JP3459700B2 - Light receiving member and method of manufacturing light receiving member - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreceptor that is 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 manufacturing a member.

[0002]

2. Description of the Related Art A solid-state image pickup device, a material for forming a photoreceptive member for electrophotography in an image forming field, or a photoconductive layer in a document reading device has a high sensitivity and an SN ratio [photocurrent (Ip) / (Id) ], And has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic wave to be radiated, has high photoresponsiveness, and has a desired dark resistance value,
It is required to be harmless to the human body during use, and further, the solid-state imaging device is required to have characteristics such that an afterimage can be easily processed within a predetermined time. Particularly in the case of the electrophotographic light-receiving member used in an office as an office machine, the above-mentioned pollution-free property at the time of use is an important point.

Materials that are drawing attention from this point of view are
Amorphous silicon whose dangling pound has been modified with a monovalent element such as hydrogen or a halogen atom (hereinafter referred to as "a-S
i ”), for example, Japanese Patent Laid-Open No. 54-8634.
Application No. 1 describes application to a light receiving member for electrophotography.

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

FIG. 4 is a schematic sectional view of a typical plasma CVD apparatus. In the figure, 5100 indicates 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 reaction vessel. The cathode electrode 5111 and the upper wall 5120 and the bottom wall 5121 are insulated from each other by an insulator 5122.

Reference numeral 5112 is a support provided in the vacuum reaction vessel, which is grounded to serve as an anode electrode. In the support 5112, the heater 51 for heating the substrate is provided.
13 is installed to heat the support to a predetermined temperature before film formation, to maintain the support at a predetermined temperature during film formation, or to anneal the support after film formation. Used for.

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 operation of the deposited film forming apparatus by the plasma CVD method is performed as follows. That is, the gas in the vacuum reaction vessel is evacuated through the exhaust pipe 5119, and the heater 5113 for heating supports 5
112 is heated and maintained at a predetermined temperature. Next, for example, in the case of forming an a-SiH deposited film through the source gas introduction pipe 5114, a source gas such as silane is introduced into the vacuum reaction container, and the source gas is the source gas of the gas introduction pipe. It is discharged into the vacuum reaction container through a discharge hole (not shown). Simultaneously with this, from the voltage applying means 5115, for example, a high frequency wave is applied to the cathode electrode 5111 and the support (anode electrode) 5.
It is applied between 112 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 ^* ( ^* represents an excited state), electrons, ionic particles, etc. are generated, and these particles or The chemical interaction between these particles and the surface of the support forms a deposited film on the surface of the support.

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 Publication No. 5-54953 discloses a technique of providing an intermediate layer which is a high resistance layer between a photoconductive layer and a surface protective layer in order to improve the potential holding ratio.

Further, in Japanese Patent Laid-Open No. 2-203350, the carbon content at the interface between the photoconductive layer and the intermediate layer and the carbon content at the interface between the intermediate layer and the surface layer are optimized to reduce dark attenuation. However, a technique for improving the surface potential is disclosed.

[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, by strictly cleaning the inside of the vacuum reaction container, it is possible to obtain a light receiving member with few defects. However, in these conventional methods for forming a light-receiving member, for products such as a light-receiving member for electrophotography, which require a large area and a relatively thick deposited film, the requirements for uniform optical quality and various optical and electrical characteristics are required. However, there remains a problem to be solved that it is difficult to obtain a deposited film that satisfies the above requirements 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, it is required to further improve the optical characteristics and the electrical characteristics, and at the same time, to extend the durability under all environments while maintaining the high charging ability and the high sensitivity.

Therefore, while the characteristics of the light receiving member itself are improved, the layer structure, the chemical composition of each layer, the manufacturing method, and the like should be improved from a comprehensive point of view so as to solve the above problems. It is necessary to plan.

An object of the present invention is to overcome various problems in the conventional method for manufacturing a light receiving member as described above, and to reduce the cost.
It is an object of the present invention to provide a method of manufacturing a light receiving member which is stable, has a high yield, and can be formed at a high speed.

[0017]

The present invention is a plasma CV.
A method for producing a light-receiving member in which a photoconductive layer, an intermediate layer, and a surface layer, which are made of an amorphous material containing at least silicon atoms as a base material, are sequentially laminated on a conductive support by the D method, The source gas for supplying silicon capable of supplying silicon atoms is 0.29 sccm / sec.
~ 27.6 sccm / sec, preferably 0.58 sc
cm / sec to 13.8 sccm / sec; the raw material gas for carbon supply capable of supplying carbon atoms is 1.33 sccm /
sec-128 sccm / sec, preferably 2.67
sccm / sec-42.7 sccm / sec; discharge power is 20 W / sec or less, preferably 0.42 W / se
c to 6.67 W / sec; internal pressure of 30 mTorr / se
c or less, preferably 0.63 mTorr / sec to 10
Provided is a method of manufacturing a light-receiving member, which is performed by changing the mTorr / sec, and a light-receiving member manufactured by the method.

The raw material gas for supplying silicon capable of supplying the silicon atoms is preferably SiH ₄ gas and / or SiF ₄ .

The raw material gas for carbon supply capable of supplying the carbon atoms is preferably CH ₄ .

A charge injection blocking layer is preferably provided between the photoconductive layer and the conductive support.

[0021]

[0022]

[0023]

[0024]

[0025]

The method of manufacturing the light-receiving member of the present invention uses plasma C
In the VD method, a method for producing a light-receiving member in which a photoconductive layer, an intermediate layer, and a surface layer, which are made of an amorphous material having at least silicon atoms as a base material, are sequentially laminated on a conductive support, The surface layer is connected to a source gas for supplying silicon capable of supplying silicon atoms at 0.29 scc.
m / sec to 27.6 sccm / sec, 1.33 sccm / s as a raw material gas for carbon supply capable of supplying carbon atoms
ec-128 sccm / sec, discharge power 20 W / s
By changing the internal pressure to ec or less and the internal pressure to 30 mTorr / sec or less, the scratch strength can be improved without changing the residual potential, and a high-quality image excellent in durability can be obtained. Although the mechanism has not been completely elucidated, the present inventors think as follows.

For example, when a deposited film is formed on a relatively large area such as an electrophotographic photosensitive member, the stress in the film increases, and as a result, the photoconductive property and the charge retention property are considered to deteriorate. . In addition, even if they have a common constituent element of silicon atoms, the stress in each layer may differ due to the compositional / structural differences due to the difference in the contained substances, or due to the characteristic differences such as the direction and size of stress. Occurs.

When an amorphous silicon deposited film is formed on a support by plasma CVD, the reaction is
The decomposition process of the source gas in the gas phase, the process of transporting active species from the discharge space to the surface of the substrate, and the process of surface reaction on the surface of the support can be considered separately. Among these, 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.

When connecting the intermediate layer and the surface layer as in the present invention, the discharge power, the internal pressure, the raw material gas for supplying silicon which can supply silicon atoms, and the raw material gas for supplying carbon which can supply carbon atoms are set. When the value is changed with a predetermined value, the strain due to the structural / characteristic difference between the intermediate layer and the surface layer is absorbed, and the stress in the intermediate layer and the surface layer is greatly reduced. It is thought that there is. From this, it is considered that the structure of the deposited film can be densified without deteriorating the charge traveling property, and as a result, the pulling strength can be improved without changing the residual potential.

Further, this effect is particularly remarkable in preventing deterioration of image characteristics during repeated use. The surface of the electrophotographic photosensitive member rubs against the transfer paper or the cleaning blade each time it is repeatedly used. Therefore, if the surface layer is weak in terms of strength, the surface is abraded during long-term use, and the image characteristics are likely to deteriorate. In the manufacturing method of the present invention, the stress in the deposited film is relieved and the structure of the deposited film is densified, so that the abrasion of the surface due to rubbing is significantly reduced, and the deterioration of the image characteristics due to long-term use is prevented. It can be reduced.

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 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, etc.), sputtering method, vacuum deposition method, ion plating method, photo CVD method, thermal CVD method, and various thin film deposition methods. These thin film deposition methods are appropriately selected and adopted according to factors such as manufacturing conditions, a load level under capital investment, manufacturing scale, and characteristics required for a light receiving member to be produced. The glow discharge method, particularly the high frequency glow discharge method using a power supply frequency in the RF band or the VHF band, is preferable because it is relatively easy to control the conditions for manufacturing the light receiving member having the above.

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 a high frequency plasma CVD (hereinafter referred to as "RF
It is a schematic diagram which shows an example of the manufacturing apparatus of the light receiving member by the (-PCVD) method.

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 5100 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) of raw material gases such as H ₂ , CH ₄ , NO, B ₂ H ₆ , and GeH ₄ and valves (5231 to 52)
36, 5241 to 5246, 5251 to 5256) and a mass flow controller (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 cylindrical support 5112 is installed in the reaction vessel 5111, and the inside of the reaction vessel 5111 is evacuated by the exhaust device 5117 (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 controlled to a predetermined temperature of 250 ° C to 500 ° C.

A raw material gas for forming a deposited film is supplied to a reaction vessel 511.
In order to make it flow into 1, the gas cylinder valves 5231-5
236, make sure that the leak valve 5123 of the reaction vessel is closed, and check the inflow valve (5251-52).
56), after confirming that the outflow valves (5241 to 5246) and the auxiliary valve 5260 are opened, first, the main valve 5118 is opened to evacuate the reaction vessel 5111 and the gas pipe 5116.

Next, the reading of the vacuum gauge 5124 is about 5 × 10 ^-6
The auxiliary valve 5260 and the outflow valve (5251 to 5256) are closed at the time of Torr.

After that, gas cylinders (5221 to 522)
From 6), each gas is introduced by opening the valves (5231 to 5236), and the pressure of each gas is adjusted by the pressure regulator (5261 to 5266) (for example, 2 Kg / cm ² ). Next, the inflow valves (5241 to 5246) are gradually opened to allow each gas to flow through the mass flow controllers (5211 to 5216).
Introduce inside.

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

When the cylindrical support 5122 reaches a predetermined temperature, the necessary ones of the outflow valves (5251 to 5256) and the auxiliary valve 5260 are gradually opened,
A predetermined gas is introduced from the gas pump (5221 to 5226) into the reaction vessel 5111 via the gas introduction pipe 5114. Next, mass flow controller (5211 to 521)
By 6), each raw material gas is adjusted so as to have a predetermined flow rate. At that time, the pressure in the reaction vessel 5111 is 1 Torr.
The opening of the main valve 5118 is adjusted while observing the vacuum gauge 5124 so that the following predetermined pressure is obtained. When the internal pressure is stable, the RF power source (not shown) is set to a predetermined power, and the RF power is introduced into the reaction vessel 5111 through the high frequency matching box 5115 to cause the RF glow discharge. The raw material gas introduced into the reaction vessel is decomposed by this discharge energy, and the cylindrical support 511
A deposited film containing a predetermined silicon as a main component is formed on the surface 2. After forming the desired film thickness, RF
The supply of electric power is stopped, the outflow valve is closed to stop the inflow of gas into the reaction vessel, and the formation of the deposited film is completed.

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

FIG. 3 is a schematic diagram showing changes in each parameter during formation of a deposited film in the manufacturing method of the present invention. The connection between the intermediate layer and the surface layer is adjusted by RF power, a mass flow controller, and an exhaust device to discharge electric power, a flow rate of a raw material gas for supplying silicon atoms capable of supplying silicon atoms, and a raw material gas for supplying carbon atoms capable of supplying carbon atoms. The flow rate and the internal pressure are changed by a predetermined value.

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 5111.
Inside, outflow valve (5251 to 5256) to reaction vessel 5
In order to avoid remaining in the pipe leading to 111, the outflow valves (5251 to 5256) are closed and the auxiliary valve 5
If necessary, the operation of opening 260 and further fully opening the main valve 5118 to evacuate the system to a high vacuum is performed.

When the film formation is to be made 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 formation conditions of 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 the above, a method such as providing a container for heating only in addition to the reaction container 5111, heating the cylindrical support 5112, and then transporting the cylindrical support 5112 in the reaction container 5111 in a vacuum is used. To be

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

RF-PC in the manufacturing apparatus shown in FIG.
By exchanging 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 a light receiving member manufacturing apparatus by the VHF-PCVD method.

This apparatus is roughly classified into a vacuum-tightened reaction vessel 6111 capable of depressurization, a source gas supply apparatus 5200, and a disposal apparatus (not shown) for reducing the pressure in the reaction vessel. There is. A cylindrical support 6112 and a heater 6 for heating the support are provided in the reaction vessel 6111.
113, a source gas introduction pipe (not shown) and an electrode 6115 are installed, and the electrode further has a high frequency matching box 61.
16 are connected. In addition, the inside of the reaction vessel 6111 is
It is connected to a diffusion pump (not shown) through an exhaust pipe 6121. Further, the inside of the reaction vessel 6111 has an exhaust pipe 6121.
Through a diffusion pump (not shown).

The source gas supply device 5200 is made of SiH ₄ ,
_{GeH 4, H 2, CH 4} , B 2 H 6, a cylinder of the source gas PH _3, etc. and (5,221 to 5,226) Valve (5231-52
36, 5241 to 5246, 5251 to 5256) and a mass flow controller (5211 to 5216), and a cylinder of each source gas is connected to a gas introduction pipe (not shown) in the reaction vessel 6111 via a valve 5260. . A space 6130 surrounded by the cylindrical support 6112 forms a discharge space.

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

First, a cylindrical support 6112 is installed in a reaction vessel 6111, and the support 6 is driven by a driving device 6120.
112 is rotated, and the inside of the reaction vessel 6111 is exhausted through an exhaust pipe 6121 by an exhaust device (not shown) (for example, a diffusion pump), and the pressure inside the reaction vessel 6111 is 1 × 10 ⁻⁷ To.
Adjust to rr or less. Then, the heater 6 for heating the support
113 the temperature of the cylindrical support 6112 to 200 to 3
It is heated and maintained at a predetermined temperature of 50 ° C.

A raw material gas for forming a deposited film is supplied to a reaction vessel 611.
The gas cylinder valve (5231 to
5236) and the leak valve (not shown) of the reaction vessel are closed, and the inflow valve (524
1 to 5246), outflow valves (5251 to 5256),
After confirming that the auxiliary valve 5260 is opened, first, the main valve (not shown) is opened to evacuate the reaction vessel 6111 and the gas pipe.

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 valve (5251 to 5256) are closed.

After that, gas cylinders (5221 to 522)
From (6), each gas is introduced by opening the valves (5231 to 5236), and the pressure of each gas is adjusted to ² Kg / cm ² by the pressure adjuster (5261 to 5266). Next, the inflow valves (5241 to 5246) are gradually opened to introduce each gas into the mass flow controllers (5211 to 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, necessary ones of the outflow valves (5251 to 5256) and the auxiliary valve 5260 are gradually opened, and a predetermined gas is discharged from the gas cylinder (5221 to 5226). It is introduced into the discharge space 6130 in the reaction vessel 6111 via an introduction pipe (not shown). 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 (not shown) is adjusted while observing the vacuum gauge (not shown) so that the pressure in the discharge space 3130 becomes a predetermined pressure of 1 Torr or less.

When the pressure is stable, the charge injection blocking layer is formed by setting a VHF power source (not shown) having a frequency of 105 MHz to a predetermined power and matching box 6 for example.
VHF power is introduced into the discharge space 6130 through 116 to cause glow discharge. Thus support 6112
In the discharge space 6130 surrounded by, the introduced source gas is excited by discharge energy and dissociates, and a predetermined deposited film is formed on the support 6112. At this time, in order to make the layer formation uniform, the support rotating motor 6120 is rotated at a predetermined 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 multilayer structure is formed.

Needless to say, all of the outflow valves other than the necessary gas are closed when forming each layer, and each gas is supplied to the reaction vessel 6111.
Inside, outflow valve (5251 to 5256) to reaction vessel 6
In order to avoid remaining in the pipe leading to 111, the outflow valves (5251 to 5256) are closed and the auxiliary valve 5
Open 260, and further fully open the main valve (not shown) to evacuate the system to a high vacuum if necessary.

Needless to say, 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. to 350 ° C., preferably 2 °
The temperature is 3 ° C to 330 ° C, more preferably 250 ° C to 300 ° C.

The heating method of the support may be any heating element having a vacuum specification, and more specifically, electric resistance heating elements such as a wound heater of a sheath heater, a plate heater, a ceramic heater, a halogen lamp, an infrared ray. Examples include a heat-radiating lamp heating element such as a lamp, and a heating element using a heat exchange means using liquid or gas 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, a method may be used in which a container dedicated to heating is provided in addition to the reaction container, and after heating, the support is conveyed into the reaction container in a vacuum.

The pressure of the discharge space in the VHF-PCVD method is preferably 1 mTorr to 500.
mTorr, more preferably 3 mTorr to 300 mT
orr, most preferably 5 mTorr to 100 mTor
Set to r.

In the VHF-PCVD method, the size and shape of the electrodes provided in the discharge space may be any as long as they do not disturb the discharge, but in practical use the diameter is from 1 mm to 10 mm.
A cylindrical shape of cm is preferable. At this time, the length of the electrodes can be arbitrarily set as long as the electric field is uniformly applied to the support.

Any material can be used as the material of the electrode as long as it has a conductive surface. For example, stainless steel, Al, Cr, Mo, Au, In, Nb, Te, V,
Metals such as Ti, Pt, Pb, Fe and their alloys;
Glass, ceramics, etc., the surface of which has been electrically conductive, are usually used. (Support) The support used in the present invention may be conductive or electrically insulating. As the conductive support, A
l, Cr, Mo, Au, In, Nb, Te, V, Ti,
Examples thereof include metals such as Pt, Pd, Fe and alloys thereof (for example, stainless steel). In addition, polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene,
It is also possible to use a support in which the surface of at least the light-receiving layer-forming side of an electrically insulating support such as a film or sheet of a synthetic resin such as polyamide, glass, or ceramics is subjected to a conductive treatment.

The shape of the support used in the present invention may be a cylindrical or plate-like endless belt having a smooth surface or an uneven surface, and its thickness is such that a desired light receiving member can be formed. When flexibility as a light receiving member is required, the thickness can be made as thin as possible within a range in which the function as a support can be sufficiently exhibited. However, the support is usually 10 μm or more in view of manufacturing and handling, mechanical strength and the like.

In particular, when image recording is performed using coherent light such as laser light, in order to more effectively eliminate image defects due to so-called interference fringe patterns that appear in visible images, the surface of the support is You may provide unevenness. The unevenness provided on the surface of the support is disclosed in JP-A-60-168156.
No. 60-178457, No. 60-225.
It is formed by a known method described in Japanese Patent No. 854, etc.

Further, as another method for more effectively eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, the surface of the support is provided with a concavo-convex shape by a plurality of spherical trace depressions. May be. That is, the surface of the support has irregularities that are smaller than the resolving power required for the electrophotographic light-receiving member, and the irregularities are due to a plurality of spherical trace depressions. The unevenness due to the plurality of spherical trace depressions provided on the surface of the support is formed by the known method described in JP-A-61-235661. (Charge Injection Blocking Layer) The charge injection blocking layer in the method for producing a photoreceptive member of the present invention is such that when the photoreceptive layer undergoes electrification treatment of constant polarity on its free surface, charges are transferred from the support side to the photoconductive layer side. It has a function of preventing injection, and has a so-called polarity dependence, which does not exhibit such a function when subjected to a charging process of opposite polarity. In order to impart such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer.

The conductivity controlling atoms contained in the layer may be evenly distributed in the layer, or they may be contained evenly in the layer thickness direction but in the layer direction. There may be an uneven distribution. When the distribution concentration is non-uniform, it is preferable that the content is so distributed as to be distributed more on the support side. 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.

As the atoms contained in the charge injection blocking layer for controlling the conductivity, so-called impurities in the field of semiconductors can be cited, and atoms belonging to Group IIIb of the periodic table which give p-type conduction characteristics (hereinafter referred to as " Group IIIb atom "
Abbreviated) or the periodic table V which gives n-type conduction characteristics
Atoms belonging to group b (hereinafter abbreviated as "Vb group atoms")
Can be used.

Specific examples of the group IIIb atom are:
There are B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), and the like, 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 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 nitrogen atom and oxygen atom, it is possible to further improve the adhesiveness with other layers provided in direct contact with the charge injection blocking layer.

The carbon atoms, nitrogen atoms or oxygen atoms contained in the layer may be uniformly distributed in the layer, or they may be contained in the layer thickness direction but not in the layer direction. There may be a non-uniform portion of the distribution. 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, 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, as the amount thereof, in the case of two or more kinds, as the sum thereof, preferably 1 × 10 ⁻³ to
The content is 50 atomic%, more preferably 5 × 10 ⁻³ to 30 atomic%, and most preferably 1 × 10 ⁻² to 10 atomic%.

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

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 flow rate of H ₂ and / or He as a diluting gas is appropriately selected in accordance with the layer design, and H ₂ and / or He is added to the Si supply gas.
In the usual case, it is controlled within a range of 1 to 20 times, preferably 3 to 15 times, and optimally 5 to 10 times.

Regarding the gas pressure in the reaction vessel, similarly, the optimum range is appropriately selected according to the layer design, but in the usual case, 1 × 10 ^{−4 to} 10 Torr, preferably 5 × 10 ^{−4 to} 5
Torr, optimally 1 × 10 ^{−3 to} 1 Torr.

Similarly, the discharge power is appropriately selected in an optimum range according to the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 0.1 to 5 times, preferably 0.5 to. The range is set to 3 times, optimally 0.7 to 2 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 ° C.
The optimum temperature is 240 to 310 ° C.

In the present invention, the desirable 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 include the above-mentioned ranges. 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 and improves the layer quality. In particular, it is essential for improving photoconductivity and charge retention characteristics. Therefore, the content of hydrogen atoms or halogen atoms, or the amount of the sum of hydrogen atoms and halogen atoms is 10 to 30 atom%, more preferably 15 to 25 atom% with respect to the total sum of silicon atoms, hydrogen atoms and / or halogen atoms. And

Materials that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ , and Si ₃ H.
₈ , silicon hydride (silanes) in a gas state such as Si ₄ H ₁₀ or capable of being gasified are mentioned as being effectively used, and further, it is easy to handle at the time of forming a layer, and has good Si supply efficiency. In this respect, 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 to these gases, H ₂ and / or H
It is necessary to mix a desired amount of e or a silicon compound gas containing hydrogen atoms 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.

Further, as a raw material gas for supplying a halogen atom used in the present invention, for example, a gaseous or gasified halogen gas, a halide, an interhalogen compound containing halogen, a silane derivative substituted with halogen, or the like is used. The halogen compound to be obtained is preferable. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains silicon atoms and a halogen atom as constituent elements, can also be cited as an effective one. Specific examples of the halogen compound that can be preferably used in the present invention include fluorine gas (F2) and Br.
F, ClF, ClF ₃ , BlF ₃ , BrF ₅ , IF ₃ , IF
An interhalogen compound such as ₇ can be mentioned. Specific examples of the silicon compound containing a halogen atom, that is, a silane derivative substituted with a halogen atom include, for example, S
Silicon fluorides such as iF ₄ and Si ₂ F ₆ can be mentioned as preferable ones.

Hydrogen atoms contained in the photoconductive layer and /
Alternatively, in order to control the amount of halogen atoms, for example, the temperature of the support, the amount of raw material used for containing hydrogen atoms and / or halogen atoms to be introduced into the reaction vessel, discharge power, etc. can be controlled. Good.

In the present invention, it is preferable that the photoconductive layer contain atoms for controlling the conductivity, if necessary.
Atoms that control conductivity may be evenly distributed in the photoconductive layer, or they may be evenly distributed in the layer thickness direction but have a non-uniform distribution in the layer direction. May be.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors, and a Group IIIb atom giving a p-type conduction characteristic or a Group Vb atom giving an n-type conduction characteristic is used. You can

Specific examples of the group IIIb atom are:
There are B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), and the like, 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.

[0095] The content of the atoms for controlling the electroconductive property, contained in the photoconductive layer, preferably 1 × 10 over ² to 1 × 10
⁴ atom ppm, more preferably 5 × 10 ^{-2 to} 5 × 10 ³ atom ppm, optimally 1 × 10 ^-1 to 1 × 10 ³ atom ppm
And

Atoms that control conductivity, eg IIIb
To introduce a group atom or a group Vb atom structurally,
At the time of forming the layer, the raw material for introducing the group IIIb atom or the raw material for introducing the group Vb atom may be introduced into the reaction vessel in a gas state together with other gas for forming the photoconductive layer. . As a raw material for introducing a group IIIb atom or a raw material for introducing a group Vb atom, a gaseous substance at room temperature and normal pressure, or at least a substance that can be easily gasified under layer forming conditions is adopted. Is desirable.

As a raw material for introducing such a group IIIb atom, specifically, for introducing a boron atom, B _{2
H 6, B 4 H 10,} B 5 H 9, B 5 H 11, B 6 H 10, B 6 H 12,
Examples thereof include boron hydride such as B ₆ H ₁₄ and boron halide such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ ,
_{GaCl 3, Ga (CH 3)} 3, InCl 3, may also be mentioned TlCl _3, etc..

As the raw material for introducing the group Vb atom, PH ₃ and P ₂ are effectively used for introducing the phosphorus atom.
Phosphorus hydride such as H ₄ , PH ₄ I, PF ₃ , PF ₅ , PCl ₃ ,
Examples thereof include phosphorus halides such as 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 , S
bCL ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃
And the like can be mentioned as effective starting materials for introducing a Group Vb atom.

Further, these raw material 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 also effective that the photoconductive layer contains carbon atoms, oxygen atoms and / or nitrogen atoms. Carbon atoms, oxygen atoms and / or nitrogen atom content of silicon atoms, carbon atoms, preferably 1 × 10 over ^5-1 on the sum of the oxygen atoms and nitrogen atoms
0 atomic%, more preferably 1 × 10 over ^4-8 atomic%, and 1 × 10 over ^3-5 atomic% and optimally. Carbon atoms, oxygen atoms and / or nitrogen atoms may be evenly and uniformly contained in the photoconductive layer, or may be uniformly distributed in the layer thickness direction of the photoconductive layer but distributed in the layer direction. There may be a non-uniform portion.

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

[0103] 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 to 1 to 20 times, preferably 2 to 15 times, and optimally 4 to 10 times.

Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, and an optimum range is selected.
0 over ⁴ to 10 Torr, preferably 5 × 10 ^-4 ~5Tor
r, optimally 1 × 10 ^{−3 to} 1 Torr.

Similarly, the discharge power is appropriately selected in the optimum range according to the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 0.5 to 7 times, preferably 0.7 to 6 times, optimally 1 to 5 times.

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

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the temperature of the support, the gas pressure, the discharge power, and the gas flow rate for forming the photoconductive layer, but the conditions are usually independent and separate. It is not determinable, but it is desirable to determine the optimum value based on mutual and organic relationships to form a light receiving member having desired characteristics. (Intermediate Layer) In the present invention, it is preferable to form an intermediate layer on the photoconductive layer. This intermediate layer has a function of preventing charges from flowing into the photoconductive layer from the surface side by hopping conduction, and is effective in improving charging ability and the like.

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

In the present invention, in order to effectively achieve the object, the intermediate 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. It 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 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 manufactured. From the viewpoint of productivity of the member, it is preferable to use the same deposition method as that for the photoconductive layer.

For example, a-Si is formed by the glow discharge method.
To form an intermediate layer composed of C: H, X, basically, a raw material gas for supplying Si that can supply silicon atoms (Si) and a raw material for supplying C that can supply carbon atoms (C). A gas and a source gas for supplying H, which can supply hydrogen atoms (H), and / or a source gas for supplying X, which can supply halogen atoms (X), are contained in a reaction vessel capable of reducing the pressure inside a desired gas. In this state, a glow discharge is generated in the reaction vessel, and a layer made of a-SiC: H, X may be formed on the support on which a photoconductive layer has been formed and which is installed at a predetermined position in advance. .

The material of the intermediate 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, and particularly, a
A material containing -SiC as a main component is preferable.

When the intermediate layer is mainly composed of a-SiC, the amount of carbon is preferably in the range of 0% to 90% with respect to the sum of silicon atoms and carbon atoms.

In the present invention, it is necessary for the intermediate 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. Further, the content of fluorine atoms is usually 0.
The amount is 01 to 15 atom%, preferably 0.1 to 10 atom%, and most preferably 0.6 to 4 atom%.

The carbon content and fluorine content in the intermediate layer are the same as the hydrogen content, such as gas flow rate, support temperature, discharge power,
It can be controlled by gas pressure or the like.

As the substance which can be used as a gas for supplying silicon (Si) used in the formation of the intermediate layer of the present invention,
SiH _4, the _{Si 2 H 6, Si 3 H} 8, Si 4 gas state of H _10, etc., or silicon hydride can be gasified (silanes) can be mentioned as being effectively used, further layers when creating SiH ₄ and Si ₂ are easy to handle and have good Si supply efficiency.
H ₆ is mentioned as a preferred one. In addition, these raw material gases for supplying Si may be added with H ₂ , He and A as needed.
It may be diluted with a gas such as r or Ne before use.

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

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

Further, in order to more easily control the introduction ratio of hydrogen atoms introduced into the formed intermediate layer, hydrogen gas or a silicon compound gas containing hydrogen atoms is mixed in a desired amount with these gases. It is preferable 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.

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

The amount of hydrogen atoms and / or halogen atoms contained in the intermediate 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, discharge power, pressure, etc. may be controlled.

Carbon atoms, oxygen atoms and / or nitrogen atoms may be uniformly contained in the intermediate layer,
Alternatively, there may be a portion in which the intermediate layer is uniformly contained in the layer thickness direction but the distribution in the layer direction is not uniform.

Further, in the present invention, it is preferable that the intermediate layer contain atoms for controlling conductivity, if necessary. Atoms that control conductivity may be evenly distributed in the intermediate layer, or they may be evenly distributed in the layer thickness direction, but there is a part where the distribution in the layer direction is not uniform. Good.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors, and a group IIIb atom giving a p-type conduction characteristic or a group Vb atom giving an n-type conduction characteristic is used. You can

Specific examples of the group IIIb atom are:
There are B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), and the like, 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.

The content of atoms controlling the conductivity contained in the intermediate layer is preferably 1 × 10 ⁻³ to 1 × 10 ^3.
Atomic ppm, more preferably 1 × 10 ^{-2 to} 5 × 10 ² atomic ppm, optimally 1 × 10 ^-1 to 1 × 10 ² atomic ppm
Is desirable. To structurally introduce a conductivity controlling atom, for example, a group IIIb atom or a group Vb atom, a raw material for introducing a group IIIb atom or a group Vb atom for introducing a group IIIb atom is formed during layer formation. The raw material may be introduced into the reaction vessel in a gas state together with another gas for forming the intermediate layer.

As the raw material for introducing the group IIIb atom or the raw material for introducing the group Vb atom, those which are gaseous at room temperature and normal pressure or which can be easily gasified under at least the layer forming conditions are mentioned. It is desirable to be adopted. As the raw material for introducing such a group IIIb atom, specifically, for introducing a boron atom, B ₂ H ₆ , B ₄
Examples thereof include boron hydrides such as H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ and B ₆ H ₁₄ , and boron halides such as BF ₃ , BCl ₃ and BBr _3. . In addition, AlCl ₃ and GaC
Other examples include l ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , and TlCl ₃ .

Effectively used as a raw material for introducing a group Vb atom is PH ₃ , P ₂ for introducing a phosphorus atom.
Phosphorus hydride such as H ₄ , PH ₄ I, PF ₃ , PF ₅ , PCl ₃ ,
Examples thereof include phosphorus halides such as 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 , S
bCL ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃
And the like can be mentioned as effective starting materials for introducing a Group Vb atom.

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

The layer thickness of the intermediate layer in the present invention is usually 100 to 5000Å, preferably 300 to 3000Å,
The optimum value is 500 to 2000Å. If the layer thickness is less than 100Å, the effectiveness as a blocking layer will be lost and 50
If it exceeds 00Å, deterioration of electrophotographic characteristics such as increase of residual potential is observed.

The interlayer according to the present invention is carefully formed so that its required properties are provided as desired.
That is, a substance having Si; C, N and / or O; H and / or X as a structural element may have a structurally crystalline to amorphous form depending on its forming condition, and an electrical property may be a conductivity to a semiconductor. Since it exhibits the properties ranging from photoconductive property to non-photoconductive property, the compound having desired properties according to the purpose is formed. Thus, the choice of forming conditions is made strictly as desired.

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

Further, when the intermediate layer is provided mainly for the purpose of improving the characteristics of continuous repeated use and the characteristics of use environment, the above-mentioned degree of electrical insulation is relaxed to some extent, and sensitivity to irradiation light is made to some extent. Is formed as a non-single crystal material having.

In order to form the intermediate layer 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 according to the layer design, but in the usual case, it is preferably 200 to 350 ° C., more preferably 230 to 330.
C, optimally 250-310C.

Similarly, the gas pressure in the reaction vessel is appropriately selected according to the layer design, but in the usual case, it is preferably 1 × 10 ^{−4 to} 10 Torr, more preferably 5 ×.
10 ^{−4 to 5} Torr, optimally 1 × 10 ^{−3 to} 1 Torr
And

Similarly, the discharge power is appropriately selected in an optimum range according to the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 0.1 to 5 times, preferably 0.5 to. The range is set to 3 times, optimally 0.7 to 2 times.

The flow rate of the CH ₄ gas used as a carbon supply source gas capable of supplying carbon atoms is appropriately selected in accordance with the layer design, but CH ₄ gas is usually used for the Si supply gas. In the case of 1 to 20 times, preferably 1.
It is controlled within a range of 5 to 15 times, and optimally 2 to 10 times.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the support temperature, the gas pressure, the discharge power and the gas flow rate for forming the intermediate layer, but the conditions are usually determined independently and separately. However, 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 desired characteristics.

A carbon atom is provided between the intermediate layer and the photoconductive layer,
A region in which the content of oxygen atoms and / or nitrogen atoms changes so as to decrease toward the photoconductive layer may be provided. Thereby, the adhesion between the intermediate layer and the photoconductive layer can be improved, and the influence of interference due to the reflection of light at the interface can be further reduced. (Surface Layer) In the present invention, it is preferable to form a surface layer on the intermediate 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.

The surface layer can be made of any material as long as it is an amorphous silicon material. For example, the above-mentioned "a-SiC: H, X", "a-SiO: H, X",
"A-SiN: H, X", "a-SiCON: H, X"
Materials such as are preferably used.

In the present invention, in order to effectively achieve the object, the surface layer is produced by the vacuum deposition film forming method by appropriately setting the numerical conditions of the 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 manufacturing scale and desired characteristics of the electrophotographic light-receiving member to be produced.
From the viewpoint of productivity of the light receiving member, it is preferable to use the same deposition method as for the intermediate layer.

For example, a-Si is formed by the glow discharge method.
To form a surface layer composed of C: H, X, basically, a raw material gas for supplying Si, which can supply silicon atoms (Si), and a raw material for supplying C, which can supply carbon atoms (C). A gas and a source gas for supplying H, which can supply hydrogen atoms (H), and / or a source gas for supplying X, which can supply halogen atoms (X), are contained in a reaction vessel capable of reducing the pressure inside a desired gas. In this state, a glow discharge is generated in the reaction vessel, and a layer made of a-SiC: H, X may be formed on the support on which a photoconductive layer has been formed and which is installed at a predetermined position in advance. .

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, and particularly 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. Further, the content of fluorine atoms is usually 0.
The amount is 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 the practical view. That is, it is known that defects existing in the surface layer (mainly dangling bonds of silicon atoms and carbon atoms) have a bad influence on the characteristics of the light receiving member for electrophotography. 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. Charge is injected,
This adverse effect is caused by the occurrence of an afterimage phenomenon during repeated use due to the trapping of charges in the defects in the surface layer. Like the hydrogen content, the fluorine content in the surface layer can be controlled by the gas flow rate, the support temperature, the discharge power, the gas pressure and the like.

As the substance which can be used as a gas for supplying silicon (Si) used in the formation of the surface layer of the present invention,
SiH _4, the _{Si 2 H 6, Si 3 H} 8, Si 4 gas state of H _10, etc., or the like as silicon hydride can be gasified (silanes) is effectively used, when further layers produced SiH ₄ and Si ₂ are easy to handle and have good Si supply efficiency.
H ₆ is mentioned as a preferred one. In addition, these raw material gases for supplying Si may be added with H ₂ , He and A as needed.
It may be diluted with a gas such as r or Ne before use.

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

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

Further, in order to more easily control the introduction ratio of hydrogen atoms introduced into the surface layer to be formed, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is further mixed with these gases. It is preferable 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.

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

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, discharge power, pressure, etc. may be controlled.

Carbon atoms, oxygen atoms and / or nitrogen atoms may be uniformly contained in the surface layer,
Alternatively, there may be a portion in which the surface layer is uniformly distributed in the layer thickness direction but the distribution in the layer direction is not uniform.

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 evenly and uniformly contained in the surface layer, or may be uniformly contained in the surface layer in the layer thickness direction, but there may be uneven distribution in the layer direction. It may be.

Examples of the atoms for controlling the conductivity include so-called impurities in the semiconductor field,
Group IIIb atoms that provide p-type conductivity properties or Group Vb atoms that provide n-type conductivity properties can be used.

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

The content of atoms controlling the conductivity contained in the surface layer is preferably 1 × 10 ⁻³ to 1 × 10 ^3.
Atomic ppm, more preferably 1 × 10 ^{-2 to} 5 × 10 ² atomic ppm, optimally 1 × 10 ^-1 to 1 × 10 ² atomic ppm
And

Atoms that control conductivity, eg IIIb
To introduce a group atom or a group Vb atom structurally,
At the time of forming the layer, the raw material for introducing the group IIIb atom or the raw material for introducing the group Vb atom may be introduced into the reaction vessel in a gas state together with another gas for forming the surface layer. As a raw material for introducing a group IIIb atom or a raw material for introducing a group Vb atom, a gaseous substance at room temperature and normal pressure, or at least a substance that can be easily gasified under layer forming conditions is adopted. Is desirable.

As a raw material for introducing such a group IIIb atom, specifically, for introducing a boron atom, B _{2
H 6, B 4 H 10,} B 5 H 9, B 5 H 11, B 6 H 10, B 6 H 12,
Examples thereof include boron hydride such as B ₆ H ₁₄ and boron halide such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ ,
_{GaCl 3, Ga (CH 3)} 3, InCl 3, may also be mentioned TlCl _3, etc..

As the raw material for introducing the group Vb atom, PH ₃ and P ₂ are effectively used for introducing the phosphorus atom.
Phosphorus hydride such as H ₄ , PH ₄ I, PF ₃ , PF ₅ , PCl ₃ ,
Examples thereof include phosphorus halides such as 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 , S
bCL ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃
And the like can be mentioned as effective starting materials for introducing a Group Vb atom.

Further, these raw material substances for atom introduction for controlling conductivity may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, 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. When 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 when it exceeds 3 μm, electrophotographic characteristics such as increase in residual potential are deteriorated.

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, N and / or O; H and / or X as a structural element may have a structurally crystalline to amorphous form depending on its forming condition, and an electrical property may be a conductivity to a semiconductor. Since it exhibits the properties ranging from photoconductive property to non-photoconductive property, the compound having desired properties according to the purpose is formed. Thus, the choice of forming conditions is made strictly as desired.

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 the characteristics of continuous repeated use and the characteristics of use environment, the degree of the above-mentioned electric insulation is alleviated to some extent and the sensitivity to the irradiated light is made to some extent. Is formed as a non-single crystal material having.

In order to form a surface layer 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 according to the layer design, but in the usual case, it is preferably 200 to 350 ° C., more preferably 230 to 330.
C, optimally 250-310C.

The gas pressure in the reaction vessel is also appropriately selected in accordance with the layer design, but in the usual case, it is preferably 1 × 10 ^{−4 to} 10 Torr, more preferably 5 ×.
10 ^{−4 to 5} Torr, optimally 1 × 10 ^{−3 to} 1 Torr
And

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 1 to 50 times, preferably 3 to 40 times. Is set in the range of 5 to 30 times.

The flow rate of the CH ₄ gas used as a carbon supply source gas capable of supplying carbon atoms is appropriately selected in accordance with the layer design, but CH ₄ gas is usually used for the Si supply gas. 1 to 100 times, preferably 1
Control is performed within a range of 0 to 80 times, optimally 30 to 70 times.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the support temperature, the gas pressure, the discharge power and the gas flow rate for forming the surface layer, but the conditions are usually determined independently and separately. However, 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 desired characteristics. (Connection between the intermediate layer and the surface layer) In the connection between the intermediate layer and the surface layer, if the change in the raw material gas for supplying silicon capable of supplying silicon atoms is less than 0.29 sccm / sec, the scratch strength is improved, but the residual strength remains. It has no effect on the electric potential. Also, 27.6
If it is higher than sccm / sec, the effect of the present invention cannot be obtained. Therefore, 0.29 to 27.6 sccm / sec is preferable, and 0.58 to 13.8 sccm / sec is more preferable.

Further, when the change of the raw material gas for supplying carbon capable of supplying carbon atoms is less than 1.33 sccm / sec, the scratch strength is improved but the residual potential is not effective.
If it is higher than 128 sccm / sec, the effect of the present invention cannot be obtained. Therefore, 1.33 to 128 sccm / sec
Is preferable, and 2.67-42.7 sccm / sec is more preferable.

Furthermore, the change in discharge power is 20 W / sec.
If it is larger, the effect of the present invention cannot be obtained. Therefore, 20
W / sec or less is preferable, 0.42 to 6.67 W / s
ec is more preferred.

Furthermore, the change in internal pressure is 30 mTorr / s.
If it is larger than ec, the effect of the present invention cannot be obtained. Therefore 3
0 mTorr / sec or less is preferable, and 0.63 to 10
More preferred is mTorr / sec.

In the connection, the silicon supply source gas capable of supplying silicon atoms, the carbon supply source gas capable of supplying carbon atoms, the discharge power, and the change pattern of the internal pressure are shown in FIG.
(A) linear change, (b) rapid change at the beginning of the change region, (c) rapid change at the end of the change region, (d) rapid change in the middle of the change region, (e) change region It is possible to use any change pattern of abrupt change at the beginning and end of (3) or (f) change on stairs.

In the present invention, the desirable ranges of the gas pressure, the discharge power, the silicon supply gas flow rate, and the carbon supply gas flow rate in the connection between the intermediate layer and the surface layer are as mentioned above. It is usually not independently determined separately, but it is desirable to determine an optimum value based on mutual and organic relationships so as to form a light receiving member having desired characteristics.

The light receiving member produced by the method of the present invention is
Not only can it be used in electrophotographic copying machines, but it can also be widely used in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making machines.

[0178]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these.

Example 1 Using the apparatus for manufacturing an electrophotographic light-receiving member by the RF-PCVD method shown in FIG. 4, the substrate contains 10 silicon atoms.
An amorphous silicon deposition film was formed under the conditions shown in Table 1 on an aluminum cylinder, which was made of 0 ppm aluminum and had a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was mirror-finished. A blocking type electrophotographic light-receiving member having the layer structure shown in was prepared.

In FIG. 1B, 101, 105, 1
Reference numerals 03, 104 and 108 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer, an intermediate layer and a surface layer, respectively.

In this example, the intermediate layer and the surface layer were connected under the following conditions.

A) The internal pressure was changed from 0.3 Torr (internal pressure at the end of formation of the intermediate layer) to 0.45 Torr (internal pressure at the beginning of surface layer formation). The change pattern of the internal pressure at this time is as shown in FIG.
By selecting between ~ 600 seconds, nine types of light receiving members were produced (a-1 to a-9).

Further, the change amount of SiH ₄ gas at this time is 2.3 sccm / sec (168 sccm for 60 seconds).
Change the CH ₄ gas change amount from 1 (change at the end of intermediate layer formation) to 30 sccm (start of surface layer formation).
0.7 sccm / sec (848 sccm for 60 seconds
(Change from the flow rate at the end of intermediate layer formation to 1488 sccm (the initial flow rate at the surface layer formation)), and change the RF power from 1.7 W / sec (150 W in 60 seconds (power at the end of intermediate layer formation) to 250 W). (Changed to the power at the initial stage of forming the surface layer), and changed according to the pattern of FIG. 2 (a) (see FIG. 3).

B) The internal pressure at the end of formation of the intermediate layer and the internal pressure at the desired surface layer formation are set to the same internal pressure (0.45 Torr), and the change amount of SiH ₄ gas is 2.3 sc in the state where the internal pressure is not changed.
cm / sec (changed from 168 sccm (flow rate at the time of completion of intermediate layer formation) to 30 sccm (flow rate at the beginning of surface layer formation) in 60 seconds), CH ₄ gas change amount of 10.7 sccm
/ Sec (change from 848 sccm (flow rate at the end of intermediate layer formation) to 1488 sccm (flow rate at the beginning of surface layer formation) in 60 seconds), and the RF power change amount is 1.7 W / sec.
(Change from 150 W (power at the end of intermediate layer formation) to 250 W (power at the initial formation of the surface layer) in 60 seconds),
The pattern was changed according to the pattern shown in FIG.

C) For comparison, the internal pressure is 0.3 Torr.
(Internal pressure at the end of intermediate layer formation) to 0.45 Torr
(Internal pressure when the surface layer is initially formed), and the SiH ₄ gas is changed from 168 sccm (the flow rate at the time when the intermediate layer is formed) to 30 s.
ccm (flow rate at the time of forming the surface layer), and change CH ₄ gas from 848 sccm (flow rate at the time of forming the intermediate layer) to 1
Change to 488 sccm (the initial flow rate of the surface layer formation),
RF power 150W (power at the time of completion of intermediate layer formation)
To 250 W (power at the initial stage of surface layer formation). Each change time was 0 second. Scratch Strength As an evaluation of the scratch strength of the manufactured light receiving member, 0.
A 1R diamond needle is placed vertically, and a device (shown in FIG. 6) that moves the light receiving member in the longitudinal direction while applying a load is used to scratch the surface, and then an electrophotographic device (Canon NP6150 is used for testing). (Remodeled) and set a halftone image (copy image of Canon's halftone chart "Part number FY9-9042") to scratch the load at the time when 80% or more scratches (white lines) on the surface can be confirmed. It was judged as strength. Residual potential Electrophotographic device (Canon NP6150 modified for testing) was set with the prepared light receiving member, 420
The dark surface potential of V was charged. Then, it was immediately irradiated with a constant light amount (0.4 lux / sec). The light image was emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the bright part of the light receiving member was measured with a surface potential meter. Then, the average of the obtained light surface potentials was taken as the residual potential. Then, with the residual potential obtained under the condition (c) as 100, relative evaluation was performed according to the following criteria. ⊚: 100 ≦ X ≦ 105 ◯: 105 <X ≦ 110 Δ: 110 <X ≦ 115 x: 115 <X. Paper passing durability The prepared light receiving member was placed in an electrophotographic apparatus, a paper passing durability test of 1 million sheets was performed, and electrophotographic characteristics and images were evaluated according to the following criteria. ⊚: Particularly good ○: Good Δ: No problem in practical use ×: Problem in practical use Overall evaluation ◎: Particularly good ○: Good Δ: No problem in practical use ×: There is a problem in practical use The results thus obtained are shown in Table 2. For example, under the condition a-5, the internal pressure change time of the connection between the intermediate layer and the surface layer is 60 seconds, and the internal pressure is 2.5 mTorr / se during that period.
It is shown that the pressure in the reaction vessel was controlled by changing the value with c. Further, the image after the endurance refers to the judgment result of the image after one million sheets have passed from the image immediately after the experiment. Further, the comprehensive evaluation shows a comprehensive result obtained by adding the above-mentioned three judgment factors and other judgment factors (contrast, etc.).

As is clear from Table 2, by changing the internal pressure at 30 mTorr / sec or less in the connection between the intermediate layer and the surface layer, the residual potential is not changed.
It was possible to prepare a photoreceptive member for electrophotography, which was capable of improving scratching strength and whose image characteristics were not deteriorated even after durability. Furthermore, the internal pressure is 0.63 to 10 mTorr / s
It has been found that the change in ec is particularly effective.

[0187]

[Table 1]

[0188]

[Table 2] (Example 2) Using the apparatus for producing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4, the content of silicon atoms in the substrate was 10
An amorphous silicon deposition film was formed under the conditions shown in Table 1 on an aluminum cylinder, which was made of 0 ppm aluminum and had a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was mirror-finished. A blocking type electrophotographic light-receiving member having the layer structure shown in was prepared.

In FIG. 1B, 101, 105, 1
Reference numerals 03, 104 and 108 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer, an intermediate layer and a surface layer, respectively.

In this example, the intermediate layer and the surface layer were connected under the following conditions.

A) The SiH ₄ gas was changed from 168 sccm (flow rate at the end of formation of the intermediate layer) to 30 sccm (flow rate at the beginning of surface layer formation). The change pattern of the SiH ₄ gas flow rate at this time is as shown in FIG. 2A, and nine types of changing time were selected from 2 seconds to 600 seconds to fabricate the light receiving member (a- 1-a-9).

Further, the change amount of the internal pressure at this time is 2.5 mT
Orr / sec (change from 300 mTorr (internal pressure at the end of intermediate layer formation) to 450 mTorr (internal pressure at the beginning of surface layer formation) in 60 seconds), CH ₄ gas change amount of 10.
7 sccm / sec (changed from 848 sccm (flow rate at the end of intermediate layer formation) to 1488 sccm (flow rate at the beginning of surface layer formation) in 60 seconds), and RF power change amount of 1.7 W
/ Sec (changed from 150 W (power at the end of intermediate layer formation) to 250 W (power at the initial formation of the surface layer) in 60 seconds), and changed according to the pattern of FIG. 2A (see FIG. 3).

The light-receiving member produced was evaluated in the same manner as in Example 1. The results thus obtained are shown in Table 3. As a light receiving member for comparison, one manufactured under the condition (c) of Example 1 was used.

As is clear from Table 3, SiH ₄ gas was used for 0.29 to 27.6 s in the connection between the intermediate layer and the surface layer.
By changing at ccm / sec, the scratching strength can be improved without changing the residual potential,
It was possible to produce an electrophotographic light-receiving member in which the image characteristics did not deteriorate even after running.

Further, SiH ₄ gas is added to 0.58 to 13.
It was found that the change was particularly effective when changed at 8 sccm / sec.

[0196]

[Table 3] (Example 3) Using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4, the substrate has a silicon atom content of 10 or less.
An amorphous silicon deposition film was formed under the conditions shown in Table 1 on an aluminum cylinder, which was made of 0 ppm aluminum and had a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was mirror-finished. A blocking type electrophotographic light-receiving member having the layer structure shown in was prepared.

In FIG. 1B, 101, 105, 1
Reference numerals 03, 104 and 108 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer, an intermediate layer and a surface layer, respectively.

In this example, the intermediate layer and the surface layer were connected under the following conditions.

A) The CH ₄ gas flow rate was changed from 848 sccm (flow rate at the time of completion of intermediate layer formation) to 1488 sccm (flow rate at the initial stage of surface layer formation). The change pattern of the CH ₄ gas flow rate at that time is as shown in FIG. 2A, and nine types of changing time were selected from 2 seconds to 600 seconds to manufacture the light receiving member (a-1). ~ A-9).

Further, the change amount of the internal pressure at this time is 2.5 mT
orr / sec (changes from 300 mTorr (internal pressure at the end of intermediate layer formation) to 450 mTorr (internal pressure at the beginning of surface layer formation) in 60 seconds), and the SiH ₄ gas change amount is 2.
3 sccm / sec (changed from 168 sccm (flow rate at the time of completion of intermediate layer formation) to 30 sccm (flow rate at the beginning of surface layer formation) in 60 seconds), RF power change amount of 1.7 W / s
ec (changes from 150 W (power at the end of intermediate layer formation) to 250 W (power at the initial formation of the surface layer) in 60 seconds)
And changed in the pattern of FIG. 2A (see FIG. 3).

The light-receiving member produced was evaluated in the same manner as in Example 1. The results obtained in this way are shown in Table 4. As a light receiving member for comparison, one manufactured under the condition (c) of Example 1 was used.

As is clear from Table 4, in the connection between the intermediate layer and the surface layer, CH ₄ gas was added at 1.33 to 128 scc.
By changing at m / sec, the scratch strength could be improved without changing the residual potential, and a photoreceptive member for electrophotography could be produced in which image characteristics were not deteriorated even after endurance.

Further, CH ₄ gas was added at 2.67 to 42.7.
It has been found that the change is particularly effective when changed at sccm / sec.

[0204]

[Table 4] (Example 4) The apparatus for producing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4 was used, and the content of silicon atoms was 10 in the substrate.
An amorphous silicon deposition film was formed under the conditions shown in Table 1 on an aluminum cylinder, which was made of 0 ppm aluminum and had a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was mirror-finished. A blocking type electrophotographic light-receiving member having the layer structure shown in was prepared.

In FIG. 1B, 101, 105, 1
Reference numerals 03, 104 and 108 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer, an intermediate layer and a surface layer, respectively.

In this example, the intermediate layer and the surface layer were connected under the following conditions.

A) The RF power was changed from 150 W (power at the end of intermediate layer formation) to 250 W (power at the initial stage of surface layer formation). The change pattern of the RF power at this time is as shown in FIG. 2A, and nine types of changing time are selected from 2 seconds to 600 seconds to manufacture the light receiving member (a-1 to a). -9).

The SiH ₄ gas change amount at this time is 2.3 sccm / sec (168 sccm for 60 seconds).
(Change from the flow rate at the end of formation of the intermediate layer) to 30 sccm (flow rate at the initial stage of surface layer formation), and change the CH ₄ gas amount to 10.
7 sccm / sec (changed from 848 sccm (flow rate at the time of completion of intermediate layer formation) to 1488 sccm (flow rate at the beginning of surface layer formation) in 60 seconds), and the internal pressure change amount is 2.5 mTorr
The pressure was changed to r / sec (change from 300 mTorr (internal pressure at the end of intermediate layer formation) to 450 mTorr (internal pressure at the initial stage of surface layer formation) in 60 seconds), and the pattern was changed in FIG. 2A (see FIG. 3).

B) The RF power at the end of formation of the intermediate layer and the RF power at the beginning of formation of the surface layer are the same (250 W), and RF
With the power unchanged, change the SiH ₄ gas change amount to 2.
3 sccm / sec (changed from 168 sccm (flow rate at the end of intermediate layer formation) to 30 sccm (flow rate at the beginning of surface layer formation) in 60 seconds), CH ₄ gas change amount of 10.7 sc
cm / sec (changed from 848 sccm (flow rate at the time of completion of intermediate layer formation) to 1488 sccm (flow rate at the beginning of surface layer formation) in 60 seconds), and the internal pressure change amount was 2.5 mTorr / s
ec (changed from 300 mTorr (internal pressure at the end of intermediate layer formation) to 450 mTorr (internal pressure at the initial stage of surface layer formation) in 60 seconds), and changed according to the pattern of FIG.

The light-receiving member produced was evaluated in the same manner as in Example 1. The results thus obtained are shown in Table 5. As a light receiving member for comparison, one manufactured under the condition (c) of Example 1 was used.

As is clear from Table 5, by changing the RF power at 20 W / sec or less in the connection between the intermediate layer and the surface layer, the scratch strength can be improved without changing the residual potential, It was possible to produce an electrophotographic light-receiving member in which the image characteristics did not deteriorate even after running.

Further, the RF power is set to 0.42 to 6.67.
It has been found that the change in W / sec is particularly effective.

[0213]

[Table 5] (Example 5) Using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in Fig. 4, the substrate has a silicon atom content of 10
An amorphous silicon deposition film was formed under the conditions shown in Table 1 on an aluminum cylinder, which was made of 0 ppm aluminum and had a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was mirror-finished. A blocking type electrophotographic light-receiving member having the layer structure shown in was prepared.

In FIG. 1B, 101, 105, 1
Reference numerals 03, 104 and 108 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer, an intermediate layer and a surface layer, respectively.

In the present embodiment, the connection between the intermediate layer and the surface layer was adjusted so that the amount of change in internal pressure was 1.25 mTorr / sec (12
0.3 Torr in 0 seconds (internal pressure at the end of intermediate layer formation)
Change to 0.45 Torr (internal pressure at the initial stage of surface layer formation), and change amount of SiH ₄ gas is 1.15 sccm / sec.
(Change from 168 sccm (flow rate at the time of completion of intermediate layer formation) to 30 sccm (flow rate at the time of surface layer formation initial stage) in 120 seconds), CH ₄ gas change amount of 5.33 sccm / sec
(Changed from 848 sccm (flow rate at the time of completion of intermediate layer formation) to 1488 sccm (flow rate at the initial stage of surface layer formation) in 120 seconds), and changed according to the pattern of FIG. 2B. In addition, the RF power change amount is 0.83 W / sec (1
Change from 150 W (power at the end of formation of the intermediate layer) to 250 W (power at the beginning of surface layer formation) in 20 seconds], and the change pattern of the RF power at this time is shown in FIGS.
The light receiving member was manufactured by changing the above six types.

The produced light-receiving member was evaluated in the same manner as in Example 1. The obtained results are shown in Table 6. As is clear from Table 6, in any of the patterns, the scratch strength could be improved without changing the residual potential, and good results were obtained in which the image characteristics were not deteriorated even after the endurance.

[0217]

[Table 6] (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 silicon atom content of 10 or less.
An amorphous silicon deposition film was formed under the conditions shown in Table 1 on an aluminum cylinder, which was made of 0 ppm aluminum and had a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was mirror-finished. A blocking type electrophotographic light-receiving member having the layer structure shown in was prepared.

In FIG. 1B, 101, 105, 1
Reference numerals 03, 104 and 108 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer, an intermediate layer and a surface layer, respectively.

In this example, the connection between the intermediate layer and the surface layer was changed to 1.15 sccm / sec in the amount of SiH ₄ gas change.
(Change from 168 sccm (flow rate at the time of completion of intermediate layer formation) to 30 sccm (flow rate at the time of surface layer formation initial stage) in 120 seconds), CH ₄ gas change amount of 5.33 sccm / sec
(Change from 848 sccm (flow rate at the time of completion of intermediate layer formation) to 1488 sccm (flow rate at the initial stage of surface layer formation) in 120 seconds), and the RF power change amount is 0.83 W / sec.
(Change from 150 W (intermediate layer, power at the end of formation) to 250 W (power at the initial formation of the surface layer) in 120 seconds]
And changed according to the pattern of FIG. In addition, the change amount of the internal pressure is 1.25 mTorr / sec (12
0.3 Torr in 0 seconds (internal pressure at the end of intermediate layer formation)
Change to 0.45 Torr (internal pressure at the initial stage of surface layer formation)), and the change pattern of the internal pressure at this time is shown in FIG.
A light-receiving member was manufactured by changing the six types of (f).

The produced light-receiving member was evaluated in the same manner as in Example 1. The results obtained are shown in Table 7. As is clear from Table 7, in any of the patterns, the scratch strength could be improved without changing the residual potential, and good results were obtained in which the image characteristics were not deteriorated even after the endurance.

[0221]

[Table 7] (Example 7) Using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4, the content of silicon atoms in the substrate was 10
An amorphous silicon deposition film was formed under the conditions shown in Table 1 on an aluminum cylinder, which was made of 0 ppm aluminum and had a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was mirror-finished. A blocking type electrophotographic light-receiving member having the layer structure shown in was prepared.

In FIG. 1B, 101, 105, 1
Reference numerals 03, 104 and 108 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer, an intermediate layer and a surface layer, respectively.

In the present embodiment, the connection between the intermediate layer and the surface layer was adjusted so that the amount of change in internal pressure was 1.25 mTorr / sec (12
0.3 Torr in 0 seconds (internal pressure at the end of intermediate layer formation)
Change to 0.45 Torr (internal pressure at the initial stage of surface layer formation), and CH ₄ gas change amount of 5.33 sccm / sec.
(Change from 848 sccm (flow rate at the time of completion of intermediate layer formation) to 1488 sccm (flow rate at the initial stage of surface layer formation) in 120 seconds), and the RF power change amount is 0.83 W / sec.
(Change from 150 W (intermediate layer, power at the end of formation) to 250 W (power at the initial formation of the surface layer) in 120 seconds]
And changed according to the pattern of FIG. Also, the SiH ₄ gas change amount is 1.15 sccm / sec.
(Changed from 168 sccm (flow rate at the time of completion of intermediate layer formation) to 30 sccm (flow rate at the beginning of surface layer formation) in 120 seconds), and the change pattern of SiH ₄ gas at this time is shown in FIG.
A light-receiving member was manufactured by changing six types of (a) to (f).

The produced light-receiving member was evaluated in the same manner as in Example 1. The results obtained are shown in Table 8. As is clear from Table 8, in any of the patterns, the scratch strength could be improved without changing the residual potential, and good results were obtained in which the image characteristics were not deteriorated even after the endurance.

[0225]

[Table 8] (Example 8) Using the apparatus for manufacturing an electrophotographic light-receiving member by the RF-PCVD method shown in FIG. 4, the content of silicon atoms in the substrate was 10
An amorphous silicon deposition film was formed under the conditions shown in Table 1 on an aluminum cylinder, which was made of 0 ppm aluminum and had a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was mirror-finished. A blocking type electrophotographic light-receiving member having the layer structure shown in was prepared.

In FIG. 1B, 101, 105, 1
Reference numerals 03, 104 and 108 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer, an intermediate layer and a surface layer, respectively.

In this example, the connection between the intermediate layer and the surface layer was changed to 1.15 sccm / sec in the amount of SiH ₄ gas change.
(Changed from 168 sccm (flow rate at the time of completion of intermediate layer formation) to 30 sccm (flow rate at the beginning of surface layer formation) in 120 seconds), and the amount of change in internal pressure was 1.25 mTorr / sec (1
In 20 seconds, 0.3 Torr (internal pressure at the end of intermediate layer formation) changed to 0.45 Torr (internal pressure at the beginning of surface layer formation), and RF power change amount at 0.83 W / sec (12
The power was changed from 150 W (intermediate layer, power at the end of formation) to 250 W (power at the initial formation of the surface layer) in 0 seconds], and the patterns were changed in the pattern of FIG. 2B. Also, CH
₄ Gas change rate from 5.33 sccm / sec (848 sccm for 120 seconds (flow rate at the end of intermediate layer formation) to 14
88 sccm (change to the initial flow rate of the surface layer)),
The change pattern of CH ₄ gas at this time is shown in FIG.
A light-receiving member was manufactured by changing the six types of (f).

The produced light-receiving member was evaluated in the same manner as in Example 1. The results obtained are shown in Table 9. As is clear from Table 9, in any of the patterns, the scratch strength could be improved without changing the residual potential, and good results were obtained in which the image characteristics were not deteriorated even after the endurance.

[0229]

[Table 9] (Example 9) Using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4, the content of silicon atoms in the substrate was 10
An amorphous silicon deposited film was formed under the conditions shown in Table 10 on an aluminum cylinder made of 0 ppm aluminum having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was mirror-finished. A blocking type electrophotographic light-receiving member having the layer structure shown in was prepared.

In FIG. 1B, 101, 105, 1
Reference numerals 03, 104 and 108 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer, an intermediate layer and a surface layer, respectively.

The produced light receiving member was evaluated in the same manner as in Example 1.

Table 11 shows the results of these evaluations. In the table,
The residual potential is shown as a relative value when the result of Comparative Example 1 shown below is 100.

(Comparative Example 1) A light-receiving member was produced in the same manner as in Example 9, but in this comparative example, the internal pressure was changed from 0.3 Torr (internal pressure at the end of intermediate layer formation) to 0.45 Torr (surface layer formation). The desired internal pressure)
And change the SiH ₄ gas from 168 sccm (flow rate at the end of intermediate layer formation) to 30 sccm (flow rate at the beginning of surface layer formation), and change the CH ₄ gas from 848 sccm (flow rate at the end of intermediate layer formation) to 1488 sccm (surface). The RF power was changed to 150 W (power at the end of intermediate layer formation) to 250 W (power at the beginning of surface layer formation). Each change time is
It was set to 0 seconds.

The produced light-receiving member was evaluated in the same manner as in Example 9. These evaluation results are shown in Example 9.
The results are shown in Table 11.

As a result, from Table 11, in the light receiving member manufactured by the method for manufacturing the light receiving member of the present invention, the residual potential is changed in any item as compared with the light receiving member manufactured by the conventional method. The scratch strength could be improved without any deterioration, and good results were obtained in which the image characteristics were not deteriorated even after the endurance.

[0236]

[Table 10]

[0237]

[Table 11] (Example 10) Using the apparatus for manufacturing a photoreceptive member for electrophotography by the VHF-PCVD method shown in FIG.
Under the conditions shown in Table 12, a light receiving member including a charge injection blocking layer, a photoconductive layer, an intermediate layer, and a surface layer was produced on an aluminum cylinder (support) having a mirror-finished surface of m.

The produced light-receiving member was evaluated in the same manner as in Example 9. As a result, very good results similar to those of Example 9 were obtained.

[0239]

[Table 12] (Example 11) Using the apparatus for manufacturing an electrophotographic light-receiving member by the RF-PCVD method shown in FIG.
An amorphous silicon deposition film was formed under the conditions shown in Table 13 on an aluminum cylinder, which was made of 0 ppm aluminum and had a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was mirror-finished. A blocking type electrophotographic light-receiving member having the layer structure shown in was prepared.

In FIG. 1C, 101, 105, 1
Reference numerals 07, 106, 103, 104 and 108 denote an aluminum substrate, a charge injection blocking layer, a charge transport layer, a charge generating layer, a photoconductive layer, an intermediate layer and a surface layer, respectively.

The light-receiving member thus produced was evaluated in the same manner as in Example 9. As a result, Example 9
Similar very good results were obtained.

[0242]

[Table 13]

[0243]

As described above, according to the present invention,
In a method for producing a light-receiving member having a charge injection blocking layer, a photoconductive layer, an intermediate layer, and a surface layer, which are made of an amorphous material having at least silicon atoms as a base material on a conductive support, the intermediate layer and the surface layer. The source gas for supplying silicon that can supply silicon atoms is 0.29 to 27.6 sc
cm / sec, carbon supply source gas capable of supplying carbon atoms is 1.33 to 128 sccm, and discharge power is 20 W / s.
By changing the internal pressure to ec or less and the internal pressure to 30 mTorr or less, it is possible to inexpensively and stably manufacture a light receiving member that is excellent in electrical characteristics such as residual potential and gives a high-quality image.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of some embodiments of a light receiving member manufactured by the manufacturing method of the present invention.

FIG. 2 is a graph schematically showing some patterns of changes in raw material gas, dilution gas, discharge power, and internal pressure when forming a photoconductive layer in an example of the present invention.

FIG. 3 is a schematic graph showing changes in each parameter when forming a deposited film in the manufacturing method of the present invention.

FIG. 4 is a schematic view of an example of an apparatus by the RF glow discharge method for carrying out the manufacturing method of the present invention.

FIG. 5 is a schematic view of an example of an apparatus by the VHF glow discharge method for carrying out the manufacturing method of the present invention.

FIG. 6 is a schematic diagram for explaining the operation of the scratch strength test device used in the examples.

[Explanation of symbols]

100 light receiving member 101 conductive support 102 Photoreceptive layer 103 Photoconductive layer 104 Middle class 105 charge injection blocking layer 106 charge generation layer 107 charge transport layer 108 surface layer 110 free surface 5100, 6100 deposition equipment 5111, 6111 Reaction vessel 5112, 6112 Cylindrical support 5113, 6113 Support heater 5114 Raw material gas introduction pipe 5115, 6115 Matching Box 5116 Raw material gas piping 5117 Reaction vessel leak valve 5118 Main exhaust valve 5119 Vacuum gauge 5200 Raw material gas supply device 5211-5216 Mass Flow Controller 5221-5226 Raw material gas cylinder 5231-5236 Raw material gas cylinder valve 5241-5246 Gas inflow valve 5251-5256 Gas outflow valve 5261-5266 Pressure regulator 6115 electrode 6120 Support rotation motor 6121 exhaust pipe 6130 discharge space

Continuation of the front page (56) Reference JP 63-2855553 (JP, A) JP 63-14164 (JP, A) JP 62-8161 (JP, A) JP 7-20649 (JP , A) JP-A-6-202361 (JP, A) JP-A-5-150532 (JP, A) JP-A-5-54953 (JP, A) JP-A-2-203350 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 5/08

Claims (6)

(57) [Claims] 1. A method for producing a light-receiving member in which a photoconductive layer, an intermediate layer and a surface layer, which are made of an amorphous material having at least silicon atoms as a base material, are sequentially laminated on a conductive support by a plasma CVD method, For the connection between the intermediate layer and the surface layer, a raw material gas for supplying silicon capable of supplying silicon atoms is 0.29 sccm / sec to 27.6 sccm / s.
ec, 1.33 sccm / sec to 128 sccm / sec as a raw material gas for supplying carbon capable of supplying carbon atoms,
Discharge power 20 W / sec or less, internal pressure 30 mTorr
/ Sec or less, the method for producing a light-receiving member is characterized in that it is carried out by changing the rate. 2. The raw material gas for supplying silicon, which can supply silicon atoms, is connected to the intermediate layer and the surface layer by 0.5 gas.
8 sccm / sec to 13.8 sccm / sec, 2.67 sc for the raw material gas for carbon supply capable of supplying carbon atoms
cm / sec-42.7 sccm / sec, discharge electric power 0.42 W / sec-6.67 W / sec, internal pressure 0.
The manufacturing method according to claim 1, wherein the method is performed by changing the pressure at 63 mTorr / sec to 10 mTorr / sec. 3. The SiH ₄ gas and / or SiF ₄ is used as a source gas for supplying silicon, which can supply the silicon atoms.
The manufacturing method according to claim 1 or 2. 4. The production method according to claim 1, wherein the raw material gas for carbon supply capable of supplying the carbon atoms is CH ₄ . 5. The manufacturing method according to claim 1, wherein a charge injection blocking layer is provided between the photoconductive layer and the conductive support. 6. The light-receiving member produced by the method according to any one of claims 1 to 5.