JPH0815883A - Forming method of electrophotographic light-receiving member - Google Patents

Abstract

PURPOSE:To suppress production of image defects and to obtain an electrophotographic light-receiving member excel lent in durability. CONSTITUTION:This light-receiving member consists of at least a photoconductive layer 102 comprising a material except for a single crystal and a surface layer 103 successively formed on a substrate 101 having conductivity. These layers are formed by plasma CVD method by introducing the source material gas into a vacuum chamber which can be evacuated and decomposing the source material gas by glow discharge to form a deposition film. At least during the photoconductive layer 102 is formed, the difference Vdelta of the potentials between the substrate 101 and the floating potential in the plasma is specified to <=50V.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to electrophotography which is sensitive to electromagnetic waves such as light (in a broad sense, ultraviolet rays, visible rays, infrared rays, x-rays, γ-rays, etc.). The present invention relates to a method for forming a light receiving member.

[0002]

2. Description of the Related Art In the field of image formation, a photoconductive material for forming a light receiving layer in a light receiving member has high sensitivity,
High SN ratio [photocurrent (Ip) / dark current (Id)], having an absorption spectrum suitable for the spectral characteristics of the electromagnetic wave to be irradiated, fast photoresponsiveness, having a desired dark resistance value, during use It is required to have characteristics such as being harmless to the human body. Particularly, in the case of an electrophotographic light receiving member incorporated in an electrophotographic apparatus used in an office as an office machine, the pollution-free property at the time of use is an important point.

Amorphous silicon is one of the photoconductive materials that has recently been attracting attention based on this point, and a part thereof has already been put to practical use as a light receiving member for electrophotography.

As a method for forming such a light receiving member for amorphous electrophotography, plasma CV by glow discharge is used.
D method (hereinafter, simply referred to as plasma CVD method) can be used.

For example, Japanese Patent Laid-Open No. 57-115551 discloses an RF plasma CVD in which an electromagnetic wave having a frequency of 13.56 MHz is used to decompose a raw material gas to cause glow discharge.
An example of depositing a surface layer by the method is disclosed. Further, JP-A-60-186849 discloses a method of forming a deposited film by a microwave plasma CVD method using a microwave having a frequency of 2.45 GHz as a decomposition source of a raw material gas. Further, Japanese Laid-Open Patent Publication No. 3-219081 discloses a method of forming a deposited film in which a bias is applied to the microwave plasma CVD method to improve the characteristics of the deposited film.

With such a technique, it has become possible to supply an electrophotographic light-receiving member having good electrical characteristics.

[0007]

However, in recent years, electrophotographic devices have been pursued to have higher added value such as higher image quality, higher speed, higher durability, etc. than ever before, and at the same time, consideration for office environment and the like. Then, making it ozoneless is another issue. In particular, for the a-Si electrophotographic light-receiving member, there is an urgent need for a contact charging method instead of the conventional ozone charging in order to reduce ozone.

Under such circumstances, in the conventional a-Si electrophotographic light-receiving member, abnormal growth of a film called a spherical protrusion is likely to occur during deposition of the a-Si film. These spherical protrusions
At the same time as causing small white speckled image defects called "white spots" on the copied image, the projections become missing during long-term use and become new image defects. By rubbing the surface,
It may also cause scratches. In addition, dielectric breakdown may occur around these spherical protrusions, and based on this, the so-called "white spot" phenomenon that causes charging failure on the entire axial surface of the electrophotographic light-receiving member is caused. The adaptability was not good.

Under such circumstances, there is a strong demand for the development of a method for forming a light-receiving member for electrophotography which suppresses the generation of spherical projections.

(Object of the Invention) The object of the present invention is to solve various problems in the method for forming a light-receiving member for electrophotography composed of a-Si as described above.

That is, the main object of the present invention is a means for suppressing the generation of spherical projections, stably supplying an electrophotographic light-receiving member having excellent durability, potential characteristics and image characteristics. It is to provide a method for forming a light receiving member for electrophotography.

Another object of the present invention is to provide a method for forming a light-receiving member for electrophotography, which is suitable for an ozoneless contact charging system and which prevents "white spots" and which is environmentally friendly to the office. is there.

[0013]

According to the method for forming a light-receiving member for electrophotography of the present invention, a raw material gas is introduced into the vacuum container capable of depressurizing, and the raw material gas is decomposed by glow discharge to form a deposited film. A method of forming a photoreceptive member for electrophotography, which comprises sequentially forming a photoconductive layer made of at least a non-single-crystal material and a surface layer on a conductive substrate by plasma CVD. The potential difference Vδ between the substrate and the floating potential in the plasma when the photoconductive layer is formed.
50V or less, preferably 40V or less, optimally 30V
It is as follows.

The present inventor has made various efforts to analyze the growth of spherical projections of an a-Si electrophotographic light-receiving member and suppress the growth thereof. As a result, the present invention has been found. The contents will be described below.

In general, the spherical projection is considered to be an abnormal growth of the film with the foreign matter as a nucleus when the foreign matter is mixed into the film. The present inventor manufactured a light-receiving member for electrophotography under various conditions and observed the cross section of the generated spherical projection. As a result, most of these spherical projections grew from the middle of the film of the photoconductive layer, and none of them occurred from the surface layer. In most cases, a nucleus was actually confirmed at the center of the spherical protrusion. Further analysis of the components of the nuclei revealed that in almost all cases, they were fragments of the a-Si film. From these facts, many of the causes of the spherical projections are generated by the delamination of the a-Si film generated in the forming apparatus during the formation of the deposited film of the photoconductive layer, and the fragments are on the surface of the substrate or the deposited film being formed. It is presumed that this is because of adhesion to the surface.

The spherical projections grow around the fragments of the a-Si film as nuclei. The spherical projections grown in such a process use, for example, dust adhered in the cutting process or cleaning process of the substrate as nuclei. Has a larger diameter than the spherical projections that occur when it grows, and it not only has a large effect on the performance of the electrophotographic light-receiving member as an image defect, but also easily causes dielectric breakdown. It is easy to cause the "whiteout" phenomenon. In addition, since the spherical projections are likely to be lost, the durability is remarkably deteriorated by inducing scratches and the like.

From the results of the above analysis, in order to improve the characteristics of the electrophotographic light-receiving member, a during formation of the photoconductive layer
It has been found that it is important to prevent the adhesion of fine fragments of the -Si film. On the other hand, in the surface layer, spherical projections that would affect the electrophotographic characteristics were not generated. This is because the spherical projections gradually grow in diameter and grow during film formation, so that the spherical projections generated from the photoconductive layer formed under the surface layer grow larger, whereas the spherical projections grow larger. Then, it is considered that it does not grow so much as to affect the characteristics.

According to the knowledge of the present inventor,
The reason why the fragments of the —Si film are taken into the deposited film and become the nuclei of the spherical protrusions is presumed to be due to the following mechanism. When the film deposited in the deposited film forming apparatus peels off, it becomes fine fragments and scatters. At this time, the film fragments move in the plasma while being electrically insulated from the ground, and are charged to a potential called floating potential by the flow of electrons and ions in the plasma. When fragments charged to such a potential pass near the substrate, the electrostatic force due to the potential gradient of the sheath formed on the surface of the substrate or near the surface of the deposited film causes electrostatic force due to the potential gradient of the substrate or a-S during formation.
It is considered to be attached to the i-film surface.

Generally, in order to prevent the adhesion of such debris, the first means is to improve the adhesion of the deposited film by modifying the shape and surface condition of the parts in the deposited film forming apparatus. Righteous. However, it is technically difficult to eliminate minute film peeling during the formation of a deposited film in a device that requires a relatively thick deposited film, such as a light receiving member for electrophotography. . Therefore, the present inventor paid attention to the process when the above-mentioned debris adheres to the substrate or the deposited film surface, and the probability that the debris will adhere to the substrate surface or the deposited film surface even if film peeling occurs. Was examined from the viewpoint of reducing

Based on the above findings, the present inventor conducted an experiment to form a photoreceptive member for electrophotography by changing the potential difference (Vδ) between the potential of the substrate and the floating potential when the photoconductive layer was formed. It was According to the experiments conducted by the present inventor, the number of spherical projections tended to decrease almost exponentially with decreasing Vδ.

As described above, a method for suppressing the generation of spherical protrusions was found by controlling Vδ to 50 V or less, preferably 40 V or less, and most preferably 30 V or less at least when forming the photoconductive layer, and completed the present invention. It has come to do.

The effects of the present invention and the method for forming the electrophotographic light-receiving member of the present invention will be specifically described below with reference to the drawings.

The electrophotographic light-receiving member formed according to the present invention comprises at least a photoconductive layer made of a non-single crystal material and a surface layer. FIG. 1 is a diagram schematically showing an example of the layer structure of a light-receiving member for electrophotography formed by the present invention. In FIG. 1, 101 is a substrate,
Reference numeral 102 denotes a photoconductive layer, and 103 denotes a surface layer (the photoconductive layer 102 and the surface layer 103 constitute the electrophotographic light receiving member 100). In the present invention, in addition to the above layer structure, for example, a lower charge injection blocking layer, an adhesion layer, etc. may be provided between the photoconductive layer 102 and the base 101.
Further, a so-called function-separated layer structure in which a charge transport layer, a charge generation layer, and the like are used as the photoconductive layer can be used.

According to the knowledge of the present inventor, since most spherical projections grow from the photoconductive layer, Vδ is 5 at least at the time of forming the photoconductive layer in any layer structure.
The effect of the present invention can be obtained by setting it to 0 V or less, preferably 40 V or less, and most preferably 30 V or less.

In the present invention, Vδ may be constant during the formation of the electrophotographic light-receiving member, or may be changed as necessary. For example, it can be changed at the time of forming the photoconductive layer and at the time of forming the surface layer, or can be changed in accordance with the formation conditions of each layer even when another layer configuration is adopted. Further, even in the same layer, it can be changed in the initial stage and the latter stage of layer formation. Thus, even when Vδ is changed by each layer during the formation of the electrophotographic light-receiving member or within the same layer, the upper limit thereof is at least 50 V or less, preferably 40 V or less, at least at the time of forming the photoconductive layer. Is 30V
The following is important for obtaining the effects of the present invention.

In the present invention, various methods can be selected as specific means for controlling Vδ to 50 V or less, preferably 40 V or less, and optimally 30 V or less. For example, Vδ can be controlled by selecting parameters such as the frequency of the electromagnetic wave used for glow discharge, the gas species used for forming the deposited film, the gas flow rate, and the pressure, and organically combining them.

In the present invention, it is also effective to install an electrode in the vacuum container (reaction container) of the deposited film forming apparatus and to use an external electric bias for applying an electric field between the electrode and the substrate. However, in this case, Vδ can also be controlled by adjusting the voltage, power, waveform, etc. of the external electric bias.

As described above, Vδ is 50 in the present invention.
There are various means for making V or less, preferably 40 V or less, and most preferably 30 V or less, but whatever method is used, Vδ is 50 V at least at the time of forming the photoconductive layer.
In order to obtain the effects of the present invention, it is important to set the voltage to 40 V or less, and preferably 30 V or less.

In the present invention, the electromagnetic wave for generating glow discharge is produced by the production scale and characteristics of the photoreceptive member for electrophotography,
The frequency is selected according to the type of gas used as a raw material and Vδ, but in general, any frequency can be used as long as it can enter and maintain stable discharge. However,
The RF band, the VHF band, the microwave, or the like is preferably used from the viewpoint of the availability of the required power source from the market.

When an external electric bias (hereinafter referred to as a bias) is also used in combination with the electromagnetic wave for generating glow discharge as described above, the bias is as follows.
A DC electric field, an AC electric field, or a combination thereof can be effectively used. In particular, when a DC electric field is applied to the AC electric field, it is effective in terms of controllability of Vδ.
Further, the DC electric field superimposed on the AC electric field may be self-biased.

The bias waveform, voltage, and power are selected depending on the characteristics of the electrophotographic light-receiving member, the type of gas used as a raw material, Vδ, the pressure in the reaction vessel, and the like. When alternating current is used, any frequency is effective for the present invention, but MF band, RF band, VHF band, microwave, etc. are preferable, and particularly 10 MHz to 550 MHz.
Can be used as the optimum range in terms of discharge stability and Vδ controllability.

In the present invention, the range of these frequency bands is, for convenience, an MF band of 300 kHz to 3 M.
Less than Hz, 3 MHz to less than 30 MHz as an RF band,
The VHF band is defined as 30 MHz to less than 300 MHz, and the microwave is defined as 300 MHz or more.

The raw material gases used in the present invention are the production scale and characteristics of the electrophotographic light-receiving member, the layer structure,
Electromagnetic wave for glow discharge, selected by Vδ.

For example, when the electrophotographic light-receiving member having the layer structure shown in FIG. 1 is formed, the inside of the photoconductive layer 102 is basically depressurized from the source gas for supplying Si, which can supply silicon atoms (Si). It is formed by introducing it into a possible reaction vessel in a desired gas state and causing a glow discharge in the reaction vessel.

Materials that can be used as a raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H
₆ , Si ₃ H ₈ , Si ₄ H _10, etc. in a gas state or gasifiable silicon hydrides (silanes) are mentioned as being effectively used, and further, they are easy to handle during layer formation, S
iH ₄ and Si ₂ H ₆ are mentioned as preferable in terms of good supply efficiency. In addition, these raw material gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, or Ne as needed before use.

Further, in the present invention, it is effective to introduce an atom for controlling conductivity into the photoconductive layer 102, and it is also effective to introduce a halogen atom such as a fluorine atom as a modifier. .

In the present invention, in the photoconductive layer 102
It is also effective to introduce atoms to control conductivity.
However, if a halogen atom such as a fluorine atom is introduced as a modifier,
It is also effective to enter. Control the conductivity of the photoconductive layer
Atoms, such as group III or group V atoms,
To introduce structurally, a group III atom conductor must be used during layer formation.
Raw material for import or raw material for introducing Group V atom
Others for forming a photoconductive layer in the reaction vessel in the gas state
It may be introduced together with the gas. Group III atom introduction
Or a raw material for introducing a group V atom.
It can be gaseous or low at room temperature and pressure.
Those that can be easily gasified under the conditions for forming at least layers are used.
It is desirable to be. Sources for introducing such group III atoms
Specifically, as a raw material, for introducing a boron atom, B is used.
₂ H₆ , B_Four H_Ten, B_Five H₉ , B _Five H₁₁, B₆ H_Ten, B
₆ H₁₂, B₆ H₁₄Borohydride, BF, etc.₃ , BCl₃ ,
BBr₃ And the like, such as fluorinated boron. Besides this, Al
Cl₃ , GaCl₃ , Ga (CH₃ )₃ , InCl₃ ,
TlCl₃ Etc. can also be mentioned.

In the present invention, a raw material for introducing a group V atom is effectively used. For introducing a phosphorus atom, phosphorus hydride such as PH ₃ , P ₂ H ₄ or the like, PH ₄ I, PF are used.
₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr
₅ , fluorinated phosphorus such as PI ₃ may be mentioned. Besides this, AsH
₃ , AsF ₃ , AsCL ₃ , AsBr ₃ , AsF ₅ , S
bH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbCl
₅ , BiH ₃ , BiCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a Group V atom.

Halogen compounds which can be preferably used in the present invention are specifically fluorine gas (F ₂ ), BrF,
ClF, ClF ₃ , BrF 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.

In the present invention, the layer thickness of the photoconductive layer 102 is appropriately determined to a desired value in view of obtaining desired electrophotographic characteristics and economic effects, and is preferably 5 to 50 μm.
m, more preferably 10 to 40 μm, most preferably 15 to 3
It is preferably set to 0 μm.

The temperature (Ts) of the substrate is appropriately selected in accordance with the layer design, but in the usual case, it is preferably 20 to 500 ° C, more preferably 50 to 480 ° C, most preferably 100 to 450 ° C. Is desirable.

When a surface layer made of, for example, amorphous silicon carbide (a-SiC) is provided as the surface layer 103 of the present invention, the above-mentioned Si supply gas capable of supplying Si is basically used, It is formed by introducing a gas for introducing C capable of supplying carbon atoms (C) into a reaction vessel whose inside can be decompressed in a desired gas state, and causing glow discharge in the reaction vessel.

In the present invention, as a material that can be used as a raw material for introducing carbon atoms, a material that is gaseous at room temperature and atmospheric pressure or that can be easily gasified under at least the above-mentioned surface layer forming conditions is adopted. desirable. Carbon atom (C)
Starting materials that are effectively used as raw material gases for introduction include C and H as constituent atoms, for example, saturated hydrocarbons having 1 to 5 carbon atoms and ethylene hydrocarbons having 2 to 4 carbon atoms. , Acetylene hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, as the saturated hydrocarbon,
(CH_Four ), Ethane (C₂ H₆ ), Propane (C₃ H
₈ ), N-butane (n-C_Four H_Ten), Pentane (C_Five H
₁₂), Ethylene-based hydrocarbons include ethylene (C₂ H
_Four ), Propylene (C₃ H₆), Butene-1 (C_Four H
₈ ), Butene-2 (C_Four H₈ ), Isobutylene (C_Four H
₈ ), Penten (C_Five H_Ten), With acetylene hydrocarbons
Then, acetylene (C ₂ H₂ ), Methyl acetylene
(C₃ H_Four ), Butin (C_Four H₆ ) And the like.

Examples of the source gas containing Si and C as constituent atoms include alkyl silicides such as Si (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ .

In the present invention, when a surface layer made of a-SiC is formed, it is also effective to introduce a halogen atom such as a fluorine atom as a modifying substance in addition to the above substances. In the present invention, as a raw material gas for introducing a halogen atom into the surface layer, in addition to the above-mentioned substances, as a substance capable of simultaneously supplying C and halogen, CF ₄ , CF
Fluorocarbon compounds such as ₃ , C ₂ F ₆ , C ₃ F ₈ and C ₄ F ₈ can also be used.

In the present invention, the layer thickness of the surface layer 103 is preferably 0.01 to 50 μm, more preferably 0.05 to 20 μm, most preferably from the viewpoint of obtaining desired electrophotographic characteristics and economical effects. It is desirable that the thickness is 0.1 to 10 μm.

In the present invention, the conditions for forming the surface layer 103 can be appropriately determined so that desired electrophotographic characteristics can be obtained. For example, the substrate temperature is appropriately selected in an optimum range, but is preferably 20 to 500 ° C, more preferably 50 to 480 ° C, and most preferably 100 to 450 ° C.

The pressure in the reaction vessel during the formation of the electrophotographic light-receiving member in the present invention is selected according to the characteristics of the electrophotographic light-receiving member, the layer structure, the electromagnetic wave for glow discharge, and Vδ. Although it varies depending on each layer forming condition, in the usual case, it is preferably 1 × 10 ^{−5 to} 100 Torr, preferably 5 × 10 ^{−5 to} 30 Torr, and most preferably 1 × 10 ⁻⁴ .
It is preferably 10 Torr.

According to the knowledge of the present inventor, Vδ can be changed by the combination of the above-mentioned parameters such as electromagnetic wave frequency, gas species, gas mixing ratio (flow ratio), dilution ratio, and pressure. it can. Therefore, these parameters are not uniquely determined in the actual formation of the electrophotographic light-receiving member for electrophotography, and the desired characteristics and layer constitution of the a-Si electrophotographic light-receiving member, V
The value of δ should be determined based on organic relevance.

Substrate 101 used in the present invention
Is, for example, Al, Cr, Mo, Au, In, Nb, T
Examples include metals such as e, V, Ti, Pt, Pb, Fe, and alloys thereof, such as stainless steel. In addition, polyester, polystyrene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride,
It is also possible to use a substrate obtained by subjecting at least the surface of the electrically insulating substrate such as a film or sheet made of a synthetic resin such as polyethylene or polyamide, glass, or ceramic to the side where the light receiving layer is formed, to a conductive treatment. Further, it is desirable that the side opposite to the side on which the light receiving layer is formed is also subjected to conductive treatment.

The substrate 101 may be in the shape of a smooth flat surface or a cylindrical or plate-shaped endless belt having an uneven surface, and its thickness is appropriately determined so that a desired electrophotographic light-receiving member can be formed. However, when flexibility is required as the light receiving member for electrophotography, the thickness can be made as thin as possible within the range in which the function as the substrate can be sufficiently exhibited. However, it is usually 10 μm or more from the viewpoint of mechanical strength and the like in manufacturing and handling the substrate.

The method for forming the electrophotographic light-receiving member of the present invention will be described in detail below.

2 to 4 are for carrying out the present invention.
FIG. 3 is a schematic view of an example of an apparatus for forming a photoreceptive member for electrophotography by a microwave plasma CVD method, FIG. 2 is a configuration diagram of a deposition apparatus and a source gas supply apparatus, FIG. 3 is a cross-sectional view of a reaction vessel of the deposition apparatus, FIG. 4 is a vertical sectional view of the deposition apparatus.

This apparatus is roughly classified into a deposition apparatus 200.
0, a source gas supply device 2200, an exhaust device (not shown) for reducing the pressure in the reaction vessel 2111, and a power source (not shown) for generating microwaves. The rotary shaft 21 is provided in the reaction vessel 2111 in the deposition apparatus 2000.
16. A heater 2113 for heating the substrate is installed, and the substrate 2112 is fixed on the rotating shaft 2116. The rotating shaft 2116 is connected to the motor 2120 via a gear so that it can rotate. Also the reaction vessel 211
A source gas introduction pipe / bias electrode 2114 is installed in the chamber 1, and is connected to a bias power source 2121. In addition, a window 21 for introducing microwaves above and below the reaction vessel 2111.
22 is installed and connected to the microwave power source via the waveguide 2115.

A probe 2123 for measuring the floating potential is inserted inside the reaction container. This probe is inserted for experimental purposes, and is not necessarily required for production purposes.

The source gas supply device 2200 is made of SiH ₄ ,
Cylinders 2221 to 2226 of raw material gases such as H ₂ , CH ₄ , He, C ₂ H ₂ , and SiF ₄ and valves 2231 to 223
6, 2241 to 2246, 2251 to 2256, pressure regulators 2261 to 2266, and mass flow controllers 2211 to 2216, and each source gas cylinder is connected to a reaction container via a valve 2260.

When an electrophotographic light-receiving member having the layer structure shown in FIG. 1 is produced using the above apparatus, the procedure is as follows.

First, the base 211 that has been degreased and washed in advance
2 is installed on the rotary shaft 2116 in the reaction container 2111, and the inside of the reaction container 2111 is exhausted by an exhaust device (not shown).
Subsequently, the substrate 211 is heated by the heater 2113 for heating the substrate.
Control the temperature of 2 to the desired temperature between 20 ° C and 500 ° C.

The raw material gas for forming the deposited film is supplied to the reaction vessel 211.
In order to make it flow into 1, the gas cylinder valves 2231-2
236, make sure that the leak valve 2117 of the reaction vessel is closed, and check the inflow valves 2241 to 224.
6, outflow valves 2251 to 2256, auxiliary valve 226
Make sure 0 is open, then first open main valve 2
118 is opened and the reaction vessel 2111 and the gas pipe 21 are opened.
Exhaust 24.

Next, the reading of the vacuum gauge 2119 is about 5 × 10 ^-6
When it becomes Torr, the auxiliary valve 2260 and the outflow valves 2251 to 2256 are closed.

Then, each gas is introduced from the gas cylinders 2221 to 2226 by opening the valves 2231 to 2236,
Each pressure of 2kg by pressure regulators 2261 to 2266
Adjust to / cm ² . Next, inflow valves 2241-22
46 is gradually opened to introduce each gas into the mass flow controllers 2211 to 2216.

After the preparation for film formation is completed as described above, a photoconductive layer and a surface layer are formed on the substrate 2112.

When the base body 2112 has reached a predetermined temperature, the necessary ones of the outflow valves 2251 to 2256 and the auxiliary valve 2260 are gradually opened to open the gas cylinder 22.
A predetermined gas is introduced from 21 to 2226 into the source gas introduction pipe / bias electrode 2114. Next, the mass flow controllers 2211 to 2216 are adjusted so that each raw material gas has a predetermined flow rate. At that time, the reaction vessel 211
The opening of the main valve 2118 is adjusted while observing the vacuum gauge 2119 so that the pressure in 1 becomes a predetermined pressure of 1 Torr or less. When the internal pressure is stable, a microwave power source (not shown) is set to a desired power, and microwaves are introduced into the reaction vessel 2111 through the waveguide 2115 to cause glow discharge. At this time, the bias power source 2121 is simultaneously and concurrently adjusted to a desired voltage or power to supply an electric bias to the source gas introduction pipe 2114.

In this way, the reaction vessel 21 is activated by glow discharge.
The raw material gas introduced into the substrate 11 is decomposed and the base 2112
A predetermined deposited film is formed on top. At this time, the base 2112
Is rotated by a motor 2120 connected to a rotating shaft via a gear, so that a deposited film can be obtained evenly on the substrate 2112. After the desired film thickness is formed, the supply of microwave power and bias power is stopped and the outflow valve 2
251 to 2256 are closed to stop the gas from flowing into the reaction vessel 2111, and the formation of the deposited film is completed.

When a multi-layer structure is adopted as the electrophotographic light-receiving member, the desired layer may be formed by the above-mentioned procedure, and then the same procedure may be repeated again. Needless to say, the substrate temperature, microwave and bias power are adjusted.

[0067]

EXAMPLES Specific examples for demonstrating the effects of the present invention will be described below, but the present invention is not limited thereto. <Experimental example 1> Using the apparatus modified from the deposited film forming apparatus shown in FIGS.
An aluminum cylinder having a diameter of 108 mm was used as a substrate, and an electrophotographic light-receiving member was produced under the production conditions shown in Table 1. In this example, direct current was used as the external electric bias. In addition, one of the bases was insulated from the ground and a DC power supply was connected to it in addition to the external electric bias so that Vδ could be changed. The reason that the single substrate is connected to the DC power source is to make other conditions as uniform as possible.

The floating potential was measured by the single probe method (Langmuir probe method) using a probe (a tungsten wire having a diameter of 0.5 mm and a length of 4 mm) installed in the reaction vessel. At this time,
In order to eliminate the influence of -Si film deposition, a voltage of proper selection-1 kV is applied to the probe, and a-S
Prevention of i-film attachment. In the deposited film forming apparatus used in this experimental example, a uniform discharge is generated in the space surrounded by the upper and lower windows and the six cylinders (in the discharge space), so that the floating potential is substantially different in each place in this space. Was constant.

On the surface of the electrophotographic light-receiving member produced by changing Vδ in this way, 10 arbitrarily selected areas of 1 cm ² were observed at a total of 10 cm ² , and the number and diameter of spherical projections were observed. did. Results are shown in FIG.

From the results shown in FIG. 5, by setting Vδ to 50 V or less during the formation of the photoconductive layer, spherical projections having a diameter of 30 μm or more did not occur at all. When Vδ is 40 V or less, spherical projections having a diameter of 20 μm to less than 30 μm do not occur. Further, it was found that spherical protrusions having a diameter of 10 μm or more were not generated by setting Vδ to 30 V or less, and the effectiveness of the present invention was confirmed.

[0071]

[Table 1] <Example 1> Using the deposited film forming apparatus shown in FIGS. 2 to 4, following the procedure described above, an aluminum cylinder having a diameter of 108 mm was used as a substrate, and the electrophotographic light-receiving member was prepared under the conditions shown in Table 2. It was made. In this embodiment, an RF power source and a DC power source having a frequency of 13.56 MHz are connected to the source gas introduction tube / bias electrode with the circuit diagram shown in FIG. 6, and Vδ is 50 V by changing the voltage of the DC power source.
Adjusted below. FIG. 6 is a vertical cross-sectional view showing a structure in which the RF power supply and the DC power supply are connected as an external electric bias in the deposited film forming apparatus of FIGS. 2 to 4. In FIG. 6, 2129 is an RF power supply and 2125 is a high frequency. Matching box, 2126 is a capacitor, 2127 is a coil,
2128 is a DC power supply. Further, all six substrates were set to the ground potential. The electrophotographic light-receiving member thus produced was set in an electrophotographic apparatus (NP6060 manufactured by Canon was subjected to contact charging [roller charging] and modified for this experiment), and a "white spot" was formed by an ordinary electrophotographic process. The image characteristics of "white spots" and "scratches" were evaluated with respect to the initial characteristics and the characteristics after a paper feed durability test of 5 million sheets.

The following criteria were used for evaluation of each item.

"White spot": The halogen lamp for image exposure is turned off, a black image (solid black image) is taken over the entire surface, and "white spot" on the image is observed and evaluated.

In the evaluation of "white spots" ◎ "white spots" are not recognized. ○ There are "white spots" but it is difficult to distinguish. △ There are clear "white spots", but there is no practical problem. Is shown.

"White spots" ... A solid black image was taken in the same manner as "white spots", and the state of "white spots" on the image was observed and evaluated.

In the evaluation of "white spots", "white spots" were not observed at all. △ "white spots" were large, and there was no practical problem.

"Scratch" ... A solid black image was taken in the same manner as "white spot", and the state of "scratch" on the image was observed and evaluated.

In the evaluation of "scratches" ◎ "Scratches" are not recognized. ○ There are "scratches" but it is difficult to distinguish. △ There are obvious "scratches", but there is no problem in practical use. .

[0079]

[Table 2] Comparative Example 1 An electrophotographic light-receiving member was manufactured in the same manner as in Example 1 using the deposited film forming apparatus shown in FIGS. In this comparative example, the voltage of the DC power supply is adjusted so that Vδ is 60
Adjusted to V or higher. The electrophotographic light-receiving member thus produced was evaluated in the same manner as in Example 1.

The results of Example 1 and Experimental Example 1 described above are shown in Table 3. As shown in Table 3, the electrophotographic light-receiving member according to the forming method of the present invention showed excellent characteristics.

[0081]

[Table 3] Example 2 Using the deposited film forming apparatus shown in FIGS. 2 to 4, following the procedure described above, an aluminum cylinder having a diameter of 108 mm was used as a substrate, and the light-receiving member for electrophotography was prepared under the conditions shown in Table 4. Was produced. In this example, an RF power supply with a frequency of 13.56 MHz was used as the external electric bias, and the RF power was adjusted so that Vδ was 50 V or less. Further, all six substrates were set to the ground potential.
The photoreceptive member for electrophotography thus manufactured is subjected to electrophotographic apparatus (NP6060 manufactured by Canon is contact-charged [roller-charged]).
Then, the image characteristics of "white spots", "white spots", and "scratches" were evaluated with respect to the initial characteristics and the characteristics after the 5 million-sheet passing durability test. .

[0082]

[Table 4] Comparative Example 2 An electrophotographic light-receiving member was manufactured in the same manner as in Example 2 using the deposited film forming apparatus shown in FIGS. In this comparative example, the RF power was adjusted so that Vδ exceeded 50V. The electrophotographic light-receiving member thus produced was evaluated in the same manner as in Example 2.

The results of Example 2 and Comparative Example 2 described above are shown in Table 5. From the results shown in Table 5, it was confirmed that the method for forming a light-receiving member for electrophotography of the present invention has excellent image characteristics and durability.

[0084]

[Table 5] <Example 3> Using the deposition film forming apparatus shown in FIGS. 2 to 4, an aluminum cylinder having a diameter of 108 mm was used as a substrate according to the procedure described above, and the light receiving member for electrophotography was prepared under the conditions shown in Table 6. Was produced. In this example, an RF power supply with a frequency of 13.56 MHz was used as the external electric bias, and the RF power was adjusted so that Vδ was 50 V or less. Further, all six substrates were set to the ground potential.
The photoreceptive member for electrophotography thus manufactured is subjected to electrophotographic apparatus (NP6060 manufactured by Canon is contact-charged [roller-charged]).
Then, the image characteristics of "white spots", "white spots", and "scratches" were evaluated with respect to the initial characteristics and the characteristics after the 5 million-sheet passing durability test. .

[0085]

[Table 6] Comparative Example 3 An electrophotographic light-receiving member was manufactured in the same manner as in Example 3 using the deposited film forming apparatus shown in FIGS. In this comparative example, the RF power was adjusted so that Vδ exceeded 50V. The electrophotographic light-receiving member thus produced was evaluated in the same manner as in Example 3.

The results of Example 3 and Comparative Example 3 described above are shown in Table 7. From the results in Table 7, it was confirmed that the method for forming a light-receiving member for electrophotography of the present invention was excellent in image characteristics and durability.

[0087]

[Table 7] <Embodiment 4> Using the deposited film forming apparatus shown in FIGS. 2 to 4, an aluminum cylinder having a diameter of 108 mm was used as a substrate in accordance with the above procedure, and under the conditions shown in Table 8, a light receiving member for electrophotography was used. Was produced. In this example, no external electrical bias was used. Further, all six substrates were set to the ground potential. The electrophotographic light-receiving member thus produced was electrophotographic device (the Canon NP6060 was contact charged [roller charged] and modified for this experiment).
The image characteristics of "white spots", "white spots", and "scratches" were evaluated with respect to the initial characteristics and the characteristics after a paper feed durability test of 5 million sheets.

[0088]

[Table 8] <Example 5> Using the deposited film forming apparatus shown in FIGS. 2 to 4, an aluminum cylinder having a diameter of 108 mm was used as a substrate in accordance with the above procedure, and under the conditions shown in Table 9, a light receiving member for electrophotography was used. Was produced. In this example, a VHF power supply with a frequency of 105 MHz was used as the external electric bias. Further, all six substrates were set to the ground potential. The photoreceptive member for electrophotography thus manufactured is subjected to electrophotographic apparatus (NP6060 manufactured by Canon is contact-charged [roller-charged]).
Then, the image characteristics of "white spots", "white spots", and "scratches" were evaluated with respect to the initial characteristics and the characteristics after the 5 million-sheet passing durability test. .

[0089]

[Table 9] <Example 6> Using the deposited film forming apparatus shown in FIGS. 2 to 4, an aluminum cylinder having a diameter of 108 mm was used as a substrate in accordance with the above procedure, and under the conditions shown in Table 10, a light receiving member for electrophotography was used. Was produced. In this embodiment,
As an external electrical bias, VHF with a frequency of 105 MHz
A power supply was used. Further, all six substrates were set to the ground potential. The electrophotographic light-receiving member thus produced was set in an electrophotographic apparatus (a Canon NP6060 was contact-charged [roller-charged and modified for this experiment)), and a "white spot", "white spot", " The image characteristics of "scratches" were evaluated with respect to the initial characteristics and the characteristics after a paper feed durability test of 5 million sheets.

The results of Examples 4 to 6 are shown in Table 11 above.
Shown in From the results of Table 11, the electrophotographic light-receiving member forming method of the present invention could provide an electrophotographic light-receiving member excellent in image characteristics and durability. Further, comparison of Example 2 and Example 5 and Example 3 and Example 6 reveals that Vδ changes depending on the frequency of the external electric bias.

[0091]

[Table 10]

[0092]

[Table 11] <Embodiment 7> Using the deposited film forming apparatus shown in FIGS. 2 to 4, an aluminum cylinder having a diameter of 108 mm was used as a substrate in accordance with the above procedure, and the electrophotographic light-receiving member was prepared under the conditions shown in Table 12. Created. In this embodiment, the frequency is 10 kHz to 550 MHz as the external electric bias.
Was changed in the range. All six cylinders were set to earth potential. The electrophotographic light-receiving member thus created was installed in an electrophotographic apparatus (a Canon NP6060 was contact-charged “roller-charged and modified for this experiment”), and a “white spot”, “white spot”, The image characteristics of "scratches" were evaluated with respect to the initial characteristics and the characteristics after a paper feed durability test of 5 million sheets.

Table 13 shows the evaluation results. From Table 13, the effect of the present invention was obtained at any frequency, and a photoreceptive member for electrophotography having excellent image characteristics was obtained. The frequency of the external electric bias is 10 MHz to 55
It can be seen that by setting the range to 0 MHz, Vδ can be suppressed to a lower level and the controllability of Vδ can be improved. In the frequency range of 10 KHz to 1 MHz, discharge interruption may occur in some cases, while that of 10 MHz to 5 MHz
In the range of 50 MHz, discharge interruption did not occur at all and good discharge stability was obtained.

[0094]

[Table 12]

[0095]

[Table 13] <Embodiment 8> Using the deposited film forming apparatus shown in FIG. 7, an aluminum cylinder having a diameter of 108 mm was used as a substrate and a light-receiving member for electrophotography was manufactured under the conditions shown in Table 14 according to the above procedure. . FIG. 7 is a schematic view of another example of the deposited film forming apparatus used in the present invention. In FIG. 7, reference numeral 4000 is a deposition apparatus, 4111 is a reaction vessel, and 411.
2 is a substrate, 4113 is a heater for heating the substrate, 4114 is a source gas introduction pipe, 4115 is a high frequency matching box, 4116 is a gas pipe, 4117 is a leak valve, 4
118 is a main valve, 4119 is a vacuum gauge, 4120 is a VHF power supply, 4200 is a gas supply device, and 4211-42.
16 is a mass flow controller, 4221-4226
Is a cylinder, 4231-4236 is a valve, 4241-4
246 is a valve, 4251 to 4256 are valves, 426
Reference numeral 0 is a valve, and reference numerals 4261 to 4266 are pressure regulators.
In addition, the floating potential was measured by the probe 4121 inserted in the deposition apparatus in the same manner as in Experimental Example 1. Also in this apparatus, the floating potential was substantially constant in various places in the deposition apparatus. In this embodiment, as an electromagnetic wave for causing glow discharge, V of 105 MHz is used.
The HF band was used. The electrophotographic light-receiving member thus prepared was placed in an electrophotographic apparatus (a Canon NP6060 was contact-charged [roller-charged and modified for this experiment), and was set to "white spot", "white spot", " The image characteristics of "scratches" were evaluated with respect to the initial characteristics and the characteristics after a paper feed durability test of 5 million sheets.

[0096]

[Table 14] <Example 9> Using the deposited film forming apparatus shown in FIG. 7, an aluminum cylinder having a diameter of 108 mm was used as a substrate and a light-receiving member for electrophotography was manufactured under the conditions shown in Table 15 according to the above procedure. . In this embodiment, as electromagnetic waves for causing glow discharge, VH of 105 MHz is used.
The F band was used. The electrophotographic light-receiving member thus produced was electrophotographic device (the Canon NP6060 was contact charged [roller charged] and modified for this experiment).
The image characteristics of "white spots", "white spots", and "scratches" were evaluated with respect to the initial characteristics and the characteristics after a paper feed durability test of 5 million sheets.

[0097]

[Table 15] <Example 10> Using the deposited film forming apparatus shown in FIG.
According to the above procedure, an aluminum cylinder having a diameter of 108 mm was used as a substrate, and a light receiving member for electrophotography was manufactured under the conditions shown in Table 16. In this embodiment, as an electromagnetic wave for causing glow discharge, V of 105 MHz is used.
The HF band was used. The electrophotographic light-receiving member thus produced was set in an electrophotographic apparatus (a Canon NP6060 was contact-charged [roller-charged and modified for this experiment)), and a "white spot", "white spot", " The image characteristics of "scratches" were evaluated with respect to the initial characteristics and the characteristics after a paper feed durability test of 5 million sheets.

[0098]

[Table 16] <Embodiment 11> Using the deposited film forming apparatus shown in FIG.
In accordance with the above procedure, an aluminum cylinder having a diameter of 108 mm was used as a substrate, and a light-receiving member for electrophotography was produced under the production conditions shown in Table 17. In this embodiment, as an electromagnetic wave for causing glow discharge, V of 250 MHz is used.
The HF band was used. The electrophotographic light-receiving member thus produced was set in an electrophotographic apparatus (a Canon NP6060 was contact-charged [roller-charged and modified for this experiment)), and a "white spot", "white spot", " The image characteristics of "scratches" were evaluated with respect to the initial characteristics and the characteristics after a paper feed durability test of 5 million sheets.

[0099]

[Table 17] <Example 12> Using the deposited film forming apparatus shown in FIGS. 2 to 4, an aluminum cylinder having a diameter of 108 mm was used as a substrate in accordance with the above procedure, and under the conditions shown in Table 18, a light receiving member for electrophotography was used. Was produced. In this embodiment, the microwave band having a frequency of 550 MHz is used as the external electric bias. The electrophotographic light-receiving member thus produced was set in an electrophotographic apparatus (a Canon NP6060 was contact-charged [roller-charged and modified for this experiment)), and a "white spot", "white spot", " The image characteristics of "scratches" were evaluated with respect to the initial characteristics and the characteristics after a paper feed durability test of 5 million sheets.

[0100]

[Table 18] <Example 13> Using the deposited film forming apparatus shown in FIGS. 2 to 4, an aluminum cylinder having a diameter of 108 mm was used as a substrate in accordance with the above procedure, and under the conditions shown in Table 19, a light-receiving member for electrophotography was used. Was produced. In this example, the microwave band having a frequency of 250 MHz was used as the external electric bias. The electrophotographic light-receiving member thus produced was set in an electrophotographic apparatus (a Canon NP6060 was contact-charged [roller-charged and modified for this experiment)), and a "white spot", "white spot", " The image characteristics of "scratches" were evaluated with respect to the initial characteristics and the characteristics after a paper feed durability test of 5 million sheets.

The results of Examples 8 to 13 are shown in Table 20. From the results of Table 20, according to the method for forming a light-receiving member for electrophotography of the present invention, a light-receiving member for electrophotography having excellent image characteristics and durability can be obtained.

Vδ depends on parameters such as gas type, pressure, and frequency of electromagnetic wave for causing glow discharge.
You can also see that changes.

[0103]

[Table 19]

[0104]

[Table 20]

[0105]

As described above, according to the present invention,
The potential difference between the potential of the substrate and the floating potential in the plasma at the time of forming the electrophotographic light-receiving member by the plasma CVD method is at least 50 V, preferably 40 V or less, most preferably 30 V or less at the time of forming the photoconductive layer. By doing so, it is possible to suppress the generation of spherical projections and obtain an electrophotographic light-receiving member having excellent image characteristics and durability.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of a light-receiving member for electrophotography formed by the present invention.

FIG. 2 is a configuration diagram of a deposition apparatus and a raw material gas supply apparatus as an example of a deposition film forming apparatus for carrying out the method for forming a light-receiving member for electrophotography used in the present invention.

FIG. 3 is a cross section of a reaction vessel of a deposition apparatus.

FIG. 4 is a vertical cross section of a reaction vessel of the deposition apparatus.

FIG. 5 is a distribution diagram of the number of spherical protrusions showing the effect of the present invention.

FIG. 6 is a diagram in which an RF power source and a DC power source are connected as an external electric bias to a longitudinal section of the deposited film forming apparatus used in the present invention.

FIG. 7 is a schematic view of another example of the deposited film forming apparatus used in the present invention.

[Explanation of symbols]

 100 Electrophotographic Photoreceptive Member 101 Substrate 102 Photoconductive Layer 103 Surface Layer 2000 Deposition Device 2111 Reaction Vessel 2112 Substrate 2113 Heater for Substrate Heating 2114 Raw Material Gas Introducing Tube / Bias Electrode 2115 Waveguide 2116 Rotating Shaft 2115 Waveguide 2117 Leak Valve 2118 Main valve 2119 Vacuum gauge 2120 Motor 2121 Bias power supply 2122 Window 2123 Probe 2124 Gas piping 2125 High frequency matching box 2126 Capacitor 2127 Coil 2128 DC power supply 2129 RF power supply 2200 Gas supply device 2211 to 2216 Mass flow controller 2221 to 2226 Cylinder 2231 to 2236 Valve 2241 to 2246 valves 2251 to 2256 valves 2260 valves 4000 deposition Installation 4111 Reaction container 4112 Substrate 4113 Substrate heating heater 4114 Raw material gas introduction pipe 4115 High frequency matching box 4116 Gas piping 4117 Leak valve 4118 Main valve 4119 Vacuum gauge 4120 VHF power supply 4200 Gas supply device 4211-4216 Mass flow controller 4221-4226 Cylinder 4231- 4236 valve 4241-4246 valve 4251-4256 valve 4260 valve 4261-4266 pressure regulator

Claims (4)

[Claims] 1. A plasma CVD method in which a raw material gas is introduced into a depressurizable vacuum vessel and the raw material gas is decomposed by glow discharge to form a deposited film, and at least a non-single crystal is formed on a conductive substrate. A method of forming a photoreceptive member for electrophotography, which comprises sequentially forming a photoconductive layer made of a material and a surface layer, wherein a potential difference Vδ between the substrate and a floating potential in plasma is formed at least when the photoconductive layer is formed. Fifty
A method for forming a light-receiving member for electrophotography, which is V or less. 2. A depressurizable vacuum container having at least a conductive substrate, a source gas introducing means, a microwave introducing means, an electrode, and a means for applying an electric field between the substrate and the electrode. While the source gas introduced by the source gas introducing means is decomposed by glow discharge by the energy of the microwave introduced by the microwave introducing means, while applying an electric field between the substrate and the electrode, The method for forming a light receiving member for electrophotography according to claim 1, wherein a deposited film is formed on the substrate. 3. The method for forming a light-receiving member for electrophotography according to claim 2, wherein an electric field in which an alternating electric field and a direct current electric field are superposed is used as an electric field applied between the electrode and the base body. A method for forming a photoreceptor member for electrophotography, wherein Vδ is controlled by the DC electric field. 4. The method of forming a light-receiving member for electrophotography according to claim 3, wherein the frequency of the alternating electric field is 10 MH.
z to 550 MHz, a method for forming a light receiving member for electrophotography.