JPS59184354A - Photoconductive material - Google Patents

Abstract

PURPOSE:To form a photoconductive material capable of obtaining an image high in density, sharp in halftone, high in resolution, and high in quality by forming a photoconductive layer contg. an amorphous material composed essentially of Si atom consisting of 3 regions on a substrate. CONSTITUTION:The first photoconductive layer 102 composed essentially of a-Si, preferably a-Si(H, X) is formed on the substrate 101 of a photoconductive material, and the second layer 106 composed essentially of Si and C atoms is formed on the layer 102. The layer 102 is successively divided into a region A (103), a region B (104), and a region C (105) in the layer thickness direction from the side of the substrate 101 in accordance with the difference of its constituent elements. The region A contains an element of group III of the periodic table, the region B contains no element of group III, and the region C contains the element of group III and N. As a result, extremely superior potential acceptance can be attained by the effects of raising resistance of the layer 102, and widening the gap of an energy band due to high concn. of N in the vicinity of the joined interface between the layers 102 and 106.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention utilizes light (herein, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.) that is sensitive to magnetic waves. It relates to a photoconductive member.

Photoconductive materials that form photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, and document reading devices have high sensitivity and low S/N ratio [photocurrent (Ip
) / (Id) ], has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, and has a desired dark resistance value.
Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use and being able to easily dispose of afterimages within a predetermined time. In the case of electrophotographic image forming members incorporated into electrophotographic apparatuses used in offices as special office equipment, the above-mentioned non-pollution during use is an important point.

Based on this viewpoint, amorphous silicon (hereinafter referred to as a-9i) is a photoconductive material that has recently attracted attention. Applications to image forming members for use in photoelectric conversion and reading devices are described in DE 2933411, respectively.

However, the conventional photoconductive member having a photoconductive layer composed of a-5i has poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are problems that need to be further improved in terms of environmental characteristics and furthermore, stability over time, which requires comprehensive improvement of characteristics.

For example 1. When applied to electrophotographic image forming members, 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 photoconductive member When used repeatedly for a long time, fatigue accumulates due to repeated use, resulting in a so-called ghost phenomenon, which causes afterimages.

1 ″・Example 7: 0 experiments by the inventors
Se,
Inorganic photoconductive materials such as CdS, ZnO or PV
Although it has many advantages compared to organic photoconductive materials such as Cz 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, the dark decay (d
arc decay) is extremely fast, making it difficult to apply normal electrophotography, and in addition, the above-mentioned tendency is remarkable in a humid atmosphere, and in some cases, it may become impossible to hold the charged charge until the phenomenon time. It has been found that there are many issues that need to be resolved.

Furthermore, when forming a photoconductive layer using an a-Si material, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive For control purposes, boron atoms, phosphorus atoms, etc.
Alternatively, other atoms may be contained in the photoconductive layer as constituent atoms to improve other properties, but depending on the content of these constituent atoms, the electrical and photoconductive properties of the formed layer may be affected. There may be problems with the characteristics.

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 in order for the photoconductive member to perform its intended function, it is necessary to control these aspects.
In many cases, it holds the key to success or failure.

In addition, if the a-5i photoconductive member is made by a generally known method, 1. When a good image density cannot be obtained, or when the image exposure amount is large, the image tends to become unclear, perhaps because excessive light carriers generated near the surface of the photoconductive layer flow in the lateral direction. teeth,
Problems often occur due to insufficient prevention of charge injection from the support side. Therefore, while efforts are being made to improve 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 photoconductive members.

The present invention has been made in view of the above points, and
As a result of comprehensive research and consideration from the viewpoint of applicability and applicability as a photoconductive member used in electrophotographic image forming members, solid-state naked image devices, reading devices, etc., we have found that a.
-8i, especially an amorphous material having a silicon atom as its base material and containing at least one of a hydrogen atom (H) and a halogen atom (X), that is, the so-called hydrogenated a-
5i, \halogenated a-Si or halogen-containing hydrogenated a-9i (hereinafter these will be collectively referred to as a-9i()1.
Regarding photoconductive members having a photoconductive layer containing X), photoconductive members designed and created with a specific layer structure exhibit extremely excellent properties in practical use. This is based on the discovery that it is superior in all respects to conventional photoconductive materials, and has particularly excellent properties as a photoconductive material for electrophotography. be.

An object of the present invention is to provide a photoconductive member for electrophotography that can easily obtain high-quality images with high density, clear halftones, and high resolution, and without 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. It is an object of the present invention to provide a photoconductive 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 image forming member for electrophotography, it has sufficient charge retention ability during charging processing for electrostatic image formation, and is preferably applicable to electrophotography very effectively. It is an object of the present invention to provide a photoconductive member having excellent electrophotographic properties that can be used.

Yet another object of the present invention is to provide a photoconductive member having high photosensitivity, high signal-to-noise ratio characteristics, and good electrical contact between laminated layers.

That is, the photoconductive member of the present invention comprises a support, a photoconductive first layer provided on the support and containing an amorphous material having silicon atoms as a host, and this first layer. In the photoconductive member, the photoconductive member has a second layer provided thereon and containing silicon atoms and carbon atoms as essential components.
The layers are sequentially formed from the support side in the layer thickness direction of the layer,
It is characterized by being composed of a region A containing atoms of group Ⅰ of the periodic table, a region B not containing atoms of group Ⅰ of the periodic table, and a region C containing atoms of group Ⅰ of the periodic table and nitrogen atoms. do.

The photoconductive member of the present invention configured to have the photoconductive layer structure 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 image forming member for electrophotography, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, has stable electrical properties, and has high sensitivity. It has a high signal-to-noise ratio, high image density, clear /＼-tones, and high resolution.
High-quality visible images can be obtained, and it has excellent light fatigue resistance and repeated use characteristics, especially in a humid atmosphere.

Hereinafter, the photoconductive member of the present invention will be explained in detail according to the drawings.

FIG. 1 is a diagram schematically showing a layer structure for explaining an embodiment of the structure of a photoconductive member of the present invention. Second
Figures a to 2h are diagrams schematically showing the concentration distribution of nitrogen atoms and atoms of group Ⅰ of the periodic table in the first layer of the photoconductive member of the present invention.

As shown in FIG. 1, the photoconductive member 100 of the present invention contains a-9i, preferably a-9i (H, A first photoconductive layer 102 is formed, and a second layer 106 containing silicon atoms and carbon atoms as essential components is further formed on the first layer 102.

The first layer 102 has a region A (1
03), area B (104), and area C (105).

The atoms of group Ⅰ of the periodic table doped (contained) in region A (103) have a nearly uniform concentration distribution state in the direction parallel to the support surface within the region A, but have a nearly uniform concentration distribution state in the direction of the layer thickness. is uniform as shown in Figures 2a to 2h (the vertical axis is the distance from the support, the horizontal axis is the atomic concentration, and the atoms of group Ⅰ of the periodic table are represented by boron). The thickness of the region A in the layer thickness direction is preferably 20A to 20U, more preferably 308 to 15μ. The scales are optimally 40A to 10U.

Further, the content of Group I atoms of the periodic table in the region is preferably 30 to 5X 10'' atomic ppm, more preferably 50 to 5X 10' atomic ppm.
, optimally 100 to 5 The maximum concentration of group m atoms is preferably 8
0 to 105105ato ppm, more preferably 100 to 5105105ato pp+s
The content area B (loa), which is optimally 150 to 105 to 105 ppm, is characterized by not containing atoms in the first half of the periodic table, and the thickness of the area B in the layer thickness direction is preferably 1 to 100 ppm. 1 to 8, more preferably 1 to 8
0u, optimally 2 to 50Q.

The atoms in the first column of the periodic table doped in region C 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 C in the layer thickness direction is preferably 20 to 15μ, more preferably 30A-10 tiles,
Optimally, it is set to aoA~5 μs. The concentration of atoms in the first part of the periodic table in the region C is preferably 0.01 to LX
104ato+sic pp■, more preferably 0.
5~5X 103103ato ppm, optimally 1~
IX 103at103ata+s.

On the other hand, the nitrogen atoms contained in region C have a substantially uniform concentration distribution within the layer in the direction parallel to the support surface, but may 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 second layer, and the manner in which the atomic concentration increases toward the second layer is also shown in FIGS. The atomic concentration scale is not the same as that for boron atoms), so it can be either continuous or stepwise. Further, even if the portion of the layer having the maximum nitrogen atom concentration near the layer junction interface with the second layer has a certain length in the layer thickness direction as shown in FIG. 2C, Good, part 2a
It is acceptable even if it is just one point as shown in the figure. Area C
When nitrogen atoms are contained in a non-uniform distribution state in the region C, the concentration of nitrogen atoms in the region C is at the maximum concentration,
That is, in the vicinity of the layer bonding interface between the layer and the second layer, preferably 0.1 to 57 atomic%, more preferably 1 to 57 atomic%, optimally 5 to 57 atomic%.
omic%, and in the part where the concentration is minimal, that is, in the boundary 2 part with area B, preferably 0 to 35a.
tosic%, more preferably 0-30 atomic%
, is optimally set to 0 to 25 atomic%.

In this way, the photoconductive member of the present invention has a first layer formed such that the concentration of nitrogen atoms and atoms in the first column of the periodic table has the above-mentioned atomic concentration distribution with respect to the layer thickness. When used as a photoreceptor for photography, image deletion does not occur even when the image density is particularly high and the image exposure is high, halftones appear clearly, and the resolution is high.
The reason why high-quality visible images can be obtained is the effect of increasing the resistance of the first layer with photoconductivity due to nitrogen atom doping, and the nitrogen near the layer bonding interface between the first layer and the second layer. Extremely good charge-accepting ability is achieved due to the wide gap in the energy band of the part due to the high atomic concentration, and the effect of preventing charge injection from the support side by doping with the atoms in the first part of the periodic table. It is estimated that it is based on In other words, if there is a layer junction interface in the upper part of the first layer (for example, the junction between region B and region C), excess carriers generated here will move anywhere when an electric field is applied, resulting in a dark region. causes the effect of canceling the electric charge of
This is understood to result in image blurring, but in the first layer of the photoconductive member of the present invention, due to the wide gap described above, even if complex bending of the energy band occurs at the layer bonding interface. The activation energy for carrier generation is large, and carrier generation does not occur easily.The reason for including the first atom of the periodic table in region C is that the donor concentration increases according to the concentration of nitrogen atoms in the region. Since the number of nitrogen atoms doped in also increases,
This is added to compensate for this.

In the present invention, specific examples of the halogen atom (X) that may be contained in the first layer include fluorine, chlorine, bromine,
Mention may be made of iodine, but particularly of chlorine and especially of fluorine.

The first atom of the periodic table doped in the first layer includes 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, AI, Cr, Mo,
Au, Nb, Ta, V, Ti, PL, Pd
Metals such as these or alloys thereof can be mentioned.

Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, and ceramic.

Mick, 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, NiC is applied to the surface of the glass.
r, A1. Or, No, Au, Ir, Nd,
Ta, V, Ti, Pt, In2O3, 5n02, IT
Conductivity can be imparted by providing a thin film made of O(In203 + 5n02), etc., or if a synthetic resin film such as polyester film is provided, NiCr,
AI, Ag, pb, Zn, old, Au, Cr, M
A thin film of metal such as O, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal to make the surface conductive. gender is given.

The shape of the support is determined as desired, but for example, if the photoconductive member lOO shown in FIG. It is desirable to have a belt shape or a cylindrical shape. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such a case, from the viewpoint of manufacturing and handling of the support, as well as mechanical strength, the number is usually 10 or more.

In the present invention, the first
To form this layer, for example, a vacuum deposition method using a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blating method is applied.

For example, in order to form the first layer composed of a-5i (H,
Depending on the raw material gas for introducing hydrogen atoms (H) and/or the raw material gas for introducing halogen atoms (X), and the raw material gas for introducing nitrogen atoms (N) according to the constituent atomic composition of the formation region, the raw material gas for introducing nitrogen atoms (N) and the periodic table No. The raw material gas for introducing group atoms may be Ar,
A glow discharge is generated in the deposition chamber by introducing an inert gas such as He into a deposition chamber whose interior can be depressurized at a predetermined mixing ratio and gas flow to generate a plasma of these scum. By forming an atmosphere, a-Si(H,
A layer consisting of X) is formed.

In addition, when forming the first layer by sputtering, a target made of Si is sputtered in an atmosphere of an inert gas such as Ar or He, or a mixed gas based on these gases. In this case, hydrogen atom (H)
and/or I＼Gas for introducing rogen atoms (X) and raw material gas for introducing nitrogen atoms (N) and raw material gas for introducing atoms of group Ⅰ of the periodic table according to the constituent atomic composition of the formation region for sputtering. It is sufficient to introduce it into the deposition chamber.

The raw material gas for Si supply used to form the first layer includes SiH4,5i2)I6.5i3Hs,5
i4) Silicon hydride (silanes) in a gaseous state such as 1to or which can be gasified can be effectively used, especially in terms of ease of handling in layer creation work and good Si supply efficiency. SiH4 and S iz 86 are preferred.

In order to introduce hydrogen atoms into the first layer in the present invention,
Mainly H2 or the above SiH4,5izH6,5i
The process is carried out by supplying a silicon hydride gas such as 3H6, 5i4Hto, etc. into the deposition chamber to generate an electric discharge.

In the present invention, many halides are effective as the raw material gas for introducing halogen atoms that can be used to form the first layer, such as halogen gas, halides, interhalogen compounds, and halogen-substituted Preferred examples include gaseous or gasifiable halogen compounds such as silane derivatives. 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 to form the first layer in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine; BrF, CI
F, ClF3. BrF3, BrF5, HF3,
Examples include interhalogen compounds such as IF7°ICI and IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, SiF
Preferred examples include silicon halides such as 4, Si2F6.5ill4, and SiBr4.

As the raw material gas for introducing halogen atoms into the first layer, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used, but in addition, HF, HCI, HBr, Old hydrogen halide, 5ihF2.5ih12.5iH2CI2
, 5i) lcI3.5iH2Brz, 5iHBr
Gaseous or gasifiable halides having a hydrogen atom as one of their constituents, such as tertiary-halogen-substituted silicon hydride, can also be mentioned as effective starting materials for forming the first layer.

These halides containing hydrogen atoms introduce halogen atoms into the layer at the same time as hydrogen atoms, which are extremely effective components for controlling electrical or photoelectric properties, are introduced into the layer during the formation of the first layer. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen atoms.

In the present invention, the raw material gas for supplying nitrogen atoms used to form the first layer includes nitrogen atoms, such as nitrogen (N2), ammonia (NHs),
Hydrazine (H2NNH2>Hydrogen azide (HNs)
.

Mention may be made of gaseous or gasifiable nitrogen such as ammonium azide (NH4N3), and nitrogen compounds such as nitrides and azides. In addition to these, halogenated nitrogen compounds such as nitrogen trifluoride (F3N) and nitrogen tetrafluoride (F4N2) can be mentioned since they can introduce halogen atoms in addition to nitrogen atoms.

In the present invention, the raw material gas for supplying atoms of group Ⅰ of the periodic table used to form the first layer is B2 H6.
, B4HIO1B5 B9, B5 Hll, B6HXl
, GaCl3, AlCl3, 8F3, BCl3,
BBr3, BI3, etc. can be mentioned.

To form the first layer made of a-Si(H, Sputtering is performed in a gas plasma atmosphere of This can be carried out by heating and evaporating the flying evaporated material using a method such as the method (method), etc., and passing the flying evaporated material through a predetermined gas plasma atmosphere.

At this time, in both the sputtering method and the ion blating method, in order to introduce predetermined atoms into the first layer to be formed, hydrogen atoms (H) and/or halogen atoms (X) must be introduced. Depending on 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 Ⅰ of the periodic table may be used as necessary.
It is sufficient to introduce an inert gas such as At into the sputtering or ion blating chamber 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 Ⅰ of the periodic table contained in the first layer, for example, hydrogen atoms (H), halogen atoms (X), nitrogen atoms ( N)
One or more of the following may be controlled: the amount of the starting material used to contain the Group I atoms of the periodic table introduced into the deposition system, the support temperature, the discharge power, and the like.

In the present invention, as the diluting gas used when forming the first layer by the glow discharge method or the sputtering method, so-called rare gases such as He, Me, ^r, etc. can be preferably mentioned. .

The second layer 106 formed on the photoconductive first layer 102 in the present invention has a free surface and is mainly characterized by moisture resistance, continuous repeated use characteristics, electrical pressure resistance, and usage environment. It is provided in order to achieve the object of the present invention in terms of characteristics and durability.

In the present invention, since each of the photoconductive first layer and the second layer has a common constituent atom, silicon atoms, chemical stability is sufficiently ensured at the laminated interface. There is.

The second layer 106 in the present invention is made of an amorphous material (hereinafter referred to as a-(Si
Xc, -x)y (H,X)ly t, where 0<x, y<1).

a-(Six (+ -x)y (H,X) +-y
The second layer is formed by a glow discharge method, a sputtering method, an ion implantation method, an ion blasting method, an electron beam method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured.
It is relatively easy to control the conditions for manufacturing a photoconductive member having desired characteristics, and it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the second layer. Due to their advantages, the glow discharge method or the sputtering method is preferably employed. In addition, the glow discharge method and the sputtering method can be used together in the same system to create a
A layer may be formed.

To form the second layer by the glow discharge method, a-(
A support on which a photoconductive first layer is formed by mixing a raw material gas for forming StXC+ -x )y (H, The introduced gas is turned into gas plasma by generating a glow discharge, and a-
(Six c, -)j)y (H,X)Iy may be deposited.

In the present invention, a-(SixCs-piece y (H,X
) Silicon atoms (S
i) Most of the gaseous substances containing at least one of carbon atoms (C), hydrogen atoms (H) and halogen atoms (X) as constituent atoms or gasified substances that can be gasified. can be used.

When using a raw material gas having Si as a constituent atom as one of St, C, H, and X, for example, a raw material gas having Si as a constituent atom, a raw material gas having C as a constituent atom,
Raw material gas and/or X as H constituent atoms as necessary
A raw material gas having constituent atoms of Si and a raw material gas having constituent atoms of C and/or C and X may be used by mixing them at a desired mixing ratio, or A raw material gas containing Si as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing Si as a constituent atom and a raw material gas containing Si, C, and H as constituent atoms or Si , C and X as constituent atoms are mixed at a desired mixing ratio.

Alternatively, as another method, a raw material gas containing Si and H as constituent atoms and a raw material gas containing C as constituent atoms may be used in combination, or a raw material gas containing Si and X as constituent atoms may be used. and a raw material gas containing C as a constituent atom may be used in combination.

In the present invention, a preferable halogen atom (X) that may be contained in the second layer is F.

C1, Br, ■, with F and CI being particularly desirable.

In the present invention, SiH containing Si and H as constituent atoms is effectively used as the raw material gas for forming the second layer.
Silicon hydride gas such as 4,5i2He, 5i3Hs, 5i4H1o; C and H as constituent atoms, for example, saturated hydrocarbons with 1-4 carbon atoms, 2-4 carbon atoms
Examples include ethylene hydrocarbons, acetylene hydrocarbons having 2 to 4 carbon atoms, simple halogens, wood halides, interhalogen compounds, silicon halides, and halogen-substituted silicon hydrides.

Specifically, methane is a saturated hydrocarbon.

Ethane, propane, n-butane, pentane; ethylene hydrocarbons include ethylene, propylene, butene-1
, butene-2, i-butylene, pentene; acetylene hydrocarbons include acetylene, methylacetylene, butyne; simple halogens include halogen gases such as fluorine, chlorine, bromine, and iodine; hydrogen halides include HF,
HI, Hlll:I, HBr; Interhalogen compounds include CIF, ClF3, ClF5, BrF
, BrF3, BrF5, IFs, IF7,
ICI.

IBr; silicon halides include SiF4, Si2
F6.5iCI4, 5iC13Br, 5iChB
r2.5iCIBr3. Transcline 5iC131, SiB
r4; As the halogen-substituted silicon hydride, SiH
2F2.5iH2C12, 5iHCI3.5iH3CI
.

Examples include 5IH3BrJiH2Br2 and 5iHBr3.

In addition to these, CF4. CCl2, CBr4, CHF
3, (l(2Fz, CH3F, CH3Cl,
(H3Br, CH31, c2u5 (halogen-substituted paraffinic hydrocarbons such as 1, fluorinated sulfur compounds such as SF4, SF6; 5i(()+3)4, Si(C2H5
)4, etc.; 5iC1(CH3)3.
Silane derivatives such as halogen-containing alkyl silicides such as 5iC12(CH3)2.5iC13C83 may also be mentioned as effective.

These second layer forming substances contain silicon atoms, carbon atoms, and optionally halogen atoms and/or hydrogen atoms in a predetermined composition ratio in the second layer to be formed. They are selected and used as desired when forming the second layer.

For example, Si, which can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and can form a layer with desired characteristics.
(CH3)4 and 5iHC13, 5iH2CI2.5iCI4 or 5i as those containing a halogen atom
By introducing HaC1 etc. in a predetermined mixing ratio into the apparatus for forming the second layer in a gas state and causing a glow discharge, a-(SL+C+-x)y(H,X)
A second layer consisting of l-V can be formed.

To form the second layer by the sputtering method, a monocrystalline or polycrystalline Si wafer and/or C wafer, or a wafer containing a mixture of Si and C is targeted, and these are sputtered as necessary. This may be performed by sputtering in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements.

For example, if a Si wafer is used as a target, the raw material gas for introducing C, H and/or
The Si wafer may be sputtered by diluting it with a diluting gas as necessary and introducing it into a deposition chamber for sputtering to form a gas plasma of these gases.

In addition, Si and C are separate targets,
Alternatively, this can be achieved by using a single target containing a mixture of Si and C, and performing sparging in a gas atmosphere containing hydrogen atoms and/or halogen atoms as necessary.

Substances that serve as raw material gases for introducing C, H and X include:
The material for forming the second layer shown in the glow discharge example described above can also be used as an effective material in the sputtering method.

In the present invention, the diluent gas used when forming the second layer by a glow discharge method or a sputtering method includes:
Suitable examples include so-called lees gases such as He, Ne, and Ar.

The second layer in the present invention is carefully formed to provide the desired properties.

In other words, the substance whose constituent atoms are Si, C, and H and/or From semiconducting properties.

In the present invention, a-(Six
The preparation conditions are strictly selected according to the desired conditions so that C,-X)y(H,X)ly is formed. For example, when the second layer is provided with the main purpose of improving electrical voltage resistance, a-(SiXC,-X)y (
H,

In addition, when a second layer is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the degree of electrical insulation mentioned above is relaxed to a certain extent, and the layer has a certain degree of sensitivity to the irradiated light. As an amorphous material, a-(Si
xcl-X)y(H,X)+-y is created.

a−(Six C+ −x)y on the surface of the first layer
When forming the second layer consisting of (H, In the invention, a-(StXC,-X)y having the desired properties
(It is desirable that the temperature of the support during layer formation be strictly controlled so that H,XL-y can be formed as desired.

In the present invention, the formation of the second layer is performed by selecting an appropriate range according to the method of forming the second layer to effectively achieve the desired purpose, but preferably, 2
The temperature is desirably 0 to 400'0, more preferably 50 to 350°C, and optimally 100 to 300°C. For forming the second layer, it is advantageous to employ the glow discharge method or sputtering method, as it is relatively easier to delicately control the composition ratio of the atoms that make up the layer compared to other methods. However, when forming the second layer using these layer forming methods, the discharge power during layer formation is created in the same manner as the support temperature described above. H,
X) It can be mentioned as one of the important factors that influence the characteristics of I-y.

a-(Six C+ -x)y (H,X) having the characteristics to effectively achieve the object of the present invention
The discharge power conditions for effectively creating ty with good productivity are preferably lO~300W, more preferably 20~250W, @ suitably 50~200W. be.

The gas pressure in the deposition chamber is preferably 0.01 to I
Torr, preferably about 0.1" to 0.5 Torr.

In the present invention, the values in the above-mentioned ranges are mentioned as the preferable numerical ranges of the support temperature and discharge power for creating the second layer, but these layer creation factors can be determined independently and separately. , but the desired characteristic (7) a
−(SIX C+ −x )y (Ht X) ly
It is preferable that the optimum value of each layer formation factor is determined based on mutual organic relationship so that a second layer consisting of The amount of atoms is the same as the conditions for forming the second layer, and the amount of the second layer is such that the desired properties that achieve the object of the present invention are obtained.
This is one of the important factors for the formation of this layer.

The amount of carbon atoms contained in the second layer in the present invention is
It can be determined as desired depending on the characteristics of the amorphous material constituting the second layer.

That is, the general formula a-(StXcl-X)y (H
,
An amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as a-SiaC: +-, where 0 < a <
1) , an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter a-(Si, , c, -b)
e Written as Hl-6, provided that 0 < b, c < 1
), an amorphous material composed of silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms (hereinafter referred to as a-(
Si7 (:1-4)e (H,X) l-0, however, it is classified as 0 < d, e < 1).

In the present invention, when the second layer is composed of a-9+1CI-a, the amount of carbon atoms contained in the second layer is preferably I x 10' to 90 atomic%, more preferably 1 ~80 atomic%, optimally 10-7
It is desirable that it be 5ato%. That is, if we display a in the previous a-9i+1Ct-a, a
is preferably 0.1 to 0.99999, more preferably 0
．． 2 to 0.99, optimally 0.25 to 0.8.

On the other hand, in the present invention, the second layer is a-(Sib C+ -b). (When composed of H, XL-e, the amount of carbon atoms contained in the second layer is preferably IXiO゛3 to 90 atomic%,
More preferably, it is 1 to 90 atomic%.

The hydrogen atom content is preferably 1 to 40 atom
mic%, more preferably 2 to 35 atomic%, optimally 5 to 30 atomic%,
Photoconductive members formed with hydrogen contents within these ranges are well suited for practical applications.

That is, the previous a-(SibC+-b). (If expressed as H, XL, e, b is preferably 0.1 to 0.11991
1111, more preferably 0.1 to 0.99, optimally 0
．． 15-0.3, C is preferably 0.6-0.98, more preferably 0.65-0.98, optimally 0.7-0.
85 is desirable.

The second layer is a−(Sia C+ −a )e (H,
X) r-*, the content of carbon atoms contained in the second layer is preferably lXl
0-3 to 80 atomic%, more preferably 1 to 11O
It is desirable that the content be atomic%, most preferably 10 to 80 atomic%. The content of halogen atoms is preferably 1 to 20 atomic%, more preferably 1 to 18 atomic%, most preferably 2 to 15 atomic%.
It is desirable that the halogen atom content be in atomic%, and photoconductive members prepared when the halogen atom content is within these ranges can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably 19
atomic% or less, more preferably 13 atomic%
(It is desirable that the following is true.) 1.

That is, the previous a-(Sia(+-a)a()1.xL-
If expressed as d and e in a, d is preferably 0.1
~0.99999, more preferably 0.1~0.9111.
! Suitably 0.15~G, 9, e, preferably 0.8~
o, 98, more preferably 0.82 to 0.98, most preferably 0.85 to 0.98.

The numerical range of the layer thickness of the second layer in the present invention is appropriately determined as desired depending on the intended purpose so as to effectively achieve the purpose of the present invention.

In addition, the thickness of the second layer is determined according to the characteristics required for each layer, including the amount of carbon atoms contained in the second layer and the relationship with the thickness of the first layer. It needs to be determined as appropriate based on the organic relationship and desired. In addition, it is desirable to take into account the economical aspects of productivity and mass production.

The thickness of the second layer in the present invention is preferably 0.
．． 003-30-1 more preferably 0.004-20μ,
The optimum thickness is preferably 0.005 to 10μ.

In the case of the glow discharge method, the amount of carbon atoms contained in the second layer can be controlled, for example, by adjusting the flow rate of a gas for introducing carbon atoms into the deposition chamber.
In addition, when layer formation is performed using a sputtering method, the sputtering area ratio of the silicon wafer and graphite wafer is changed when forming the target, or the mixing ratio of silicon powder and graphite powder is changed and the target is molded. , can be controlled as desired. The amount of halogen atoms contained in the second layer can be controlled by adjusting the flow rate of a raw material gas for introducing halogen atoms introduced into the deposition chamber.

Next, an example of a method for manufacturing a photoconductive member produced by a glow discharge decomposition method will be described.

FIG. 3 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method.

Gas cylinders 1102 to 1106 in the figure are sealed with raw material gas for forming the amorphous layer of the photoconductive member of the present invention.
H4 gas (purity 913.99%) cylinder, 1103 is B
B2) 16 gas (purity 99.99%, hereinafter abbreviated as B2H6/B2 gas) diluted with 2, 1104 is NH
3 gas (99.99% purity) cylinder, 1105 is CH4
Gas (purity 1119.99%) cylinder, 1106 is Si
A cylinder of F4 gas (purity 89.8θ%) is not shown, but other desired gas types can be added as needed.

To flow these gases into the reaction chamber 1101.

Each valve 1122-1 of gas pump 1102-110B
12B and leak valve 1135 are closed, and also ensure that inlet valves 1112-111B, outlet valves 1117-1121 and auxiliary valve 1132.1 are closed.
After confirming that 133 is open, first open the main valve 1134 to exhaust the reaction chamber 1101 and the gas piping. Next, the reading of vacuum gauge 1138 is about 5 x 10°'
When the tarr is reached, the auxiliary valve 1132.1133
and close the outflow valves 1117-1121. Next, SiH4 gas from the gas cylinder 1102 and gas cylinder 110
B2H6/B2 gas from 3, N from gas pump 1104
H3 gas, CH4 gas from gas pump 1105, and SiF4 gas from gas pump 1106 are supplied through valves 112, respectively.
Open 2 to 1126 and check the outlet pressure gauges 1127 to 1131.
Adjust the pressure to 1Kg/am2, and inflow valve 1112~
Gradually open 111B and install mass flow controller t1
07-1111. followed by outflow valves 1117-1121 and auxiliary valves 1132.1133
are gradually opened to allow each gas to flow into the reaction chamber port 01. At this time, adjust the outflow valves 1117 to 1121 so that the ratio of these gas flow rates becomes the desired value, and also adjust the main valve while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber becomes the desired value. Adjust the aperture of 1134.

And the temperature of gas cylinder 1!37 is heating heater 1
After confirming that the temperature is set at 50 to 400° C. by step 138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101.

At the same time, NHa gas and B2H6/
In order to appropriately change the H2 gas flow rate and correct the changing plasma state, the discharge power,
Region A of the first layer is formed by controlling the substrate temperature and the like.

Further, while one layer is being formed, the base cylinder 1137 is rotated at a constant speed by a motor 1138 in order to ensure uniform layer formation.

Next, close all the gas operation system valves used and close the reaction chamber 1.
101 is once evacuated to high vacuum. When the reading on the vacuum gauge 1138 reaches approximately 5X 104 torr, repeat the same operation as above, open the SiH4 and SiF4 operation system valves, control the flow rate of each raw material gas to the desired value, and Glow discharge is generated in the same manner as described above to form region B of the first layer.

Regarding the region C of the first layer, by repeating the same operations as described above, a region having a content distribution curve of each constituent atom designed in advance is formed.

Next, close all the gas operation system valves used and close the reaction chamber 1.
101 is once evacuated to high vacuum. When the reading on the vacuum gauge 1138 reaches approximately 5X 10' torr, repeat the same operation as above, open the operating system valves for SiH4, CH4, and if necessary He, etc., and adjust the flow rate of each raw material gas. is controlled to a desired value, and a glow discharge is generated in the same manner as in the case of the first layer to form the second layer. When halogen atoms are contained in the second layer, the SiF4 operating valve may be opened at the same time to generate glow discharge.

Examples will be described below.

Example 1 Using the photoconductive member manufacturing apparatus shown in FIG. 3, an amorphous layer was formed on an AI cylinder according to the manufacturing conditions shown in Table 1 by the glow discharge decomposition method detailed above. . A part of the obtained photoreceptor drum 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. . In addition, the remaining part of the photoreceptor drum was set in the electrophotographic device, and the charging corona voltage was +6KV, and the image exposure was 0.13~
A latent image was formed at 1.51 ux/sec, and then the development, transfer, and fixing processes were performed using well-known methods, and one image was evaluated.The 0 image evaluation was performed using A4 size paper under normal conditions. Images equivalent to a total of 10,000 images were produced, and images equivalent to 10,000 images were produced in a high-temperature, high-humidity environment, and the [density] [resolution] [floor] of each image was Tonal reproducibility] and image defect 1 were evaluated, and extremely good evaluations were obtained for all of the above items, regardless of the environmental conditions or the number of durable sheets. In particular, the item [Concentration] deserves special mention, and it was confirmed that a product with extremely high concentration could be obtained. This is also supported by the results of potential measurements; for example, when compared with a case where no treatment is applied to the surface of the amorphous layer, 1.
It was found that the acceptance potential was improved by about 2 to 1.5 times, and it was inferred that the effect of preventing charge injection from the surface by nitrogen atom doping was 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 showed that extremely clear images can be maintained under any environmental conditions. This is considered to be the effect of providing the nitrogen atom concentration distribution in region C of the amorphous layer as shown in Figure 4, and there is a clear difference under high humidity conditions from that which does not have such a nitrogen atom concentration distribution. appeared.

Example 2.3 and Comparative Example 1.2 Example 1 except that the thickness of the third layer (area C) of the first layer was variously changed by changing the deposition time. A photoreceptor drum was produced in the same manner as in Example 1. When the same image evaluation as in Example 1 was performed on this photoreceptor drum, the results shown in Table 2 were obtained.

Example 4.5 and Comparative Examples 3 to 5 The conditions were the same as in Example 3, except that the flow rate of ammonia gas was variously changed in the formation of the third layer (area C) of the first layer. A photoreceptor drum was manufactured using the method. When the same image evaluation as in Example 1 was performed on this photoreceptor drum, the results shown in Table 3 were obtained.

Examples 6 and 7 Photoreceptor drums 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 photoreceptor drum were as shown in FIGS. 5 and 6, respectively. As a result of performing image evaluations on these photoreceptor drums in exactly the same manner as in Example 1, good results almost equivalent to those in Example 1 were obtained in all cases.

Example 8 The first layer was formed on a drum-shaped photoconductive member formed according to the same conditions and procedures as in Example 1.6.7, respectively. Sample 9 in which the second layer was formed by the sputtering method according to the conditions shown in Table 6-1.
Example 1 except that the species and conditions shown in Table 6-2 were changed.
15 types of samples (Samples at 8-1-1 to 8-1-8.8-6-1 to B -6-
A total of 24 samples (8, 8-7-1 to 8-7-8) were created.

Each of the electrophotographic image forming members obtained in this manner was individually installed in a copying machine, and
Corona charging was performed for a while, and a light image was irradiated.

゛The light source uses a tungsten lamp, and the light intensity is 1.01u.
x fist sec. The latent image was developed with a highly charged developer (containing toner and carrier) and transferred to regular paper. The transferred image was extremely good.

Toner that was not transferred and remained on the electrophotographic imaging member was cleaned with a rubber blade. Even when this process was repeated over 10,000 times, no image deterioration was observed in any case.

Table 7 shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability through repeated and continuous use.

Example 9 When forming the second layer by the sputtering method, the target area ratio of the silicon wafer and graphite was changed, and the content ratio of silicon atoms and carbon atoms in the second layer was changed. Each of the imaging members was made in exactly the same manner as in Example 1. For each of the imaging members thus obtained, similar to Example 1,
After repeating the steps of image formation, development, and cleaning 10,000 times, image evaluation was performed, and the results shown in Table 8 were obtained.

Example 1O Completely the same method as in Example 1 except that when forming the second layer, the flow rate ratio of SiH4 gas and C2H4 gas was changed to change the content ratio of silicon atoms and carbon atoms in the second layer. Each of the imaging members was prepared by: For each of the image forming members thus obtained, the image forming, developing, and cleaning steps similar to those in Example 1 were repeated 10,000 times, and then image evaluation was performed, and the results shown in Table 9 were obtained. .

Example 11 When forming the second layer, SiH4 gas, SiF4 gas, C2
Example 1 except that the content ratio of silicon atoms and carbon atoms in the second layer was changed by changing the flow rate ratio of H4 gas.
Each of the imaging members was made in exactly the same manner. For each of the imaging members thus obtained,
When image evaluation was performed after repeating the same steps of image formation, development, and cleaning 100,000 times as in Example 1, the 10th
The results shown in the table were obtained.

Table 6-1 During sputtering, supplying Ar at 200 SCCM No. 6
- 2 Table x+5iH4/He=t, xzsiH4/He=0
．． 5, HsiF4/He=0.5

[Brief explanation of the drawing]

FIG. 1 is a diagram schematically showing a layer structure for explaining an embodiment of the structure of a photoconductive member of the present invention. Second
Figures a to 2h are diagrams schematically showing the concentration distribution of nitrogen atoms and atoms of group Ⅰ of the periodic table in the first layer of the photoconductive member of the present invention. FIG. 3 is a diagram showing an apparatus for manufacturing a photoconductive member using a glow discharge decomposition method. 4 to 6 are diagrams showing the analysis results of the concentration distribution of constituent atoms of the photoconductive member in the example of the present invention. 100: Photoconductive member 101: Support 102: First layer 103: Area AlO4: Area B 1
05: Region C106: Second layer 1101: Reaction chamber 1102~ll0EI: Gas cylinder 1107~1111: Mass flow controller 1112~
111B: Inflow valves 1117-1121: Outflow valves 1122-1126: Valves 1127-1131: Pressure regulator +132: M auxiliary valve 1133: Main valve 11
34: Gate valve 1135: Leak valve 113
6: Vacuum gauge 1137: Base cylinder 113
8: Heater 1139: Motor 1140:
High frequency power supply (matching box) 11E 2a
' Figure 2b Figure 2c Figure 2d Figure 2
e Figure 21 Figure II 2
9 Figure III 2h
Figure 4

Claims (1)

[Claims] l) a support, and a photoconductive Ml provided on the support and containing an amorphous material based on silicon atoms;
and a second layer provided on the first layer and containing silicon atoms and carbon atoms as essential components, wherein the first layer is a layer of the layer. In order from the support side in the thickness direction, a region A containing atoms of group (I) of the periodic table, a region B not containing atoms of group (I) of the periodic table,
and a region C containing an atom of Group I of the periodic table and a nitrogen atom.