JPH08179536A - Electrophotographic photoreceptor and its manufacture - Google Patents

Abstract

PURPOSE: To provide the manufacturing method of the electrophotographic photoreceptor capable of forming a high-quality image superior in electric characteristics. CONSTITUTION: The electrophotographic photoreceptor provided on a conductive substrate with at least a charge injection hindrance layer made of an amorphous material composed essentially of silicon atoms and a photoconductive layer is manufactured by changing, at the time of forming the photoconductive layer, the feed of a gaseous material for forming the silicon atoms in a rate of 0.29-12 sccm/sec and the feed of a diluting gas in a rate of 2.2-73sccm/sec, a discharge power of 0.7-27W, and an inside pressure of 0.33-13μTorr.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to light sensitive to electromagnetic waves such as light (light in a broad sense, which means ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.). The present invention relates to a method for continuously and stably producing a receiving member and an electrophotographic photosensitive member.

[0002]

2. Description of the Related Art As a material for forming a photoconductive layer in a solid-state image pickup device, an electrophotographic light-receiving member in the field of image formation, or a document reading device, the SN ratio [photocurrent (Ip) / (Id)] is high. Of high absorption rate, having absorption spectrum characteristics matched with the spectrum characteristics of electromagnetic waves to be radiated, having fast photoresponsiveness and having a desired dark resistance value, being harmless to the human body when in use, and further solid-state imaging device In the case of (1), characteristics such as that afterimages can be easily processed within a predetermined time are required. Particularly in the case of the electrophotographic light-receiving member used in an office as an office machine, the above-mentioned pollution-free property at the time of use is an important point.

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

Conventionally, as a forming method for forming a light-receiving member made of a-Si on a cylindrical support, a sputtering method, a method of decomposing a raw material gas by heat (thermal CVD
Method), a method of dispersing a raw material gas by light (optical CVD
Method), a method of decomposing a raw material gas with plasma (plasma CVD method), and the like. Among them, the plasma CVD method, that is, the method of decomposing a raw material gas by direct current or high frequency, microwave glow discharge, etc. to form a deposited film on a cylindrical support is currently in practice, such as the method of forming a photoreceptive member for electrophotography. It is very advanced.

FIG. 4 is a schematic sectional view of a typical plasma CVD apparatus. In the figure, 5100 shows the entire vacuum reaction vessel, 5111 is a cathode electrode which also serves as a side wall of the vacuum reaction vessel, 5120 is a gate which is an upper wall of the vacuum reaction vessel, and 5121 is a bottom wall of the vacuum reactor. The cathode electrode 5111 and the top wall 5120 and the bottom wall 5121 are
Each is insulated by an insulator 5122.

Reference numeral 5112 is a support installed in the vacuum reaction vessel, and the base 5112 is grounded to serve as an anode electrode. A heater 5113 for heating the substrate is installed in the support 5112 to heat the support to a predetermined temperature before film formation, maintain the temperature of the support at a predetermined temperature during film formation, or It is used for annealing the support after film formation.

Reference numeral 5114 is a source gas introducing pipe for forming a deposited film, which is provided with a large number of gas release holes (not shown) for releasing the source gas in the vacuum reaction space. The other end of 5114 communicates with a deposited film forming source gas supply system 5200 via a valve 5260.

Reference numeral 5119 is an exhaust pipe for evacuating the inside of the vacuum reaction container, which communicates with a vacuum exhaust device 5117 via an exhaust valve 5118. Reference numeral 5115 is a voltage applying means to the cathode electrode 5111.

The operating method of the deposited film forming apparatus by the plasma CVD method is performed as follows. That is,
The gas in the vacuum reaction container is evacuated through the exhaust pipe 5119, and the heater 5113 for heating heats and holds the support 5112 at a predetermined temperature. Next, starting gas introduction from the raw material gas introduction pipe 5114, for example, when forming an a-SiH deposited film, a raw material gas such as silane is introduced into the vacuum reaction vessel, and the raw material gas The raw material gas is discharged into the vacuum reaction container through a hole (not shown). Simultaneously with this, a high frequency, for example, is applied between the cathode electrode 5111 and the support (anode electrode) 5112 from the voltage application means 5115 to generate plasma discharge. Thus, the raw material gas in the vacuum reaction vessel is excited and excited to generate seeds, and radical particles such as Si ^* , SiH ^*, etc. ( ^* represents an excited state), electrons, ionic particles, etc. are generated, and these particles or These particles and support 51
The chemical interaction with the 12 surface forms a deposited film on the surface of the support 5112.

As a method of manufacturing such a deposited film, a method of changing the conditions during formation of the deposited film is being studied.

For example, Japanese Patent Application Laid-Open No. 58-21257 discloses a technique for changing the temperature of the support during the formation of the photoconductive layer to change the band gap, thereby producing a photoconductor having a wide photosensitivity region. Is disclosed.

Further, Japanese Patent Laid-Open No. 58-136037,
JP-A-58-142582, JP-A-61-116
Japanese Patent No. 361 discloses a technique in which the hydrogen content of the photoconductive layer is changed depending on the temperature of the support, the hydrogen partial pressure, and the discharge power, so that the chargeability sensitivity is excellent and the occurrence of pinholes is reduced.

[0013]

With such a conventional method for forming a light receiving member, it has become possible to obtain a light receiving member having practical properties and uniformity to some extent. Further, if the inside of the vacuum reaction vessel is rigorously cleaned, it is possible to obtain a light-receiving member with few defects. However, in these conventional methods of forming a light-receiving member, a product having a large area and a relatively thick deposited film, such as a light-receiving member for electrophotography, has a uniform film quality and various optical and electrical characteristics. There is still a problem to be solved in which it is difficult to obtain a deposited film which satisfies the above requirement and has few image defects at the time of image formation by an electrophotographic process with high yield.

Further, at present, the electrophotographic apparatus is required to have higher image quality, higher speed and higher durability. As a result, in the electrophotographic light-receiving member, while further improving the optical characteristics and electrical characteristics, while maintaining high charging ability and high sensitivity,
It is required to extend durability under all environments.

Further, in recent years, in order to improve the image characteristics of the electrophotographic apparatus, the optical exposure system, the developing apparatus, the transfer apparatus and the like in the electrophotographic apparatus have been improved. The above-mentioned improvement in image characteristics has been demanded. In particular, as a result of improving the resolution of images, reduction of white spot or black spot image defects commonly known as “potches”, especially the reduction of microscopic “potches” which has not been a problem in the past, is required. It has become possible to be.

Furthermore, it corresponds to the speeding up of the electrophotographic apparatus,
There is also a demand for speeding up the copying process.

Therefore, the afterimage that occurs when the light receiving member is repeatedly used, that is, a so-called "ghost" phenomenon is not always a pain in a conventional speed copying system and can be neglected in some cases. High-speed continuous image forming systems such as high-speed copying systems, facsimile systems, printer systems, etc. that use coherent light sources, especially digital high-speed continuous image systems, and full-color image systems that have become popular in recent years, Therefore, it is a serious problem, and it is the one that needs to be solved.

Therefore, while improving the characteristics of the light-receiving member itself, a comprehensive viewpoint such as the layer structure of the light-receiving member, the chemical composition of each layer, and the preparation method is provided so that the above problems can be solved. It is necessary to improve from. [Object of the Invention] An object of the present invention is to overcome the various problems in the conventional method for manufacturing an electrophotographic photosensitive member as described above, to enable inexpensive, stable, high-yield formation at high speed, and an easy-to-use light-receiving member and electron. Another object of the present invention is to provide a method for manufacturing a photographic photoreceptor.

[0019]

The electrophotographic photosensitive member manufacturing method of the present invention uses at least a raw material gas for supplying silicon and a diluting gas capable of supplying silicon atoms, and a conductive support is formed by a plasma CVD method. In the method of manufacturing an electrophotographic photosensitive member having a photoconductive layer made of an amorphous material having at least silicon atoms as a base material, discharge power is 0.7 W / sec or more and 27 W from the initial stage when the photoconductive layer is formed.
/ Sec or less, internal pressure 0.33 Torr / sec or more,
13 Torr / sec or less, 0.29 sccm / source gas for supplying silicon capable of supplying silicon atoms
The method for producing an electrophotographic photosensitive member is characterized in that the dilution gas is changed at sec or more and 12 sccm / sec or less and the dilution gas is changed at 2.2 sccm / sec or more and 73 sccm / sec or less.

In the method of manufacturing the light receiving member under better conditions, the discharge power is 0.8 W / sec or more and 13.5 W / sec or less and the internal pressure is 0.38 mm Torr / from the initial stage when the photoconductive layer is formed. sec or more, 4.4 mm
Torr or less, and a source gas for supplying silicon capable of supplying silicon atoms is 0.4 sccm / sec or more, 4
sccm / sec or less, diluent gas 2.5 sccm / s
It is characterized in that it is changed in a range of ec or more and 29 sccm / sec or less.

Here, the discharge power when the photoconductive layer is formed,
The region for changing the internal pressure, the raw material gas for supplying silicon capable of supplying silicon atoms, and the diluting gas may be 0.12% or more and 1.0% or less of the total production of the photoconductive layer.

The source gas for supplying silicon, which can supply the silicon atoms, may be SiH ₄ gas and / or SiF ₄ .

Further, the diluent gas may be H ₂ and / or He gas.

A charge injection blocking layer may be provided between the photoconductive layer and the conductive support.

A surface layer may be provided on the photoconductive layer.

The layer thickness on the photoconductive layer is 25 to 4
It may be 0 μm.

The layer thickness of the charge injection blocking layer may be 1 to 4 μm.

The thickness of the surface layer is 0.1 to 1 μm.
m may be sufficient.

[0029]

The method for producing an electrophotographic photosensitive member of the present invention uses at least a raw material gas for supplying silicon capable of supplying silicon atoms and a diluent gas, and at least silicon atoms are provided on a conductive support by a plasma CVD method. In the method for producing an electrophotographic photosensitive member having a photoconductive layer made of an amorphous material, the discharge power of which is 0.7 W / sec or more and 27 W / sec or less from the initial stage when the photoconductive layer is formed. Is 0.33 Torr / sec or more, 13 Torr / se
c or less, 0.29 sccm / sec or more, and 12 s for the raw material gas for supplying silicon capable of supplying silicon atoms
ccm / sec or less, dilution gas 2.2 sccm / se
By changing the speed from c to 73 sccm / sec to form a deposited film, electrophotographic characteristics such as ghost or residual potential are improved, and white dot or black dot images commonly known as "potty" Defects are greatly reduced.

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

When used in an electrophotographic photoreceptor, the photoconductive layer must have high sensitivity, high SN ratio [photocurrent (Ip) / (Id)], fast photoresponsiveness, and a desired dark resistance value. There is. However, in the band gap of a-Si: H, S
Tail level based on structural disorder of i-Si bond, and S
There are deep levels resulting from structural defects such as dangling bonds of i. When there are many such levels, the functions required for the photoconductive layer cannot be sufficiently exhibited. In order to reduce such so-called defects in the film, hydrogen atoms and / or halogen atoms may be contained to compensate for dangling bonds of silicon atoms and improve photoconductivity and charge retention characteristics. However, as in the case of an electrophotographic photoreceptor, a relatively large film thickness is required, and when a film having such a film thickness is formed in a large area, the stress in the film becomes large, and as a result, the light Conductive properties,
It is considered that the charge retention property is deteriorated. Particularly, in the initial region of the photoconductive layer, not only the internal stress of the photoconductive layer itself, but also the material of the surface to be deposited or the difference in structural characteristics, stress is more likely to occur in the deposited film. For example, when it is directly deposited on an aluminum or stainless steel support, it is distorted due to the difference in material and the difference in thermal expansion coefficient between the support and s-Si. Further, even when it is deposited on the charge injection blocking layer having a-Si as a base material, it may be affected by the difference in the composition, the structural difference due to the difference in the contained substance, or the difference in the characteristic such as the direction and size of the stress. Stress is generated in the conductive layer.

When, for example, an amorphous silicon deposited film is formed on the support by the plasma CVD method, the reaction includes the decomposition process of the source gas in the vapor phase, the transport process of the active species from the discharge space to the substrate surface, The surface reaction process on the surface of the support can be divided into three parts. this house,
The parameters for controlling the decomposition process and the transportation process include the flow rate of the raw material gas, the discharge power, and the internal pressure. Therefore, the properties of the deposited film can be controlled by controlling these parameters.

As in the present invention, from the initial stage of the formation of the photoconductive layer, the discharge power, the internal pressure, the silicon-supplying raw material gas capable of supplying silicon atoms, and the diluting gas are changed to predetermined values to form in this region. The deposited film absorbs the strain caused by the difference in the structural characteristics between the surface on which the deposited film is deposited and the deposited film, and thus the stress in the deposited film formed in this region is significantly relieved, and the light formed thereafter is absorbed. It is considered that the internal stress of the conductive layer also has a function of relaxing. As a result, it is considered that the ghost is improved by improving the charge running property, reducing the residual potential, and improving the film quality.

Further, according to the present invention, white spot-like or black spot-like image defects commonly referred to as "potty" can be reduced, and the increase of "potty" due to long-term use can be reduced. “Pochi” is mainly caused by spherical projections in which the deposited film abnormally grows due to dust such as dust, dust, or metal pieces attached to the surface of the support. In particular, when the spherical protrusion is missing, an image defect is always generated regardless of the size of the spherical protrusion. According to the manufacturing method of the present invention, the adhesion between the photoconductive layer and the surface on which the photoconductive layer is deposited is improved, and the stress in the deposited film is relieved, so that the loss of spherical projections is greatly reduced. As a result, the image characteristics are significantly improved. This effect is particularly remarkable in preventing deterioration of image characteristics during repeated use. The surface of the electrophotographic photosensitive member rubs against the transfer paper or the cleaning blade every time it is repeatedly used. Therefore, the spherical protrusions are easily lost. Since the adhesion of the deposited film is improved and the stress in the deposited film is alleviated by the manufacturing method of the present invention, the lack of spherical projections is greatly reduced even with respect to rubbing, and "potty" after long-term use Can be reduced. [Detailed Description of the Invention] The method for forming the light receiving member of the present invention will be described in detail below with reference to the drawings.

The manufacturing method of the present invention is performed by a vacuum deposition film forming method. Specifically, for example, a glow discharge method (low frequency CVD method, high frequency CVD method or microwave C
AC discharge CVD method such as VD method, or DC discharge CVD method
Method), a sputtering method, a vacuum deposition method, an ion plating method, a photo CVD method, a thermal CVD method, and various thin film deposition methods. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be prepared. Since it is relatively easy to control the conditions for manufacturing a photoreceptive member having characteristics, a glow discharge method including a high frequency plasma CVD method, particularly a high frequency glow using a power supply frequency in the RF band or VHF band. The discharge method is preferred.

The apparatus and method for forming the deposited film by the high frequency plasma CVD method will be described in detail below.

FIG. 4 shows high frequency plasma CVD (hereinafter referred to as "RF
It is a typical block diagram which shows an example of the manufacturing apparatus of the electrophotographic photosensitive member by the method (it describes with -PCVD).

The structure of the apparatus for producing a deposited film by the RF-PCVD method shown in FIG. 4 is as follows. This apparatus is roughly classified into a deposition apparatus 5110 and a source gas supply apparatus 520.
0, an exhaust device 5 for reducing the pressure inside the reaction vessel 5111
It is composed of 117. Inside the reaction vessel 5111 in the deposition apparatus 5100, a conductive cylindrical support 5112, a heater 5113 for heating the support, and a source gas introduction pipe 5114.
Is installed, and a high frequency matching box 5115 is further connected.

The source gas supply device 5200 is made of SiH ₄ ,
Cylinders 5221 to 5226 for raw material gases such as H ₂ , CH ₄ , NO, B ₂ H ₆ , and GeH ₄ and valves 5231 to 523
6, 5241 to 5246, 5251 to 5256 and mass flow controllers 5211 to 5216, and each source gas cylinder is connected to a gas introduction pipe 5114 in the reaction vessel 5111 via a valve 5260.

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

First, the cathode electrode 5111 in the reaction vessel
A cylindrical support 5112 is installed inside, and an exhaust device 511 is installed.
7. The inside of the reaction vessel is evacuated by, for example, a vacuum pump.

Subsequently, the heater 5113 for heating the support is turned on, and the temperature of the cylindrical support 5112 is set to 250 ° C. to 50 ° C.
Control to a predetermined temperature of 0 ° C.

In order to flow the raw material gas for forming the deposited film into the reaction vessel, valves 5231 to 523 of the gas cylinder are used.
6. Confirm that the leak valve 5123 of the reaction container is closed, and check the inflow valves 5251 to 5256,
Make sure that the outflow valves 5241 to 5246 and the auxiliary valve 5260 are opened, and first check the main valve 511.
8 is opened, and the inside of the reaction vessel and the inside of the gas pipe 5116 are exhausted.

Next, the reading of the vacuum gauge 5124 is about 5 × 10 ^-6
When it becomes Torr, the auxiliary valve 5260 and the outflow valves 5251 to 5256 are closed.

Then, each gas is introduced from the gas cylinders 5221 to 5226 by opening the valves 5231 to 5236,
Each gas pressure (for example, 2 kg / cm ² ) is adjusted by the pressure adjusters 5261 to 5266. Next, the inflow valve 524
1 to 5246 are gradually opened, and each gas is introduced into the mass flow controllers 5211 to 5216.

After the preparation for film formation is completed as described above, a charge injection blocking layer, for example, a charge injection blocking layer, is formed on the cylindrical support 5112.
Each layer such as a photoconductive layer and a surface layer is formed.

When the cylindrical support 5112 reaches a predetermined temperature, the necessary ones of the outflow valves 5251 to 5256 and the auxiliary valve 5260 are gradually opened, and a predetermined gas is supplied from the gas cylinders 5221 to 5226 to the gas introduction pipe 5.
It is introduced into the reaction vessel via 114. 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 container becomes a predetermined pressure of 1 Torr or less. When the internal pressure of the reaction vessel became stable, an RF power source (not shown) was set to a desired power, and the RF power was introduced to the cathode electrode 5111 in the reaction vessel through the high frequency matching box 5115, and between the cylindrical supports 5112. Generate an RF glow discharge. The source energy introduced into the reaction vessel is decomposed by this discharge energy, and a predetermined deposited film containing silicon as a main component is formed on the cylindrical support 5112. After the desired film thickness is formed, the supply of RF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, an electrophotographic photosensitive member having a multilayer structure is formed on the cylindrical support 5112.

FIG. 3 is a schematic explanatory view showing changes in each parameter during formation of a deposited film in the manufacturing method of the present invention. At the same time as the introduction of RF power, the photoconductive layer is
The mass flow controller and the exhaust device are adjusted to change the discharge power, the flow rate of the raw material gas for supplying silicon atoms capable of supplying silicon atoms, the flow rate of the diluting gas, and the internal pressure at predetermined values.

Needless to say, all the outflow valves other than the necessary gas are closed when forming each layer, and the respective gases reach the reaction container from the outflow valves 5251 to 5256 in the reaction container. In order to avoid remaining in the pipe, the outflow valves 5251-52
56 is closed, the auxiliary valve 5260 is opened, the main valve 5118 is fully opened, and the system is temporarily evacuated to a high vacuum, if necessary.

In order to make the film formation uniform, the cylindrical support 5112 is rotated at a predetermined speed by a driving device (not shown) during the film formation.

It goes without saying that the above-mentioned gas species and valve operation may be changed according to the conditions for forming each layer.

The heating method of the cylindrical support 5112 may be any heating element having a vacuum specification, and more specifically, an electric resistance heating element such as a wound heater of a sheath heater, a plate heater, a ceramic heater, or a halogen. Examples include a heat-radiating lamp heating element such as a lamp and an infrared lamp, and a heating element using a heat exchange means using liquid, gas or the like as a heating medium. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used. In addition to this, a container dedicated to heating is provided in addition to the reaction container, and the cylindrical support 5112 is provided.
After heating, the cylindrical support 51
A method such as transporting 12 is used.

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

RF-PC in the manufacturing apparatus shown in FIG.
By replacing the deposition apparatus 5100 by the VD method with the deposition apparatus 6100 shown in FIG. 5 and connecting it to the source gas supply apparatus 5200, it is possible to obtain an electrophotographic receiving member manufacturing apparatus by the VHF-PCVD method. This apparatus is, so to speak, a manufacturing apparatus suitable for mass production of photoconductors, as compared with the manufacturing apparatus shown in FIG.

This apparatus is roughly classified into a reaction vessel 6111 that forms a vacuum airtight structure and can be depressurized, a source gas supply apparatus 5200, and an exhaust apparatus (not shown) for depressurizing the inside of the reaction vessel 6111. Has been done. A cylindrical support 6112, a heater 6113 for heating the support, a source gas introduction pipe (not shown), and an electrode 6115 are installed in the reaction vessel 6111, and a high-frequency matching box 6116 is further connected to the electrode. In addition, the reaction container 61
The inside of 11 is connected to a diffusion pump (not shown) through an exhaust pipe 6121.

The source gas supply device 5200 is made of SiH ₄ ,
Cylinders 5221 to 5226 for raw material gases such as GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , and PH ₃ and valves 5231 to 52
36, 5241 to 5246, 5251 to 5256, and mass flow controllers 5211 to 5216, and each source gas cylinder is connected to a gas introduction pipe (not shown) in the reaction vessel 6111 via an auxiliary valve 5260. A space 6130 surrounded by a plurality of cylindrical supports 6112 arranged concentrically around the electrode 6115 forms a glow discharge space.

The deposition film can be formed by this apparatus by the VHF-PCVD method as follows.

First, a cylindrical support 6112 is installed in the reaction container 6111, the support 6112 is rotated by a motor driving device 6120, and an exhaust pipe 6121 is formed in the reaction container 6111 by an exhaust device (not shown) (for example, a diffusion pump). The reaction vessel 6111 is evacuated to a pressure of 1 × 10 ⁻⁷
Adjust to less than Torr. Then, the temperature of the cylindrical support 6112 is set to 200 by the support heating heater 6113.
It is heated and maintained at a predetermined temperature of ℃ to 350 ℃.

A raw material gas for forming a deposited film is supplied to a reaction vessel 611.
In order to make it flow into 1, the gas cylinder valves 5231-5
236, make sure that the leak valve (not shown) of the reaction vessel is closed, and inflow valves 5241 to 524
6, outflow valves 5251 to 5256, auxiliary valve 526
After confirming that 0 is opened, the main valve (not shown) is first opened to exhaust the inside of the reaction vessel 6111 and the gas pipe through the exhaust pipe 6121.

Next, the reading of the vacuum gauge (not shown) is about 5 × 10.
^{When the} pressure reaches ^-6 Torr, the auxiliary valve 5260 and the outflow valves 5251 to 5256 are closed.

Thereafter, each gas is introduced from the gas cylinders 5221 to 5226 by opening the valves 5231 to 5236,
2 kg of each gas pressure by pressure regulators 5261-5266
Adjust to / cm ² . Next, inflow valves 5241 to 52
46 is gradually opened and each gas is introduced into the mass flow controllers 5211-5216.

After the preparation for film formation is completed as described above, each layer is formed on the cylindrical support 6112 as follows.

When the cylindrical support 6112 reaches a predetermined temperature, the necessary ones of the outflow valves 5251 to 5256 and the auxiliary valve 5260 are gradually opened, and a predetermined gas is supplied from the gas cylinders 5211 to 5226 to a gas introduction pipe (not shown). The discharge space 61 in the reaction vessel 6111 is shown in FIG.
Introduce to 30. Next, mass flow controller 521
1 to 5216 are adjusted so that each raw material gas has a predetermined flow rate. At that time, the pressure in the discharge space 6130 is 1
The opening of the main valve (not shown) is adjusted while observing the vacuum gauge (not shown) so that the predetermined pressure is equal to or lower than Torr.

When the pressure is stable, the charge injection blocking layer is formed by setting a VHF power source (not shown) having a frequency of, for example, 500 MHz to a desired power and matching box 6 is formed.
VHF power is introduced into the discharge space 6130 through 116 to cause glow discharge between the electrode 6115 and the support band 6112. Thus, in the discharge space 6130 surrounded by the support 6112, the introduced source gas is excited by the discharge energy and dissociated, and the support 6112 is released.
A predetermined deposited film is formed on top. At this time, in order to make the layer formation uniform, the support rotation motor 6120
Rotate at desired rotation speed.

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

By repeating the same operation a plurality of times, a desired light-receiving layer having a multi-layer structure is formed on the support band 6112.

FIG. 3 is a schematic explanatory view showing changes in each parameter during formation of a deposited film in the manufacturing method of the present invention. The photoconductive layer adjusts the RF power, the mass flow controller, and the exhaust device at the same time when the VHF power is introduced, and the discharge power, the flow rate of the raw material gas for supplying silicon, which can supply silicon atoms, the flow rate of the diluting gas, and the internal pressure are predetermined Change with the value of.

Needless to say, all the outflow valves other than the necessary gas are closed when forming each layer, and each gas is supplied to the reaction vessel 6111.
Inside, outflow valves 5251 to 5256 to reaction vessel 611
In order to avoid remaining in the pipe up to 1, the outflow valves 5251 to 5256 are closed, the auxiliary valve 5260 is opened, and the main valve (not shown) is fully opened to temporarily exhaust the system to a high vacuum. Do as needed.

It goes without saying that the above-mentioned gas species and valve operation may be changed according to the conditions for forming each layer.

In either method, the temperature of the support during the formation of the deposited film is particularly 200 ° C. or higher and 350 ° C. or lower, preferably 230 ° C. or higher and 330 ° C. or lower, and more preferably 250.
C. or higher and 300.degree. C. or lower are preferable.

Any method of heating the support 6112 may be used as long as it is a heating element having a vacuum specification, and more specifically, an electric resistance heating element such as a wound heater of a sheath heater, a plate heater, a ceramic heater, a halogen lamp, Examples thereof include a heat-radiating lamp heating element such as an infrared lamp, and a heating element using a heat exchange means using liquid, gas or the like as a heating medium. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used.

In addition to the above, there is used a method in which a container dedicated to heating is provided in addition to the reaction container, and after heating in the container, the support is conveyed into the reaction container in a vacuum.

In particular, the pressure in the discharge space in the VHF-PCVD method is preferably 1 mTorr or more and 50 or more.
0 mTorr or less, more preferably 3 mTorr or more 3
It is desirable to set it to 00 mTorr or less, most preferably to 5 mTorr or more and 100 mTorr or less. (Electrode 6115) In the VHF-PCVD method, the size and shape of the electrode 6115 provided in the discharge space may be any as long as they do not disturb the discharge, but in practice a cylindrical shape having a diameter of 1 mm or more and 10 mm or less is preferable. This time,
The length of the electrode can also be arbitrarily set as long as the electric field is uniformly applied to the support.

The electrode 6115 may be made of any material as long as it has a conductive surface. For example, stainless steel, Al, Cr, Mo, Au, In, Nb, T.
Metals such as e, V, Ti, Pt, Pb, and Fe, or alloys of these or glass or ceramics whose surface is subjected to a conductive treatment are usually used. (Support 6112) Support 6 used in the present invention
112 may be conductive or electrically insulating. As the conductive support, Al, Cr, Mo, Au,
Examples include metals such as In, Nb, Te, V, Ti, Pt, Pb, and Fe, and alloys thereof such as stainless steel. In addition, a side of the electrically insulating support such as a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, or polyamide, which is electrically insulating support such as glass or ceramic, on which at least the light receiving layer is formed. A support whose surface is treated with a conductive layer can also be used.

Support 6112 used in the present invention
Can have a cylindrical or plate-like endless belt shape with a smooth surface or an uneven surface, and its thickness is appropriately determined so that a desired electrophotographic light-receiving member can be formed. When flexibility as a photographic light-receiving member is required, it can be made as thin as possible within a range in which the function as a support can be sufficiently exerted. However, the thickness of the support is usually 10 μm or more in terms of manufacturing and handling, mechanical strength and the like.

In particular, in the case of performing image recording using coherent light such as laser light, in order to more effectively eliminate the image defect due to the so-called interference fringe pattern that appears in the visible image, the surface of the support is You may provide unevenness. The unevenness provided on the surface of the support is described in JP-A-60-168156, JP-A-60-178457, and JP-A-60-.
It is created by a known method described in Japanese Patent No. 225854.

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 for irradiation of the photoconductor, a plurality of spherical traces are formed on the surface of the support. You may provide the uneven shape by a hollow. That is, the surface of the support has irregularities that are smaller than the resolving power required for the electrophotographic light-receiving member, and the irregularities are due to a plurality of spherical trace depressions. Unevenness due to a plurality of spherical trace depressions provided on the surface of the support is disclosed in JP-A-61-
It is created by the known method described in Japanese Patent No. 231561. (Charge Injection Blocking Layer) The charge injection blocking layer in the method for producing an electrophotographic photosensitive member of the present invention is such that when the photoreceptive layer undergoes a constant polarity charging treatment on its free surface, the charge is transferred from the support side to the photoconductive layer side. Has a function of preventing the injection of cations, and does not exhibit such a function when subjected to a charging process of the opposite polarity, which is so-called polarity dependence. In order to impart such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer.

The conductivity controlling atoms contained in the charge injection blocking layer may be evenly distributed in the layer or may be evenly distributed in the layer thickness direction. However, the portion containing the non-uniformly distributed state may be suitable. When the distribution concentration is non-uniform, it is preferable to contain a large number of conductivity controlling atoms on the support side.

However, in any case, it is necessary that the particles are uniformly distributed in the in-plane direction parallel to the surface of the support in order to make the characteristics in the in-plane direction uniform. .

As the atoms contained in the charge injection blocking layer for controlling the conductivity, so-called impurities in the field of semiconductors can be mentioned.
It is possible to use an atom belonging to Group IIIb (hereinafter abbreviated as “Group IIIb atom”) or an atom belonging to Group Vb of the periodic table (hereinafter abbreviated as “Group Vb atom”) that provides n-type conductivity. it can.

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

In the present invention, the content of atoms for controlling the conductivity contained in the charge injection blocking layer is appropriately determined according to need so that the object of the present invention can be effectively achieved, but is preferably. 10 to 1 × 10 ⁴ atoms pp
m, more preferably 50 to 5 × 10 ³ atomic ppm, most preferably 1 × 10 ² to 1 × 10 ³ atomic ppm.

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

The carbon atoms, nitrogen atoms or oxygen atoms contained in the charge injection blocking layer may be evenly distributed in the layer or may not be evenly distributed in the layer thickness direction. However, there may be a portion containing the non-uniformly distributed state. However, in any case, it is necessary that the content be evenly distributed in the in-plane direction parallel to the surface of the support in order to obtain uniform properties in the in-plane direction.

The content of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in the entire layer region of the charge injection blocking layer in the present invention is appropriately determined so that the object of the present invention can be effectively achieved. However, in the case of one kind, the amount thereof, and in the case of two or more kinds, the sum thereof, preferably 1
X10 ^-3 to 50 atom%, more preferably 5 x 10 ^-3 to 30
Atomic%, optimally 1 × 10 ⁻² to 10 atomic% is desirable.

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

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

In order to form the charge injection blocking layer having the characteristics capable of achieving the object of the present invention, the mixing ratio of the gas for supplying Si and the diluting gas, the gas pressure in the reaction vessel, the discharge power and the amount of the support. It is necessary to set the temperature appropriately.

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

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

Similarly, the discharge power is appropriately selected according to the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 1 to 7 times, preferably 2 to 6 times. 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, but in the usual case, it is preferably 200 to 350 ° C., more preferably 220 to 330.
It is desirable to set the temperature to 240 ° C, optimally 240 to 310 ° C.

In the present invention, the ranges described above are mentioned as desirable numerical ranges of the mixing ratio of the diluent gas for forming the charge injection blocking layer, the gas pressure, the discharge power, and the temperature of the support. Are usually not independently determined separately, but it is desirable to determine the optimum value of each layer formation factor based on mutual and organic relationships so as to form a charge injection blocking layer having desired characteristics. (Photoconductive layer) It is necessary for the photoconductive layer in the production method of the present invention to contain hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms,
This is because it is indispensable for improving the layer quality, particularly for improving the photoconductivity and the charge retention property. Therefore, the content of hydrogen atoms or halogen atoms, or the sum of hydrogen atoms and halogen atoms is calculated as silicon atoms and hydrogen atoms or /
And 10 to 30 atom%, more preferably 15 to 25 atom% with respect to the sum of halogen atoms.

The substances that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ and Si.
Silicon hydrides (silanes) in a gas state such as ₃ H ₈ and Si ₄ H ₁₀ or capable of being gasified are mentioned as being effectively used, and further, they are easy to handle during layer formation and have good Si supply efficiency. In view of the above, SiH ₄ and Si ₂ H ₆ are preferable.

To structurally introduce hydrogen atoms into the photoconductive layer to be formed so as to make it easier to control the introduction ratio of hydrogen atoms, and to obtain film characteristics that achieve the object of the present invention. In addition, it is necessary to form a layer by further mixing these gases with a gas of a silicon compound containing H ₂ and / or He or a hydrogen atom. Further, each gas may be mixed not only with a single kind but also with a plurality of kinds at a predetermined mixing ratio.

The halogen source used in the present invention
For example, a halogen gas is effective as a raw material gas for child supply.
Halogen between gases including halogen gas, halide, and halogen
Compound, halogen-substituted silane derivative, etc.
Or a halogen compound which can be gasified is preferably mentioned.
It Further, a silicon atom and a halogen atom are further composed.
Gaseous or gasifiable halogen source as a component
Silicon hydride compounds containing a child are also listed as effective ones.
You can Halogenation preferably used in the present invention
As the compound, specifically, fluorine gas (F₂), BrF,
ClF, ClF ₃, BrF₃, BrF_Five, IF₃, IF
₇Interhalogen compounds such as Halogen
Substituted with so-called halogen atom
The silane derivative thus prepared is, for example, S
iF_Four, Si₂F₆As silicon fluorides such as
Can be mentioned.

Hydrogen atoms contained in the photoconductive layer 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 the discharge power and the like.

In the present invention, the photoconductive layer preferably contains atoms for controlling the conductivity, if necessary. The atoms for controlling the conductivity are evenly distributed in the photoconductive layer. It may be contained in such a state, or may be contained in a portion having a non-uniform distribution in the layer thickness direction.

Examples of the atoms for controlling the conductivity include so-called impurities in the semiconductor field,
An atom belonging to Group IIIb of the Periodic Table giving p-type conduction characteristics (hereinafter abbreviated as “Group IIIb atom”) or an atom belonging to Group Vb of the Periodic Table giving n-type conduction characteristics (hereinafter “V
(abbreviated as “group b atom”) can be used.

Specific examples of the group IIIb atom include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). Particularly, B, Al, and Ga are It is suitable. 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 the atoms controlling the conductivity contained in the photoconductive layer is preferably 1 × 10 ^-2 to 1 × 10.
⁴ atomic ppm, more preferably 5 × 10 ^{-2 to} 5 × 10 ³
Atomic ppm, optimally 1 × 10 ^-1 to × 10 ³ atomic ppm
Is desirable.

Atoms that control conductivity, eg IIIb
To introduce a group atom or a group Vb atom structurally,
If a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom is introduced in a gas state into a reaction vessel together with another gas for forming the photoconductive layer 103, when the layer is formed. Good. 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 an ordinary pressure, or at least a substance that can be easily gasified under a layer forming condition is adopted. Is desirable.

Raw materials for introducing such Group IIIb atoms
Specifically, for introducing a boron atom, B
₂H₆, B_FourH_Ten, B_FiveH₉, B_FiveH₁₁, B₆H_Ten, B
₆H₁₂, B ₆H₁₄Borohydride, BF, etc.₃, BCl₃,
BBr₃And the like. Besides this,
AlCl₃, GaCl₃, Ga (CH₃)₃, InCl
₃, TlCl₃Etc. can also be mentioned.

As a raw material for introducing a Group Vb atom, PH ₃ , P for introducing a phosphorus atom is effectively used.
Phosphorus hydride such as ₂ H ₄ , 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 materials for atom introduction for controlling the conductivity may be diluted with H ₂ and / or He as necessary and used.

Further, in the present invention, it is effective that the photoconductive layer contains carbon atoms and / or oxygen atoms and / or nitrogen atoms. The content of carbon atoms and / or oxygen atoms and / or nitrogen atoms is preferably 1 with respect to the sum of silicon atoms and carbon atoms, oxygen atoms and nitrogen atoms.
× 10 ⁻⁵ to 10 atom%, more preferably 1 × 10 ⁻⁴ to 8
Atomic%, optimally 1 × 10 ^{−3 to} 5 atomic% is desirable. Carbon atom and / or oxygen atom and / or nitrogen atom,
The photoconductive layer may be evenly and uniformly contained, or may have a portion having an uneven distribution such that the content of the photoconductive layer varies in the layer thickness direction.

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

In order to achieve the object of the present invention and form a photoconductive layer having desired film characteristics, the mixing ratio of the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power and the support are set. It is necessary to set the body temperature appropriately.

[0110] The flow rate of H ₂ and / or He used as a dilution gas is properly selected within an optimum range in accordance with the layer design, to Si-feeding gas H ₂ and / or He
Is usually controlled in the range of 3 to 20 times, preferably 4 to 15 times, and optimally 5 to 10 times.

At the time of forming the photoconductive layer, if the initial change of the Si supply gas is less than 0.29 sccm / sec, sufficient adhesion cannot be obtained, and if it is more than 12 sccm / sec, the effect of the present invention cannot be obtained. Therefore 0.29 sccm / sec
12 sccm / sec or less is preferable and 0.4 sc
More preferably, it is not less than cm / sec and not more than 4 sccm / sec.

Further, at the time of forming the photoconductive layer, if the initial change of the dilution gas is less than 2.2 sccm / sec, sufficient adhesion cannot be obtained, and if it is greater than 73 sccm / sec, the effect of the present invention cannot be obtained. Therefore, 2.2 sccm / sec or more and 73 sccm / sec or less are preferable, and 2.5 sccm / sec or less.
More preferably, it is not less than cm / sec and not more than 29 sccm / sec.

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

Further, at the time of forming the photoconductive layer, if the initial change in internal pressure is more than 13 mmTorr / sec, the residual potential cannot be sufficiently reduced, and if it is less than 0.33 mmTorr / sec, sufficient adhesion cannot be obtained. Therefore 0.33 mm
3. Torr / sec or more and 13 mm Torr / sec or less are preferable, and 0.38 mm Torr / sec or more, 4.
4 mmTorr / sec or less is more preferable.

Similarly, the discharge power is appropriately selected in an optimum range according to the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 2 to 7 times, preferably 2.5 to 6 times. Optimally, it is desirable to set the range of 3 to 5 times.

Further, when the initial change in discharge power during the formation of the photoconductive layer is larger than 27 W / sec, the residual potential cannot be sufficiently reduced, and when it is less than 0.7 W / sec, sufficient adhesion cannot be obtained. Therefore, 0.7 W / sec or more, 27 W / s
ec or less is preferable, 0.8 W / sec or more, 13.5
W / sec or less is more preferable.

Further, the temperature of the support is appropriately selected according to the layer design, but in the usual case, preferably 200 to 350 ° C., more preferably 230 to 330 ° C.
It is desirable to set the temperature to ° C.

Further, the region in which the temperature of the discharge power, internal pressure, Si supply gas, H ₂ gas and / or He gas support is changed when the photoconductive layer is formed is 0.1% or less of the photoconductive layer. The effect of the present invention cannot be obtained, and if it is 2.5% or more, the residual potential cannot be reduced sufficiently. Therefore, 0.
It is preferably 12% or more and 1.0% or less.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the temperature and the gas pressure of the support for forming the photoconductive layer, but the conditions are not usually independently determined separately. It is desirable to determine the optimum value based on the mutual and organic relationships to form a light receiving member having the desired properties. (Surface Layer) In the present invention, it is preferable to further form an amorphous silicon-based surface layer on the photoconductive layer. This surface layer has a free surface and is provided mainly for achieving the object of the present invention in moisture resistance, continuous repeated use characteristics, electric pressure resistance, use environment characteristics, and durability.

Further, in the present invention, since each of the amorphous materials forming the photoconductive layer forming the light receiving layer and the surface layer has a common constituent element of silicon atom, at the stacking interface. The chemical stability is fully ensured.

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

In the present invention, in order to effectively achieve the object, the surface layer is formed by the vacuum deposition film forming method by appropriately setting the numerical conditions of film forming parameters so that desired characteristics can be obtained. Specifically, for example, glow discharge method (low-frequency CVD method, high-frequency CVD method, alternating-current discharge CVD method such as microwave CVD method, or direct-current discharge CVD method), sputtering method, vacuum deposition method, ion plating method, It can be formed by various thin film deposition methods such as a photo CVD method and a thermal CVD method. These thin film deposition methods are based on manufacturing conditions, load level under capital investment,
It is appropriately selected and adopted depending on factors such as desired characteristics of the electrophotographic light-receiving member to be produced, but it is preferable to use the same deposition method as that for the photoconductive layer from the viewpoint of productivity of the light-receiving member.

For example, a-Si is formed by the glow discharge method.
In order to form a surface area composed of C: H, X, basically, a source gas for supplying Si, which can supply silicon atoms (Si), and a source gas for supplying C, which can supply carbon atoms (C), are used. A raw material gas for supplying H, which can supply hydrogen atoms (H), and / or a raw material gas for supply, which can supply halogen atoms (X), are introduced in a desired gas state into a reaction vessel in which pressure can be reduced. To generate a glow discharge in the reaction vessel,
A layer made of a-SiC: H, X may be formed on the support 101 on which the photoconductive layer 103 has been formed in advance at a predetermined position.

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

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

In the present invention, it is necessary for the surface layer to contain hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, especially photoconductivity. It is indispensable for improving the oxidative property and the charge retention property. The hydrogen content is usually 30 to 70 atom%, preferably 35 to 65 atom%, and most preferably 40 to 60 atom% with respect to the total amount of the constituent atoms. The content of fluorine atoms is usually 0.01 to 15 atom%, preferably 0.1 to 10 atom%, and most preferably 0.6 to 4 atom%.

The light-receiving member formed within the range of the hydrogen and / or fluorine content can be sufficiently applied as a remarkably excellent one in practical use. That is, it is known that defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer adversely affect the characteristics as the electrophotographic light-receiving member. For example, the deterioration of the charging characteristics due to the injection of electric charges from the free surface, the fluctuation of the charging characteristics due to the change of the surface structure under the usage environment, for example, high humidity. This adverse effect is caused by the injection of charges and the trapping of the charges in the defects in the surface layer, resulting in the occurrence of an afterimage phenomenon during repeated use.

However, if the hydrogen content in the surface layer is 30
By controlling the content to be atomic% or more, the defects in the surface layer are significantly reduced, and as a result, the electrical characteristics and the high-speed continuous usability can be dramatically improved as compared with the conventional one.

On the other hand, when the hydrogen content in the surface layer is 71 atomic% or more, the hardness of the surface layer decreases, and it becomes impossible to withstand repeated use. Therefore, controlling the hydrogen content in the surface layer to be within the above range is one of the very important factors in obtaining the desired electrophotographic properties that are remarkably excellent. The hydrogen content in the surface layer can be controlled by the flow rate of H ₂ gas, the temperature of the support, the discharge power, the gas pressure and the like.

Further, by controlling the fluorine content in the surface layer to be in the range of 0.01 atomic% or more, it is possible to more effectively achieve the generation of the bond between silicon atoms and carbon atoms in the surface layer. Becomes Further, as a function of fluorine atoms in the surface layer, it is possible to effectively prevent the breaking of the bond between the silicon atom and the carbon atom due to damage such as corona.

On the other hand, the fluorine content in the surface layer is 15 atom%.
When it exceeds, the effect of generating the bond between the silicon atom and the carbon atom in the surface layer and the effect of preventing the breakage of the bond between the silicon atom and the carbon atom due to damage such as corona are hardly recognized. Further, since excess fluorine atoms impede the mobility of carriers in the surface layer, the residual potential and image memory are noticeable. Therefore, controlling the fluorine content in the surface layer within the above range is one of the important factors in obtaining desired electrophotographic characteristics. Like the hydrogen content, the fluorine content in the surface layer can be controlled by the flow rate of H ₂ gas, the support temperature, the discharge power, the gas pressure and the like.

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

As a substance which can be a gas for supplying carbon,
A hydrocarbon in a gas state such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ , C ₄ H ₁₀ or a gasifiable hydrocarbon can be effectively used, and further, it is easy to handle during layer formation and Si.
CH ₄ and C ₂ H ₆ are preferable as they have good supply efficiency. In addition, these raw material gases for supplying carbon may be diluted with a gas such as H ₂ , He, Ar, or Ne, if necessary.

Examples of substances that can be used as a gas for supplying nitrogen or oxygen include NH ₃ , NO, N ₂ O, NO ₂ , O ₂ and C.
Compounds in a gas state such as O, CO ₂ and N ₂ or compounds that can be gasified are mentioned as being effectively used. Further, these raw material gases for supplying nitrogen and oxygen may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

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

Effective as a source gas for supplying halogen atoms
For example, halogen gas, halide, halogen
Compounds containing halogen, compounds substituted with halogen
Gaseous or gasifiable halogenations such as orchidyne derivatives
Compounds are preferred. In addition, silicon raw
Gas or gas composed of a child and a halogen atom.
There are also silicon hydride compounds containing halogen atoms
Can be listed as effective. Suitable in the present invention
Specific examples of the halogen compound that can be used for
Gas (F₂), BrF, ClF, ClF₃, BrF₃,
BrF_Five, IF ₃, IF₇Interhalogen compounds such as
Can be Silicon compounds containing halogen atoms,
As the silane derivative substituted with a loose halogen atom,
Specifically, for example, SiF_Four, Si₂F₆Fluorinated silica
The element can be mentioned as a preferable example.

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

The carbon atom and / or the oxygen atom and / or the nitrogen atom may be uniformly contained in the surface layer, or may be nonuniform such that the content varies in the layer thickness direction of the surface layer. There may be a portion with a distribution.

Further, in the present invention, it is preferable that the surface layer contains atoms for controlling conductivity, if necessary. Atoms that control conductivity may be contained in the surface layer in a uniformly distributed state, or may be contained in an uneven distribution in the layer thickness direction. .

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors, and atoms belonging to Group IIIb of the periodic table that give p-type conductivity (hereinafter referred to as “Group IIIb atoms”). Or an atom belonging to Group Vb of the periodic table (hereinafter abbreviated as “Group Vb atom”) that gives n-type conductivity.

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

Atoms contained in the surface layer for controlling conductivity
The content of is preferably 1 × 10^-3~ 1 × 10³
Atomic ppm, more preferably 1 × 10^-2~ 5 × 10²original
Pp ppm, optimally 1 x 10^-1~ 1 × 10²Atomic ppm
Is desirable. Atoms that control conductivity, even if
For example, structurally introducing a group IIIb atom or a group Vb atom.
In order to form a layer, a raw material for introducing a Group IIIb atom
Quality or raw material for introducing Group Vb atoms in gas state
Other gas for forming the surface layer 104 in the reaction vessel
It should be introduced together with. Source for introduction of Group IIIb atoms
Can be a raw material or a raw material for introducing a Group Vb atom
As a thing, it is gaseous at room temperature and normal pressure, or at least
Also adopted is one that can be easily gasified under layer forming conditions.
Is desirable. Raw materials for introducing such Group IIIb atoms
Specifically, as a material for introducing a boron atom, B is used.₂H
₆, B_FourH_Ten, B_FiveH₉, B_FiveH₁₁, B₆H_Ten, B₆H
₁₂, B₆H₁₄Borohydride, BF, etc.₃, BCl₃, BB
r₃And the like. Besides this, Al
Cl₃, GaCl₃, Ga (CH₃)₃, InCl ₃,
TlCl₃Etc. can also be mentioned.

As a raw material for introducing a Group Vb atom,
In order to introduce a phosphorus atom, P is effectively used.
H₃, P₂H_FourPhosphorus hydride, PH, etc._FourI, PF₃, PF
_Five, PCl₃, PCl_Five, PBr₃, PBr_Five, PI₃
And the like. Besides this, AsH₃, A
sF₃, AsCl₃, AsBr₃, AsF_Five, Sb
H ₃, SbF₃, SbF_Five, SbCl₃, SbCl_Five,
BiH₃, BiCl₃, BiBr₃Etc. is also group Vb atom conduction
Can be listed as valid starting materials for the
It

Further, these raw materials for atom introduction for controlling the conductivity may be diluted with a gas such as H ₂ , He, Ar or Ne, if necessary.

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

The surface layer according to the invention is carefully formed in order to give it the desired properties.
That is, a substance having Si, C and / or N and / or O, H and / or X as a structural element structurally takes a form from crystalline to amorphous depending on its forming condition,
In terms of electrical properties, the properties from conductive to semiconductor and insulating properties and from photoconductive to non-photoconductive properties are shown. The formation conditions are rigorously selected as desired so that a compound having the desired properties is formed.

For example, in order to provide the surface layer mainly for the purpose of improving the pressure resistance, the surface layer is formed as a non-single crystal material having a remarkable electric insulating behavior in the use environment.

Further, when the surface layer is provided mainly for the purpose of improving continuous repeated use characteristics and use environment characteristics, the above-mentioned degree of electrical insulation is relaxed to a certain extent, and the surface insulation layer has a degree to the irradiation light. It is formed as a non-single crystal material with sensitivity.

In order to form the surface area having the characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the temperature of the support and the gas pressure in the reaction vessel as desired.

The temperature (Ts) of the support is appropriately selected in the optimum range according to the layer design, but in the usual case, it is preferably 200 to 350 ° C., more preferably 230 to 330.
It is desirable that the temperature is set to 0 ° C, optimally 250 to 310 ° C.

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

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 surface layer, but the conditions are not usually independently determined separately, and are desired. It is desirable to determine the optimum value on the basis of mutual and organic relationships so as to form a light receiving member having the above characteristics.

Further, in the present invention, a blocking layer (lower surface layer) in which the content of carbon atoms, oxygen atoms and nitrogen atoms is smaller than that of the surface layer is provided between the photoconductive layer and the surface layer. It is effective for further improving the characteristics of.

Further, a region where the content of carbon atoms and / or oxygen atoms and / or nitrogen atoms changes so as to decrease toward the photoconductive layer may be provided between the surface layer and the photoconductive layer. This can improve the adhesion between the surface layer and the photoconductive layer, and further reduce the influence of interference due to the reflection of light at the interface.

The electrophotographic photosensitive member manufactured by the method of the present invention is not only used in an electrophotographic copying machine, but also applied to electrophotographic applications such as a laser beam printer, a CRT printer, an LED printer, a liquid crystal printer, and a laser plate making machine. It can also be used widely.

[0156]

EXAMPLES The effects of the present invention will be specifically described below using experimental examples, but the present invention is not limited to these. [Experimental Example 1] An apparatus for producing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4 was used, and the substrate had a diameter of 1 including aluminum having a silicon atom content of 100 ppm.
A cylindrical silicon substrate having a length of 08 mm, a length of 358 mm, and a wall thickness of 5 mm was mirror-finished on an aluminum cylinder, and an amorphous silicon deposition film was formed on the substrate under the conditions shown in Table 1, and shown in FIG. A blocking type electrophotographic photoreceptor having a layer structure was prepared. In FIG. 1B, 100, 10
Reference numerals 1, 105, 103 and 104 denote a photoconductor, an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer, respectively. Incidentally, in FIG.
No. 00 has a charge injection blocking layer 105 formed on a substrate 101 as a support and a photoconductive layer 103 formed thereon, and a free surface 110 is irradiated with a laser beam or a beam to form a photosensitive layer 10.
2 includes a charge injection blocking layer 105 and a photoconductive layer 103. Further, in FIG. 1C, the photoreceptor 100 has a charge injection blocking layer 105 formed on a substrate 101, a charge transfer layer 107, a charge generation layer 106, and a surface layer 104 formed thereon, and a laser is formed on a free surface 110. When exposed to light or a beam, the photosensitive layer 102 includes a charge injection blocking layer 105, a charge transfer layer 107, a charge generation layer 106, and a surface layer 104.

In this experimental example, the initial stage of the photosensitive layer was prepared under the following conditions.

(A) The gas flow rate of the source gas SiH ₄ is set to 19
Change from 5 sccm to 430 sccm, then 43
It is constant at 0 sccm. The change pattern of the SiH ₄ gas flow rate at this time is shown in FIG. 2A, and the initial change time was changed from 5 sec to 900 sec, and 10 types were produced.

Further, the H ₂ gas change amount at this time is 14.
6 sccm / sec (3 at 120 seconds H ₂ gas flow rate)
Change from 90 sccm to 2150 sccm, then 21
It is fixed at 50 sccm. ), RF power variation from high frequency matching box 5115 is 4.5w
/ Sec (160w at 120 seconds with RF Power)
From 700w to 700w, and then fixed at 700w. ), The amount of change in internal pressure is 2.2 mm Torr / sec
(55 mm from 285 mm Torr at 120 sec.
Change to 0mm Torr, then 550mm Torr
Is constant. ), And changed according to the pattern of SiH ₄ gas flow rate in FIG.

(B) From the initial stage of formation of the photosensitive layer 102, Si
H_FourGas flow rate 430sccm, H ₂Gas flow rate 2150
sccm, RF Power 700w, internal pressure 550
It is fixed at mmTorr.

The prepared light receiving member was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing),
The residual potential, ghost and image defects (white spots) were evaluated by the following methods.

[Residual Potential] A light-receiving member for electrophotography is provided with 4
The surface potential of the dark part of 20 v is charged. Then, a fixed amount of light (0.4 lux / sec) is immediately irradiated. The light image is 550n using a xenon lamp light source and a filter.
Light excluding light in the wavelength range of m or less was irradiated. At this time, the surface potential of the light portion of the electrophotographic light-receiving member is measured with a surface potential meter. Then, the average of the obtained light surface potentials is taken as the residual potential. Then, relative evaluation was performed by setting the residual potential obtained under the condition (b) to 100.

◎: × ≦ 90 ○: 90 <× ≦ 95 Δ: 95 <× ≦ 100 ×: 100 <× “Ghost” Canon Ghost Test Chart (Part No. FY9-9040) had a reflection density of 1.1, φ5 mm
Place the black circle on the top of the image on the platen,
On top of that, a Canon halftone chart (part number: FY9
-9042) in the copied image when placed on top of each other,
5mm of ghost chart recognized on the intermediate copy
The difference between the reflection density of the sample and the reflection density of the halftone part was measured.

◎: "Especially good" ○: "Good" △: "No problem in practical use" ×: "There is a problem in practical use""WhitePot" Canon full black chart (part number: FY
9-9073) was placed on a platen and copied, and white spots having a diameter of 0.2 mm or less within the same area of the copy image obtained were evaluated.

⊚ was “particularly good”, that is, it was confirmed that there were almost no white spots. ◯ was “good”. Δ was “no problem in practical use” x was “problem in practical use”. The member was set in an electrophotographic apparatus, and a paper passing durability test of 2 million sheets was performed. Then, the electrophotographic characteristics such as ghost and white spot were similarly evaluated.

The results thus obtained are shown in Table 2.
You. For example, under the condition a-5, SiH _FourInitial change of gas
The time is set to 235 seconds, and the SiH_FourGas flow
Change the amount of change by 1 sccm / sec
It shows that it has flowed in. In addition, ghost (GST)
Before and after the endurance of Molly and image defects (white spots) are actually
Image judgment immediately after the start of the test and image judgment after passing 2 million sheets
It shows the disconnection result. In addition, the overall evaluation is based on the above three judgments
Comprehensive addition of elements and other judgment elements (contrast, etc.)
The results are shown.

As is clear from Table 2, the flow rate of SiH ₄ is 0.29 sccm in the initial region of formation of the photosensitive layer.
By changing the pressure in the range from 1 sec / sec to 12 sccm / sec, the residual potential is improved, and it is possible to prepare an electrophotographic photoconductor in which the image characteristics such as white spots and ghosts are not deteriorated even after the endurance. . Further, it was found that it is more effective by changing the SiH ₄ flow rate at 0.4 sccm / sec or more and 4 sccm / sec or less.

[0168]

[Table 1]

[0169]

[Table 2]

Change in SiH _{4 in the} initial stage of the photoconductive layer (235 s
ccm) / initial change time = SiH ₄ change amount.

H ₂ change amount → 14.6 sccm / sec Power change amount → 4.5 w / sec Internal pressure change amount → 2.2 mm Torr / sec
Experiment was carried out by fixing with. [Experimental Example 2] An apparatus for producing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4 was used, and the substrate had a diameter of 1 including aluminum having a silicon atom content of 100 ppm.
A cylindrical silicon substrate having a length of 08 mm, a length of 358 mm, and a wall thickness of 5 mm was mirror-finished on an aluminum cylinder, and an amorphous silicon deposition film was formed on the substrate under the same conditions shown in Table 1 above. A blocking type electrophotographic photosensitive member having a layer structure shown in FIG. In FIG. 1 (b), 10
Reference numerals 1, 105, 103 and 104 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer, respectively.

In this experimental example, the initial stage of the photosensitive layer was prepared under the following conditions.

(A) The gas flow rate of H ₂ was changed from 390 sccm to 2150 sccm, and then 2150 sccm
m constant. The change pattern of the H ₂ gas flow rate at this time is shown in FIG.
(A), changing time from 16sec to 900s
10 types were created between ec. In addition, SiH at this time
₄ gas change rate of 2 sccm / sec (SiH ₄ gas flow rate changed from 195 sccm to 430 sccm in 120 sec, and then fixed at 430 sccm), RF
The power change amount is 4.5 w / sec (RF Power
The value r is changed from 160w to 700w in 120 seconds, and then kept constant at 700w. ), The amount of change in internal pressure is 2.2 m
m Torr / sec (285m at 120sec internal pressure)
Change from m Torr to 550 mm Torr, then 5
It is constant at 50 mm Torr. ), And FIG.
The pattern was changed according to the pattern (a).

(B) For comparison, the same conditions as (b) in Experimental Example 1 were used.

The light receiving member thus prepared was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing),
The residual potential, ghost and image defects (white spots) were evaluated by the following methods.

"Residual potential" The same as in Experimental Example 1.

"Ghost" Same as Experimental Example 1.

"White Pot" Same as Experimental Example 1.

The results thus obtained are shown in Table 3.

As is clear from Table 3, the flow rate of H ₂ was set to 2.2 sccm / se in the initial region of formation of the photosensitive layer.
By changing it from c to 73 sccm / sec, the residual potential is improved, and it is possible to prepare an electrophotographic photoreceptor in which image characteristics such as white spots and ghosts are not deteriorated even after endurance. Furthermore, H ₂ flow rate is 2.5
It was found that it was more effective by changing the sccm / sec or more and 29 sccm / sec or less.

[0181]

[Table 3]

Amount of H ₂ change at the initial stage of the photoconductive layer (1760 sc
cm) / initial change time = H ₂ change amount.

SiH ₄ change amount → 2 sccm / sec Power change amount → 4.5 w / sec Internal pressure change amount → 2.2 mm Torr / sec
Experiment was carried out by fixing with. [Experimental Example 3] An apparatus for producing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4 was used, and the substrate had a diameter of 1 including aluminum having a silicon atom content of 100 ppm.
An amorphous silicon deposition film was formed on the aluminum cylinder, which was obtained by mirror-finishing a cylindrical substrate having a length of 08 mm, a length of 358 mm, and a wall thickness of 5 mm, under the conditions shown in Table 1 as in the above. A blocking type electrophotographic photoreceptor having the layer structure shown in was prepared. In FIG. 1 (b), 10
Reference numerals 1, 105, 103 and 104 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer, respectively.

In this experimental example, the initial stage of the photosensitive layer was prepared under the following conditions.

(A) Set RF Power from 160w to 7
It was changed to 00w, and then it was kept constant at 700w. The change pattern of RF Power at this time is shown in FIG.
Then, 10 kinds of changing time were created from 16 seconds to 900 seconds. Further, the SiH ₄ gas change amount at this time is 2 sccm / sec (SiH ₄ gas flow rate is 12
Change from 195 sccm to 430 sccm in 0 sec,
After that, it was kept constant at 430 sccm. ), H ₂ gas change amount of 14.6 sccm / sec (H ₂ gas flow rate of 12
It was changed from 390 sccm to 2150 sccm in 0 sec, and then kept constant at 2150 sccm. ), The amount of change in internal pressure is 2.2 mm Torr / sec (internal pressure is 120
285 mm Torr to 550 mm Tor in sec
The value was changed to r and then kept constant at 550 mm Torr. ), And changed in the pattern of FIG.

The light-receiving member thus prepared was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing),
The residual potential, ghost and image defects (white spots) were evaluated by the following methods.

"Residual potential" The same as in Experimental Example 1.

[Ghost] Same as Experimental Example 1.

"White Pot" Same as Experimental Example 1.

Table 4 shows the results thus obtained.

As is clear from Table 4, RF Power is 0.7 w / se in the initial region of formation of the photosensitive layer.
By changing from c to 27 w / sec, the residual potential is improved, and it is possible to prepare an electrophotographic photoreceptor in which image characteristics such as white spots and ghosts are not deteriorated even after endurance. Furthermore, RF Power is 0.8
It was found that it was more effective by changing it from w / sec to 13.5 w / sec.

[0192]

[Table 4]

An experiment was conducted by setting the RF power change amount in the initial stage of the photoconductive layer (540 w) / initial change time = RF Power change amount.

SiH ₄ change amount → ₂ sccm / sec H ₂ change amount → 14.6 sccm / sec Internal pressure change amount → 2.2 mm Torr / sec
Experiment was carried out by fixing with. [Experimental Example 4] Silicon (S) was used as a substrate by using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
i) The conditions shown in Table 1 similar to those of Experimental Examples 1 to 3 on a mirror-finished aluminum cylinder of a cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm made of aluminum having an atomic content of 100 ppm. Then, an amorphous silicon deposited film is formed on the substrate, and as shown in FIG.
A blocking type electrophotographic photoreceptor having the layer structure shown in (b) was prepared. As shown in FIG. 1B, the aluminum substrate 10
1, the charge injection blocking layer 105, the photoconductive layer 103, and the surface layer 104.

In this experimental example, the initial stage of the photosensitive layer was prepared under the following conditions.

(A) The internal pressure is 285 mm Torr to 5
Change to 50mm Torr, then 550mm T
It was fixed at orr. The change pattern of the internal pressure at this time is shown in FIG. 2A, and the changing time is changed from 16 seconds to 9 seconds.
Ten types were created in 00 seconds. Further, the change amount of SiH ₄ gas at this time is 2 sccm / sec (from 195 sccm to 430 sccm when the SiH ₄ gas flow rate is 120 sec).
The value was changed to cm, and then fixed at 430 sccm. ), H ₂ gas change amount of 14.6 sccm / sec
(The flow rate of H ₂ gas is 120 seconds from 390 mm to 215 mm
It was changed to 0 sccm, and then fixed at 2150 sccm. ), RF Power change amount of 4.5 w / sec
(Internal pressure changes from 160w to 700w in 120sec,
After that, it was kept constant at 700 w. ), And changed in the pattern of FIG.

The light receiving member thus prepared was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing),
The residual potential, ghost and image defects (white spots) were evaluated by the following methods.

"Residual potential" The same as in Experimental Example 1.

"Ghost" Same as Experimental Example 1.

[White pot] The same as in Experimental Example 1.

The results thus obtained are shown in Table 5.

As is clear from Table 5, the residual potential is improved by changing the internal pressure within the range of 0.33 mm Torr or more and 13 mm Torr / sec or less in the initial region of the formation of the photosensitive layer, and the white potential is maintained even after the endurance. It has become possible to create an electrophotographic photoreceptor that does not deteriorate in image characteristics such as spots and ghosts. Furthermore, the internal pressure is 0.38m
m Torr / sec or more, 4.4 mm Torr / s
It was found that it was more effective by changing it at ec or less.

[0203]

[Table 5]

Internal pressure change amount in the initial stage of the photoconductive layer (265 mm
Torr) / initial change time = internal pressure change amount.

The experiment was conducted by fixing the amount of SiH ₄ change → ₂ sccm / sec, the amount of H ₂ change → 14.6 sccm / sec, the RF Power change → 4.5 w / sec. [Experimental Example 5] Silicon (S) was used as a substrate by using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
i) The conditions shown in Table 1 in the same manner as in Experimental Examples 1 to 4 on a mirror-finished aluminum cylinder made of a cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm made of aluminum having an atomic content of 100 ppm. On the substrate,
Amorphous silicon deposited film is formed, and then, as shown in FIG.
A blocking type electrophotographic photoreceptor having the layer structure shown in was prepared. FIG.
In (b), 101, 105, 103 and 104
Indicate an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer, respectively.

In this experimental example, the H ₂ gas change amount at the time of forming the photosensitive layer was 14.6 sccm / sec (H ₂ gas flow rate was 12
It was changed from 390 sccm to 2150 sccm in 0 sec, and then kept constant at 2150 sccm. ), RF
The amount of power change is 4.5 w / sec (RF Po
Change wer from 160w to 700w in 120sec,
After that, it was kept constant at 700 w. ), The amount of change in internal pressure is 2.2 mm Torr (285 m at 120 seconds internal pressure)
It was changed from m Torr to 550 mm Torr, and then kept constant at 550 mm Torr. ), The change pattern of the quadratic function rise in FIG.

The amount of change in SiH ₄ gas is 2 sccm / sec.
(SiH ₄ gas flow rate changed from 195 sccm to 430 sccm in 120 sec, and then fixed to 430 sccm.), And the flow rate change pattern of SiH ₄ gas in this initial change period of 120 sec is shown in (a) to (f) of FIG. 6 kinds were done.

Here, in FIG. 2, after the charge injection blocking layer is formed, during the initial change period of the formation of the photoconductive layer, FIG. 2A shows a linear change, and FIG. 2B shows a quadratic function change. c) an inverse logarithmic change, (d) an abrupt change in the middle of the initial change period, (e) an abrupt change in the first and last regions of the initial change period, and (f) a stepwise change ing.

The prepared light receiving member was set in an electrophotographic device (Canon NP6150 was modified for testing),
The residual potential of charging ability, ghost and image defects (white spots) were evaluated by the same method as in Experimental Example 1.

The results obtained are shown in Table 6.

As is clear from Table 6, very good results were obtained with any of the patterns.

[0212]

[Table 6]

[Experimental Example 6] Using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4, the substrate has a diameter of 108 mm and a length of 358 mm made of aluminum having a silicon atom content of 100 ppm. In the same manner as in Experimental Examples 1 to 5, an amorphous silicon deposition film was formed on a substrate having a thickness of 5 mm on a mirror-finished aluminum cylinder under the conditions shown in Table 1.
A blocking type electrophotographic photoreceptor having the layer structure shown in (b) was produced. In FIG. 1B, 101, 105, 103 and 104 respectively indicate an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer.

In this experimental example, the change amount of SiH ₄ gas at the time of forming the photosensitive layer was 2 sccm / sec (SiH ₄ gas flow rate was 1
It was changed from 195 sccm to 430 sccm in 20 sec, and then kept constant at 430 sccm. ), RF
The change amount of Power is 4.5 w / sec (RF Power
er was changed from 160 w to 700 w in 120 sec, and then was kept constant at 700 w. ), The change amount of the internal pressure is 2.
2mm Torr (285mm at 120sec internal pressure
Change from Torr to 550 mm Torr, then 55
It was constant at 0 mm Torr. ), And the change pattern is changed according to the change pattern of FIG. H ₂ gas change amount is 14.6 sccm / sec (H ₂ gas flow rate is 120 s
The change in ec from 390 sccm to 2150 sccm was made constant at 2150 sccm thereafter. ), And the change pattern of the H ₂ gas at this time was performed for 6 kinds of (a) to (f) in FIG.

The prepared light receiving member is set in an electrophotographic apparatus (NP6150 manufactured by Canon is modified for testing),
The residual potential of charging ability, ghost and image defects (white spots) were evaluated by the same method as in Experimental Example 1.

The results obtained are shown in Table 7.

As is clear from Table 7, very good results were obtained with any of the patterns.

[0218]

[Table 7]

[Experimental Example 7] An electrophotographic light-receiving member manufacturing apparatus according to the RF-PCVD method shown in FIG. 4 was used, and the substrate had a diameter of 108 mm and a length of 358 mm made of aluminum having a silicon atom content of 100 ppm. A cylindrical silicon substrate having a thickness of 5 mm was mirror-finished on an aluminum cylinder, and an amorphous silicon deposition film was formed on the substrate under the conditions shown in Table 1 in the same manner as in Experimental Examples 1 to 6.
A blocking type electrophotographic photoreceptor having the layer structure shown in (b) was produced. In FIG. 1B, 101, 105, 103 and 104 respectively indicate an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer.

In this experimental example, the change amount of SiH ₄ gas at the time of forming the photosensitive layer was 2 sccm / sec (the SiH ₄ gas flow rate was 1
It was changed from 195 sccm to 430 sccm in 20 sec, and then kept constant at 430 sccm. ), H ₂ gas change amount of 14.6 sccm / sec (H ₂ of 120
Change from 390 sccm to 2150 sccm in sec,
After that, it was kept constant at 2150 sccm. ), The amount of change in internal pressure is 2.2 mm Torr (internal pressure of 2
Change from 85mm Torr to 550mm Torr,
After that, the pressure was kept constant at 550 mm Torr. )age,
The pattern was changed according to the change pattern shown in FIG.

RF Power change amount is 4.5 w / se
c (RF Power 120w for 160w700)
Wi change and then constant at 700w. ), And the change pattern of the H ₂ gas at this time was performed for 6 kinds of (a) to (f) in FIG.

The prepared light receiving member is set in an electrophotographic apparatus (NP6150 manufactured by Canon is modified for testing),
The chargeability, ghost and image defects (white spots) were evaluated in the same manner as in Experimental Example 1.

The results obtained are shown in Table 8.

As is clear from Table 8, very good results were obtained with any of the patterns.

[0225]

[Table 8]

[Experimental Example 8] Using the apparatus for manufacturing an electrophotographic light-receiving member by the RF-PCVD method shown in FIG. 4, the substrate has a diameter of 108 mm and a length of 358 mm made of aluminum having a silicon atom content of 100 ppm. A cylindrical silicon substrate having a thickness of 5 mm was mirror-finished on an aluminum cylinder, and an amorphous silicon deposition film was formed on the substrate under the conditions shown in Table 1 in the same manner as in Experimental Examples 1 to 7.
A blocking type electrophotographic photoreceptor having the layer structure shown in (b) was produced. In FIG. 1B, 101, 105, 103 and 1
04 is an aluminum substrate, a charge injection blocking layer,
A photoconductive layer and a surface layer are shown.

In this experimental example, the change amount of SiH ₄ gas at the time of forming the photosensitive layer was 2 sccm / sec (the SiH ₄ gas flow rate was 1
It was changed from 195 sccm to 430 sccm in 20 sec, and then kept constant at 430 sccm. ), The amount of change in H ₂ gas was 14.6 scm / sec (H ₂ gas flow rate was changed from 390 sccm to 2150 sccm in 120 sec, and then was kept constant at 2150 sccm), R
The change amount of F Power is 4.5 w / sec (RF P
Change from 160w to 700w in ower 120sec,
After that, it was kept constant at 700 w. ) And FIG. 2 respectively.
The pattern was changed according to the change pattern of (b).

The inner pressure change amount is set to 2.2 mm Torr / se.
c (5mm from 285mm Torr at 120sec internal pressure)
Change to 50mm Torr, then 550mm Torr
It was fixed at r. ), And six types of change patterns of the internal pressure at this time were performed from (a) to (f) of FIG.

The prepared light receiving member is set in an electrophotographic apparatus (NP6150 manufactured by Canon is modified for testing),
The chargeability, ghost and image defects (white spots) were evaluated in the same manner as in Experimental Example 1.

The results obtained are shown in Table 9.

As is clear from Table 9, very good results were obtained with any of the patterns.

[0232]

[Table 9]

[Experimental Example 9] An apparatus for producing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4 was used, and the substrate had a diameter of 108 mm and a length of 358 mm made of aluminum having a silicon atom content of 100 ppm. A cylindrical silicon substrate having a thickness of 5 mm was mirror-finished on an aluminum cylinder, and an amorphous silicon deposited film was formed on the substrate under the conditions shown in Table 10 as in Experimental Examples 1 to 8.
A blocking type electrophotographic photoreceptor having the layer structure shown in (b) was produced. In FIG. 1B, 101, 105, 103 and 104 respectively indicate an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer.

In this experimental example, (a) when the photosensitive layer was formed, the SiH ₄ gas flow rate was 195 sccm during the initial 60 seconds.
Change to 430 sccm (4 sccc with linear change)
m / sec. ), And then constant at 430 sccm, and H ₂ gas flow rate from 390 sccm to 2150
change to sccm (29.3 sccm /
sec. ), And then constant at 2150 sccm, RF Power was changed from 160 w to 700 w (linear change is 9 w / sec.), And then fixed at 700 w, and the internal pressure was 285 mm Tor.
from r to 550 mm Torr (linear change is 4.4 mm Torr), and then 550 m
It was constant at m Torr. At this time, each change pattern was linearly changed as shown in FIG. The initial change time was set to 60 seconds as described above, but the time taken to form the photosensitive layer 102 was changed to 1
0 kinds were created.

(B) The SiH ₄ gas flow rate at the time of forming the photosensitive layer is constant at 430 sccm, and the H ₂ gas flow rate is 2150 sccm.
Constant, RF Power 700w constant, internal pressure 550
With a constant mmTorr, ten kinds of photosensitive layers were prepared by changing the photosensitive layer preparation time as in (a).

The prepared light receiving member is set in an electrophotographic apparatus (NP6150 manufactured by Canon is modified for testing),
The chargeability, ghost and image defects (white spots) were evaluated in the same manner as in Experimental Example 1.

The results obtained are shown in Table 11. In addition, Table 1
1, the residual potential was 430 sccm for SiH ₄ gas, 2150 sccm for H ₂ gas, and RF when the photosensitive layer was formed.
Power 700w, internal pressure 550mm Torr
And (b) in the case of the same photosensitive layer formation time and the same photosensitive layer formation time as 100 are shown by relative evaluation.

As is clear from Table 11, SiH of the photosensitive layer
_Since the initial change region of ₄ gas, H ₂ gas, RF Power and internal pressure was set to 60 sec (= 1 min), from the ratio of 60 sec to the photosensitive layer preparation time, the initial change region was 0.12% or more of all layers, When it is 1.0% or less, very good results can be obtained.

[0239]

[Table 10]

[0240]

[Table 11]

The constitution of the present invention was determined by the above experimental examples. Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. [Example 1] An apparatus for producing a photoreceptive member for electrophotography by the RF-PCVD method shown in Fig. 4 was used, and the substrate had a diameter of 1 including aluminum having a silicon atom content of 100 ppm.
A cylindrical substrate having a length of 08 mm, a length of 358 mm, and a wall thickness of 5 mm was mounted on a mirror-finished aluminum cylinder.
An amorphous silicon deposited film was formed on the substrate under the conditions shown in (1) to produce a blocking electrophotographic photoreceptor having the layer structure shown in FIG. 1 (b). In FIG. 1B, 101,10
5, 103 and 104 are aluminum bases,
The charge injection blocking layer, the photoconductive layer and the surface layer are shown.

The prepared light receiving member is set in an electrophotographic apparatus (Canon NP6150 is modified for testing),
The charging ability, the ghost, and the image defect (white spots) shown as the residual potential were evaluated in the same manner as in Experimental Example 1.

"Residual potential" The same as in Experimental Example 1.

[Ghost] Same as Experimental Example 1.

[White Pot] Same as Experimental Example 1.

The thirteenth result of these evaluations is shown. In the table,
The residual potential is shown by relative evaluation with the result of Comparative Example 1 shown below as 100. [Comparative Example 1] Compared to Example 1, in this comparative example, the SiH ₄ gas flow rate of the photosensitive layer was 430 sccm, the H ₂ gas flow rate was 2150 sccm, and the RF power was 700 w.
An electrophotographic photoreceptor was prepared in the same manner as in Example 1, except that the internal pressure was 550 mm Torr.

The electrophotographic photosensitive member thus prepared was evaluated in the same manner as in Example 1.

The results of these evaluations are shown in Table 13 together with Example 1.
Shown in

The electrophotographic photosensitive member manufactured by the method for manufacturing an electrophotographic photosensitive member of the present invention is very good in all items as compared with the electrophotographic photosensitive member manufactured by the conventional method in which the gas flow rate is constant. Results were obtained.

[0250]

[Table 12]

[0251]

[Table 13]

[Embodiment 2] VHF-PCVD shown in FIG.
Using an apparatus for producing a photoreceptive member for electrophotography by the method, a charge injection blocking layer and a photoconductive layer were formed on an aluminum cylinder (support) having a diameter of 108 mm and mirror-finished in the same manner as in Example 1 under the conditions shown in Table 14. A light receiving member including a surface layer was prepared.

The electrophotographic photosensitive member thus prepared was evaluated in the same manner as in Example 1.

As a result, the result was very good as in Example 1.

[0255]

[Table 14]

[Embodiment 3] Using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4, the substrate has a diameter of 108 mm and a length of 358 mm made of aluminum having a silicon atom content of 100 ppm. , A cylindrical substrate having a thickness of 5 mm was mirror-finished on an aluminum cylinder, and an amorphous silicon deposition film was formed on the substrate under the conditions shown in Table 15, and the blocking structure of the layer structure shown in FIG. An electrophotographic photoreceptor was produced. In FIG. 1 (c), 1
01, 105, 107, 106, 103 and 104 are
An aluminum substrate, a charge injection blocking layer, a charge transport layer, a charge generation layer, a photoconductive layer and a surface layer are shown respectively.

The electrophotographic photosensitive member thus prepared was evaluated in the same manner as in Example 1.

As a result, the result was very good as in Example 1.

[0259]

[Table 15]

[0260]

As described above, according to the present invention, an electrophotography having a photoconductive layer and a charge injection blocking layer made of an amorphous material having at least silicon atoms as a base material on a conductive support. In the method of manufacturing a photoconductor, a raw material gas for supplying silicon capable of supplying silicon atoms is 0.29 sccm / sec during the initial change time when the photoconductive layer is formed.
Above, 12 sccm / sec or less, with a dilution gas of 2.2 s
ccm or more, 73 sccm or less, discharge power 0.7 w /
sec or more, 27 w / sec or less, internal pressure 0.33 mm
By changing the pressure in the range from Torr to 13 mm Torr, it is possible to inexpensively and stably manufacture an electrophotographic photosensitive member having excellent electrical characteristics such as residual potential and providing a high-quality image.

Further, when the photoconductive layer is formed, the adhesion of the deposited film and the stress in the deposited film are alleviated by changing the source gas, the diluent gas, the discharge power, and the internal pressure at a predetermined ratio. It has become possible to inexpensively and stably obtain an electrophotographic photosensitive member which is capable of reducing the potential and which provides a high-quality image with good image defects and ghost.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram for explaining each layer of a photoconductor of a preferred embodiment of a method for manufacturing an electrophotographic photoconductor according to the present invention.

FIG. 2 is a graph showing changes in the initial change region in the raw material gas, the dilution gas, the discharge power, and the internal pressure, which are used in forming the photoconductive layer in the method for producing an electrophotographic photosensitive member according to the present invention.

FIG. 3 is a graph showing changes in raw material gas, dilution gas, discharge power, and internal pressure with time in the case of forming a photoconductive layer in the present invention.

FIG. 4 shows an example of an apparatus for forming an electrophotographic photosensitive member according to the present invention, and is a schematic explanatory view of an apparatus for manufacturing an electrophotographic photosensitive member by an RF glow discharge method.

FIG. 5 shows an example of an apparatus for forming an electrophotographic photosensitive member according to the present invention, and is a schematic explanatory view of an electrophotographic photosensitive member manufacturing apparatus by a VHF glow discharge method.

[Description of Reference Signs] 100 Photoreceptive member 101 Conductive support 102 Photoreceptive layer 103 Photoconductive layer 104 Surface layer 105 Charge injection blocking layer 106 Charge generation layer 107 Charge transport layer 110 Free surface 5100, 6100 Deposition apparatus 5111 Cathode electrode 5112 , 6112 Cylindrical support 5113, 6113 Support heating heater 5114 Raw material gas introduction pipe 5115, 6115 High frequency matching box 5116 Raw material gas pipe 5117 Reaction vessel leak valve 5118 Main exhaust valve 5119 Vacuum gauge 5200 Raw material gas supply device 5211-5216 Mass flow Controllers 5221 to 5226 Raw material gas cylinders 5231 to 5236 Raw material gas cylinder valves 5241 to 5246 Gas inflow valves 5251 to 5256 Gas outflow valves 5261 to 52 6 the pressure regulator 6111 reactor 6115 electrodes 6120 support rotating motor 6121 exhaust pipe 6130 discharge space

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C23C 16/50 H01L 21/205

Claims (11)

[Claims] 1. An amorphous material containing at least silicon atoms as a base material on a conductive support by a plasma CVD method using at least a raw material gas for supplying silicon and a diluting gas capable of supplying silicon atoms. In the method of manufacturing an electrophotographic photosensitive member having a photoconductive layer, the discharge power is 0.7 W / s from the beginning when the photoconductive layer is formed.
ec or more, 27 W / sec or less, internal pressure 0.33 mm
Torr / sec or more and 13 mm Torr or less, and a raw material gas for supplying silicon capable of supplying silicon atoms is 0.29 sccm / sec or more and 12 sccm / se.
c or less, dilution gas 2.2 sccm / sec or more, 73
A method for manufacturing an electrophotographic photosensitive member, characterized in that the change is performed at a rate of sccm / sec or less. 2. The discharge power, internal pressure, and
Raw material gas for supplying silicon, which can supply silicon atoms,
The method for producing an electrophotographic photosensitive member according to claim 1, wherein the region where the flow rate of the diluent gas is changed is 0.12% or more and 1.0% or less of the region where the photoconductive layer is formed. 3. The material gas for supplying silicon, which can supply the silicon atoms, is SiH ₄ gas and / or SiF.
_{4. The} method for producing an electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is 4. 4. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the diluent gas is H ₂ gas and / or He gas. 5. The method for producing an electrophotographic photosensitive member according to claim 1, further comprising a charge injection blocking layer provided between the photoconductive layer and the conductive support. 6. The method for producing an electrophotographic photosensitive member according to claim 1, wherein a surface layer is provided on the photoconductive layer. 7. The photoconductive layer has a layer thickness of 25 to 40 μm.
7. The method for producing an electrophotographic photosensitive member according to claim 1, wherein 8. The thickness of the charge injection blocking layer is 1 to 4 μm.
8. The method for manufacturing an electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is m. 9. The method for manufacturing an electrophotographic photosensitive member according to claim 1, wherein the surface layer has a layer thickness of 0.1 to 1 μm. 10. An amorphous material containing at least silicon atoms as a base material on a conductive support by a plasma CVD method using at least a raw material gas for supplying silicon and a diluting gas capable of supplying silicon atoms. In the method for producing a light receiving member having a photoconductive layer, the discharge power is 0.7 W / s from the beginning when the photoconductive layer is formed.
ec or more, 27 W / sec or less, internal pressure 0.33 mm
Torr / sec or more and 13 mm Torr or less, and a raw material gas for supplying silicon capable of supplying silicon atoms is 0.29 sccm / sec or more and 12 sccm / se.
c or less, dilution gas 2.2 sccm / sec or more, 73
A method for producing a light-receiving member, characterized in that the light-receiving member is changed within a range of sccm / sec or less. 11. An amorphous material containing at least silicon atoms as a base material on a conductive support by a plasma CVD method using at least a raw material gas for supplying silicon and a diluting gas capable of supplying silicon atoms. In the method for producing a photoreceptive member having a photoconductive layer, the discharge power is 0.8 W / s from the beginning when the photoconductive layer is formed.
ec or more, 13.5 W / sec or less, internal pressure 0.38 m
m Torr / sec or more and 4.4 mm Torr or less, and a raw material gas for supplying silicon capable of supplying silicon atoms is 0.4 sccm / sec or more and 4 sccm /
sec or less, diluent gas 2.5 sccm / sec or more,
A method of manufacturing a light-receiving member, characterized in that the light-receiving member is changed within a range of 29 sccm / sec or less.