2607) for creating a vacuum inside the container, an exhaust valve (2608) for creating a vacuum between the gates, and a leak valve (2706) for returning the space between the gates to the atmosphere. A support chucking (2905) and a moving rail (2952) are provided. The number of the support charging container (2201), the heating container (2201), the reaction containers (2301a to c), and the cooling and taking out container (2401) are selected so that there is no waste depending on the processing time. It Further, a plurality of vacuum containers (2901) dedicated to transfer can be provided so that a plurality of supports can be transferred at the same time, and the transfer device (2900) can be moved linearly or in a circumferential direction.

Such a continuous production apparatus is performed, for example, as follows. The support is put into the support feeding container (2101), 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 (2901) dedicated to transportation is used to transfer to a vacuum support heating container (2201), and heating gas is supplied to the auxiliary valve (27).
It is made to flow from 02) so that it may become a predetermined pressure, and it heats to a predetermined temperature using the heater (not shown) installed in the container. The heated support is a vacuum container (29
01), and transferred into a vacuum reaction container (2301a-c). A deposited film is formed in the reaction container by a predetermined means, and then the film is transferred to a vacuum cooling and discharge container (2401) and cooled to a predetermined temperature, and then a leak gas is discharged from a leak valve (2705). Flow until atmospheric pressure, then discharge. Each vacuum container (2101, 2
201, 2301a to c, 2401) and the vacuum container (2901) dedicated to the transfer of the support, first, the transfer device (2900) moves to the vacuum container taken out and the gate (2807) takes out the vacuum container. Gate of (280
1 to 2806). After that, the space between the gates is evacuated by the exhaust means (2507) and the exhaust valve (2608). When the inside of the vacuum container (2901) does not have a predetermined degree of vacuum, the exhaust valve (2607) evacuates. When the degree of vacuum between the gates reaches a predetermined level, both gates are opened to transfer the support. After the delivery is completed, both gates are closed, and a leak gas (2706) between the gates is used to flow a leaking gas to bring the pressure between the gates to atmospheric pressure. After that, the gate (2807) of the vacuum container (2901) dedicated to the transfer is cut off, and the transfer device (290
0) moves to the next process. The transfer of the support is performed by using chucking (2951). 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 (5200), an opening / closing gate (5120), and an exhaust device (not shown) for reducing the pressure inside the reaction vessel (5111). Inside the reaction vessel (5111) in the deposition apparatus (5100), a cylindrical support (5112) and a heater for heating the support (511)
3), the raw material gas introduction pipe (5114) is installed, and the high frequency matching box (5115) is connected. The source gas supply device (5200) is made of SiH4, Ge.
H4, H2, CH4, B2H6, PH3, etc. source gas cylinders (5221 to 5226) and valves (5231 to 523)
6, 5241 to 5246, 5251 to 5256) and a mass flow controller (5211 to 5216), and a cylinder of each source gas is a gas introduction pipe (511) in a reaction vessel (5111) via a valve (5260).
4) is connected.

Formation of a deposited film using such a deposited film forming apparatus is performed, for example, as follows. First, a reaction container (51) evacuated to a vacuum by an evacuation unit (not shown).
11) a cylindrical support (51) heated to a predetermined temperature.
12) is charged through a gate (5120) for opening and closing by a vacuum container (not shown) exclusively for transportation, and the heater (5113) for heating the support controls the temperature of the cylindrical support (5112) to a predetermined temperature. . To flow the raw material gas for forming the deposited film into the reaction vessel (5111), make sure that the gas cylinder valves (5231 to 5236) and the leak valve (5123) of the reaction vessel are closed. (5241 to 5246), outflow valve (5251)
~ 5256), and confirm that the auxiliary valve (5260) is open, first open the main valve (5118) to the reaction vessel (5111) and the gas pipe (5116).
Exhaust. Next, the reading of the vacuum gauge (5124) is 5 × 10.
At the time of ^-6 Torr, the auxiliary valve (5260) and the outflow valve (5251 to 5256) are closed. Then, each gas is introduced from the gas cylinder (5221 to 5226) by opening the valve (5231 to 5236), and each gas pressure is adjusted to 2 kg / cm by the pressure regulator (5261 to 5266).
Adjust to ² . Next, inflow valves (5241-524)
6) is gradually opened to introduce each gas into the mass flow controller (5211 to 5216).

After the preparation for film formation is completed as described above, each layer is formed by the following procedure. Cylindrical support (5
When the temperature of (112) reaches a predetermined temperature, the outflow valve (5
251-5256) and the auxiliary valve (5260) are gradually opened to open the gas cylinder (5221-5).
A predetermined gas is introduced from 226) into the reaction vessel (5111) through the gas introduction pipe (5114). Next, the mass flow controllers (5211 to 5216) are adjusted so that each raw material gas has a predetermined flow rate. At that time, the opening of the main valve (5118) is adjusted while observing the vacuum gauge (5124) so that the pressure in the reaction vessel (5111) becomes a predetermined pressure of 1 Torr or less. When the internal pressure became stable, a high frequency power source (not shown) with a frequency of 13.56 MHz was set to the desired power, and high frequency power was introduced into the reaction vessel (5111) through the high frequency matching box (5115) to cause glow discharge. Let 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 support (5112). After forming the desired film thickness, stop the high frequency power supply,
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 multi-layered light-receiving layer can be formed. Needless to say, all the outflow valves other than the necessary gas were closed when forming each layer, and each gas was added to the reaction vessel (5111).
In order to avoid remaining in the pipe from the outflow valve (5251 to 5256) to the reaction vessel (5111), the outflow valve (5251 to 5256) is closed, the auxiliary valve (5260) is opened, and the main valve ( 511
If necessary, operation 8) is fully opened and the system is once evacuated to high vacuum. During this period, all is performed by automatic control.

In this way, when forming a deposited film having a large area such as an electrophotographic photosensitive member, 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 Laid-Open Patent Publication No. 60-26667, a cylindrical support is formed in a device having a rotation axis and forming a deposited film while rotating the cylindrical support by a technique of grounding the cylindrical support. When the body and the rotating shaft in an electrically conductive state are brought into close contact with each other, and mercury is interposed in the sliding portion to ground the discharge stability, the film thickness and when used as an electrophotographic photoreceptor A technique for improving the characteristic unevenness of is disclosed. According to Japanese Patent Laid-Open No. 80370/1992, in a device having a rotation shaft and forming a deposited film while rotating a cylindrical support, the cylindrical support and the rotation shaft are grounded to make circular line contact. At the same time, by having a rotation mechanism that has a degree of freedom that allows the cylindrical support to be vertically aligned by its own weight, a technique for suppressing uneven rotation, improving film thickness, and uniformity of film quality is disclosed. There is. Further, regarding an automatic device, see Japanese Patent Laid-Open No. 60-184.
The technology is disclosed in Japanese Patent No. 678.

[0009]

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, the above-mentioned conventional techniques have made it possible to make the film thickness and film quality uniform to some extent with respect to the above problems, but it is still insufficient to further improve the stability of production. In particular, as an issue to further improve the image quality of the amorphous silicon type photoreceptor,
Further, it is possible 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. To that end, it is necessary to establish the stability of the discharge in the reaction space. In particular, polysilane and film fragments generated in the reaction space during film formation accumulate on the grounding part of the substrate during transfer of the cylindrical support, and the effect of this is that the grounding state of the cylindrical support changes over time during continuous production. As a result, the discharge becomes unstable, and the film thickness and film quality change. Therefore, it is necessary to make the shape of the grounded portion of the cylindrical support member free from the influence of polysilane and film pieces, to stabilize the discharge in continuous production, and to stabilize the film thickness and film quality.

Therefore, in order to solve the above-mentioned problems in the conventional one, the present invention can stabilize the discharge in the reaction vessel and can constantly form a deposited film having a uniform film thickness and film quality. It is possible to improve the properties of the formed film, the film forming speed, and the reproducibility, and to improve the productivity of the film and the yield in the case of mass production. It is to supply a continuous production how.

[0011]

The present invention SUMMARY OF] In order to solve the above problems, production how light receiving members are those having the following structure. That is, the method for producing the light receiving member of the present invention includes a support charging container, a support heating container, a reaction container,
The support cooling and discharge containers are each formed by a vacuum container,
The transfer vacuum container is moved between the respective vacuum containers such as the support charging container, and the transfer vacuum container and the respective vacuum containers such as the support charging container are connected through an opening / closing gate, and the support is fixed. It has a support so that it can be moved in and out between the transfer vacuum container and each vacuum container such as the support input container.
Repeat the cycle of photo-receiving member fabrication and dry etching.
In the method of continuously producing a light receiving member by returning ,
The cylindrical support installed in the reaction container is grounded to the cylindrical support installation base in the reaction container or / and the rotating shaft through a grounding connection means for stabilizing discharge. have br /> is not Ru step, the ground connecting means, electroless nickel
-Phosphorus plating surface treatment has a thickness of 0.5 μm to 50 μm
It is characterized by being a metal leaf spring . Method for producing a light-receiving member or the present invention, the metal plate spring, characterized in that it is a precipitation hardening stainless steel. In the method for manufacturing a light receiving member of the present invention, the metal constant of the precipitation hardening stainless steel has a spring constant of 0.5 kg / mm to 5 kg.
It is characterized by being kg / mm.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention can achieve the above-mentioned object of the present invention by the above-mentioned constitution, which is due to the above-mentioned problems of the present inventors in the conventional method for forming a deposited film. The stability of the discharge, which was obtained by repeated studies to overcome the above-mentioned problems of the present invention, was confirmed by the cylindrical support, the installation base in an electrically conductive state, and the grounding state with the rotating shaft. It is based on the finding that it has a great relationship with. This point will be explained. Particularly, in the conventional device, continuous production is performed by simply bearing the support and ground-connecting the support with an installation base having a surface-bearing shape such that the lower surface of the support is electrically conductive. In this case, since the cylindrical support is moved in a vacuum by mechanical transfer, polysilane and film fragments generated during film formation are deposited on the cylindrical support grounding part after the cylindrical support is taken out. Go. Due to the influence, the grounding state of the cylindrical support to be charged next becomes gradually unstable, causing instability of the discharge, and as a result, the film thickness and the film quality change over time, and the characteristic It causes change. In view of the above, the present invention provides a means for effectively connecting the grounding of the cylindrical support body, in which the conductive metal is closely attached to the cylindrical support installation base and the inner surface of the cylindrical support body is made of a conductive metal. So that the ones you put in close contact,
By connecting to the ground, it is possible to stabilize the discharge, and as a result, even in a continuous production device, changes in the ground state over time are suppressed, and the quality and thickness of the deposited film are always made uniform. It makes it possible. Further, the metal leaf spring, which is the means for grounding connection, has a spring constant and a bending angle set in a specific range so as not to affect the transfer of the cylindrical support, and further, is corroded by fluorine or the like in dry etching. In order to prevent this and increase the durability, it is possible to further improve the effect of the continuous production apparatus by subjecting the metal leaf spring to a surface treatment. That is, by providing a metal leaf spring with a spring constant and a bending angle within a specific range and having a surface treatment for corrosion prevention, it is possible to more effectively ground the cylindrical support, the installation base, and the rotation axis. It has been found that the film quality and film thickness of the deposited light-receiving member can be eliminated and the productivity in continuous production can be dramatically improved.

The present invention has been completed based on these findings, and the details of the present invention will be described below with reference to the drawings. FIG. 4 is a sectional view schematically showing the arrangement of the cylindrical support and the installation base in the apparatus for manufacturing a light receiving member by the plasma CVD method of the present invention. In the figure, 5112 is a cylindrical support, 5113 is a heater for heating the support, 58
02 is a cylindrical reaction container that also serves as an electrode and a counter electrode,
Cylindrical support means an installation table in an electrically conductive state, 5801
Indicates metal leaf springs mounted on the installation table. Further, FIG. 5 is a cross-sectional view schematically showing the arrangement of the cylindrical support and the rotation shaft in the apparatus for manufacturing a light receiving member by the plasma CVD method having the rotation shaft of the present invention, which is 6112.
Is a cylindrical support body, 6113 is a heater for heating the support body, 6
Reference numeral 802 denotes a cylindrical reaction vessel which also serves as an electrode and a counter electrode, and a rotation shaft which is in an electrically conductive state with the cylindrical support, 68.
Reference numeral 01 denotes a metal leaf spring mounted on the rotation shaft.

In the conventional apparatus, the cylindrical support installation base and the rotation shaft are grounded so that they are only in contact with the support by the bearing, but in the case of the continuous production apparatus, the cylindrical support is provided. Is moved in a vacuum by mechanical transportation, and therefore polysilane and film fragments generated during film formation are deposited on the grounded portion of the cylindrical support after the cylindrical support is taken out. Due to the influence, the grounding state of the cylindrical support to be introduced next gradually becomes unstable and causes instability of discharge, and as a result, the film thickness and film quality change with time. There was a problem. In order to solve these problems, we expanded the grounding area between the support installation base and the support, and performed regular maintenance of the installation base, etc. The problem is still insufficient. The present invention comprises a support charging container, a support heating container, a reaction container, a support cooling and discharging container, and a transfer-dedicated vacuum container that can be moved between these containers. In the continuous production method in which the transfer container and the support can be moved in and out, the cylindrical support installed in the reaction container is replaced with a cylindrical support installation table in the reaction container. Or / and by providing a means for ground connection with the rotation axis, the ground connection state can be stabilized, that is, the discharge can be stabilized, and the quality and thickness of the deposited film that is always deposited can be made uniform. Will be planned. Further, as a means for ground connection, a precipitation-hardened stainless steel metal leaf spring having a spring constant of preferably 0.5 kg / mm to 5 kg / mm, and more preferably 1 kg / mm to 2 kg / mm is used for continuous production. It is possible to stabilize the ground connection without hindering the delivery of the support. Further, it is suitable for the present invention that the metal leaf spring is subjected to a surface treatment of electroless nickel-phosphorus plating having a thickness of preferably 0.5 to 50 μm, more preferably 2 to 15 μm. Although the number of metal springs is nine in FIG. 6, the number of metal springs is 3 to 12 so that it does not hinder the transfer of the support and can be effectively grounded. Suitable for Further, it is suitable for the present invention that the bending angle of the metal leaf spring (FIG. 5A) is in the range of 10 ° to 30 ° so that the support is not hindered from being delivered and the support is closely attached.

The support used in the present invention may be electrically conductive or electrically insulating. As the conductive support, Al 2, Cr, Mo, Au, In, Nb,
Examples thereof include metals such as Te, V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. Also,
Polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride,
It is also possible to use a support in which at least the surface of the electrically insulating support of the synthetic resin film or sheet of polystyrene, polyamide or the like, glass, ceramic or the like on which the light receiving layer is formed is subjected to a conductive treatment. The shape of the support used in the present invention may be a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface, and its thickness is
It is appropriately determined so that a desired electrophotographic photoreceptor can be formed, but when flexibility as an electrophotographic photoreceptor is required, it is possible within a range in which the function as a support can be sufficiently exhibited. It can be made as thin as possible. However,
The support is usually 10 μm or more in terms of manufacturing and handling, mechanical strength and the like. In particular, when performing image recording using coherent light such as laser light, unevenness is provided on the surface of the support in order to more effectively eliminate image defects due to so-called interference fringe patterns that appear in visible images. May be. The unevenness provided on the surface of the support is formed by a known method described in JP-A-60-168156, JP-A-60-178457, JP-A-60-225854 and 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 support is provided with a concavo-convex shape formed 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. To form a deposited film by the glow discharge method using the method of the present invention,
Basically, a source gas for supplying Si, which can supply silicon atoms (Si), and a source gas for supplying H, which can supply hydrogen atoms (H), and / or an X supply, which can supply halogen atoms (X). A raw material gas for use in the reaction vessel in a desired gas state to cause glow discharge in the reaction vessel, and a-Si: H on a predetermined support previously set at a predetermined position. , X may be formed.

The substances that can be used as the Si supply gas in the present invention include SiH4, Si2H6 and Si3H.
8, silicon hydrides (silanes) in a gas state such as Si4H10 or capable of being gasified are mentioned as being effectively used, and SiH4 is more advantageous in terms of ease of handling during layer formation and good Si supply efficiency. , Si2H6 are preferred. Then, structurally introducing hydrogen atoms into the deposited film 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 further mixing the gas with a desired amount of H2 and / or He or a silicon compound gas containing hydrogen atoms. 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 containing a halogen, a silane derivative substituted with a halogen 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.

Halogen compounds which can be preferably used in the present invention include fluorine gas (F2), BrF,
Interhalogen compounds such as ClF, ClF3, BrF3, BrF5, IF3 and IF7 can be mentioned. Specific examples of the silicon compound containing a halogen atom, that is, a silane derivative substituted with a halogen atom include, for example, SiF.
4, silicon fluorides such as Si2 F6 can be mentioned as preferable ones. Hydrogen atoms contained in the deposited film or /
And the amount of halogen atoms can be controlled, for example, by the temperature of the support, the amount of the raw material used to contain hydrogen atoms and / or halogen atoms introduced into the reaction vessel,
It suffices to control discharge power and the like. In the present invention, it is preferable that the deposited film contain atoms for controlling conductivity, if necessary. Atoms for controlling conductivity 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. .

Examples of the atoms for controlling the conductivity include so-called impurities in the semiconductor field,
Atoms belonging to Group IIIb of the periodic table giving p-type conductivity (hereinafter abbreviated as “Group IIIb atoms”) or atoms belonging to Group Vb of the periodic table giving n-type conductivity (hereinafter “Vb group atom”) Abbreviated) can be used. Specific examples of the group IIIb atom include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl), and B, Al, and Ga are particularly preferable. . Specific examples of the Group Vb atom include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and the like, with P and As being 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
It is desirable that the concentration be ˜1 × 10 ³ atomic ppm. To structurally introduce a conductivity controlling atom, for example, a Group IIIb atom or a Group Vb atom, a
The raw material for introducing the group IIIb atom or the raw material for introducing the group Vb atom may be introduced in a gas state into the reaction vessel together with another gas for forming the deposited film. No. II
As the raw material for introducing the group Ib atom or the raw material for introducing the group Vb atom, a gaseous material at room temperature and normal pressure or at least a gas which can be easily gasified under the layer forming condition is adopted. Is desirable. Specific examples of the raw material for introducing the group IIIb atom include B2H6, B4H10, B5H9, B5H11, and B6 for introducing the boron atom.
Boron hydride such as H10, B6H12, B6H14, BF3, BC
Examples thereof include boron halides such as 13 and BBr3. In addition, AlCl3, GaCl3, Ga (CH3) 3, InCl
3, TlCl3 and the like can also be mentioned.

Effectively used as a raw material for introducing a group Vb atom is PH3 or P2H for introducing a phosphorus atom.
Phosphorus hydride such as 4, PH4I, PF3, PF5, PCl3, P
Examples thereof include phosphorus halides such as Cl5, PBr3, PBr5 and PI3. In addition, AsH3, AsF3, AsCl3, A
sBr3, AsF5, SbH3, SbF3, SbF5, Sb
Cl3, SbCl5, BiH3, BiCl3, BiBr3 and the like can also be mentioned as effective starting materials for introducing a Group Vb atom. Further, these raw material substances for atom introduction for controlling the conductivity may be diluted with H2 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. It is necessary to determine the temperature appropriately. The flow rate of H2 and / or He used as a diluting gas is appropriately selected in accordance with the layer formation. However, H2 and / or He is used for the Si supply gas in the usual case of 1
-20 times, preferably 2 to 15 times, and optimally 4 to 10 times. Similarly, the gas pressure in the reaction vessel is appropriately selected according to the layer design, but in the usual case, it is 1 × 10 ^{−4 to} 10 Torr, preferably 5 × 10 ^{−4 to} 5 Torr, most preferably 1 × 10 ^{−. 3 ~1To}
It is preferably rr. Similarly, the discharge power is also appropriately selected according to the layer design, but the discharge power relative to the flow rate of the gas for supplying Si is usually 0.5 to
It is desirable to set in the range of 7 times, preferably 0.7 to 6 times, and optimally 1 to 5 times. Furthermore, the temperature of the support is
The optimum range is appropriately selected according to the layer design, but in the usual case, it is preferably 200 to 350 ° C. In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the support temperature and gas pressure for forming the deposited film, but these conditions are not usually independently determined separately, It is desirable to determine the optimum value based on the mutual and organic relationships so as to form the electrophotographic photoreceptor having the characteristics.

[0022]

EXAMPLES The following information on the onset bright, Reference Examples, Examples, is described in more detail with reference to comparative examples, the present invention is not intended to be limited to these. [ Reference Example 1] An Al holder (length 1000 mm) on which a mirror-finished Al cylinder (cylindrical support) having a length of 358 mm and an outer diameter of 108 mm is mounted is shown in FIGS. 1 and 2. In the continuous production apparatus, the reaction container having the configuration shown in FIG.
It was repeated 0 times and the change of the metal spring was observed. In this reference example , the material of the cylindrical support base made of aluminum is SUS63.
A metal leaf spring of No. 1 (precipitation hardening stainless steel) was attached and manufactured. The spring constant of the metal leaf spring is 1.537.
kg / mm, the bending angle was 25 °, and the number of springs was 5. The results are shown in Table 1. The evaluation method is as follows. Using a spring load tester, measure the height of the spring when a load of X (kg) is H1 (mm) and the height of the spring when a load of Y (kg) is H2 (mm). Then, the spring constant (kg / mm) = Y−X / H 2 −H 1 was calculated. Measurement was performed on 5 springs, and the calculated average value of the spring constants was −5 with respect to the average value of the spring constants before the execution.
% Within ◎, -10% within ○, -10%
The evaluation was carried out in a three-stage evaluation with a value exceeding Δ as Δ.

(Comparative Example 1) Except that the material of the metal spring attached to the cylindrical support installation base is (1) SUS304 (austenitic stainless steel), (2) SUS420J2 (martensitic stainless steel). It is carried out under the same conditions as in reference example 1, was evaluated by the same means as in reference example 1. The results of these evaluations are shown in Table 1 together with Reference Example 1. From Table 1 results, in Comparative Example 1, as both becomes large delivery times, whereas the spring constant has been changing, ginseng
In Consideration 1, no change in spring constant is observed. The SUS631 (precipitation hardened stainless steel) used by the manufacturing method of the present invention has a stable spring connection with no change in the spring constant over time in continuous production as compared with other materials. The results were obtained.

[0024]

[Table 1] [ Reference Example 2] An Al holder (1000 mm in length) on which a mirror-finished Al cylinder (cylindrical support) having a length of 358 mm and an outer diameter of 108 mm is mounted is shown in FIGS. 1 and 2. In a continuous production apparatus, the reaction container having the configuration shown in FIG.
The measurement was repeated 0 times to check the change of the metal spring constant and the scratched state on the inner surface of the support. In this reference example , a cylindrical support base made of aluminum is made of SUS631 (precipitation hardening type stainless steel) with a bending angle of 25 ° and a metal plate spring having a number of springs of 5 and a spring constant of 0.2 kg /. The value varied from mm to 7 kg / mm.

Comparative Example 2 In Comparative Example 2 shown in Table 2, the metal spring was not attached to the cylindrical support base, and the other conditions were the same as those of Reference Example 2. The results are shown in Table 2 together with Reference Example 2. The evaluation method is as follows. "Change in metal spring constant" Evaluation was performed by the same means as in Reference Example 1. "Scratches on the inner surface of the support" The depth of the scratches on the inner surface of the support was measured using a surface shape measuring instrument. A scratch within 0.05 mm was marked with ◎, a scratch within 0.1 mm was marked with ○, and 0.1 mm was marked. The scratches to be crossed were evaluated as Δ and evaluated in three levels. As a comprehensive evaluation, ◎ if the spring constant does not change and the support is not damaged, ◎, if the spring constant is slightly changed or the support is slightly damaged, ○, the spring constant is large The change, which was considerably scratched on the support, was judged as Δ. From the results of Table 2, the metal spring constant is 0.5k.
If it is less than g / mm, the inner surface of the support is not damaged, but the spring constant changes as the number of times of delivery increases. If the spring constant exceeds 5 kg / mm, the inner surface of the support will be damaged. Therefore, the spring constant of the metal leaf spring is preferably 0.5 kg / mm to 5.0 kg / mm.
, And more preferably 1.0 kg / mm to 2.0 kg /
It was found to be good in the mm range.

[0026]

[Table 2] [ Reference Example 3] An Al holder (length 1000 mm) on which a mirror-finished Al cylinder (cylindrical support) having a length of 358 mm and an outer diameter of 108 mm is mounted is shown in FIGS. 1 and 2. Continuous production apparatus, using the reaction vessel of the configuration shown in FIG.
Structure An electrophotographic photosensitive member comprising a charge injection blocking layer, a photoconductive layer and a surface layer is formed on the support under the manufacturing conditions shown in Table 3-1, and then a dummy substrate is charged under the conditions shown in Table 3-2. After that, dry etching was performed. A dummy base is provided between the reaction container and the cooling and discharging container (not shown) of the production apparatus of FIG. 1 , and is automatically transferred to each reaction container from there by a vacuum container dedicated to transportation. Is to do. With this as one cycle, a total of 30 cycles of electrophotographic photosensitive member were produced. In this reference example , a metal leaf spring made of SUS631 (precipitation hardening stainless steel) was attached to a cylindrical support base made of aluminum to fabricate it. The spring constant of the metal leaf spring is 1.537 kg / m.
The bending angle was 25 °, and the number of springs was 5.

[0027]

[Table 3-1]

[0028]

[Table 3-2] The film thickness of the produced electrophotographic photosensitive member was evaluated with respect to time, and the support installation table was stained (the deposition state of polysilane or the like). The results are shown in Table 4. The evaluation method is as follows. "Change in film thickness with time" Using an eddy current film thickness meter (Ket Science Institute: Permascope E111 type), a total of 40 in the longitudinal direction of the electrophotographic photosensitive member and in the circumferential direction of 8 positions.
The locations were measured, and the average film thickness was -3% or less of the average film thickness of the first cycle, ◯ was -5% or less, and Δ was -5% or more. The evaluation was performed according to the following three-stage evaluation. "Dirt on the support base" After dry etching, after discharging the dummy, place a glass plate on the gate of the reaction vessel, apply a vacuum between the gate and the glass plate, open the gate, and visually check the dirt on the support base. confirmed. The evaluation standard is ◎ that there is absolutely no stain (no deposit of polysilane, etc. on the receiving surface), and slightly (somewhat polysilane is deposited on the receiving surface, but the aluminum surface of the installation table is visible) ) ○,
Significant things (polysilane etc. are deposited on the receiving surface and the aluminum surface of the installation base is hardly visible) are marked with △, and (aluminum surface of the mounting base is completely invisible because the polysilane, etc. are deposited on the receiving surface) Sensory judgment was made by visual observation in four stages.

(Comparative Example 3) An electrophotographic photosensitive member was produced under the same conditions as in Reference Example 3 except that a metal spring was not attached to the cylindrical support base. The produced electrophotographic photosensitive member was evaluated by the same means as in Reference Example 3. The results of these evaluations are shown in Table 4 together with Reference Example 3. From the results of Table 4, in Comparative Example 3, the film thickness changes as the dirt of the installation table progresses, whereas in Reference Example 3 , the dirt of the installation table progresses in the Comparative Example.
It is equivalent to 3 , but no change in film thickness is observed. The electrophotographic photosensitive member manufactured by the manufacturing method of the present invention showed good results with no change in film thickness over time in continuous production, as compared with the electrophotographic photosensitive member manufactured by the conventional manufacturing method.

[0030]

[Table 4] [Example 1 ] An Al cylinder (length 1000 mm) on which a mirror-finished Al cylinder (cylindrical support) having a length of 358 mm and an outer diameter of 108 mm was placed was used and shown in FIGS. 1 and 2. Using a continuous production apparatus and a reaction vessel having the structure shown in FIG. 4, an electrophotographic photosensitive member including a charge injection blocking layer, a photoconductive layer and a surface layer is formed on the support by the manufacturing conditions shown in Table 3-1. Then, after the dummy substrate was introduced under the conditions shown in Table 3-2, dry etching was performed. A dummy base is provided between the reaction container and the cooling and discharging container (not shown) of the production apparatus of FIG. 1 , and is automatically transferred to each reaction container from there by a vacuum container dedicated to transportation. Is to do. This is one cycle and a total of 10
A zero-cycle electrophotographic photosensitive member was produced. In this embodiment,
Material is SUS631 for aluminum cylindrical support stand
A metal leaf spring (precipitation hardened stainless steel) was attached and manufactured. The spring constant of the metal leaf spring is 1.537k.
The surface treatment of the electroless nickel-phosphorus plating was changed between 0.2 μm and 70 μm using g / mm, the bending angle was 25 °, and the number of springs was 5. The temporal change of the film thickness of the produced electrophotographic photosensitive member and the corrosion state of the metal leaf spring were evaluated. The results are shown in Table 5. The evaluation method is as follows. “Change in film thickness over time” The same evaluation as in Reference Example 3 was performed. "Corrosion of metal leaf spring" After completion of dry etching, the dummy was discharged and the reaction vessel was returned to the atmosphere, and the corrosion of the metal leaf spring was visually confirmed. As the evaluation criteria, a sensory judgment was made by three-step visual inspection, in which no corrosion was ◎, slightly corroded (slightly discolored) was ○, and considerably corroded was △. .

Comparative Example 4 An electrophotographic photosensitive member was prepared under the same conditions as in Reference Example 3.
The produced electrophotographic photosensitive member was evaluated by the same means as in Example 1 . The results of these evaluations are shown in Table 5 together with Example 1 . From the results of Table 5, electroless nickel was added to the metal leaf spring.
Good results were obtained against corrosion by the surface treatment of phosphorus plating. The thickness of the surface treatment of electroless nickel-phosphorus plating is preferably 0.5 μm to 50 μm,
It was found that the range is more preferably 2 μm to 15 μm.

[0032]

[Table 5] [Example 2 ] An Al holder (length 1000 mm) on which a mirror-finished Al cylinder (cylindrical support) having a length of 358 mm and an outer diameter of 108 mm was placed was used and shown in FIGS. 1 and 2. Continuous production apparatus, using the reaction vessel of the configuration shown in FIG.
Structure An electrophotographic photosensitive member comprising a charge injection blocking layer, a photoconductive layer and a surface layer is formed on the support under the manufacturing conditions shown in Table 3-1, and then a dummy substrate is charged under the conditions shown in Table 3-2. After that, dry etching was performed. A dummy base is provided between the reaction container and the cooling and discharging container (not shown) of the production apparatus of FIG. 1 , and is automatically transferred to each reaction container from there by a vacuum container dedicated to transportation. Is to do. With this as one cycle, a total of 500 cycles of electrophotographic photosensitive member were produced. In this example, a metal leaf spring made of SUS631 (precipitation hardening stainless steel) was attached to a cylindrical support base made of aluminum to fabricate it. The spring constant of the metal leaf spring is 1.537 kg / m.
m, the bending angle was 25 °, the number of springs was 5, and the surface treatment of electroless nickel-phosphorus plating was 5 μm. The film thickness of the produced electrophotographic photosensitive member was evaluated with respect to time, the corrosion state of the metal leaf spring, and the stain on the cylindrical support installation table.
The results are shown in Table 6. The evaluation method is as follows. "Change in film thickness over time" The same evaluation as in Reference Example 3 was performed. "Dirt of installation table" The evaluation was performed in the same manner as in Reference Example 3. "Corrosion state of metal leaf spring" The same evaluation as in Example 2 was performed. The electrophotographic photosensitive member manufactured by the manufacturing method of the present invention showed good results with no change in film thickness over time even in continuous production.

[0033]

[Table 6] [Example 3 ] Using the apparatus described in Example 2 , 500 cycles of an electrophotographic photosensitive member including a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer were manufactured under the manufacturing conditions shown in Table 7. Example 2
When the same evaluation as in Example 2 was performed, good results were obtained as in Example 2 .

[0034]

[Table 7] [Example 4 ] Using the apparatus described in Example 2 , 500 cycles of an electrophotographic photosensitive member including a charge injection blocking layer, a charge transport layer, a charge generation layer, an intermediate layer and a surface layer was prepared under the production conditions shown in Table 8. Made,
When the same evaluation as in Example 2 was performed, good results were obtained as in Example 2 .

[0035]

[Table 8] Example 5 Using an Al holder (length 650 mm) on which a mirror-finished Al cylinder (cylindrical support) having a length of 358 mm and an outer diameter φ108 mm is mounted, the autorotation shown in FIGS. 1 and 3 is performed. Using a continuous production apparatus having a shaft and a reaction vessel having the configuration shown in FIG. 5, a photoreceptive layer including a charge injection blocking layer, a photoconductive layer and a surface layer was produced on the support under the production conditions shown in Table 8. When the same evaluation as in Example 2 was performed,
Good results were obtained as in 2 .

[0036]

As described above, according to the present invention, the cylindrical support provided in the reaction vessel is connected to the cylindrical support in the reaction vessel through the ground connection means for stabilizing the discharge. installation base, and / or by the ground connected to the rotation axis, it is possible to stabilize the discharge of the light-receiving continuous production side in <br/> Ru reaction vessel put on methods of members by the plasma CVD method,
In particular, prevents corrosion due to fluorine during dry etching
To improve the effect of continuous production equipment
Therefore, it is possible to constantly form a deposited film having a uniform film thickness and film quality, improve the physical properties of the formed film, the film formation speed, and the reproducibility, and improve the productivity of the film. It is possible to dramatically improve the yield in the case of production and mass production.

[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 plasma CV used in Reference Examples and Examples of the present invention.
FIG. 5 is a schematic explanatory view showing a cylindrical reaction container that also serves as an electrode, a counter electrode including a cylindrical support, a gas introduction branch pipe, and the like in a deposited film forming apparatus by the D method.

FIG. 3 is a plasma CV used in Reference Examples and Examples of the present invention.
FIG. 5 is a schematic explanatory view showing a cylindrical reaction container that also serves as an electrode, a counter electrode including a cylindrical support, a gas introduction branch pipe, and the like in a deposited film forming apparatus by the D method.

FIG. 4 shows a light receiving member manufactured by the plasma CVD method of the present invention.
It is sectional drawing which shows typically the arrangement of a cylindrical support body, an installation stand, and a metal leaf spring in a manufacturing method .

FIG. 5 shows a light receiving member produced by the plasma CVD method of the present invention.
It is sectional drawing which shows typically the cylindrical support body, the rotating shaft, and arrangement | positioning of a metal leaf spring in a manufacturing method .

FIG. 6 is a sectional view schematically showing a metal leaf spring of the present invention.

[Explanation of symbols]

2100/2101: Support charging device / support charging container 2200/2201: Support heating device / support heating container 2300 / 2301a-c: Reactor / reaction container 2400/2401: Cooling and discharging device / Cooling and discharging container 2501-2507: Exhaust means (vacuum pump) 2601-2608: Exhaust valves 2701, 2705, 2706: Leak valve 2702: Heating gas auxiliary valves 2703a-c, 2704: Gas outflow valves 2801-2807: Open / close gate 2900/2901: Transport device / dedicated transport vacuum container 2951: Transport chucking 2952: Transport transfer rails 5100, 6100: Deposition devices 5111, 6111: Reaction vessels 5112, 6112: Cylindrical supports 5113, 6113: Heating heater 5114: Raw material gas Introductory pipe 5115 , 6115: Matching box 5116: Raw material gas pipe 5117: Reaction vessel leak valve 5118: Main exhaust valve 5119: Vacuum gauge 5200: Raw material gas supply devices 5211-5216: Mass flow controllers 5221-5226: Raw material gas cylinders 5231-5236: Raw material gas cylinder valves 5241-5246: Gas inflow valves 5251-5256: Gas outflow valves 5261-5266: Pressure regulators 5801/6801: Metal leaf springs 5802/6802: Cylindrical support installation base 6115: Electrodes 6120: Support rotation motor 6121: Exhaust pipe 6130: discharge space

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-329883 (JP, A) JP-A-62-54913 (JP, A) Fukuihei 7-10934 (JP, U) (58) Survey Field (Int.Cl. ⁷ , DB name) H01L 21/205 C23C 16/50

Claims (3)

(57) [Claims] 1. A support charging container, a support heating container, a reaction container, a support cooling and discharging container are each formed of a vacuum container, and a transporting vacuum container is moved between the respective vacuum containers such as the support charging container. Then, the transfer vacuum container and each vacuum container such as the support charging container are connected through an opening / closing gate, and a support is provided between the transfer vacuum container and each vacuum container such as the support charging container. The support can be moved in and out.
Of photo-receptive member with and cycle of dry etching
In the method for continuously producing a light-receiving member by repeating the above procedure, the cylindrical support provided in the reaction vessel is connected to the inside of the reaction vessel via a ground connecting means for stabilizing discharge. cylindrical support mount base, and / or the rotation axis and a step of Ru is a ground connection, the ground connecting means, electroless two
The surface treatment of nickel-phosphorus plating is 0.5μm-50μm
A method of manufacturing a light receiving member, which is a metal leaf spring having a thickness of 1 . 2. The method for manufacturing a light receiving member according to claim 1 , wherein the metal leaf spring is precipitation hardening stainless steel. 3. The method for producing a light receiving member according to claim 2 , wherein the spring constant of the metal leaf spring of precipitation hardening stainless steel is 0.5 kg / mm to 5 kg / mm.