JPH023985B2 - - Google Patents

Description

[Detailed description of the invention]

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 photoconductive members for electrophotography that are sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
It has a high signal-to-noise ratio [photocurrent (Ip)/(Id)], has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic wave to be irradiated, has fast photoresponsiveness, has the desired dark resistance value, and when used. Fixed imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time. Especially,
In the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on this perspective, amorphous silicon (hereinafter a-
Si), for example, the German publication No.
No. 2746967 and No. 2855718 disclose applications to electrophotographic image forming members, and German Publication No.
No. 2933411 describes the application to a photoelectric conversion/reading device. However, conventional imaging members having a photoconductive layer composed of a-Si have low dark resistance, photosensitivity,
Further improvements require comprehensive improvements in electrical, optical, and photoconductive properties such as photoresponsivity, use environment properties such as moisture resistance, and stability over time. The reality is that there are issues that need to be addressed. For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use, and this type of image forming member When a member is used repeatedly for a long period of time, fatigue due to repeated use may accumulate, resulting in a number of disadvantages such as a so-called ghost phenomenon in which an afterimage occurs. Furthermore, according to many experiments conducted by the present inventors, for example, a-Si as a material constituting the photoconductive layer of an electrophotographic image forming member can be used with conventional inorganic photoconductive materials such as Se, CdS, and ZnO. Although it has many advantages compared to organic photoconductive materials such as PVCz and TNF, it has a single-layer photoconductive layer made of a-Si that has properties suitable for use in conventional solar cells. Even if the photoconductive layer of the photographic image forming member is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast, making it difficult to apply ordinary electrophotographic methods; In addition, it has been found that there are many issues that need to be resolved, such as the above-mentioned tendency being remarkable in a humid atmosphere, and in some cases, it may be impossible to hold the charged charge until the time of occurrence. ing. Furthermore, when forming a photoconductive layer with an a-Si material, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms for the purpose of controlling In some cases, problems may arise with the electrical and photoconductive properties of the formed layer. In particular, at the interface between adjacent layers, dangling bonds are likely to be formed due to the manufacturing process, and complex bending of energy bands is likely to occur, depending on the content and distribution of atoms contained therein. For this reason, the various changes in charge behavior and structural stability issues are particularly important, and control of these areas holds the key to success or failure in order for the image forming member to perform its intended function. There are quite a few. In addition, when an a-Si image forming member is made by a generally known method, for example, photocarriers generated in the formed photoconductive layer due to light irradiation may not have a sufficient lifespan in the layer. If sufficient image density cannot be obtained based on the image density, or if the image exposure amount is large, the image tends to become blurred and or even,
Problems often occur due to insufficient prevention of charge injection from the support side. Therefore,
While improvements are being made in the properties of the a-Si material itself, it is necessary to take measures to obtain the desired electrical and optical properties as described above when designing an imaging member. The present invention has been made in view of the above points, and includes a
-As a result of comprehensive research and consideration regarding Si from the viewpoint of applicability and applicability as an image forming member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we have found that a-Si, In particular, silicon atoms are used as the base material, hydrogen atoms (H) and halogen atoms (X)
Amorphous materials containing at least one of the above, i.e., so-called hydrogenated a-Si, halogenated a-Si, or halogen-containing hydrogenated a-Si
(hereinafter referred to generically as a-Si (H, The image forming member not only exhibits extremely superior properties in practical use, but also surpasses conventional image forming members in all respects;
This is based on the discovery that it has particularly excellent properties as an image forming member for electrophotography. An object of the present invention is to provide an image forming member for electrophotography that can easily obtain high-quality images with high density, clear halftones, high resolution, and no image defects or image deletion. purpose. Another object of the present invention is to provide an all-environment type product whose electrical, optical, and photoconductive properties are almost unaffected by the usage environment and are always stable, and which has excellent light fatigue resistance and does not deteriorate even after repeated use. An object of the present invention is to provide an electrophotographic image forming member that does not cause any phenomenon, has excellent durability, and has no or almost no residual potential observed. Another object of the present invention is that when applied as an electrophotographic image forming member, it has sufficient charge retention ability during charging processing for electrostatic image formation, and ordinary electrophotographic methods can be applied extremely effectively. An object of the present invention is to provide an electrophotographic imaging member having excellent electrophotographic properties that can be used in various applications. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide an electrophotographic imaging member having high signal-to-noise ratio characteristics and good electronic contact between laminated layers. That is, the electrophotographic image forming member (hereinafter referred to as "image forming member") of the present invention includes a support, a photoconductive material provided on the support, and containing an amorphous material having silicon atoms as a matrix. In the electrophotographic imaging member having a layer, the photoconductive layer has an average density of 30 to 5 from the support side in the layer thickness direction of the layer.
Region A of 20 Å to 20 μm containing periodic table group atoms at a concentration of ×10 ⁴ atomic ppm and, in the case of non-uniformity, a maximum concentration of 80 to 1 × 10 ⁵ atomic ppm and 0.01 to 1 × 10 ³ a lower layer having a 1 to 100 μm thick region B containing periodic table group atoms at a concentration of atomic ppm and lower than the minimum concentration of the region A, nitrogen atoms and 0.01 to 1×10 ⁴ .
It is characterized by having an upper layer having a thickness of 20 Å to 15 μm and containing atoms of Group Group of the periodic table almost uniformly in the layer thickness direction at a concentration of atomic ppm. The image forming member of the present invention configured to have the photoconductive layer structure as described above can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates usage environment characteristics. In particular, when applied as an electrophotographic image forming member, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, and has stable and high electrical properties. It has high sensitivity and high signal-to-noise ratio, can obtain high-quality visible images with high image density, clear halftones, and high resolution, and has excellent light fatigue resistance, repeated use characteristics, and It has excellent characteristics for repeated use in humid atmospheres. Hereinafter, the image forming member of the present invention will be described in detail with reference to the drawings. FIG. 1 and FIGS. 2a to 2i are diagrams schematically showing the layer structure for explaining embodiments of the structure of the image forming member of the present invention. The imaging member 100 of the present invention comprises a-
A photoconductive layer 102 containing Si, preferably a-Si (H, X) as a main component is formed and configured,
The photoconductive layer 102 is divided into a lower layer 103 and an upper layer 104 from the support side in the thickness direction of the layer 102 due to differences in their constituent atomic compositions. The periodic table group atoms doped (contained) in the lower layer 103 have a substantially uniform concentration distribution state in the direction parallel to the support surface, but have a concentration distribution state of 2a in the layer thickness direction. As shown in figures 2i to 2i (the vertical axis shows the distance from the support, the horizontal axis shows the atomic concentration, and the periodic table group atoms are represented by boron), the concentration distribution is non-uniform. be made into The lower layer part 103 includes a region A located on the support side that contains atoms of group group of the periodic table at a relatively high concentration, and an upper layer side that contains atoms of group group of the periodic table at a lower concentration than the region A. In a preferred embodiment, the region B is located at . In region A and region B, the concentration distribution of atoms of group group of the periodic table may be uniform,
It may be non-uniform. Alternatively, any of these regions may have a distribution in which the concentration decreases toward the upper layer. The thickness of region A in the layer thickness direction is preferably 20 Å to
20μm, more preferably 30Å to 15μm, optimally 40
It is estimated to be Å~10μm. Further, the content of atoms of group group of the periodic table in the region A is preferably 30 to 5×
¹⁰⁴ atomic ppm, more preferably 50 to 5× ¹⁰⁴
atomic ppm, optimally 100 to 5×10 ³
It is considered to be atomic ppm. When the periodic table group atoms are contained in a non-uniform concentration distribution state in region A, the maximum concentration of the periodic table group atoms in the region is preferably 80 to 1×10 ^Five
Atomic ppm, more preferably 100-5× ¹⁰⁵
atomic ppm, optimally 150 to 1×10 ⁵ atomic
Defined as ppm. The thickness of region B in the layer thickness direction is preferably 1 to 1.
100μm, more preferably 1-80μm, optimally 2
It is estimated to be ~50μm. It is preferable that the atoms of Group Group of the periodic table doped in the region B have a substantially uniform concentration distribution in the direction parallel to the support surface and in the layer thickness direction. The thickness of the region B in the layer thickness direction is preferably 1 to 100 μm, more preferably 1 to 100 μm.
The thickness is 80 μm, optimally 2 to 50 μm. It is desirable that the concentration of the atoms of Group Group of the periodic table in the region B is lower than the concentration of the atoms in the region A. Further, it is desirable that the atoms be contained at a lower concentration than the concentration of the atoms in the upper layer 104, preferably 0.01 to 1×10 ³ atomic ppm, more preferably 0.5 to 3×10 ² atomic ppm, optimally It is said to be 1 to 100 atomic ppm. The periodic table group atoms doped into the upper layer 104 have a substantially uniform concentration distribution in the direction parallel to the support surface and in the layer thickness direction. The thickness of the upper layer in the layer thickness direction is preferably 20 Å to 15 μm, more preferably 30 Å to 10 μm, and optimally 40 Å to 5 μm.
It is said that The concentration of atoms of Group Group of the periodic table in the upper layer is usually 0.01 to 1×10 ⁴ atomic ppm,
It is preferably 0.5 to 5×10 ³ atomic ppm, optimally 1 to 1×10 ³ atomic ppm. On the other hand, the nitrogen atoms contained in the upper layer 104 have a substantially uniform concentration distribution in the direction parallel to the support surface, but have a uniform concentration distribution in the layer thickness direction. Alternatively, the concentration distribution state may be such that the atomic concentration increases toward the surface. The concentration scale is not the same as for boron atoms), so it can be continuous or stepwise. Further, the portion having the maximum nitrogen atom concentration near the surface may have a certain length in the layer thickness direction as shown in FIG. 2c, or it may have a single point as shown in FIG. 2a. It's okay if it is. When nitrogen atoms are contained in the upper layer in a non-uniform distribution, the concentration of nitrogen atoms in the upper layer is preferably 0.1 to 57 atomic % at the maximum concentration, that is, at the surface of the photoconductive layer. ,
More preferably 1 to 57 atomic%, optimally 5 to 57 atomic%
The concentration is preferably 0 to 35 atomic %, more preferably 0 to 35 atomic % in the lowest concentration area, that is, the boundary with the lower layer.
30 atomic%, optimally 0 to 25 atomic%. The image forming member of the present invention having a photoconductive layer formed in such a way that the concentration of nitrogen atoms and atoms of group group of the periodic table has the above-mentioned atomic concentration distribution with respect to the layer thickness is suitable for use in electrophotography. When used as an image forming member, the image density is particularly high;
The reason why it is possible to obtain high-quality visible images with clear halftones and high resolution without image blurring even when the image exposure amount is high is because the photoconductive layer is highly enhanced by doping with nitrogen atoms. Extremely good charge-accepting ability is achieved due to the resistance effect and the wide gap in the energy band of the photoconductive layer due to the high concentration of nitrogen atoms on the surface of the photoconductive layer, and the fact that the support side is doped with atoms from group 3 of the periodic table. It is presumed that this is based on the effect of preventing charge injection from the photoconductive layer and the effect of increasing the resistance of the photoconductive layer. In other words, if there is an interface in the upper layer of the photoconductive layer, the excess carriers generated here will move anywhere an electric field is applied and will cancel out the charge in the dark area, resulting in image blurring. However, in the photoconductive layer of the present invention, due to the wide cap described above, even if complex bending of energy bands occurs at the layer interface, the activation energy for carrier generation becomes large and it is easy to No carrier generation occurs. The reason for containing periodic table group atoms at a low concentration in region B in the lower layer is that by increasing the resistance of region B, the charge acceptance ability is improved, and as a result, higher density images can be expected. This is because higher sensitivity is also expected based on the increase in hole mobility. Note that the reason for containing atoms of group group of the periodic table in the upper layer is that the number of nitrogen atoms doped as donors increases according to the concentration of nitrogen atoms in the region, so the nitrogen atoms are added to compensate for this. It is something. Furthermore, although unconfirmed, it is expected that the photoconductive layer will be consistent due to the inclusion of Group Group atoms of the periodic table throughout the photoconductive layer, although the doping concentration is different, and this will also work effectively to prevent image blurring. It is assumed that the In the present invention, specific examples of the halogen atom (X) that may be contained in the photoconductive layer include fluorine, chlorine, bromine, and iodine, and chlorine, especially fluorine, is particularly preferred. be able to. The periodic table group atoms to be doped into the photoconductive layer include boron, aluminum, gallium, indium, thallium and the like, with boron being particularly preferred. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. That is, for example, if it is glass, its surface may contain NiCr, Al, Cr, Mo, Au, Ir, Nd, Ta,
V, Ti, Pt, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ + SnO ₂ )
Conductivity can be imparted by providing a thin film consisting of NiCr, Al, Ag, Pb, Zn, etc., or if it is a synthetic resin film such as polyester film.
Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt
Conductivity is imparted to the surface by providing a thin film of a metal such as by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. The shape of the support is determined depending on the need, but for example, the image forming member 1 shown in FIG.
If 00 is used as an electrophotographic image forming member, it is preferably in the form of an endless belt or a cylinder for continuous high-speed copying. The thickness of the support is determined appropriately so that the desired image forming member is formed, but when flexibility is required as an image forming member, the support function can be fully demonstrated. It is made as thin as possible within this range. However, in such cases, in terms of manufacturing and handling of the support, as well as mechanical strength, it is usually
It is considered to be 10μm or more. In the present invention, to form a photoconductive layer composed of a-Si (H, be done. For example, by glow discharge method, a-Si(H,X)
In order to form a photoconductive layer made up of
Alternatively, depending on the raw material gas for introducing halogen atoms (X) and the constituent atomic composition of the formation region, the raw material gas for introducing nitrogen atoms (N) and the raw material gas for introducing atoms of group 3 of the periodic table may be optionally mixed with Ar, A plasma atmosphere of these gases is created by introducing a predetermined mixing ratio and gas flow rate together with an inert gas such as He into a deposition chamber that can reduce the pressure inside the chamber to generate a glow discharge in the deposition chamber. By forming a layer of a-Si (H, In addition, when forming by sputtering method,
For example, for introducing hydrogen atoms (H) and/or halogen atoms (X) when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases. A raw material gas for introducing nitrogen atoms (N) and a raw material gas for introducing atoms of group 3 of the periodic table may be introduced into the deposition chamber for sputtering according to the gas and the constituent atomic composition of the formation region. As the raw material gas for supplying Si used in the present invention, silicon hydrides (silanes) in a gaseous state or that can be gasified such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ are effective. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred from the viewpoint of ease of layer formation work and good Si supply efficiency. In the present invention, hydrogen atoms are mainly introduced into the photoconductive layer using H ₂ or the above-mentioned SiH ₄ , Si ₂ H ₆ ,
This is carried out by supplying a silicon hydride gas such as Si ₃ H ₈ or Si ₄ H ₁₀ into a deposition chamber to generate an electric discharge. Effective raw material gases for introducing halogen atoms that can be used in the present invention include many halides, such as gaseous or gasified halogen gases, halides, interhalogen compounds, and halogen-substituted silane derivatives. Preferred examples include the halogen compounds obtained. Furthermore, a silicon compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Halogen gas such as iodine, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₃ , BrF ₅ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . can. As the raw material gas for introducing halogen atoms into the photoconductive layer, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used, but HF, HCl,
Hydrogen halides such as HBr and HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , etc., and halides that have a hydrogen atom as one of their constituents in a gaseous state or can be gasified. It can be mentioned as an effective starting material for forming a photoconductive layer. These halides containing hydrogen atoms can be used to introduce halogen atoms into the photoconductive layer at the same time as hydrogen atoms, which are extremely effective components for controlling electrical or photoelectric properties, are introduced into the layer. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen atoms. The raw material gas for supplying nitrogen atoms used in the present invention includes gases containing N as a constituent atom, such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), and hydrogen azide (HN ₃ ). ), gaseous or gasifiable nitrogen such as ammonium azide (NH ₄ N ₃ ), and nitrogen compounds such as nitrides and azides. In addition to this, in addition to introducing nitrogen atoms, it is also possible to introduce halogen atoms,
Examples include halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ). The raw material gases used in the present invention for supplying atoms of Group Group of the Periodic Table include B ₂ H ₆ , B ₄ H ₁₀ ,
_B5H9 , _B5H11 , _B6H10 , _{GaCl3 , AlCl3 , BF3 ,}
BCl ₃ , BBr ₃ , BI ₃ and the like can be mentioned. To form a photoconductive layer made of a-Si (H, In the case of sputtering in a gas plasma atmosphere and ion plating method, polycrystalline silicon or single crystal silicon is housed in the evaporation port as an evaporation source, and this silicon evaporation source is used by resistance heating method or electron beam method (EB method). ), etc., and the flying evaporates are passed through a predetermined gas plasma atmosphere. At this time, in both the sputtering method and the ion plating method, in order to introduce the specified atoms into the layer to be formed, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) and a Sputtering of raw material gas for introducing nitrogen atoms (N) and raw material gas for introducing periodic table group atoms according to the constituent atomic composition of the formation region, including inert gases such as He and Ar as necessary, It is sufficient to introduce the gas into a deposition chamber for ion plating to form a plasma atmosphere of the gas. In order to control the amount of hydrogen atoms, halogen atoms, nitrogen atoms, and atoms of group group of the periodic table contained in the photoconductive layer, for example, hydrogen atoms (H), halogen atoms (X)
One or more of the following may be controlled: the amount of the starting material used to contain nitrogen atoms (N) and atoms of group group of the periodic table introduced into the deposition system, the support temperature, and the discharge power. In the present invention, the diluting gas used when forming the photoconductive layer by the glow discharge method or sputtering method is a so-called rare gas, such as He, Ne,
Preferred examples include Ar. Next, an example of a method for manufacturing an image forming member produced by a glow discharge decomposition method will be described. FIG. 3 shows an apparatus for manufacturing an image forming member using a glow discharge decomposition method. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming the photoconductive layer of the image forming member of the present invention is sealed, for example, 1102 is a SiH ₄ gas (99.99% purity) cylinder, and 1103 is B diluted with H _{2. 2 H6} gas (purity
99.99%, hereinafter abbreviated as B ₂ H ₆ /H ₂ gas) cylinder, 1
104 is NH ₃ gas (99.99% purity) cylinder, 11
05 is CH ₄ gas (99.99% purity) cylinder, 110
6 is a SiF ₄ gas (purity 99.99%) cylinder. Although not shown in the drawings, it is possible to add cylinders of desired gas types in addition to these as needed. In order to flow these gases into the reaction chamber 1101, each valve 1 of the gas cylinders 1102 to 1106 is opened.
122 to 1126 and leak valve 1135 are closed, and inlet valve 1
112-1116, outflow valve 1117-112
1 and auxiliary valves 1132 and 1133 are open, first open the main valve 1134.
is opened to exhaust the reaction chamber 1101 and gas piping. Next, the reading on vacuum gauge 1136 is approximately 5×10 ^-6 torr.
When the temperature reaches 100, the auxiliary valves 1132, 1133 and the outflow valves 1117 to 1121 are closed. Next, SiH ₄ gas from gas cylinder 1102, B ₂ H ₆ /H ₂ gas from gas cylinder 1103, and gas cylinder 11.
NH ₃ gas from 04, from gas cylinder 1105
Inject CH ₄ gas and SiF ₄ gas from gas cylinder 1106 by opening valves 1122 to 1126 to adjust the pressure of outlet pressure gauges 1127 to 1131 to 1 Kg/cm ² , gradually opening inflow valves 1112 to 1116, and supplying SiF 4 gas to the mass flow controller. 1107 to 1111. Subsequently, the outflow valve 1117~
1121 and auxiliary valves 1132 and 1133 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, the outflow valves 1117 to 1121
Also, while checking the reading on the vacuum gauge 1136, adjust the opening of the main valve 1134 so that the pressure inside the reaction chamber reaches the desired value. After confirming that the temperature of the gas cylinder 1137 is set at 50 to 400° C. by the thermal heater 1138, the power source 1140 is set to a desired power to generate glow discharge in the reaction chamber 1101. At the same time, in order to obtain a pre-designed boron atom content curve, the B ₂ H ₆ /H ₂ gas flow rate is changed appropriately, and the discharge power and substrate are adjusted as necessary to compensate for the changing plasma state. Region A, which constitutes the lower layer of the photoconductive layer, is formed by controlling the temperature and the like. Further, during layer formation, the base cylinder 1137 is rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Next, close all gas operation system valves used.
The reaction chamber 1101 is once evacuated to high vacuum. When the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, repeat the same operation as above to remove SiH ₄ ,
Open the operation system valves for SiF ₄ and B ₂ H ₆ /H ₂ and control the flow rate of each raw material gas to the desired value, generate a glow discharge in the same manner as above, and remove the lower layer of the photoconductive layer. A constituent region B is formed. By repeating the same operations as described above, the upper layer constituting the photoconductive layer is formed to have a nitrogen atom and boron atom content distribution curve designed in advance. Examples will be described below. Example 1 Using the image forming member manufacturing apparatus shown in FIG.
A photoconductive layer was formed on an Al cylinder by the glow discharge decomposition method detailed above according to the manufacturing conditions shown in Table 1. A part of the obtained drum-shaped image forming member was cut out, and the concentration of boron atoms and nitrogen atoms in the layer thickness direction was determined using a secondary ion mass spectrometer, and the concentration distribution results shown in Figure 4 were obtained. I got it. Also, set the remaining part of the image forming member drum in the electrophotographic device and apply a charging corona voltage of +6KV.
A latent image is formed by image exposure 0.8~1.51ux・sec,
Subsequently, development, transfer, and fixing processes were carried out using well-known methods, and the images were evaluated. Image evaluation was performed using A4 size paper under normal conditions, and a total of 10 images were evaluated.
Images equivalent to 10,000 sheets were taken out, and images equivalent to 100,000 sheets were taken out under a high temperature and high humidity environment. ] [Image defects] etc., and extremely good evaluations were obtained for all of the above items, regardless of environmental conditions or number of durable sheets. especially,
There is something worth mentioning about the [Concentration] item.
It was confirmed that extremely high concentration could be obtained. This is also supported by the results of potential measurements; for example, when compared to a photoconductive layer without any treatment, it was found that the acceptance potential was improved by about 1.4 to 1.7 times. It was inferred that the effect of preventing charge injection from the surface due to atomic doping and the effect of doping a small amount of boron atoms were sufficiently effective. This improvement in charge acceptance ability not only improves image density but also has the great advantage that a wide latitude of corona conditions can be obtained and the range of image quality selection can be expanded. Another item worth mentioning is resolution, and this series of tests revealed that extremely clear images can be maintained under any environmental conditions. This appears to be the effect of providing the upper layer of the photoconductive layer with a nitrogen atom concentration distribution as shown in Figure 4.
There was a clear difference under high humidity conditions from those that did not have such a nitrogen atom concentration distribution. Examples 2 and 3 and Comparative Examples 1 and 2 The same method as in Example 1, except that in Example 1, the thickness of the third layer (upper layer) was variously changed by changing the deposition time. A drum-shaped imaging member was prepared. When the image forming member was subjected to the same image evaluation as in Example 1, it was found that
Obtained the results in the table. Examples 4 and 5 and Comparative Examples 3 to 5 A drum-shaped image was formed under the same conditions and method as in Example 3, except that the flow rate of ammonia gas was variously changed in forming the third layer (upper layer). A forming member was produced. When this image forming member was subjected to the same image evaluation as in Example 1, the results shown in Table 3 were obtained. Examples 6 and 7 Drum-shaped image forming members were produced in the same manner as in Example 1 according to the production conditions shown in Tables 4 and 5, respectively. The concentration distribution forms of nitrogen atoms and boron atoms in the obtained image forming member are 5th and 6th, respectively.
It was something like the picture. As a result of performing image evaluations on these image forming members in exactly the same manner as in Example 1, good results almost equivalent to those in Example 1 were obtained in all cases.

【table】

【table】

【table】

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a diagram schematically showing a layer structure for explaining an embodiment of the structure of an image forming member of the present invention. FIGS. 2a to 2i are diagrams schematically showing the concentration distribution of nitrogen atoms and atoms of group 3 of the periodic table in the amorphous layer of the image forming member of the present invention. Figure 3 shows
1 is a diagram showing an apparatus for manufacturing an image forming member using a glow discharge decomposition method. 4 to 6 are diagrams showing the analysis results of the constituent atomic concentration distribution of the image forming member in the example of the present invention. 100...Image forming member, 101...Support, 102...
Photoconductive layer, 103... lower layer part, 104... upper layer, 1
101...Reaction chamber, 1102-1106...Gas cylinder, 1107-1111...Mass flow controller, 1112-1116...Inflow valve, 1117
~1121...Outflow valve, 1122~1126
...Valve, 1127-1131...Pressure regulator, 1
132...Auxiliary valve, 1133...Auxiliary valve, 1
134... Main valve, 1135... Leak valve, 1136... Vacuum gauge, 1137... Base cylinder, 1138... Heater, 1139... Motor, 1140... High frequency power supply (matching box).

Claims (1)

[Claims] 1 a support, a photoconductive layer provided on the support and containing an amorphous material having silicon atoms as a matrix;
In the photoconductive member for electrophotography, the photoconductive layer has an average concentration of 30 to 5×10 ⁴ atomic ppm from the support side in the layer thickness direction, and when the concentration is nonuniform, the maximum concentration 80～1× ¹⁰⁵
20 Å to 20 μm thick region A containing periodic table group atoms at a concentration of atomic ppm and 0.01 to 1×10 ³
a lower layer having a thickness of 1 to 100 μm containing periodic table group atoms at a concentration of atomic ppm and lower than the minimum concentration of the region A;
An upper layer having a thickness of 20 Å to 15 μm and containing nitrogen atoms and atoms of Group Group of the periodic table substantially uniformly in the layer thickness direction at a concentration of 0.01 to 1×10 ⁴ atomic ppm. conductive member.