JPS6212509B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
The present invention relates to a method of manufacturing an electrophotographic image forming member used for forming images using electromagnetic waves such as electromagnetic waves.

[Conventional technology]

Conventionally, photoconductive materials constituting the photoconductive layer of electrophotographic image forming members include inorganic photoconductive materials such as Se, CdS, and ZnO, poly-N vinyl carbazole (PVK), and trinitrofluorenone (TNF). Organic photoconductive materials (OPC) are commonly used.

[Problem that the invention seeks to solve]

However, in electrophotographic image forming members using these photoconductive materials, there are still various issues that can be resolved, and the conditions may be relaxed to a certain extent to suit individual circumstances. In reality, each suitable electrophotographic imaging member is used.

For example, in an electrophotographic image forming member using Se as a photoconductive layer-forming material, Se alone has a narrow spectral sensitivity range when using light in the visible light region, so Te or As is added to produce a spectral sensitivity. The aim is to expand the sensitivity range.

However, although electrophotographic image forming members having such Se-based photoconductive layers containing Te and As certainly improve the spectral sensitivity range, optical fatigue increases, making it difficult to print the same original. Continuously copying may result in a decrease in the image density of the copied image or background stains (fogging of white areas), and if you continue to copy other documents, the image of the previous document may be copied as an afterimage ( It has disadvantages such as ghost phenomenon).

However, since Se, especially As and Te, are extremely harmful substances to the human body, it is necessary to devise ways to use manufacturing equipment that does not come into contact with the human body during manufacturing. The capital investment is significantly large. Furthermore, if the photoconductive layer is exposed even after manufacturing, the surface of the photoconductive layer will be directly rubbed during cleaning and other treatments, and a portion of it will be scraped off, causing the developer to They may get mixed into the printer, be scattered inside the copying machine, or be mixed into the copied images, resulting in contact with the human body. Furthermore, when the surface of a Se-based photoconductive layer is continuously and repeatedly exposed to corona discharge many times, crystallization or oxidation occurs near the surface of the layer, leading to deterioration of the electrical properties of the photoconductive layer. There are many cases. Alternatively, if the surface of the photoconductive layer is exposed, when a liquid developer is used to visualize (develop) an electrostatic latent image, it may come into contact with the solvent, resulting in poor solvent resistance (liquid development resistance). However, it is difficult to say with certainty that Se-based photoconductive layers are necessarily satisfactory in this respect.

In order to improve these points, it has been proposed to cover the surface of the Se-based photoconductive layer with a surface coating layer called a so-called protective layer, electrically insulating layer, or the like.

However, with regard to these improvements, there are improvements in terms of adhesion between the photoconductive layer and the surface coating layer, electrical contact properties, and electrical properties, surface properties, moisture resistance, etc. required for the surface coating layer. At present, it is difficult to say that a satisfactory solution has been achieved.

In addition, Se-based photoconductive layers are usually formed by vacuum evaporation, which requires significant investment in equipment, and it is difficult to form photoconductive layers with desired photoconductive properties. To obtain good reproducibility,
It is necessary to strictly adjust various manufacturing parameters such as deposition temperature, deposition substrate temperature, degree of vacuum, and cooling rate.

Furthermore, the surface coating layer can be formed by laminating a film-like material onto the surface of the photoconductive layer via an adhesive, or
Because it is formed by applying a surface coating layer forming material,
It is necessary to install equipment separate from the equipment for forming the photoconductive layer, and there is a significant increase in capital investment.
This is extremely unfavorable in the current period of slow economic growth.

In addition, the Se-based photoconductive layer is formed in an amorphous state in order to have high dark resistance as a photoconductive layer of an electrophotographic image forming member, but Se crystallization occurs at an extremely low temperature of approximately 65°C. Therefore, it is greatly influenced by the ambient temperature during manufacturing, handling after manufacturing, and frictional heat due to rubbing with other parts during the electrophotographic image forming process. It also has a drawback in terms of heat resistance, in that it tends to cause crystallization, leading to a decrease in dark resistance.

On the other hand, an electrophotographic image forming member using ZnO, CdS, etc. as a material for forming a photoconductive layer has a photoconductive layer in which particles of a photoconductive material such as ZnO or CdS are uniformly dispersed in a resin binder. It is formed by This image-forming member having a so-called binder-based photoconductive layer is advantageous in manufacturing compared to an image-forming member having an Se-based photoconductive layer, and can be manufactured at relatively low manufacturing costs. That is, the binder-based photoconductive layer is prepared by applying a coating solution prepared by kneading ZnO or CdS particles and a suitable resin binder using a suitable solvent onto a suitable substrate using a doctor blade method, dipping method, etc. Since it can be formed by simply applying and solidifying it using the coating method described above, compared to image forming members with Se-based photoconductive layers, it is not necessary to invest as much capital in manufacturing equipment, and the manufacturing method itself is simple. And it's easy.

However, the binder-based photoconductive layer is basically a two-component system consisting of a photoconductive material and a resin binder, and the photoconductive material particles are uniformly dispersed in the resin binder. Due to the specific nature of the formation, there are many parameters that determine the electrical and photoconductive properties as well as the physical and chemical properties of the photoconductive layer, and therefore, these parameters must be precisely adjusted to achieve the desired results. There is a drawback that a photoconductive layer having specific characteristics cannot be formed with good reproducibility, leading to a decrease in yield and a lack of mass productivity.

Furthermore, due to the unique nature of the binder-based photoconductive layer being a dispersed system, the entire layer is porous, and as a result, it is highly dependent on humidity, resulting in deterioration of electrical properties when used in a humid atmosphere. In many cases, it becomes impossible to obtain a copy of the image.

Furthermore, the porous nature of the photoconductive layer causes developer to enter the layer during development, which not only reduces mold releasability and cleaning properties but also makes it unusable. When a developer is used, the above point becomes significant because the developer penetrates into the layer along with its carrier solvent due to capillary action, and as in the case of the Se-based photoconductive layer, the surface of the photoconductive layer is It is necessary to cover with a covering layer.

However, even with this improvement by providing a surface coating layer, the surface of the photoconductive layer is uneven due to the porous nature of the photoconductive layer, so the interface is not uniform and the adhesion between the photoconductive layer and the surface coating layer is poor. Another disadvantage is that it is difficult to obtain good electrical contact.

In addition, when using CdS, since CdS itself has an effect on the human body, care must be taken to prevent it from coming into contact with the human body or scattering into the surrounding environment during manufacturing and use. It is necessary to
When using ZnO, there is almost no effect on the human body, but ZnO binder-based photoconductive layers have low photosensitivity, a narrow spectral sensitivity range, and significant optical fatigue.
It has drawbacks such as poor photoresponsiveness.

In addition, in electrophotographic image forming members using organic photoconductive materials such as PVK and TNF, which have recently been attracting attention, PVK, TNF, etc. This method has the advantage in manufacturing that a photoconductive layer can be formed simply by forming a coating film of an organic photoconductive material, and the advantage that an electrophotographic image forming member with excellent flexibility can be manufactured. On the other hand,
It lacks moisture resistance, corona ion resistance, and cleaning properties, and has drawbacks such as low photosensitivity, and a narrow spectral sensitivity range in the visible light region that is biased toward short wavelengths, and has an extremely limited range. It is only used for this purpose. However, some of these organic photoconductive materials are suspected of being carcinogenic, and there is no guarantee that many of them are completely harmless to the human body.

As described above, electrophotographic image forming members using photoconductive materials, which have been pointed out in the past as materials for forming the photoconductive layer of electrophotographic image forming members, have both advantages and disadvantages, so to some extent, At present, manufacturing and usage conditions are relaxed, and electrophotographic image forming members suitable for each use are selected and put into practical use.

〔the purpose〕

The present invention has been made in view of the above-mentioned points.Due to the fact that the device can be easily made into a closed system at the time of manufacture, it is possible to avoid any effects on the human body, and once the device is manufactured, it cannot be used. In addition, it is non-polluting, has no effect on the human body, other living things, or the natural environment, has excellent heat resistance and moisture resistance, and has stable electrophotographic properties at all times.
It is an all-environment type with almost no restrictions on the usage environment.
The main object of the present invention is to provide a method for manufacturing an electrophotographic image forming member that has excellent light fatigue resistance and corona ion resistance and does not cause deterioration even after repeated use.

Another object of the present invention is to provide a method for manufacturing an electrophotographic imaging member that can easily produce high-quality images with high density, clear halftones, and high resolution. .

Another object of the present invention is to have high photosensitivity, a wide spectral sensitivity range covering almost the entire visible light range, fast photoresponsiveness, and good abrasion resistance, cleaning properties, and solvent resistance. It is also an object of the present invention to provide a method for manufacturing an electrophotographic imaging member having excellent properties.

[Means to solve problems]

An intended object of the present invention is to (a) form a plasma atmosphere in the space within the deposition chamber in which silicon (silicon) or/and a silicon compound (silicon compound) is present by means of discharge energy; (b) forming an amorphous silicon (hereinafter referred to as "a-Si")-based photoconductive layer on the support placed on the substrate; (b) depositing a gas used for forming the surface coating layer; (c) converting the gas into a plasma state by discharge energy in the deposition chamber; (d) forming a surface coating layer of a desired thickness on the a-Si photoconductive layer; maintaining said plasma state for a sufficient period of time to
This is accomplished through a manufacturing process that includes.

The most typical structural example of the electrophotographic image forming member according to the present invention is shown in FIG. An electrophotographic image forming member 1 shown in FIG. 1 is composed of a support 2 for electrophotographic image forming members, an a-Si photoconductive layer 3, and a surface coating layer 4. It has a free surface 5 which serves as an imaging surface.

The support 2 may be electrically conductive or electrically insulating. Examples of the conductive support include stainless steel, A, Cr, Mo, Au, Ir, Nb, Ta,
Examples include metals such as V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose triacetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. It is desirable that at least one surface of these electrically insulating supports is electrically conductive treated.

For example, if it is glass, its surface has been conductively treated with In ₂ O ₃ or SnO ₂ , or if it is a synthetic resin film such as polyester film, A,
The surface is subjected to conductive treatment by vacuum evaporation treatment with a metal such as Ag, Pb, Zn, Ni, or Au, or by lamination treatment with the metal. The shape of the support is
It can be of any shape such as cylindrical, belt-like, plate-like, etc.
Its shape is determined as desired, but in the case of continuous high-speed copying, an endless belt or cylindrical shape is preferable. The thickness of the support is appropriately determined so as to form a desired electrophotographic image forming member, but if flexibility is required as an electrophotographic image forming member, the thickness of the support may be determined as appropriate. It is made as thin as possible within a range that allows for sufficient functionality. However, in such cases, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is usually 10
It is considered to be more than μ.

The a-Si photoconductive layer 3 is formed on the support 2 by glow discharge, sputtering, ion plating, or the like. These methods are selected and adopted as appropriate depending on factors such as the manufacturing method, manufacturing conditions, level of equipment capital investment, manufacturing scale, and the desired electrophotographic characteristics of the electrophotographic image forming member to be manufactured. Substitution type is relatively easy to control to produce an electrophotographic imaging member having desired electrophotographic properties. The glow discharge method is preferably employed because of its advantages such as the ability to introduce impurities of the group or groups.

Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in a unified device to achieve a-
A Si-based photoconductive layer may also be formed.

The a-Si-based photoconductive layer can provide an electrophotographic image forming member having desired electrophotographic properties.
Its dark resistance and photoelectric gain are controlled, for example, by containing H. Here, "H is contained in the a-Si photoconductive layer" means "H is contained in the a-Si photoconductive layer".
A state in which H is combined with Si, a state in which H is ionized and incorporated into the layer, or a state in which H is incorporated into the layer as _H2 , or a combination of these states. means. The inclusion of H in the a-Si photoconductive layer is achieved by introducing silicon hydride such as SiH ₄ or Si ₂ H ₆ into the manufacturing equipment system in the form of a compound or H ₂ when forming the layer, and then discharging it. These compounds or H ₂
is decomposed and incorporated into the a-Si photoconductive layer as the layer grows.

According to the findings of the present inventors, the H content in the a-Si photoconductive layer is one of the major factors that determines whether or not the formed image forming member can be applied in practice. It has been found to be extremely important, especially as an element for controlling the formed a-Si photoconductive layer to be p-type or n-type.

In the present invention, in order to make the formed image forming member sufficiently applicable to practical applications, the amount of H contained in the a-Si photoconductive layer is usually 10 to 10.
It is desirable that it be 40 atomic%, preferably 15 to 30 atomic%. The theoretical basis for the reason why the H content in the a-Si photoconductive layer is limited to the above numerical range has not yet been clarified and remains in the realm of speculation. However, numerous experimental results have shown that it is extremely difficult to control the H content to meet the requirements of a photoconductive layer of an image forming member for electrophotography, for example, if the H content is outside the above numerical range. The produced electrophotographic image forming members have extremely low sensitivity to irradiated electromagnetic waves, or in some cases, the sensitivity is hardly recognized or the carrier increases little due to electromagnetic wave irradiation. It has been proven that it is a necessary condition that the content be within the above numerical range. The inclusion of H in the a-Si photoconductive layer can be achieved by using, for example, a glow discharge method in which a silicon hydride compound such as SiH ₄ or Si ₂ H ₆ is used as the starting material for forming the a-Si photoconductive layer. Therefore, if the conditions described below are followed, when a silicon hydride compound such as SiH ₄ or Si ₂ H ₆ is decomposed to form an a-Si photoconductive layer, H will automatically be contained in the layer. However, in order to more efficiently incorporate H into the layer, when forming the a-Si photoconductive layer, H ₂ is added to the glow discharge device system.
It would be better to introduce gas.

When using the sputtering method, H ₂ gas is Alternatively, a silicon hydride compound gas such as SiH ₄ or Si ₂ H ₆ or a gas such as B ₂ H ₆ or PH ₃ which also serves as impurity doping may be introduced.

In order to control the amount of H contained in the a-Si photoconductive layer in order to achieve the object of the present invention, the substrate temperature or/and the manufacturing equipment system of the starting material used to contain H can be controlled. All you have to do is control the amount introduced into the body. Furthermore, after forming the a-Si photoconductive layer,
The layer may be exposed to an activated hydrogen atmosphere.
Further, at this time, one method is to heat the a-Si photoconductive layer below the crystallization temperature. In particular, the heat treatment method is an effective means for improving the dark resistance of the a-Si photoconductive layer. Another effective method is to improve the dark resistance of the a-Si photoconductive layer by irradiating it with electromagnetic waves such as high-intensity light.

The a-Si photoconductive layer can be made intrinsic by doping with impurities during manufacturing, and its conductivity type can be controlled, so that it can be easily charged when forming an electrostatic image on an electrophotographic imaging member. It has the advantage that the polarity of can be arbitrarily selected.

This advantage lies in the fact that, for example, when forming a conventional Se-based photoconductive layer, for example, the substrate temperature
Depending on the manufacturing conditions such as the type of impurity and the amount of doping, p-type or at most intrinsic type (i-type) can be formed, and even in order to form p-type, the substrate temperature must be strictly controlled. It is much more convenient than having to do it.

The impurities doped into the a-Si photoconductive layer include:
Elements of group A of the periodic table, such as B, A,
Ga, In, T, etc. are listed as suitable ones,
In the case of n-type, an element of group A of the periodic table,
For example, N, P, As, Sb, Bi, etc. are suitable. Since the amount of these impurities contained in the a-Si photoconductive layer is on the order of ppm, it is not necessary to pay as much attention to their pollution properties as the main substances constituting the photoconductive layer, but it is necessary to minimize their pollution potential as much as possible. It is preferable to use one that does not exist. From this point of view, the electrical properties of the a-Si photoconductive layer formed are
Considering optical properties, for example, B, As, P,
Sb etc. are optimal. In addition, for example, by interstitial doping with Li etc. by thermal diffusion or ion implantation, n
It is also possible to control the shape.

The amount of impurity doped into the a-Si photoconductive layer is appropriately determined depending on the desired electrical and optical properties, but in the case of impurities in group A of the periodic table, it is usually 10 ^{- 6} to 10 ^-3 atomic%, preferably 10 ^-5
~10 ^-4 atomic%, in the case of impurities of group A of the periodic table, usually 10 ^-8 to 10 ^-5 atomic%, preferably 10 ^-8
It is desirable that it be ~10 ^-7 atomic%.

The method of doping these impurities into the a-Si photoconductive layer differs depending on the manufacturing method adopted when forming the a-Si photoconductive layer, and specifically, This will be explained in detail in the following description or examples.

The layer thickness of the a-Si photoconductive layer is determined as appropriate depending on the desired electrophotographic properties and usage conditions, such as whether flexibility is required, but case 5~80μ, preferably 10~70
μ, preferably 10 to 50 μ.

The surface coating layer 4 is formed by introducing a reactive gas, which is a raw material for forming the surface coating layer, into a deposition chamber that can be kept in a reduced pressure state after forming the a-Si photoconductive layer 3, and then introducing a reaction gas into the deposition chamber. to generate discharge energy, apply the discharge energy to the reaction gas to create a gas plasma state, and deposit the generated reaction product on the a-Si-based photoconductive layer. .

The reactive gas used in the present invention is nitrogen as a reaction partner gas in which silicon compound gas reacts with the silicon compound to produce silicon nitride, silicon dioxide, or silicon nitride oxide as a reaction product. It consists of a chemical compound, oxygen, an oxygen compound, or a mixture thereof.

The silicon compounds that are effective in the present invention include silicon hydrides such as SiH ₄ and Si ₂ H ₆ , silicon halides such as Sic ₄ and SiBr ₄ , SiHC ₃ , SiHBr ₂ , and SiH ₂ Examples include inorganic silicon compounds such as halosilane such as _C2 .

As a reaction partner gas other than nitrogen and oxygen, NH ₃
Nitrogen compounds such as _CO2 , oxygen compounds such as _N2O ,
Preferred examples include compounds of nitrogen and oxygen such as NO.

The mixing ratio of the silicon compound gas constituting the reaction gas and the reaction partner gas varies depending on the type of gas to be mixed, the desired characteristics of the surface coating layer, the method of generating discharge energy, etc. However, when the reaction partner gas is usually 1 volume of silicon compound, the reaction partner gas is 1 to 50 volumes, preferably 2 to 25 volumes, The optimum volume is 2 to 20 volumes.

The reaction gas is Ar to control the reaction rate.
If necessary, it may be diluted with an inert gas such as N2 or a diluent gas such as _N2 . In particular, when SiH ₄ and O ₂ react explosively even at room temperature, such as when the reaction gas is SiH ₄ -O ₂ , etc., the reaction rate must be reduced by sufficiently diluting with diluting gas. We need to ease it up.

In the present invention, particularly effective reactive gases include SiH ₄ -N ₂ O-based, SiH ₄ -O ₂ (-Ar)-based,
SiH ₄ -NO ₂ system, SiH ₄ -O ₂ -N ₂ system, SiC ₄ -CO ₂
−H ₂ system, SiC ₄ −NO−H ₂ system, etc., and
When forming a silicon nitride surface coating layer,
These are SiH ₄ -NH ₃ -based, SiC ₄ -NH ₃ -based, SiH ₄ -N ₂ -based, etc., and in the case of forming a surface coating layer of silicon nitride oxide, SiH ₄ -NH ₃ -NO-based etc. are used.

Glow discharge method, sputtering method, ion brating method, etc. are used as methods for generating discharge energy and applying the discharge energy to reactant gas to turn it into gas plasma.Glow discharge method is particularly effective. It's a method.

In the present invention, in order to generate sufficient discharge energy in the deposition chamber to turn the reaction gas into plasma, the discharge current density is normally set at 0.1 to 10 mA/cm ² ,
The AC or DC current is preferably 1 to 5 mA/ ^cm2 , and in order to obtain sufficient power, the voltage is usually adjusted to 100 to 5000 V, preferably 300 to 5000 V, and the input voltage is Usually 0.1 as the power
~50W, preferably 0.1~10W.
Moreover, in the case of AC, its frequency is usually 0.2
It is desirable that the frequency is ~30MHz, preferably 5~20MHz.

The total gas pressure when introducing a reactive gas as a raw material for forming a surface coating layer into the deposition chamber and converting it into gas plasma is determined as appropriate to obtain the desired gas plasma, but the usual If 10 ^-2 ~
Maintained at 3torr. The thickness of the surface coating layer is appropriately determined depending on the desired characteristics and the material used, but is usually about 0.5 to 70 μm. In particular, when the surface coating layer is required to function as the above-mentioned protective layer, 10
On the contrary, when the function as an electrically insulating layer is required, the thickness is usually set to be 10μ or more. However, the layer thickness value that differentiates the protective layer from the electrically insulating layer depends on the materials used, the applied electrophotographic process, and the structure of the electrophotographic imaging member.
The value of 10μ is not absolute as it fluctuates.

As a modification of the electrophotographic image forming member 1 shown in FIG. 1, a lower insulating layer 10 may be provided between the a-Si photoconductive layer and the support. The lower insulating layer is formed of a suitable insulating material such as nitrides such as Si ₃ N ₄ , SiNO, SiO ₂ , and Al ₂ O ₃ , oxides, and various resins such as polyester, polyparaxylylene, and polyurethane. Ru.

Next, the method for manufacturing the electrophotographic image forming member of the present invention will be explained in more detail.

FIG. 2 is a schematic explanatory diagram of a glow discharge deposition apparatus for producing an electrophotographic image forming member by a glow discharge method.

6 is a glow discharge deposition chamber, inside which is a-
A substrate 7 for forming a Si-based photoconductive layer is fixed to a fixing member 8, and a heater 9 for heating the substrate 7 is installed on the lower side of the substrate 7. At the top of the deposition chamber 6, capacitance type electrodes 11, 1 connected to a high frequency power source 10 are installed.
1' is wound, and when the high frequency power supply 10 is turned on, a high frequency is applied to the electrodes 11 and 11', and a glow discharge is generated in the deposition chamber 6.

A gas introduction pipe is connected to the upper end of the deposition chamber 6, and the gas in each cylinder is introduced into the deposition chamber 6 from the gas cylinders 12, 13, 14, and 15 when necessary. 16, 17, 18,
Each of 19 is a flow meter and is a meter for detecting the flow rate of gas, and 20, 2
1, 22, 23 are valves, 24, 25, 26, 2
7 is a flow control valve, and 28 is an auxiliary valve.

Further, the lower end of the deposition chamber 6 is connected to an exhaust device (not shown) via a main valve 29. 30 is a valve for breaking the vacuum in the deposition chamber 6.

To form an a-Si photoconductive layer with desired characteristics on the substrate 7 using the glow discharge device shown in FIG.
First, the substrate 7 that has been subjected to a predetermined cleaning process is fixed to the fixing member 8 with the cleaned side facing upward.

To clean the surface of the substrate 7, a commonly used method, for example, a chemical treatment method using a neutral detergent, pure water, an alkali, an acid, etc., is employed.
Also, after cleaning to some extent, it is installed in the deposition chamber 7,
Glow discharge treatment may be performed before forming an a-Si photoconductive layer thereon. In this case, since the process from cleaning the substrate 7 to forming the a-Si photoconductive layer can be performed in the same system, it is possible to avoid dirt and impurities from adhering to the cleaned substrate surface. After fixing the board 7 to the fixing member 8, the main valve 29
is fully opened to exhaust the air in the deposition chamber 6 and make the degree of vacuum approximately 10 ^-5 torr. After the inside of the deposition chamber 6 reaches a predetermined degree of vacuum, the heater 9 is ignited to heat the substrate 7, and once the predetermined temperature is reached, the temperature is maintained.

Next, the auxiliary valve 28 is fully opened, and then the valve 20 of the gas cylinder 12 and the valve 21 of the gas cylinder 13 are fully opened. The gas cylinder 12 is for dilution gas such as Ar gas, and the gas cylinder 13 is for a-
For raw materials for forming Si, for example,
SiH ₄ , Si ₂ H ₆ , Si ₄ H ₁₀ , or a mixture thereof is stored. The cylinder 14 can be replaced with a if necessary.
- It is used as a raw material for introducing impurities into the Si-based photoconductive layer, and PH ₃ , P ₂ H ₄ , B ₂ H ₆ and the like are stored therein.

The cylinder 15 is for raw materials for forming a surface coating layer on the a-Si photoconductive layer, and is for raw materials such as NH ₃ ,
NO, N ₂ O, etc. are stored. Thereafter, the flow rate control valves 24 and 25 of the gas cylinders 12 and 13 are gradually opened while watching the flow meters 16 and 17, and a diluting gas, such as Ar, is introduced into the deposition chamber 6.
For example, SiH ₄ gas is introduced as a gas and a source gas for forming a-Si. At this time, a dilution gas is not necessarily required, and only the raw material gas for forming a-Si may be introduced. When introducing dilution gas and raw material gas for a-Si formation, their quantitative ratios are determined according to requirements, but in normal cases, the raw material gas for a-Si formation is 10Vo% or more relative to the dilution gas. It is said that Also, Ne gas may be used instead of Ar gas.

When the gas is introduced into the deposition chamber 6 from the cylinders 12 and 13, the main valve 29 is adjusted to a predetermined degree of vacuum, usually 10 at the raw material gas pressure for forming a-Si. Keep at ^-2 ~3torr. Next, a high frequency of a predetermined frequency, typically 0.2 to 30 MHz, is applied by the high frequency power source 10 to the capacitance type electrodes 11 and 11' wound outside the deposition chamber 6 to generate a glow discharge inside the deposition chamber 6. Then, for example, SiH ₄ gas is decomposed and Si is deposited on the substrate 7 to form an a-Si photoconductive layer.

When introducing impurities into the a-Si photoconductive layer to be formed, gas for impurity generation may be introduced into the deposition chamber 6 using the cylinder 14 at the time of forming the a-Si photoconductive layer. In this case, flow control valve 2
6, the amount of gas introduced from the cylinder 14 into the deposition chamber 6 can be appropriately controlled, thereby reducing the amount of impurities introduced into the a-Si photoconductive layer to be formed. can be arbitrarily controlled, and furthermore, the amount of impurities can be easily changed in the thickness direction of the a-Si photoconductive layer.

As described above, after the a-Si photoconductive layer is formed on the substrate 7, the valve 21, the flow rate adjustment valve 24,
Close 25 and 26. After that, in order to form a surface coating layer on the a-Si photoconductive layer, the valve 23 is fully opened, and the flow rate adjustment valves 24, 25, 27 are gradually opened while observing the flow meters 16, 17, 19. For example, a silicon compound gas such as SiH ₄ , a dilution gas such as Ar gas, and N ₂ O or NH ₃ are placed in the deposition chamber 6.
Introduce a reaction partner gas such as The quantitative ratio is usually N ₂ O to silicon compound gas such as SiH ₄ ,
Reaction partner gas such as NH ₃ is assumed to be 1VO% or more.
When the desired gas is introduced into the deposition chamber 6 from the cylinders 12, 13, and 15, the main valve 29 is adjusted to achieve a predetermined degree of vacuum, usually to form a surface coating layer. 10 ^-3 ~ at feed gas pressure of
Keep at 3torr.

In the glow discharge device shown in FIG.
Although the RF (radio frequency) bipolar type glow discharge method is employed, other glow discharge methods such as RF coil type and DC bipolar type are also employed in the present invention. Further, the electrode for glow discharge may be provided outside the deposition chamber 6 or may be provided inside the deposition chamber 6.

In the present invention, in order to generate discharge energy in the deposition chamber 6 that is effective for forming an a-Si photoconductive layer, the discharge current density must be set at 0.1 to 10 mA/cm ² .
It is best to use a constant AC or DC current, and to obtain sufficient power, it is best to adjust the voltage to between 100 and 5000V.

Since the characteristics of the a-Si photoconductive layer and the surface coating layer to be formed largely depend on the substrate temperature during growth, it is preferable to strictly control them. In the present invention, the substrate temperature is usually in the range of 50 to 350°C, preferably 100 to 200°C when forming the a-Si photoconductive layer,
When forming the surface coating layer, the temperature is 100-500℃, preferably 200-500℃.
It is said to be 400℃. This substrate temperature is equal to the temperature of the formed a
-Since it is one of the elements that determines the physical properties of the Si-based photoconductive layer and the surface coating layer, sufficient control is required.
Further, the substrate temperature may be kept constant during the formation of the a-Si photoconductive layer and the surface coating layer, or may be raised, lowered, or raised or lowered as the layers grow. For example, in the initial stage of forming an a-Si photoconductive layer, the substrate temperature is kept at a relatively low temperature _T1 ,
After _the a-Si photoconductive layer has grown to _a certain extent, a
- Form a Si-based photoconductive layer and a surface coating layer, and at the final stage of layer formation, lower the substrate temperature again to a temperature T ₃ lower than T ₂ to form an a-Si-based photoconductive layer and a surface coating layer. I can do it. By doing so, the electrical and optical properties of the a-Si photoconductive layer and the surface coating layer can be changed uniformly or continuously in the layer thickness direction.

In addition, the layer growth rate of a-Si is slower than that of other materials such as Se, so when the layer thickness is increased, the a-Si formed at the initial stage of layer formation (a-Si near the substrate side) Since there is a strong possibility that the characteristics at the initial stage of layer formation may change until the layer formation is completed, a-Si) has uniform characteristics in the thickness direction.
In order to form a photoconductive layer, it is desirable to form layers while increasing the substrate temperature from the start of layer formation to the end of layer formation. Furthermore, the growth rate of the a-Si photoconductive layer and the surface coating layer is also a factor that greatly influences the layer properties, and to achieve the purpose of the present invention, the growth rate is usually 0.5 to 100 Å/sec, preferably 1~50Å/
It is preferable to set it as sec.

The present invention will be specifically explained below using Examples.

Example 1 Using the apparatus shown in FIG. 2, an electrophotographic image forming member was prepared in the following manner, and a predetermined image forming process was performed on the member to form an image.

Prepare an aluminum substrate with a thickness of 1 mm and a size of 10 cm x 10 cm, which has been surface-treated with a 1% NaOH solution, thoroughly washed with water, and dried to clean the surface. The heater 9 was firmly fixed at a predetermined position of the fixing member 8 at a distance of about 10 cm from the heater 9.

Next, the main valve 29 is fully opened to open the deposition chamber 6.
The air inside was evacuated to create a vacuum of approximately 5×10 ^-5 torr. Thereafter, the heater 9 was ignited to uniformly heat the aluminum substrate to 150° C., and the temperature was maintained at this temperature. After that, the valve 28 is fully opened, and then the valve 20 of the cylinder 12 and the valve 21 of the cylinder 13 are fully opened, and then the flow rate adjustment valves 24 and 25 are fully opened.
was gradually opened, and Ar gas from cylinder 12 and SiH ₄ gas from cylinder 13 were introduced into deposition chamber 6.
At this time, the main valve 29 was adjusted so that the degree of vacuum in the deposition chamber 6 was maintained at approximately 0.75 torr.

Subsequently, the high frequency power source 10 was turned on and a high frequency of 13.56 MHz was applied between the electrodes 11 and 11' to generate a glow discharge, thereby forming an a-Si photoconductive layer on the aluminum substrate. The glow discharge power at this time was about 5W. Also, a-Si at this time
The growth rate of the photoconductive layer was approximately 4 Å/sec, and the deposition was performed for 15 hours on the aluminum substrate.
An a-Si photoconductive layer having a thickness of 20 μm was formed.

Next, the flow control valves 24 and 25 were closed, and the high frequency power source 10 was turned off to stop the glow discharge.

Next, after fully opening the valve 23 of the cylinder 15, the flow control valves 24, 25, and 27 are gradually opened to supply Ar gas from the cylinder 12, SiH ₄ gas from the cylinder 13, and NH ₃ gas from the cylinder 15 into the deposition chamber 6. After that, the main valve 29 was adjusted so that the degree of vacuum in the deposition chamber 6 was maintained at the same value as when forming the a-Si photoconductive layer. Subsequently, glow discharge was performed under the same conditions as when forming the a-Si photoconductive layer.
A surface coating layer made of Si ₃ N ₄ was formed on the Si-based photoconductive layer.

The growth rate of the Si ₃ N ₄ layer at this time was 6 Å/sec, and the deposition was carried out for 7 hours to form a layer of 15 Å on the a-Si photoconductive layer.
_Four μ-thick Si ₃ N layers were formed. The electrophotographic image forming member thus produced is connected to the main valve 29,
Auxiliary valve 28, flow rate adjustment valves 24, 25, 2
7. Close the valves 20, 21, and 23, and open the valve 30 instead to break the vacuum in the deposition chamber 6 and take it out. The surface of the surface coating layer (insulating layer) of this electrophotographic image forming member is temporarily charged at the power supply voltage.
When corona discharge was performed at 6000V for 0.2 seconds, it was charged to 2000V. Next, as secondary charging, corona discharge was performed at a power supply voltage of 5500 V, and at the same time image exposure was performed at an exposure amount of 15 ux·sec, and then the entire surface of the image forming member was uniformly irradiated to form an electrostatic image. When this electrostatic image was developed with toner charged by the cascade method and transferred and fixed onto transfer paper, an image of extremely good quality was obtained.

When this image forming process was repeated on the electrophotographic image forming member and the durability of the electrophotographic image forming member was tested, the image obtained on the 100,000th sheet of transfer paper was also extremely poor. It is of good quality and there is no difference in comparison with the image on the first sheet of transfer paper, and this electrophotographic image forming member has excellent corona ion resistance, abrasion resistance, cleaning properties, etc., and is extremely durable. It has been proven that

Further, for this electrophotographic image forming member, the surface of the surface coating layer was subjected to corona discharge as primary charging, then corona discharge as secondary charging, and at the same time image exposure was performed at a light intensity of 15 ux·sec, and the same process as above was performed. When image formation was carried out under these conditions, the image quality on the resulting transfer paper was lower than in the case of corona charging.

From this experiment, it was found that the electrophotographic image forming member obtained in this example had charge polarity dependence.

Example 2 A 20μ thick a-Si photoconductive layer was formed on an aluminum substrate under the same conditions and procedures as in Example 1.
After forming a surface coating layer of Si ₃ N ₄ with a thickness of 2 μm on the -Si-based photoconductive layer, the layer was taken out of the deposition chamber 6 .
On this electrophotographic image forming member, corona discharge was applied to the surface of the surface coating layer in the dark with a power supply voltage of 5500 V, and then image exposure was performed with an exposure amount of 20 ux x sec to form an electrostatic image. When the electrostatic image was developed with toner charged by the cascade method and transferred and fixed onto transfer paper, an extremely clear image was obtained.

Example 3 Similar to Example 1, using the apparatus shown in FIG.
An electrophotographic image forming member of the present invention was prepared in the following manner, and an image was formed by performing an image forming process.

Prepare an aluminum substrate with a thickness of 1 mm and a size of 10 cm x 10 cm, which has been surface-treated with a 1% NaOH solution, thoroughly washed with water, and dried to clean the surface. The heater 9 was firmly fixed at a predetermined position of the fixing member 8 at a distance of about 10 cm from the heater 9.

Next, the main valve 29 is fully opened to open the deposition chamber 6.
The air inside was evacuated to create a vacuum of approximately 5×10 ^-5 torr. Thereafter, the heater 9 was ignited to uniformly heat the aluminum substrate to 150° C., and the temperature was maintained at this temperature. After that, the auxiliary valve 28 is fully opened, and then the valve 20 of the cylinder 12 and the valve 21 of the cylinder 13 are fully opened, and then the flow rate adjustment valves 24 and 25 are gradually opened to supply Ar gas from the cylinder 12 and SiH gas from the cylinder 13. ₄ gases were introduced into the deposition chamber 6. At this time, the main valve 29 was adjusted so that the degree of vacuum in the deposition chamber 6 was maintained at about 0.75 torr. Also, in this case, while watching the flow meters 16 and 17, the flow control valves 24 and 2
5 was adjusted so that the flow rate of SiH ₄ gas was 10Vo% of the flow rate of Ar gas.

Next, the valve 22 of the cylinder 14 is fully opened, and then the flow rate adjustment valve 26 is gradually opened to control the flow rate to be 5×10 ^-5 Vo% of the flow rate of SiH ₄ gas, while the deposition chamber B ₂ H ₆ gas was introduced into the chamber. At this time as well, the main valve 29 was adjusted to maintain the degree of vacuum in the deposition chamber 6 at 0.75 torr.

Subsequently, the switch of the high frequency power supply 10 was turned on, and a high frequency of 13.56 MHz was applied between the electrodes 11 and 11' to generate a glow discharge, thereby forming an a-Si photoconductive layer on the aluminum substrate. The glow discharge power at this time was about 5W. Also, a-Si at this time
The growth rate of the photoconductive layer was approximately 4 Å/sec, and the growth rate was 15
20μ on an aluminum substrate by time-deposition.
A thick a-Si photoconductive layer was formed.

Next, the flow control valves 24, 25, and 26 were closed, and the high frequency power source 10 was turned off to stop the glow discharge.

Next, the valve 23 of the cylinder 15 is fully opened, and the flow rate adjustment valves 24, 25, and 27 are gradually opened to supply Ar gas from the cylinder 12, SiH ₄ gas from the cylinder 13, and NH ₃ gas from the cylinder 15 into the deposition chamber 6. After introducing the a-Si photoconductive layer, the main valve 29 was adjusted so that the degree of vacuum in the deposition chamber 6 was maintained at the same value as when forming the a-Si photoconductive layer. Subsequently, glow discharge was performed under the same conditions as when forming the a-Si photoconductive layer.
-A surface coating layer made of Si ₃ N ₄ was formed on the Si-based photoconductive layer.

The growth rate of the Si ₃ N ₄ layer at this time was 6 Å/sec, and the deposition was carried out for 7 hours to form a layer of 15 Å on the a-Si photoconductive layer.
A surface coating layer made of Si ₃ N ₄ with a thickness of μ was formed. After forming the electrophotographic image forming member thus prepared, the main valve 29, the auxiliary valve 28, the flow rate adjustment valves 24, 25, 27, and the valves 20, 21, 23 are closed, and the valves are closed instead. 30
was opened to break the vacuum in the deposition chamber 6 and taken out to the outside. As a primary charge on the surface of the surface coating layer (insulating layer) of this electrophotographic image forming member, the power supply voltage
When corona discharge was performed at 6000V for 0.2 seconds, it was charged to 2000V. Next, as secondary charging, corona discharge was performed at a power supply voltage of 5500 V, and at the same time image exposure was performed at an exposure amount of 15 ux·sec, and then the entire surface of the photoreceptor was uniformly irradiated to form an electrostatic image. When this electrostatic image was developed with toner charged by the cascade method and transferred and fixed onto transfer paper, an image of extremely good quality was obtained.

Next, for the electrophotographic image forming member described above, corona discharge was performed for 0.2 seconds at a power supply voltage of 5500 V as a primary charge on the surface of the surface coating layer, and then a + corona discharge was performed at a power supply voltage of 6000 V as a secondary charge. At the same time, perform image exposure with an exposure amount of 15ux・sec,
Then, the entire surface of the image forming member was uniformly irradiated to form an electrostatic image. When this electrostatic image was developed using toner charged by the cascade method and then transferred and fixed onto transfer paper, an extremely clear image was obtained.

From this result and the previous results, it was found that the electrophotographic image forming member obtained in this example had bipolar characteristics without dependence on charging polarity.

Example 4 In Example 3, an aluminum substrate was fabricated in the same manner as in Example 3, except that the flow rate of B ₂ H ₆ gas was adjusted to be 5 × 10 ^-4 Vo% of the flow rate of SiH ₄ gas. 20μ thick a-Si photoconductive layer and 15μ thick a-Si photoconductive layer.
A Si ₃ N ₄ insulating layer was formed to obtain an electrophotographic image forming member.

Regarding this electrophotographic image forming member, Example 3
When an image was formed on a transfer paper under the same conditions and procedures as above, corona discharge was performed as a primary charge, and corona discharge was performed as a secondary charge, and image exposure was performed at the same time to form an image. The image quality was superior and extremely clear compared to images formed by performing image exposure at the same time as performing corona discharge as electrification.

From this result, it was found that the electrophotographic image forming member obtained in this example had charge polarity dependence. However, the polarity dependence was opposite to that of the electrophotographic image forming member obtained in Example 1.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view schematically showing the layer structure of an electrophotographic image forming member according to the present invention, and FIG. 2 embodies a method for manufacturing the electrophotographic image forming member of the present invention. FIG. 2 is a schematic explanatory diagram schematically showing an example of an embodiment of a device for the purpose of the present invention. 1... Electrophotographic image forming member, 2... Support,
3...Photoconductive layer, 4...Surface coating layer, 5...Free surface, 6...Deposition chamber, 10...High frequency power source, 1
2, 13, 14, 15... Gas cylinder, 16, 1
7, 18, 19...flow meter.

Claims (1)

[Scope of Claims] 1. A method for producing an electrophotographic image forming member having a support, a photoconductive layer, and a surface coating layer, comprising: (a) applying discharge energy to a space in a deposition chamber in which silicon or/and a silicon compound is present; (b) forming an amorphous silicon-based photoconductive layer on a support placed in advance in the deposition chamber by forming a plasma atmosphere; (b) used for forming a surface coating layer; introducing a gas into the deposition chamber; (c) bringing the gas into a plasma state by discharge energy within the deposition chamber; (d) forming a surface of a desired thickness on the amorphous silicon-based photoconductive layer; A method of manufacturing an electrophotographic imaging member, comprising: maintaining the plasma state for a sufficient time to form a coating layer. 2. Production of an electrophotographic image forming member according to claim 1, wherein the discharge energy in step (c) is generated with an AC or DC current having a discharge current density of 0.1 to 10 mA/cm ² and an applied voltage of 100 to 5000 V. Method. 3. The gas in step (b) comprises a silicon compound gas and a reaction partner gas that reacts with the silicon compound to produce silicon nitride, silicon dioxide, or silicon nitride oxide as a reaction product. 1
1. Method for manufacturing an electrophotographic image forming member according to item 1. 4. The method for producing an electrophotographic image forming member according to claim 3, wherein the reaction partner gas comprises nitrogen, a nitrogen compound, oxygen, an oxygen compound, a compound of nitrogen and oxygen, or a mixture thereof. 5. The method for producing an electrophotographic image forming member according to claim 3, wherein the silicon compound is silicon hydride. 6. The method for producing an electrophotographic image forming member according to claim 3, wherein the silicon compound is a silicon halide. 7. The method for producing an electrophotographic image forming member according to claim 3, wherein the silicon compound is a halosilane. 8. The method for producing an electrophotographic image forming member according to claim 3, wherein the reaction partner gas is present in an amount of 1 to 50 volumes per 1 volume of the silicon compound gas.