JPS5875157A - Image forming member for electrophotography - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic photoreceptor having high resolution, high sensitivity and excellent durability by forming amorphous silicon (a-Si) layers having a depletion layer that forms carriers when irradiated with electromagnetic waves (light) as a photoconductive layer on the barrier layer on a substrate. CONSTITUTION:A barrier layer not shown is formed with a thin layer of Al2O3, SiO, MgF2, etc. on a conductive substrate 9, and an a-Si layer is formed as a layer contg. 1-40atom% H which is not doped or a p type a-Si layer contg. B, etc. or an n type a-Si layer contg. P, etc. on the barrier layer, whereby an inside a-Si layer 12 is formed. Thereafter, an outside a-Si layer 13 of the type differing from the layer 12 is formed on the layer 12 or said layer is formed with the same p type or n type layer at different quantity of doping. A depletion layer 11 is formed between the layers 12 and 13 by such formation, whereby a photoconductive layer 10 is formed. Thus the photoreceptor having various characteristics superior to those in the prior art is obtained. A surface coating layer 14 to serve both as a protecting layer and an antireflecting layer may be provided on the layer 13.

Description

Detailed Description of the Invention The present invention forms images using electromagnetic waves such as light (here, light in a broad sense, including ultraviolet light, visible light, infrared light, X-rays, R-rays, etc.). The present invention relates to an electrophotographic imaging member used for.

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

In electrophotographic image forming members using these photoconductive materials, there are still various issues that can be solved, and the conditions should be relaxed to some extent. When using Se alone as a material for electrophotographic image forming members, for example, when using light in the visible light range, the spectral sensitivity range is narrow, so it is recommended to add Te or M to expand the spectral sensitivity range. ing.

Higashi et al., such an electrophotographic image forming member having a Si-based photoconductive layer containing Te or As certainly improves the spectral sensitivity range, but because the optical fatigue increases, it is difficult to continuously print the same original. Repeated copying may cause a decrease in the image density of the copied image or background stains (capri on the white background), and if you subsequently copy another original, the image of the previous original will be copied as an afterimage (ghost). phenomenon).

However, since Se, especially As + Te, is an extremely harmful substance 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, preventing development. They may be mixed into agents, dispersed within copying machines, or mixed into copied images, resulting in contact with the human body.

In addition, when the surface of a cylindrical photoconductive layer is continuously and repeatedly exposed to corona discharge many times, crystallization or oxidation occurs near the surface of the layer, resulting in 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). It is required to be excellent in this respect.
Therefore, it is difficult to say that the Se,% photoconductive layer is necessarily satisfactory.

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

Hyakunen et al., ``These improvements have been made in terms of adhesion and electrical contact between the photoconductive layer and the surface coating layer, as well as the electrical properties and surface properties required for the surface coating layer, as well as improvements in Se The system light guiding layer is usually formed by vacuum evaporation, which requires a significant investment in equipment, and
In order to obtain a photoconductive layer having desired photoconductive properties with good reproducibility, it is necessary to strictly adjust various manufacturing parameters such as vapor deposition temperature, vapor deposition substrate temperature, degree of vacuum, and cooling rate.

Furthermore, since the surface coating layer is formed by pasting a film on the surface of the photoconductive layer via an adhesive or by applying a surface coating layer forming material, it is difficult to form the photoconductive layer. It is necessary to install equipment separate from the equipment used to create the system, and there is a significant increase in capital investment, which is extremely unfavorable in the current period of slow economic growth.

In addition, the 'SsSe photoconductive layer is formed in an amorphous state in order to have a high dark resistance as a continuous conductive layer of an electrophotographic image forming member, but Se crystallization occurs at an extremely low temperature of approximately 65°C. Because of this, crystallization occurs during handling after manufacturing or during use, due to the influence of ambient temperature and frictional heat caused by rubbing against other members during the image forming process. It also has a drawback in terms of heat resistance, which tends to cause a decrease in dark resistance.

On the other hand, in electrophotographic imaging members using ZnO, CdS, etc. as photoconductive layer constituent materials, the photoconductive layer is made of ZnO, CdS, etc.
It is formed by uniformly dispersing particles of a photoconductive material such as O or CdS in a suitable resin binder. This image-forming member having a so-called binder-based photoconductive layer is advantageous in manufacturing compared to an image-forming member having a Se-based photoconductive layer, and the manufacturing cost can be relatively reduced. That is,
The binder-based photoconductive layer is prepared by applying a coating solution prepared by mixing ZnO or °CdS particles with 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 it using a coating method and then solidifying it, compared to an image forming member having a Se-based conductive layer, it is not necessary to invest as much capital in manufacturing equipment, and the manufacturing method itself is simple and easy. According to Hyakunen et al., 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 distributed in the resin binder. Due to the special characteristics of the photoconductive layer that must be dispersed and formed, there are many parameters that determine the electrical and photoconductive properties as well as the physicochemical properties of the photoconductive layer, and therefore, these parameters must be precisely adjusted. However, there is a drawback that a photoconductive layer having desired characteristics cannot be formed with good reproducibility, leading to a decrease in yield and lack of mass productivity.

Furthermore, due to the unique nature of the binder-based photoconductive layer being a dispersion system, the entire layer is porous, and as a result, it has significant humidity dependence, resulting in deterioration of electrical properties when used in a humid atmosphere. In many cases, it is no longer possible to obtain a quality 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 causes unusability. When a liquid developer is used, the above point becomes significant because the developer penetrates into the layer together 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 surface coating layer.

Although 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, the interface is not uniform, and the adhesion between the photoconductive layer and the surface coating layer is poor. A drawback 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 drawbacks such as low photosensitivity, narrow spectral sensitivity range, significant optical fatigue, and poor photoresponsiveness. have.

In addition, in electrophotographic image forming members using organic photoconductive materials such as PVK and π-rays, which have recently been attracting attention, PW or It has the advantage in manufacturing that a photoconductive layer can be formed simply by forming a coating film of an organic photoconductive material such as straw, and the advantage that an electrophotographic image forming member with excellent flexibility can be manufactured. However, on the other hand,
It has drawbacks such as moisture resistance, corona ion resistance, and poor resistance, so it can only be used in a very limited range. However, there is no guarantee that many of these organic photoconductive materials are completely harmless to the human body, as some of them contain carcinogenic substances.

- In this way, electrophotographic image forming members using photoconductive materials, which have been pointed out as materials for forming the photoconductive layer of electrophotographic image forming members, have both advantages and disadvantages, so to some extent, The current practice is to relax the manufacturing and usage conditions and select an appropriate electrophotographic image forming member suitable for each application and provide it for the actual situation.

Therefore, there is a need for a third material for forming the photoconductive layer of an electrophotographic image forming member that can provide an excellent electrophotographic image forming member that overcomes the above-mentioned problems.

Among such materials that have recently been viewed as promising is amorphous silicon (hereinafter abbreviated as a-8i).

In the early stages of development, the a-8i film showed a variety of electrical and optical properties because its structure was influenced by its manufacturing method and manufacturing conditions, and it had major problems in terms of reproducibility. Ta. For example, in the early stages, the A-8I film formed by vacuum evaporation or sputtering contained a large amount of voids, etc., which greatly affected its electrical and optical properties. It has not received much attention as a research material for physical properties, and no research and development has been carried out for its application.However, it was thought that P+n control was impossible with amorphous, but in a-8t. In early 1976, it was reported that a p-n junction could be realized for the first time using an amorphous material.
; VO128, A2.

15 January 1976) was completed,
Much interest was gathered, and since then, in addition to the above-mentioned p-n junction being obtained, very weak luminescence has been observed in crystalline silicon (abbreviated as c-8t) with high efficiency in a- and Si. Since then, research and development efforts have been focused mainly on application to solar cells.In this way, the Si films that have been reported so far have been developed for use in solar cells. In terms of its electrical and optical properties, it converts the energy into a current and extracts it, so in order to efficiently extract a large current, the bright resistance of the A-8I film (when irradiated with electromagnetic waves) is resistance) must be kept below a certain level. On the other hand, with an a-8t film whose dark resistance (resistance when not irradiated with electromagnetic waves) is too small, a large current cannot be extracted efficiently. From this point of view, for application to solar cells, the dark resistance of the a-8i film is required to be approximately 10'' to 10 8 Ω.

Heigo et al. tried to apply the a-8i film with this level of dark resistance as a photoconductive layer of an electrophotographic image forming member as it is, but the dark resistance was too low, and currently,
It cannot be used in any known electrophotographic methods.

In addition, the material for forming the photoconductive layer of an electrophotographic image forming member is required to have a bright resistance that is about 2 to 4 orders of magnitude smaller than the dark resistance, but the a-8i films that have been reported so far are at most Since it is about 2 digits, in this respect as well, the conventional A-8i
Even if the film was applied as it is as a photoconductive layer of an electrophotographic image forming member, it could not be a fully satisfactory photoconductive layer.

In addition, according to a separate report regarding the A-8i film, for example, the A-8i film with a dark resistance of -100·(7) has a reduced photoelectric gain (photocurrent per incident photon). In this respect as well, the conventional A-8T film could not be used as a perfect photoconductive layer for an electrophotographic image forming member. Regarding other requirements other than the above, such as electrostatic properties, corona ion resistance, -solvent resistance, light fatigue resistance, moisture resistance, heat resistance, abrasion resistance, and cleanability, etc. , which was previously completely unknown.

The present invention has been made in view of the above points, and as a result of intensive research and study on the a-8i from the viewpoint of application to the photoconductive layer of an electrophotographic image forming member, certain characteristics have been found. If the a-8i layer has a specific layer structure, it can not only be applied very effectively as a photoconductive layer of an electrophotographic imaging member, but also have a higher It is based on the fact that it is superior in most respects.

In the present invention, since the device can be easily made into a closed system during manufacturing, it is possible to avoid adverse effects on the human body, and once manufactured, when using it,
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 always stable electrophotographic characteristics, making it suitable for almost any usage environment. The main object of the present invention is to provide an electrophotographic image forming member that can be used in any environment without limitation, 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 an electrophotographic image forming 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 spectral sensitivity range that covers almost the entire visible light range, a low dark decay rate, fast photoresponsiveness, and excellent abrasion resistance, cleaning properties, and
Another object of the present invention is to provide an electrophotographic imaging member having excellent solvent resistance.

The intended object of the present invention is achieved by forming the photoconductive layer into an a-8i photoconductive layer having the characteristics described in detail below, and by forming a depletion layer in the layer.

The most typical structural example of the electrophotographic image forming member of the present invention is shown in FIGS. 1 and 2. The electrophotographic imaging member 1 shown in FIG. 1 includes a support 2. a-8i photoconductive layer 3
The photoconductive layer 3 is composed of a free surface WI which becomes an image forming surface.
4, and a depletion layer 5 is formed in the layer 3.

In the present invention, in order to provide the depletion layer 5 in the a-8i photoconductive layer 3, the photoconductive layer 3 is made of a-8iO of the following type.
This is accomplished by selecting at least two of these types and forming layers in which the different types are joined.

■N-type a-8i...Contains only a donor, or a donor and acceptor (acc)
eptor ); and the donor concentration (N
d) is high.

■n”ma-8i・・・・・・ Among the ■types, especially n
Those with strong mold characteristics (higher Nd).

■pWa-8t... Contains only acceptor. Alternatively, one that contains both a donor and an acceptor and has a high acceptor concentration (Na).

■p+ type a-8i... Among the ■types, especially p
Strong physical properties (higher Na content).

■Setting type a-8i...Na':: Na = Q's or.

Na = NaO.

That is, the depletion layer 5 is formed, for example, by first forming an i-type a-8i layer with a predetermined thickness on the support 2 having desired surface characteristics, and then forming an i-type a-8i layer on the i-type a-8t layer. , p-type a-
By forming the 8i layer, the i-type a-8i layer and the p-type a
-8i layer (hereinafter, depletion layer 5
The a-8i layer on the support 2 side is the inner layer, the free surface 4
The a-8i layer on the side is called the outer layer). When the photoconductive layer 3 is formed so that different types of a-8i layers are joined, the clogging and depletion layer 5 is formed by forming an inner a-8i layer and an outer a-8i layer.
It is formed in the boundary transition region with the i layer.

The depletion layer 5 in the present invention absorbs non-electromagnetic waves that are irradiated during the electromagnetic wave irradiation step, which is one step in the process of forming an electrostatic image on an electrophotographic image forming member, and creates movable carriers. It functions as a generation layer. Furthermore, in a steady state, the depletion layer 5 is depleted of free carriers, so it behaves as a so-called intrinsic semiconductor.

In the present invention, the inner layer 6 and the outer layer 7, which are the layers constituting the photoconductive layer 3, are made of the same material, a-8t, and their junction (depletion layer 5) is homogeneous. Since they are bonded, the inner layer 6 and the outer layer 7 are electrically and optically well bonded, and the energy bands of the inner layer and the outer layer are smoothly bonded. Furthermore, in the depletion layer 5, there exists a unique electric field (diffusion potential) (inclination of energy band) that is formed when the layer is formed. For this reason, not only the carrier generation efficiency is improved, but also the recombination probability of the generated carriers is reduced, that is, the quantum efficiency is increased, the photoresponse speed is increased, and the generation of residual charges is prevented. arise.

Therefore, the present invention has the advantage that carriers generated in the depletion layer 5 by irradiation with electromagnetic waves such as light work effectively in forming an electrostatic image.

Furthermore, in order to utilize the growth more effectively, the image forming member of the present invention applies a reverse bias (in a reverse direction) to the depletion layer 5 formed in the photoconductive layer 3 when forming an electrostatic image. bias)
Select the charging polarity so that a voltage is applied such that
A charging process is applied to the surface of the outer layer. When this reverse bias is applied to the depletion layer 5, the thickness of the depletion layer 5 increases by approximately the IA power of the voltage applied to the layer. for example,
Under high voltage (104v/D11 or more), the thickness of the depletion layer 5 becomes several to several tens of times as large as the thickness when no charging treatment is performed. Furthermore, application of a reverse bias to the depletion layer 5 makes the inherent electric field (diffusion potential) formed by the junction even steeper.

This makes the effect mentioned above even more remarkable.

In the present invention, as described above, the inner layer 6 and the outer layer 7
Since the depletion layer 5 is formed by joining the inner layer 6 and the outer layer 7, there is an advantage that the entire photoconductive layer 3 can be formed in a continuous manufacturing process. .

The thickness of the depletion layer 5 depends on the dielectric constant of the inner layer 6 and the outer layer 7 to be bonded, and the difference in the Fermi level of both layers before bonding. It is determined by the density of impurities doped into the layer in order to control It can be used in a wide range from 100x to several tens of microns. Therefore, depending on the degree of reverse bias, the depletion layer 5
The layer thickness of can be changed as appropriate.

However, when applying a high electric field reverse bias onto the depletion layer 5, it is necessary to determine the impurity concentration and applied voltage, which will be described later, to an extent that does not cause tunneling or avalanche breakdown.

In other words, if the impurity concentration is too high, tunneling or avalanche destruction will occur with a relatively low reverse bias, and sufficient expansion of the depletion layer 5 (reduction in 1 capacitance) and sufficient electric field to the depletion layer 5 can be obtained. I won't be able to do that.

In the present invention, considering that the depletion layer 5 has the role of absorbing electromagnetic waves and generating carriers, the depletion layer 5
It is better to make the layer thicker in order to absorb as much electromagnetic waves as possible. On the other hand, the strength per unit thickness of the inherent electric field formed in the depletion layer 5, which is an important factor for reducing the recombination probability of carriers generated in the depletion layer 5, is as follows: Since it is inversely proportional to the thickness of the layer, from this point of view, the thinner the thickness of the depletion layer 5, the better.

Therefore, in the present invention, the above two points need to be taken into consideration in order to fully achieve the object. That is, in the present invention, carriers are mostly generated in the depletion layer 5 by electromagnetic wave irradiation, so depending on the irradiation direction when electromagnetic wave is irradiated to the image forming member 1, either the inner layer 6 or the outer layer 7 is generated. is formed in such a way that sufficient carriers can be generated in the depletion layer 5 to form a static electricity with sufficient contrast, that is, so that the irradiated electromagnetic waves can sufficiently reach the depletion layer 5. need to be done. By the way, visible light is employed as the electromagnetic wave to be irradiated in an electrophotographic image forming member that is used for normal use. Therefore, the a-8itD optical absorption coefficient is in the wavelength range 4oo to 7oon.
'WL range is 5 x 10' to 1 (j'cm-'), so in order to achieve the above objective, at least 5,000 people from the layer surface on the light irradiation side should be charged when charging is performed. It is necessary to form either the inner layer 6 or the outer layer 7 as the layer on the light irradiation side so that at least a part of the depletion layer 5 exists in Since the depletion layer 5 only needs to be formed by the junction between the inner layer 6 and the outer layer 7, the thinner the layer, the higher the carrier generation efficiency in the depletion layer 5 with respect to the amount of electromagnetic wave irradiation. Therefore, the thickness is made as thin as possible based on manufacturing technology.

On the other hand, when p-type (p" type) or n-type (n+ type) is used as the outer layer, the dark resistance changes greatly depending on the impurity concentration, but from the conventional electrophotographic viewpoint, most of the dark resistance changes. It is completely unusable.

The reason for this is that if the resistance is too low, it cannot be used because it does not have enough surface resistance to prevent charges from escaping in the lateral direction of the layer when an electrostatic image is formed.

In the present invention, the layer thickness of the depletion layer 5 is expanded due to the aforementioned reverse bias to the depletion layer 5, and this fact means that free carriers are swept away, which means that the outer layer Even if the resistance is relatively low, the apparent resistance will be high, and the charging in the reverse bias direction is
A similar change is induced in the outer layer to have the effect of sweeping the 7 JJ-carriers in the outer layer toward the surface.

Therefore, if the above-described depletion layer spreading effect and free carrier sweeping effect can be expected to the extent that the object of the present invention is achieved as a component of the outer layer, from the conventional electrophotographic viewpoint, This makes it possible to use even those with relatively low resistance values that were considered unusable.

Either one of the inner layer 6 and the outer layer 7, which is not the layer on the electromagnetic wave irradiation side, in other words, the layer on the opposite side of the electromagnetic wave irradiation side with respect to the depletion layer 5 is charged with the charge generated in the depletion layer 5. The photoconductive layer 3 can be formed so as to have the function of effectively transporting the photoconductive layer 3 and to greatly contribute to the capacitance of the photoconductive layer 3.

For this reason, such a layer is usually 0.5 to 100 microns, preferably 1 to 50 microns, optimally, taking into account economic considerations including manufacturing cost and manufacturing time of the imaging member to be manufactured. It is desirable that the layer thickness be in the range of 1 to 30 microns. Furthermore, in the case of an image forming member that requires flexibility, it is preferably formed to have a thickness of 3-θμ or less as an upper limit, although it also depends on the degree of flexibility of other layers and the support 20. It is desirable that the

In FIG. 1, in a preferred embodiment of the image forming member of the present invention, two different types of a- Select 8i layer, for example, p type and n type, p+ type and p type, n type and n type, p
The superiority of the photoconductive layer 3 over the conventional one has been explained using an example in which the photoconductive layer 3 is formed by selecting a combination of type and n type, etc., and bonding them. ,
The present invention can also be carried out well when the photoconductive layer is constructed by bonding three different types of a-Si layers from ■ to ■, such as p-1-n and n-1-p. It can be a mode. In this case, two depletion layers will exist in the photoconductive layer.

In this case, since a high electric field can be applied by dividing the depletion layer into two depletion layers, a large electric field can be applied, and it becomes easier to obtain a high surface potential.

When the photoconductive layer has a layer structure of n-1-p or p-i-n from the support side, it has the following features and can be applied to various electrophotographic processes. become.

In other words, it has the effect of preventing charge injection into the photoconductive layer from the support side, and furthermore, it is possible to irradiate electromagnetic waves from both the surface side and the support side, so it is possible to irradiate both sides with the same image or with different images. Simultaneous add-on image irradiation is also possible. Furthermore, backside irradiation (irradiation from the support side) for erasing electrostatic images, backside irradiation using the NP method (to promote charge injection from the support side) described later, and backside irradiation for improving durability are also possible. Become.

The a-Si layer of type 1 to 2 as a layer constituting the photoconductive layer of the electrophotographic image forming member of the present invention can be formed by a glow densification method, a reactive sputtering method, or the like, as will be described in detail later. At the time, n-type impurity (formed a-8i layer
The amount of p-type impurity (to make the formed a-8i layer type ■ or ■), or both impurities in the formed a-8i layer is controlled. It is formed by doping.

In this case, according to the findings from the experimental results of the present inventors,
From a stronger n-type (or stronger p-type) a-8i layer to a weaker n-type (or weaker n-type) by adjusting the concentration of impurities in the layer to within the range of 1015-1019 crn-3 A-8i layer can be formed.

The a-8i layers of types (1) to (2) are formed by a glow discharge method, a sputtering method, an ion implantation method, an ion blating method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, equipment capital investment load, manufacturing scale, and electrophotographic characteristics desired for the image forming member to be manufactured. In order to control the types of ■ to ■, which are relatively easy to control to produce an image forming member having characteristics, a -S
When introducing impurities into the i-layer, the glow discharge method is preferably employed because of its advantages such as being able to introduce impurities of group 111 or group V in a substitutional manner.

Furthermore, in the present invention, the a-Si layer may be formed by using a glow discharge method and a sputtering method in the same system. The dark resistance and photoelectric gain of the a-Si layer can be controlled by containing H, for example, so that the electrophotographic image forming member targeted by the present invention can be obtained. Here, ``H is contained in the a-Si layer 1'' means ``a state in which H is combined with St''' and ``a state in which H is ionized and incorporated into the layer.'' ” or “incorporated into the layer as H2” or a combination thereof.

a - When forming the layer, H is introduced into the manufacturing equipment system in the form of a compound such as SiH4, 5iyHa, or H7, and then it is introduced by a method such as thermal decomposition or glow discharge decomposition. or H3 may be decomposed and incorporated into the a-8i layer as the layer grows, or may be incorporated by ion implantation.

According to the findings of the present inventors, the H content in the a-8i layer is one of the major factors that influences whether or not the formed image forming member can be applied in practice. Therefore, it has been found that it is extremely heavy, especially as an element for controlling the formed a-Si layer to be p-type or n-type.

In the present invention, the amount of H contained in the a-8i layer is usually 1 to 40 atomic, preferably 5 to 3, in order to make the formed stone image forming member sufficiently applicable to the actual surface.
It is desirable to set it to 0 atomic%. The theoretical basis for the reason why the H content in the a-8i layer is limited to the above-mentioned numerical range has not yet been clarified and remains in the realm of speculation. Hyakunen et al. have found from numerous experimental results that when the H content is outside the above numerical range, it is difficult to control the properties to meet the requirements for the inner layer or outer layer constituting the photoconductive layer of the image forming member of the present invention, for example. The electrophotographic image forming members manufactured have extremely low sensitivity to irradiated electromagnetic waves, or in some cases, the sensitivity is hardly recognized or the increase in carriers due to electromagnetic wave irradiation is small. It is confirmed that it is a necessary condition that the H content is within the above numerical range. H into the a-8i layer
For example, in the glow discharge method, hydrides such as SiH4 and 5i2Ha are used as starting materials to form a-8t, so hydrides such as 5sH4@512Ha are decomposed to form the a-8i layer. When forming the a-8i layer, H is automatically contained in the layer, but in order to more efficiently contain H into the layer, when forming the a-8i layer, it is necessary to All you have to do is introduce H2 gas.

When using the sputtering method, S is removed in an atmosphere of an inert gas such as Ar or a mixed gas based on these gases.
When performing sputtering using t as a target, H2
B gas may be introduced, or silicon hydride gas such as SiH4, St, L, etc., or B may also be doped with impurities.
A gas such as 2H6 or P)Is may be introduced.

In order to control the amount of H contained in the a-8i layer to achieve the objectives of the present invention, the temperature of the deposition substrate or/and the production equipment system of the starting material used to incorporate H can be controlled. It is best to control the amount introduced. Furthermore, after forming the a-8i layer, the layer may be exposed to an activated hydrogen atmosphere.

Further, at this time, one method is to heat the a-8t layer below the crystallization temperature. In particular, this heat treatment method is an effective means for improving the dark resistance of the a-8i layer. Another effective method is to improve the dark resistance of the a-8i layer by irradiating it with electromagnetic waves such as high-intensity light.

The impurities doped into the a-8i layer include a-
To make the 8i layer p-type, suitable elements include elements in group 111 A of the periodic table, such as B, Aj, Ga, In, Tj, etc., and to make it n-type, elements in group 111 A of the periodic table are suitable. Elements of group V A, e.g. N + P + As +S
Preferred examples include b + B i and the like. The amount of these impurities contained in the =a-8i layer is ppm
Since the photoconductive layer is of the order of magnitude, it is not necessary to pay as much attention to its pollution properties as the main material constituting the photoconductive layer, but it is preferable to use materials that are as non-pollution-prone as possible. From this point of view, taking into account the electrical and optical properties of the a-8i layer to be formed, for example, B+ All P* Sb is optimal. In addition, it is also possible to control the n-type by, for example, interstitial doping with Li or the like by thermal diffusion or implantation.

The amount of impurity doped into the a-8i layer is appropriately determined depending on the desired electrical and optical properties, but in the case of impurities belonging to Group 111 A of the periodic table, it is usually 10'.
~10' atomic%, preferably 10-5 to 10'
atomic%, in the case of impurities of group V A of the periodic table, usually 10-8 to 10' atomic%, preferably 1
It is desirable that the content be 0' to 10-40-4 ato%.

The method of doping these impurities into the a-8i layer is as follows:
-Si They differ depending on the manufacturing method adopted when forming the layer, and will be specifically explained in detail in the following explanations or examples.

An imaging member, such as the electrophotographic imaging member shown in FIG. In this case, it is more preferable to provide a barrier layer between the photoconductive layer 3 and the support 2, which functions to prevent injection of carrier from the support 2 side during charging treatment during electrostatic image formation. It is something. The material for forming the barrier layer that functions to prevent carrier injection from the side of the support 2 may be appropriately selected depending on the type of support selected and the electrical characteristics of the photoconductive layer to be formed. An appropriate one is selected and used. Examples of such barrier layer forming materials include “20111 8i
Inorganic insulating compounds such as O5Sin2, organic insulating compounds such as polyethylene, polycarbonate, polyurethane, parylene, etc. Au, Ir+ pt, Rh, Pd+ M
It is a metal such as o.

The support 2 may be electrically conductive or electrically insulating. As the conductive support, for example, stainless steel, ^/
, Cry Ilo@Au, Ir, Nb, Te
, VrTi, PL, Pd, or alloys thereof. As the electrically insulating support, polyester, polyethylene, polycarbonate, cellulose triacetate, polypropylene, polyvinyl chloride,
Films or sheets of synthetic resins such as polychlorinated pyrinib/polystyrene, polyamide, glass, ceramics, 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 is conductive treated with In2O5+ ``'a, etc., or if it is a synthetic resin film such as polyester film, ^/+Ag+Pbl Z
n6 Ni, Au, Cr, Mo, Ir, N
b+ Ta, V, Ti.

Treated with a metal such as PT by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal,
One surface thereof is treated to be conductive. The shape of the support is
It can be in any shape, such as a cylinder, a belt, or a plate, and the shape is determined depending on the needs, but in the case of continuous high-speed copying, it is preferably in the shape of an endless belt or a cylinder.

The thickness of the support is determined as appropriate so that the desired image forming member is formed, but if flexibility is required as an image forming member, the thickness of the support may be determined to sufficiently exhibit its function as a support. It is made as thin as possible within the specified range. In such cases, the thickness is usually set to 10μ or more from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.

As shown in FIG. 1, in a layered image forming member in which the surface of the photoconductive layer is exposed and electromagnetic waves are irradiated from the outer layer side, the refractive index n of a-8i is approximately 3.35, which is relatively large, when compared to conventional photoconductive layers, reflection is more likely to occur on the surface of the photoconductive layer when irradiated with electromagnetic waves, and therefore the proportion of the amount of electromagnetic waves absorbed by the photoconductive layer decreases. , the loss rate of the irradiated electromagnetic waves increases. In order to reduce this loss rate as much as possible, it is preferable to provide an antireflection layer on the photoconductive layer.

The material for forming the antireflection layer must not have any adverse effect on the photoconductive layer and have excellent antireflection properties, but must also have electrophotographic properties, such as the ability of the layer to form electrostatic images. It must have a certain level of surface resistance to prevent lateral charge flow, and if a liquid development method is used, it must have excellent solvent resistance, and it must also meet the conditions for forming an antireflection layer. Therefore, conditions such as not degrading the characteristics of the photoconductive layer that has already been formed are required.

a, which is one of the necessary conditions for achieving the purpose of the present invention.
- The amount of H contained in the Si layer is within the above-mentioned numerical range, and the amount of H contained is determined as appropriate so that the properties required for the layer are satisfied within the range. However, what is important is that 11 must be contained in a state that effectively contributes to imparting the required properties.

Further, the concentration of the impurity doped into the B-Si layer, which is another necessary condition for achieving the object of the present invention, is within the above-mentioned numerical range, and the amount of warp doping is within the range. In order to form a particularly effective depletion layer, the value □ must be determined as appropriate as possible while satisfying the characteristics required for that layer.
It is more preferable to determine the NalNd0 value in the Nd range. That is, the upper limit of the value of Na + Nd is determined so that avalanche breakdown and tunneling phenomena do not occur when a predetermined reverse bias voltage is applied to the depletion layer, and is usually set to 1018 to 4. As a lower limit, the formed a
- The value is larger than the number N of free dangling bonds of Si per unit volume in the Si layer, preferably at least 7 orders of magnitude larger than N, optimally at least 1 order of magnitude larger than N. It is something.

In the imaging member 1 shown in FIG. 1, the photoconductive layer 3 has a free surface 4, and on the surface of the photoconductive layer 3 there is formed a surface of a conventional electrophotographic imaging member. Similarly, a surface coating layer such as a so-called protective layer or an electrically insulating layer may be provided.

An imaging member having such a surface coating layer is shown in FIG.

The imaging member 8 shown in FIG. 2 includes a depletion layer 11, an inner layer 12 and an outer layer 13 similar to the photoconductive layer 3 in FIG.
A surface coating layer 1 having a free surface on a photoconductive layer 10 having a
4, the structure is not essentially different from the imaging member 1 shown in FIG. The characteristics required for the surface coating layer 14 differ depending on the electrophotographic process to which it is applied. That is, for example,
If an electrophotographic process such as the NP method described in Publication No. 2-23910 to Publication No. 43-24748 is applied, the surface coating layer 14 is electrically insulating and cannot be subjected to charging treatment. It has sufficient static charge retention ability during
Although it is required that the thickness be at a certain degree of convergence, if electrophotographic processes such as Eva and Carlson processes are to be applied, it is desirable that the potential of the bright area after electrostatic image formation be very small. The surface coating layer 14 is required to be extremely thin. In addition to satisfying its desired electrical properties, the surface coating layer 14 should not have any adverse chemical or physical effects on the photoconductive layer 10, and should have good electrical contact and adhesion with the photoconductive layer IO. It is formed taking into consideration the properties, moisture resistance, abrasion resistance, cleanability, etc.

Typical materials effectively used for forming the surface coating layer 14 include polyethylene terephthalate, polycarbonate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, polyamide, and polytetrafluoroethylene. , polychloroethylene trifluoride, polyvinyl fluoride, polyvinylidene fluoride, propylene hexafluoride-ethylene tetrafluoride copolymer, ethylene trifluoride-vinylidene fluoride copolymer, polypuden, polyvinyl butyral, polyurethane, and other synthetic resins;
Examples include cellulose derivatives such as diacetate and triacetate. These synthetic resins or cellulose derivatives may be formed into a film and laminated onto the photoconductive layer 10, or a coating solution thereof may be formed and applied onto the photoconductive layer 10 to form a layer. It may be formed.

The layer thickness of the surface coating layer 14 is appropriately determined depending on the desired characteristics and the material used, but is usually about 0.5 to 70 μm. Especially the surface coating layer 14
When the above-mentioned function as a protective layer is required,
In normal cases, the thickness is set to 10μ or less, and conversely, when a function as an electrically insulating layer is required, the thickness is usually set to 10μ or more. According to Hyakunen et al., the layer thickness value that distinguishes between the protective layer and the electrically insulating layer varies depending on the materials used, the applied electrophotographic process, and the designed structure of the imaging member. It's not absolute.

Furthermore, if this surface coating layer 14 is also given the role of an antireflection layer as described above, its function will be further expanded and it will become more effective.

Next, an outline of the case where the electrophotographic r-image forming member of the present invention is manufactured by a glow discharge method and a sputtering method will be explained.

FIG. 3 is a schematic illustration of a glow discharge deposition apparatus for manufacturing the electrophotographic image forming member of the present invention using the inductance type glow discharge method.

Reference numeral 16 denotes a glow discharge deposition tank, in which a substrate 17 for forming an a-3i-based photoconductive layer is fixed to a fixing member 18, and a lower part of the substrate 17 is used to heat the substrate 17. A heater 19 is installed for this purpose. At the top of the vapor deposition tank 16, there is an induction coil 2 connected to a high frequency power source 20.
When the high frequency power supply 20 is turned on, high frequency power is applied to the induction coil 21 and glow discharge is generated in the deposition tank 16.

A gas introduction port is connected to the upper end of the vapor deposition tank 16, and a gas cylinder 22. 23. 24 The gas in each cylinder is introduced into the vapor deposition tank 16 when necessary. 25. 26 + 27 are each flow meters, which are meters for detecting the flow rate of gas, and 2'8
．． 29. 30 is an inlet valve, 3t, 32, 33 are outlet valves, and 34 is an auxiliary pulp.

Further, the lower end of the vapor deposition tank 16 is connected to an exhaust device (not shown) via a main pipe 35. 1
5 is a leak pulp for breaking the vacuum in the vapor deposition tank 10.

In order to form a photoconductive layer with desired characteristics on the substrate 17 using the glow discharge apparatus shown in FIG. 1
Fixed at 8.

To clean the surface of the substrate 17, a commonly used method, for example, a chemical treatment method using an alkali or an acid, is employed. Alternatively, after being cleaned to some extent, it may be placed in a predetermined position in the vapor deposition tank 16, and glow discharge treatment may be performed before forming a photoconductive layer thereon. In this case, since the process from cleaning the substrate 17 to forming the photoconductive layer can be carried out in the same system without breaking the vacuum, it is possible to avoid dirt and impurities from adhering to the cleaned substrate surface. Board 17
After fixing to the fixing member 18, the main pulp 35 is fully opened to exhaust the air in the vapor deposition tank 1.6 as indicated by the arrow, so that the degree of vacuum is about 104'torr.

Next, the auxiliary pulp 34 is fully opened, and then the outflow pulp 31,
32.33, fully open inflow pulps 28, 29+30, flow meter 25. ．． 26. Also evacuate the inside of 27. After that, when the inside of the vapor deposition tank 16 reaches a predetermined degree of vacuum, the auxiliary pulp 34
, inflow valve 28°29.30, outflow pulp 31.32
．． Close 33. Subsequently, the heater 19 is ignited to heat the substrate 17, and once it reaches a predetermined temperature, it is maintained at that temperature.

The gas pump 22 is for raw material gas for forming a-Si, for example, SiH4,5=2H6, 5t4H
1o or a mixture thereof etc. are stored. In addition, the cylinders 23 and 24 have a-8t layers formed by ■・-
It is for source gas for introducing impurities into the layer to control the type (2), PH.

P2H4r, B2H65AsH3, etc. are stored.

After confirming that the substrate 17 has reached a predetermined temperature, the pulp 36 of the cylinder 22 is opened, the pressure of the outlet pressure gauge 39 is adjusted to a predetermined pressure, and then the inflow nozzle 28 is gradually opened.
a-3i such as 5tH4 into the flow meter 25
A raw material gas for formation is introduced. Subsequently, open the auxiliary pulp 34 to a predetermined position, and then open the Villany gauge 42.
While observing the value indicated by , the outflow pulp 31 is gradually opened to adjust the flow rate of the gas supplied from the cylinder 22 into the vapor deposition tank 16 . If the impurity described above is not forcibly doped into the 5-Si layer to be formed, the Billany gauge 42 should be watched carefully at the time when the raw material gas for forming 8-8i is introduced from the cylinder 22 into the vapor deposition tank 16. Meanwhile, the main pulp 35 is adjusted to a predetermined degree of vacuum, in the normal case,
The gas pressure when forming the a-8i layer is 1o-", +~3
Keep torr. Next, high frequency power of a predetermined frequency (normally 0.2 to 30 MHz) is supplied from the high frequency power source 20 to the induction coil 21 wound outside the deposition tank 16 to cause glow discharge inside the deposition tank 16, a. The raw material gas for -8i formation, for example, SiH4 gas, is decomposed and Si is deposited on the substrate 17 to form an internal layer.

When introducing impurities into the a-Si layer to be formed, a gas for impurity generation is introduced from the port 23 or 24 into the a-Si layer.
- It may be introduced into the vapor deposition tank 16 at the time of forming the Si layer.

In this case, for example, by appropriately adjusting the outflow pulp 32, the amount of gas introduced into the vapor deposition tank 16 from the cylinder 23 can be appropriately controlled. Therefore, a formed
In addition to being able to arbitrarily control the amount of impurities introduced into the -8t layer, it is also possible to easily change the amount of impurities in the thickness direction of the a-Si layer.

After first forming an inner layer to a predetermined thickness on the substrate 17 as described above, an outer layer is formed as follows to form the entire photoconductive layer.

First, as a first example, when the inner layer is formed by introducing only the raw material gas for forming a'-8i supplied from the cylinder 22 or 1:) 1 into the vapor deposition tank 1, the outer layer When forming the a-Si, the raw material gas for impurity from the cylinder 23 or 24 is mixed with the raw material gas for forming a-Si in the cylinder 22 and introduced into the vapor deposition tank 16 to remove the already formed internal layer. form a different type of outer layer.

As a second example, the inner layer can be
a When the material gas for forming Si is mixed with the material gas for impurities from the cylinder 23 and introduced into the vapor deposition tank 16 to form the external layer,
Only raw material gas for Si formation or a from the cylinder 22
-8L forming raw material gas is mixed with impurity raw material gas from cylinder 24 and introduced into vapor deposition tank 16 to form an outer layer of a different type from the already formed inner layer.

As a third example, the inner layer is aS from the cylinder 22.
After the mixed gas of the raw material gas for i formation and the raw material gas for impurities from the cylinder 23 is introduced into the vapor deposition tank 16 and the internal layer is formed, the internal layer is formed. A mixed gas with a different mixing ratio of the raw material gas and the raw material gas for impurities is introduced into the vapor deposition tank 16 to form an outer layer.

By forming the inner layer and the outer layer by the method described above, a depletion layer is formed at the junction between the inner layer and the outer layer, and the photoconductive layer of the electrophotographic image forming member, which is the object of the present invention, is formed. was formed.

In order to form a photoconductive layer having two depletion layers, such as a layer structure such as p"l@nm9+/p-n, it is sufficient to select one of the above three methods as desired and form the layer. It is.

In the four-discharge deposition apparatus shown in FIG.
(radio frbuency) Although an inductance type f'a-discharge method is employed, glow discharge methods such as an FLF capacitance type and a DC bipolar type are also employed.

Since the characteristics of the a-Si photoconductive layer to be formed largely depend on the substrate temperature during growth, it is preferable to strictly control the characteristics. In the present invention, the substrate temperature is usually 50 to 35
By setting the temperature to 0°C, preferably 100 to 200°C, the BSS has effective characteristics for electrophotography.
An i-based photoconductive layer is formed. Furthermore, the substrate temperature is a Si
The growth rate of the bifurcated layer, which can be changed continuously or intermittently during layer formation to obtain predetermined properties, is also a factor that greatly influences the physical properties of the a-Si layer.
In order to achieve the purpose of the present invention, in the normal case, 0.5 to 100
λ/sec is preferably 1 to 56 λ/sec.

FIG. 4 is a schematic explanatory diagram showing one of the apparatuses for manufacturing the image forming member of the present invention by a sputtering method.

Reference numeral 43 denotes a vapor deposition tank, in which a substrate 44 for forming an a-Si photoconductive layer is fixed to a conductive fixing member 45 that is electrically insulated from the vapor deposition tank 43, and is fixed to a predetermined position. installed in position. A heater 46 for heating the substrate 44 is disposed below the substrate 44, and a polycrystalline or single crystal silicon target 47 is placed above the sputtering electrode 48 at a position facing the substrate 44 with a predetermined spacing therebetween. is installed and located.

A high frequency voltage is applied by a high frequency power supply 364 between the fixing member 45 on which the substrate 44 is installed and the silicon target 47. Further, in the vapor deposition tank 43, cylinders 49e50-51.52 each contain inflow pulp 5.
3.54.55゜56.7 a - meter 57e 5
8t 591 60゜Outflow pulp 61y 62y
63t 64, auxiliary bar.

Connected via Pro 4, 49° so, 5
1.52, desired gases are introduced into the vapor deposition tank 43 when necessary.

Now, in order to form a Si-based photoconductive layer having a depletion layer on the substrate 44 using the apparatus shown in FIG. Similarly, the auxiliary pulp 65, the inflow pulps 53-56, and the outflow pulps 61-6 are evacuated using a suitable exhaust device.
4 is fully opened to bring the inside of the vapor deposition tank 43 to a predetermined degree of vacuum.

Next, the heater 46 is ignited to heat the substrate 44 to a predetermined temperature. When forming the a-Si photoconductive layer by the sputtering method, the heating temperature of the substrate 44 is as follows:
The temperature is usually 50 to 350°C, preferably 100 to 200°C. The substrate temperature influences the growth rate of the a-St layer, the structure of the layer, the presence or absence of voids, etc., and is one element that determines the physical properties of the formed a-St layer, so it must be sufficiently controlled. Further, the substrate temperature may be kept constant during the formation of the a-54 layer, or may be raised, lowered, or raised or lowered as the a-Si layer grows.

For example, in the initial stage of formation of the a-St layer, the substrate temperature is maintained at a relatively low temperature T1, and once the a-Si layer has grown to a certain extent, the a-St layer is grown while increasing the substrate temperature to a temperature T24 higher than T1. Then, at the final stage of forming the a-8t layer, the substrate temperature is lowered again to a temperature T lower than T2, thereby forming an aSi layer. By doing so, the electrical and optical quality of the a-Si layer can be changed uniformly or continuously in the layer thickness direction.

・Also, a8i has a layer growth rate that is higher than that of other, for example, B
Since it is slower than e, etc., 1 and a-8i formed at the initial stage of layer formation (closer to the substrate side @ -S)
i) Since there is a strong possibility that the characteristics at the initial stage of layer formation may change before the layer formation is completed, layer formation is necessary to form an a-Si layer with uniform characteristics in the thickness direction of the layer. It is desirable to form the layer while increasing the substrate temperature from the start to the end of the layer formation. This substrate temperature control operation is also applied when employing the gummy discharge method.

After detecting that the substrate 44 has been heated to a predetermined temperature, the inflow pulps 53 to 5.6, the outflow pulps 61 to 64, and the auxiliary pulp 65 are closed.

Next, while watching the outlet pressure gauge 73, the pulp 68 is gradually opened to adjust the outlet pressure of the cylinder 50 to a predetermined pressure.

Subsequently, the inflow pulp 54 is fully opened and the flow meter 5g
For example, an atmospheric gas such as 4R gas is introduced into the chamber. After that, the auxiliary pulp 65 is fully opened, and then the main pulp 6
6 and the outflow pulp 62 while introducing the atmosphere into the deposition tank 43 and maintaining the inside of the deposition tank 43 at a predetermined degree of vacuum.Next, while watching the outlet pressure gauge 72, The outlet pressure of the cylinder 49 is adjusted by gradually opening the pulp 68. Next, the inflow pulp 53 is fully opened to allow the filtrate gas to flow into the flow meter 57.Then, while adjusting the main pulp 66 and the outflow pulp 61, the filtrate gas is introduced into the vapor deposition tank 43 and maintained at a predetermined degree of vacuum. . For this reason, the introduction of gas into the vapor deposition tank 43 is omitted if there is no need to include H in the a-8t layer formed as an internal layer on the substrate 44. The flow rate of atmospheric gas such as phosphor gas and Ar gas into the deposition tank 43 is appropriately determined so that an a-8i skin having desired physical properties is formed. For example, when mixing atmospheric gas and phosphor gas, the pressure of the mixed gas in the vapor deposition tank 43 is set to a degree of vacuum, usually 10 to 10 torr, preferably 5 x 2 1 (J - 3 x 10 torr.

Ar gas can also be replaced with rare gas such as He gas.

If the a-Si layer to be formed is not forcibly doped with the impurities or substances mentioned above, the atmosphere gas and the atmosphere gas are introduced into the vapor deposition tank 43 until a predetermined degree of vacuum is reached, and then high-frequency The power source 76 applies a high frequency voltage at a predetermined frequency and voltage between the fixing member 45 on which the substrates 4 are installed and the sputtering electrode 48 to cause a discharge, and the generated atmospheric gas such as Ar ions is removed. A silicon target is sputtered with ions to form an a-8i layer as an internal layer on the substrate 44.

When introducing impurities into the a-8i layer to be formed,
The raw material gas for impurity formation from the cylinder 50 or 51 is
It may be introduced into the vapor deposition tank 43 at the time of forming the -8i layer.

The introduction method in this case is the same as that described in FIG.

After first forming an internal layer to a predetermined thickness on the substrate 44 as described above, an external layer is formed on the internal layer in the same manner as described with reference to FIG.

In the explanation of FIG. 4, a sputtering method using high frequency electric field discharge is used, but a sputtering method using direct current electric field discharge may also be adopted.

In the sputtering method using high-frequency voltage application, the frequency is usually 0.2 to 301111z, and 5 for IH.
~20 tuna, and the discharge current density is usually 0, 1~10
The desired value is mA/crI, preferably 1 to 5 mA/7. Also, in order to obtain sufficient power, usually 10
The voltage is preferably adjusted to 0 to 5000V, preferably 300 to 5000V.

The growth rate of the A-8i layer when manufactured by the sputtering method is mainly determined by the substrate temperature and discharge conditions, and is one of the major factors that influences the physical properties of the formed layer. a- for achieving the object of the present invention;
The growth rate of the 8i layer is usually 0.5 to 100λ/
Sec % is preferably 1 to 50 A/see. In the sputtering method, as in the glow discharge method, the a-8i layer formed can be adjusted to be n-type or p-type by doping with impurities. The method of introducing impurities is the same in the sputtering method as in the glow discharge method, for example, PHs + P2H4, B2H1
When forming the a-8i layer, a substance such as No. 1 is introduced in a gaseous state into the deposition tank 43 to dope the a-8i layer with P or B as an impurity. In addition, a-8i was also formed.
Impurities may be introduced into the layer by ion implantation.

<Example 1> Using the apparatus shown in FIG. 3 installed in a completely shielded clean room, an electrophotographic image forming member was produced by the following operations.

Surface cleaned Q,'l yaw thickness 5(1'll
Glow discharge vapor deposition 1
It was firmly fixed to the fixing member 1B located at a predetermined position inside a16. The substrate 17 is heated with an accuracy of ±0.5° C. by the heater 9 within the fixing member 18.

Temperature was measured directly on the back side of the substrate by a thermocouple (alumel-calomel).

Next, after confirming that all the pulps in the system are closed, the main pulp 35 is fully opened, and the inside of the tank 16 is evacuated to a vacuum level of approximately 5 x 10 (torr).Then, the input voltage of the heater 19 is The input voltage was varied while detecting the temperature of the molybdenum substrate, and was stabilized until it reached a constant value of 150°C.

After that, the auxiliary pulp 34 and then the outflow pulp 31.32
．． 33 and influent pulp 28 , 29 .

31-932.33 with the flowmeters 25 and 26.27 sufficiently degassed and vacuumed.
After closing the silane gas (99°999% purity) pulp 36 of the pump 22, the pressure of the outlet pressure gauge 39 was set to 1k.
ylcr&, the inflow pulp 28 was gradually opened to allow Hesilane gas to flow into the flow meter 25. Continuing, gradually open the outflow pulp 31, then gradually open the auxiliary pulp 34, and adjust the opening of the auxiliary pulp 34 while watching the reading on the Billany gauge 42, until the inside of the tank is IX.
The auxiliary pulp 34 was opened until the pressure reached 10' torr. After the internal pressure of the tank became stable, the main valve 35 was gradually closed and the opening was narrowed until the Villany gauge 42 indicated 0.5 torr. After confirming that the internal pressure has calmed down,
The switch of the high-frequency power source 20 was turned on, and high-frequency power was applied to the induction coil 21 in five orders to generate a glow discharge inside the coil (at the top of the tank) in the tank 16, resulting in an input power of 30 W. After growing a silicon film on the substrate using a superposition and keeping the open condition for 4 hours, a high frequency power source of 20
is turned off and glow discharge is stopped, open the pulp of the Diporan gas (purity 99.999%) cylinder 23, adjust the pressure of the outlet pressure gauge 40 to 1 to 9/cd, and gradually increase the inflow pulp 29. After diborane gas flows into the flow meter 26, the outflow pulp 32 is gradually opened so that the reading on the flow meter 26 is 0.00000000000000000000000000000000000000000000000000000000000000000000000000.
The opening of the outflow pulp 32 was determined and stabilized so as to achieve 0.08 vo/%.

Subsequently, the high frequency power supply 20 is turned on again, and the glow discharge is set to F! -I let it happen. After continuing the glow discharge for another hour in this way, the heating heater 9 is turned off, the high frequency power supply 20 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow pulp 31 and 32 are closed and the main nozzle is turned off. 35 was fully opened to reduce the pressure inside the tank to 10 torr or less, the main pulp 35 was closed, and the inside of the tank 16 was brought to atmospheric pressure using the leak pulp 15, and the substrate was taken out.The sample thus obtained was designated as image forming member A. case,
The total thickness of the a-8t layer formed was about 6 microns.

The image forming member A thus obtained was placed in a charging exposure experimental device, and corona charging was performed at e6Kv for 0.2 seconds.
A light image was immediately irradiated. The optical image was created by using a xenon lamp light source and using a filter (V-058, manufactured by Toshiba Corporation) to remove light in the wavelength range of 550 nm or less.
8eC was irradiated through a transmission test chart.

Immediately thereafter, by cascading a charged developer (containing toner and carrier) onto the surface of member A,
A good toner image was obtained on the surface of member A. When the toner image on Member A was transferred onto transfer paper using +5 KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

On the other hand, after performing corona charging at 6KV and exposure under the same conditions as above, I tried developing with an e-charging developer, but a blurry image with a lower image density than the above results was obtained. .

Furthermore, if e6KV charging is performed, and three-color filters B, G, and H are used in place of the V-058 filter described above using a chargeable developer, in either case. Almost equally good images were obtained on the transfer paper.

<Example 2> Using the apparatus shown in FIG. 4, an electrophotographic image forming member was produced by the following operations.

A film with a thickness of about 8 mm was deposited on a 0.21 m thick 10XIOα stainless steel plate whose surface was cleaned by electron beam vacuum evaporation.
A substrate having a platinum thin film deposited thereon was fixed on a fixing member 45 containing a heater 46 and an electrothermal couple in a sputtering deposition tank 43. On the electrode facing the substrate 44, a polycrystalline silicon plate (purity 99.999
%) The target 47 is approximately 4.5 cIr parallel to the substrate 44.
They were fixed facing each other with L distance apart.

Inside the tank 43, the main pulp 66 is fully opened and 5X
A vacuum is applied to about 10' torr (at this time, all the pulps in the system are closed), and the auxiliary pulp 65 and the outflow pulps 61, 62, 63, and 64 are opened and sufficiently degassed, and then the outflow is carried out. The 0 substrate 44 with the pulps 61, 62, 63, and 64 and the auxiliary pulp 65 closed was maintained at 200° C. by inputting the heater power. Then, the pulp 68 of the hydrogen (purity 99.99995%) cylinder 49 was opened, and the outlet pressure was adjusted to 1 ky/ct/l using the outlet pressure gauge 72. Subsequently, the inflow pulp 53 was gradually opened to allow hydrogen gas to flow into the flow meter 57, and then the outflow pulp 61 was gradually opened and the auxiliary pulp 65 was opened.

While detecting the internal pressure of the tank 43 with a pressure gauge 67, the outflow pulp 61 was adjusted to flow in to 5×10 torr. Subsequently, the pulp 69 of the argon (purity 99.9999%) gas cylinder 50 is opened, and after adjusting the reading of the outlet pressure gauge 73 to be 1 ky/ct/l, the inflow pulp 54 is opened, and then the outflow pulp 62 is opened. was gradually opened to allow argon gas to flow into the tank. Tank pressure gauge 67
until the indication is 5X10 torr, the effluent pulp 62
is gradually opened, and after the flow rate has stabilized in this state,
The main pulp 66 is gradually closed, and the tank internal pressure is 1X10.
The aperture was narrowed down to torr. Next, pulp 7 of phosphine gas (purity 99.9995) cylinder 52
1, adjust the outlet pressure gauge 75 to 1 #/cdl, open the inlet valve group, and gradually open the outflow pulp 64 from the reading of the flow meter 60 to approximately 1 of the flow rate indicated by the hydrogen gas 70 meter 57. ．． Ovol! The outflow pulp No. 64 was adjusted so that it would flow in at a flow rate of 50%. Flow meter 57゜5
8. After confirming that 60 is stable, turn on the high frequency power supply 76.
is turned on, and a voltage of 13.56IIllz, 500V, 1.6 K is applied between the target 47 and the fixed member 45.
AC power of V was input. Under these conditions, the layers were formed while performing matching so that stable discharge could continue. After discharging in this manner for 4 hours, the inner layer was formed. Thereafter, the high frequency power supply 71 was turned off to temporarily stop the discharge. Subsequently, the outflow pulps 61, 62, and 64 were closed, and the main pulp 66 was fully opened to remove gas from the tank.
Vacuum was applied to torr 4. After that, as in the case of internal layer formation, hydrogen gas and Ar gas are introduced to form the main pulp 6.
The internal pressure of the tank was adjusted to 2×10 torr by adjusting the opening of No. 6.

Next, the pulp 70 of the diborane gas (purity 99.9995%) cylinder 51 is opened and the outlet pressure is measured using the outlet pressure gauge 74.
Adjust so that the reading is 1 kg/cfI, open the inflow pulp 55, gradually open the outflow pulp 63, and
1 of the hydrogen gas flow rate by the 0-meter 59. Ovoe
Adjust the flow rate to %. After the gas flow rates of hydrogen, argon, and diborane became stable, the high frequency power source 76 was turned on again and 1.6 KV was applied to restart the discharge.

After continuing to discharge for 40 minutes under these conditions, the high frequency power source 7
6 is turned off, and the power to the heater 46 is also turned off.
state. After waiting for the substrate temperature to fall below 100°C, the outflow pulps 57, 58, and 59 were closed, the auxiliary pulp 65 was closed, and then the main pulp 66 was fully opened to vent the gas in the tank. Thereafter, the main pulp 66 was closed and the leak pulp 77 was opened to leak to atmospheric pressure, and then the substrate was taken out. This sample was designated as image forming member B.

- In this case, the thickness of the a-8i layer formed was 8μ.

The thus obtained image forming member B was tested in the same manner as in Example 1, and it was found that an image with excellent resolution, gradation, and image density was obtained in the case of the combination of e6KV corona chargeable developer. Example 3 Surface-cleaned Corning 7059 glass (II
ITO (rnz
os: 5n0220: 1 molded, fired at 600℃)
After being vapor-deposited by 1200 people, the sample was heat-treated at 500° C. in an oxygen atmosphere and placed on the fixing member 18 of the same apparatus as in Example 1 (FIG. 3) with the ITO-deposited surface facing upward.

Subsequently, the glow discharge tank 1 was prepared in the same manner as in Example 1.
After creating a vacuum of 5 x 10'torr in the tank and maintaining the substrate temperature at 170°C, silane gas was flowed into the tank, and the inside of the tank was as follows.
It was adjusted to 0.8 torr. At this time, phosphine gas is added to 0.1 vol of silane gas! '4 from the phosphine gas cylinder 24 through the pulp 38 to a gas pressure of 1 kg/d (reading of the outlet pressure gauge 41).
70 by adjusting the inflow pulp 30 and outflow pulp 33.
- Based on the reading of the meter 27, a mixture of silane gas and silane gas was flowed into the tank 16. After the gas inflow was stabilized, the tank internal pressure was constant, and the substrate temperature was stabilized at 170° C., the high frequency power source 20 was turned on as in Example 1 to start glow discharge.

After sustaining the glow discharge for 1130 minutes under these conditions, the high frequency power supply 20 was turned off to stop the glow discharge and complete the formation of the inner layer. Then the outflow pulp 31.33
was closed, the auxiliary pulp 34 and the main pulp 35 were fully opened, and the inside of the tank was evacuated to 5×10't6rr. Thereafter, the reinforcing pulp 34 and main pulp 35 are closed, and the outflow pulp 31 is gradually opened, and the auxiliary pulp 34 and main pulp 35 are restored to the same 7 run gas flow rate state as at the time of internal layer formation and formation. I was woken up. Next, the high frequency power source 2-0 is turned on again to restart the glow group τ, and after this state is maintained for 8 hours, the heating heater 9 and the high frequency power source 20 are turned off, and the substrate temperature becomes 100°C. , close the a outlet valve 31, fully open the main valve 35 and the auxiliary pulp 34, and once the inside of the tank 16 is
After reducing the pressure to below O-5 torr, the main valve 35 was closed, and the inside of the tank 16 was leaked using the leak pulp 15, and the substrate was taken out. In this way, an image forming member C was produced.

The total thickness of the a-8i layer formed was about 11 microns. The image forming member C thus obtained was tested for image formation. When the image formation process was performed using a combination of e6KV corona charge back exposure and e chargeable developer, it was possible to obtain a high quality image that could be used for practical purposes.

<Example 4> Similar to Example 3, ITO was heated using glass steamed rice (Corning 7
059) After forming a similar layered structure using the substrate deposited on the substrate under the same conditions and procedures as in Example 3, the high frequency power source 20 was turned off while the substrate heater was kept on. And so. Subsequently, the pulp 37 of the diborane gas cylinder 23 was opened, the pressure of the outlet pressure gauge 40 was adjusted to xkylcr&, and the inflow pulp 29 was gradually opened to allow diborane gas to flow into the 70-meter 26. Furthermore, the outflow pulp 32 is gradually opened, and the flow meter 26 is
The reading is 0.08 vat of the flow rate of silane gas! The opening of the outflow valve 32 was set so that the flow rate was 10%, and the flow rate was waited for to become stable along with the flow rate of the 7-run gas into the tank. Next, the high frequency power source 20 is turned on again to start glow discharge, and after the glow discharge is maintained under these conditions for 45 minutes, the heating heater 9 and the high frequency power source 20 are turned off to bring the substrate temperature to 100°C. I waited. after that,
After closing the outflow valves 31 and 32 and fully opening the main pulp 35 to reduce the pressure inside the tank 16 to below 10 torr, the main valve 35 is closed and the inside of the tank 16 is brought to atmospheric pressure by the leak pulp 15, and then the i-plate is I took it out. An imaging member was thus obtained. The total thickness of the a-8i layer formed was approximately 12μ.

-The thus obtained image forming member was placed in a charging exposure experimental device in the same manner as in Example 1, and an image formation test was conducted. Very good quality, high contrast toner images were obtained on the transfer paper.

<Example 5> 0, whose surface was pub-polished to a mirror finish and then cleaned.
A MgFt layer with a thickness of 2,000 layers was uniformly deposited on an A/plate (4 x 4 cm) with a thickness of 1 layer by electron beam evaporation. This substrate was used as a substrate and placed on the fixing member 18 of the apparatus shown in FIG. 3 with the MgF's evaporated surface facing upward in the same manner as in Example 1.

Subsequently, the glow discharge tank 16 was prepared in the same manner as in Example 1.
A vacuum of 5×10 torr was applied to the internal and all gas inlet systems, and the substrate temperature was maintained at 220°C.

Subsequently, silane gas was introduced into the tank 16 by operating each pulp in the same manner as in Example 1, and the tank internal pressure was adjusted to 1. I changed it to Otorr. After the silane gas flow rate and substrate temperature have stabilized, the high frequency power supply 2
0 was turned on, and glow discharge was started. Under these conditions, after sustaining the glow discharge for 5 hours, the high frequency power supply 2
0 was set as the off state to stop the glow discharge. Subsequently, the opening of the pulp 38, 30, 33 is adjusted so that the phosphine gas flow rate from the phosphine gas cylinder 24 is 0.05 vat % of the silane gas flow rate.
- While paying close attention to the reading on the meter 27, it was introduced into the tank 16 while keeping it stable. Thereafter, the high frequency power supply 20 was turned on again to restart the glow discharge. During this glow discharge,
The mixing ratio with silane changes from the initial value of 0.05 vat % to 0.01 vat % during approximately 10 minutes when the outflow valve 33 is opened.
After the glow discharge continues for one hour, the high frequency power source 20 and the heater 9 are turned off.
state. After waiting for the substrate temperature to naturally cool to below 100°C, the outflow valves 31 and 33 are closed, and the main pulp 35 is then fully opened, and the inside of the tank 16 is
After that, the main pulp 35 is closed and the tank 1 is opened by opening the leak pulp 15.
6 was returned to high pressure, and the layer-formed substrate was taken out. In this way, an image forming member E was obtained. formed a-8i
The total thickness of the layer was approximately 7.5μ.

The obtained image forming member E was charged and exposed in the same manner as in Example 1.
When a development test was conducted, it was found that an extremely high quality image could be obtained using the combination of (2) 6KV corona charging and e-charge electrode developer.

Next, the image forming member E was fixed so as to be grounded to the photosensitive drum (A/drum without a photosensitive layer) of a commercially available copying machine (NP-L7, an experimental machine partially modified from Canon Inc.). A good quality image was obtained on plain paper by the following steps: (1) 6KV charging, exposure, development (e-chargeable liquid developer, commercially available product), liquid squeezing, e-charging, and transfer (2) charging. Even after repeating this process and continuously copying 100,000 sheets, there was no change in image quality.

<Example 6> Surface-cleaned Q, l IIK thick Ai substrate (4x
4 cm ) was placed stationary on the fixing member 18 of the apparatus shown in FIG. 3 in the same manner as in Example 1. Subsequently, the inside of the glow discharge deposition tank 16 and the entire gas inflow system were made into a vacuum of 5 x 10' torr by the same operation as in Example 1, and the substrate temperature was maintained at 250°C. Silane gas is flowed into the tank 16 in each pulp operation similar to Example 1, and the tank internal pressure is 0.3.
It was turned into torr.

Furthermore, the pulp 37 of the Diporane gas cylinder 23 is opened, the outlet pressure gauge 40 pressure is adjusted to 1 kg/cII, the inflow port 29 is gradually opened, and the reading of the flow meter 26 is 0.15 vo/% of the silane gas flow rate. The outflow pulp 32 was also gradually opened to allow the diporane gas to flow in. The flow rate of both silane gas and diborane gas is stabilized,
After the substrate temperature stabilizes at 250℃, turn on the high frequency power supply 20℃.
was turned on to start glow discharge in the tank 16.

After performing glow discharge for 30 minutes under these conditions, while continuing glow discharge, gradually close the outflow pulp 32 of Diporan while watching the 70-meter 26, so that the flow rate of Diporan gas becomes well over 0.05 with respect to the silane gas flow rate. I narrowed the aperture until it was clear. After continuing the glow discharge for another 6 hours under these conditions, both the outflow valve loops 31 and 32 are closed, and the inside of the tank 16 is temporarily
The vacuum state was reduced to 0 torr. Subsequently, silane gas is again flowed under the same conditions, and the inside of the tank 16 is again 0.3 to
rr, the inflow pulp 3 is passed from the phosphine gas cylinder 24 through the pulp 38 at a gas pressure of 1 to 9/cr/I.
0. By adjusting the outflow pulp 33, the flow rate of the tank 16 is adjusted to 0.08% of the silane gas based on the reading of the flow meter 27.
The mixture was mixed and flowed into the tank. After the gas inflow is stabilized, the high frequency power source 20 is turned on to start glow discharge, and after continuing for 45 minutes, the high frequency power source 20° and the heater 9 are turned off, and then the substrate is removed.

Wait for the temperature to reach 100℃, and drain the pulp 31.3.
3 are closed, the main pulp 35 is fully opened and the tank 16
Once the pressure was reduced to below 10' torr, the main pulp 35 was closed and the leak pulp 15 was opened to return the inside of the tank 16 to atmospheric pressure, and then the substrate was taken out.

The total thickness of the a-8i layer formed was approximately 9μ.

The sample obtained in this manner was immersed vertically into a 30-titoluene solution of polycarbonate resin after marking the back A/side of the sample with adhesive tape at a speed of 1.5 cm/66 (, Pull up a-
A 15μ layer of polycarbonate resin was provided on the 8i layer. The adhesive tape was then removed.

In this way, an image forming member F was obtained.

The obtained image forming member F was transferred to a commercially available copying machine (NP-L7;
Canon Co., Ltd.) was fixed so as to be grounded to the photoconductor drum (A/drum without photosensitive layer) of a modified experimental machine, and 07Kv primary, charging, exposure simultaneous AC6KV charging, development (Charging liquid development agent), liquid squeezing (roller squeezing),
A clear image with high contrast was obtained on plain paper by the transfer e5KV charging coupling process. Even after repeating this process and making more than 100,000 copies, the original high-quality images were maintained.

[Brief explanation of the drawing]

1 and 2 are schematic cross-sectional views showing an example of the structure of an electrophotographic image forming member of the present invention, and FIGS. 3 and 4 are respectively schematic cross-sectional views of an electrophotographic image forming member of the present invention. FIG. 2 is a schematic explanatory diagram showing an example of an apparatus for manufacturing. 1.8... Image forming member for electrophotography 2.9...
...Support, 3,10...Photoconductive layer 4...
...Free surface, 14...Surface coating layer 1
6, 43... Vapor deposition tank

Claims (1)

[Claims] An electrophotographic image forming member 0 comprising a support, a barrier layer, and a photoconductive layer made of amorphous silicon, and the photoconductive layer has a depletion layer.