JPS59184357A - Photoconductive material - Google Patents

Abstract

PURPOSE:To form an electrophotographic photoconductive material capable of obtaining an image high in density, sharp in halftone, high in resolution, and superior in quality by forming a photoconductive layer contg. an amorphous material composed essentially of Si atom consisting of 2 specified layers 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 further, the second layer 105 composed essentially of Si and C is formed on the layer 102. The layer 102 is divided into a lower layer region 103 and an upper layer region 104 in the layer thickness direction from the side of the substrate 101 in accordance with the difference of its constituent elements. The lower region 103 is doped with an element of group III of the periodic table in an almost uniform concn. distribution, and the upper region 104 is doped with an element of group III and N.

Description

Detailed Description of the Invention The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (herein, light in a broad sense refers to ultraviolet light, visible light, infrared light, X-rays, gamma rays, etc.). Regarding.

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. 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 point of view, amorphous silicon (hereinafter referred to as a-8i) is a photoconductive material that has recently attracted attention. The application to an image forming member for use in photoelectric conversion is described, and the application to a photoelectric conversion/reading device is described in German Published Publication No. 2,933,411.

However, the conventional photoconductive member having a photoconductive layer composed of a-3i has poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and temperature resistance. The reality is that there are problems that need to be further improved in terms of usage environment characteristics and furthermore, stability over time, which requires comprehensive improvement of characteristics.

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 photoconductive When a member is used repeatedly for a long period of time, fatigue due to repeated use may accumulate, resulting in a so-called ghost phenomenon in which an afterimage occurs.

Further, for example, according to many experiments conducted by the present inventors, it has been found that -c noa
-si has many advantages compared to conventional inorganic photoconductive materials such as c7)Se, CdS, and ZnO, or organic photoconductive materials such as PVGz and TNF, but its characteristics for use in conventional solar cells are a-9i given
Even when the photoconductive layer of an electrophotographic image forming member having a single-layer photoconductive layer is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast; It is 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 phenomenon time. .

Furthermore, when the photoconductive layer is composed of a-3i material,
In order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and boron atoms and phosphorus atoms to control the electrical conductivity type, or other properties modification. For 1°L, other atoms are
Each of these constituent atoms is contained in the photoconductive layer, but depending on the manner in which these constituent atoms are contained, problems may occur in the electrical and photoconductive properties of the formed layer.

In particular, at the interface between adjacent layers, the content of contained atoms,
Depending on the distribution state, etc., dangling bonds are likely to occur during the manufacturing process, and complex bending of energy bands is likely to occur.

For this reason, the various changes in charge behavior and structural stability issues are especially important, and control of these areas holds the key to success or failure in order for the photoconductive member to perform its intended function. There are quite a few.

In addition, in the case where the a-Si photoconductive member is made by a generally known method, for example, the lifetime of photocarriers generated in the formed photoconductive layer by light irradiation is not sufficient. You may not be able to obtain a good image density, or
Alternatively, when the image exposure amount is large, the image tends to become blurred due to the lateral flow of excess optical carriers generated near the surface of the photoconductive layer, and furthermore, charge injection from the support side In many cases, problems arise due to insufficient prevention. Therefore, while efforts are being made to improve the properties of the a-3i material itself, it is necessary to take measures to obtain the desired electrical and optical properties as described above when designing photoconductive members. be.

The present invention has been made in view of the above points, and from the viewpoint of applicability and applicability of a-Si as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive and intensive research, a-
An amorphous material based on Si, especially a silicon atom, and containing at least one of a hydrogen atom ()l) and a halogen atom (X), that is, the so-called hydrogenated a-S
i, halogenated a-8i or halogen-containing hydrogenated a
- Designed and created to specify the layer structure of a photoconductive member having a photoconductive layer containing Si (hereinafter referred to generically as a-9i(H,X)) The resulting photoconductive material not only exhibits extremely superior properties in practical use, but also surpasses conventional photoconductive materials in all respects, and is particularly superior as a photoconductive material for electrophotography. This is based on the discovery that it has certain characteristics.

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 electrophotographic image forming member, it has sufficient charge retention ability during charging processing for electrostatic image formation, and that ordinary electrophotography is extremely effective. An object of the present invention is to provide a photoconductive member having excellent electrophotographic properties that can be applied.

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. and a second layer containing silicon atoms and carbon atoms as essential components.
From the support side with respect to the layer thickness direction of the layer, a lower layer containing atoms of group Ⅰ of the periodic table throughout the layer thickness direction, and an upper layer containing atoms of group Ⅰ of the periodic table and nitrogen atoms. It is characterized by consisting of.

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, can obtain high-quality visible images with high image density, clear halftones, and high resolution, and has excellent light fatigue resistance and repeated use characteristics, especially Excellent for repeated use under humid atmosphere.

The photoconductive member of the present invention will be described in detail below with reference to one drawing.

FIG. 1 and FIGS. 2a to 21 are diagrams schematically showing the layer structure for explaining embodiments of the structure of the photoconductive member of the present invention.

The photoconductive member 100 of the present invention, as shown in FIG. A conductive Ml layer 102 is formed, and a second layer 105 containing silicon atoms and carbon atoms as essential components is further formed on this first layer 102.

The first layer 102 is formed from the support side to the lower layer (lo
3) and an upper layer (104).

The atoms of group Ⅰ of the periodic table doped (contained) in the F part layer (+o3) have a nearly uniform concentration distribution state in the direction parallel to the support surface in the lower layer, but the layer thickness Regarding the direction, as shown in FIGS. 28 to 21 (the vertical axis shows the distance from the support, the horizontal axis shows the atomic concentration, and the atoms of group Ⅰ of the periodic table are represented by boron), The concentration distribution becomes non-uniform. The lower layer (103) is
A region A located on the support side that contains atoms of Group II of the Periodic Table at a relatively high concentration, and a region A located on the upper layer side that contains atoms of Group II of the Periodic Table at a lower concentration than the region A. Area B
A preferred embodiment is comprised of the following. Area A
In region B, the concentration distribution of atoms of group m of the periodic table may be uniform or non-uniform, or in any of these regions, It may have a distribution in which the concentration decreases toward the layer.

The thickness of region A in the layer thickness direction is preferably 20A to 20μ.
, more preferably 30A to 15μ, optimally 40A to 1
It is considered to be 0 scales. Further, the content of atoms of group Ⅰ of the periodic table in the region A is preferably 30 to 5× 10′ atoms
c ppa+, more preferably 50-5X 104a
tomicppm, optimally 100-5X 1103
It is referred to as atoIlicpp. When the atoms of group M of the periodic table are contained so as to have an unrestricted concentration distribution in region A, the maximum concentration of atoms of group I of the periodic table in the region is preferably 80 to IXIO5 atomic pp.
m, more preferably 100-5X 105atoIl
ic”ppm, optimally 150~IX 105105a
to ppm.

The thickness of region B in the layer thickness direction is preferably 1 to +007L
II, more preferably 1 to 80 houses, optimally 2 to 50 houses. It is preferable that the atoms of group 1 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 80 μm, and most preferably 2 to 50 μm.

The concentration of atoms of group m of the periodic table in the region B is as follows:
It is desirable that the atom is contained in a lower concentration than the concentration of the atom in the atom. Further, it is desirable that the atoms are contained at a lower concentration than the concentration of the atoms in the upper layer (104), preferably 0.01 to 1 x 103atoIIlic pp
m, more preferably 0.5-3X 102102ato
ppm, optimally 1-100100ato ppm
It is said that

The atoms of Group 1 of the periodic table doped into the upper layer (+04) 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 20A-15IIJI, more preferably 30A-10u, and optimally 40A-5μ. The concentration of Group I atoms of the periodic table in the upper layer is preferably 0.01" IX 10' atomic ppm,
More preferably 0.5-5X103 atomic pp
m, optimally 1-I X 103103ato pp
It is assumed that m.

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 second layer. As shown in the figure (the atomic concentration scale on the horizontal axis is not the same as for boron atoms), it does not matter whether the change is continuous or stepwise. Further, the portion having the maximum nitrogen atom concentration near the second layer may have a certain length in the layer thickness direction as shown in FIG. 2C, or may have a certain length in the layer thickness direction as shown in FIG. 2A. Even if it's just one point, it's okay. When nitrogen atoms are contained in the upper layer in a non-uniform distribution state, the concentration of nitrogen atoms in the upper layer is at the maximum concentration, that is,
At the layer interface with the second layer, preferably 0.1 to 57
ato+sic%, more preferably 1 to 5? atoa+
ic%, optimally 5 to 57 ato+*ic%, and in the part where the concentration is minimal, that is, the boundary with the lower layer, preferably θ to 35 atomic%, more preferably θ to 30 atomic%, optimally Q ~25a
tomic%.

The photoconductive member of the present invention has a first layer formed such that the concentration of nitrogen atoms and atoms of group Ⅰ of the periodic table has the above-mentioned atomic concentration distribution with respect to the layer thickness. When used as an image forming member for photography, it is a high-quality product that does not cause image deletion even when the image density is particularly high and the image exposure amount is high, halftones appear clearly, and high resolution is achieved. The reason why a visible image can be obtained is the effect of increasing the resistance of the first layer by doping with nitrogen atoms, and the high concentration of nitrogen atoms at the interface between the first layer and the second layer, which increases the energy of this part. Extremely good charge-accepting ability is achieved by widening the gap of the band, and the effect of preventing charge injection from the support side and the effect of increasing the resistance of the first layer due to doping with atoms of group Ⅰ of the periodic table. It is presumed that it is based on In other words, if there is an interface between the upper and lower layers of the first layer, excess carriers generated there will move wherever an electric field is applied, canceling out the charge in the dark area, and It is understood that image blurring occurs as a result, but in the first layer of the present invention, due to the wide gap described above, even if complex bending of the energy band occurs at the interface of this layer, carrier generation is prevented. The reason why atoms from group Ⅰ of the periodic table are contained at a low concentration in region B in the lower layer, where the activation energy for This is because the charge acceptance ability is improved, and as a result, higher turbidity of the image can be expected, and furthermore, higher sensitivity is also expected due to the increase in hole mobility. Note that the reason for containing Group I atoms 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 they are added to compensate for this. It is something. Furthermore, although it has not been confirmed, it is expected that the first layer will have consistency due to the fact that the entire first layer contains atoms from group Ⅰ of the periodic table, although the doping concentration is different, and this also helps prevent image blurring. It is presumed that it is working effectively.

In the present invention, specific examples of the halogen atom (X) that may be contained in the first layer include fluorine, IM chlorine, bromine, and iodine, and chlorine, particularly fluorine, is particularly preferred. be able to.

Examples of the Group I atoms of the periodic table to be doped into the first layer include boron, aluminum, gallium, indium, thallium, etc., and boron is particularly preferred.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the electrically conductive support include NiCr, stainless steel, AI, Cr, Mo,
Au, Nb, Ta, V, Ti, Pt, Pd
Metals such as these or alloys thereof can be mentioned.

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.

In other words, for example, if it is glass, Ni is deposited on its surface.
(:r, AI, Cr, Mo, Au, Ir, Nd
, Ta, V, Ti, Pt, In2O3,5110
2. Conductivity is imparted by providing a thin film made of ITO (In20* + 5JI02), etc., or if it is a synthetic resin film such as polyester film 11, NiCr, AI, Ag, Pb, Zn, Ni
, Au, Or, No, Ir, Nb, Ta, V
, Ti, Pt, or the like is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, or the like, or the surface is laminated with the metal to impart conductivity to the surface.

The shape of the support is determined as desired, but for example, if the photoconductive member 100 of 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, etc., it is usually set to 1O 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, by the glow discharge method, a-9i()1. X)
In order to form the first layer composed of, basically, together with a raw material gas for supplying Si that can supply silicon atoms (Si), a raw material gas for introducing hydrogen atoms (H) and/or halogen atoms. (X) Depending on the raw material gas for introduction and the constituent atomic composition of the formation region, the raw material gas for nitrogen atom (N) introduction and the raw material gas for introduction of Group Ⅰ atoms of the periodic table may be added to A as desired.
A glow discharge is generated in the deposition chamber by introducing it into a deposition chamber that can reduce the pressure inside the deposition chamber together with an inert gas such as r, He, etc., to generate a glow discharge in the deposition chamber. By forming a plasma atmosphere, a-9i (
A layer consisting of H, X) is formed.

In addition, when forming the first layer by a sputtering method, for example, when sputtering a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, , a gas for introducing hydrogen atoms (H) and/or halogen atoms (X), a raw material gas for introducing nitrogen atoms (N), and a raw material for introducing atoms of Group Ⅰ of the periodic table, depending on the atomic composition of the formation region. The gas may be introduced into a deposition chamber for sputtering.

The raw material gas for Si supply used to form the first layer includes SiH4, Si286, Si3HB
Hydrogenated silicon silicon (silanes) in a gaseous state or that can be gasified, such as , Si, +H+O, can be used effectively, and in particular, they are easy to handle in layer creation work and have good Si supply efficiency. SiH4 and Si286 are preferred in these respects.

In the present invention, in order to introduce hydrogen atoms into the MSL layer, mainly N2 or the above-mentioned 5iH4,5izH6,5
This is carried out by supplying a silicon hydride gas such as i3HB, 5i4H1o, etc. into the deposition chamber 1 to generate an electric discharge.

j′ 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 gases. Preferred examples include gaseous or gasifiable halogen compounds such as silane derivatives. Furthermore, a gaseous or gasifiable compound containing a silicon atom and a halogen atom,
Silicon compounds containing halogen atoms can also be mentioned as effective.

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, CIF;
, ClF3, BrF3, BrF5, HF3, H
Examples include interhalogen compounds such as F7°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, 5il14.3iBz.

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 halides, SiH2F2.5iH21z, 5iH2G
h, 5iHC:13.5iH2Br2.5iHBr
Gaseous or cassizable halides having a hydrogen atom as one of their constituents, such as halogen-substituted silicon hydride 1 such as 3, etc., 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 as constituent atoms.
For example, nitrogen (N2), ammonia (NH3), hydrazine (N2 NNN2), hydrogen azide (HNa),
Mention may be made of gaseous or gasifiable nitrogen such as ammonium azide (NH4N3), and nitrogen compounds such as nitrides and azides. In addition, 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 gases for supplying atoms of group Ⅰ of the periodic table used to form the first layer include B2H6,
N4 Hto, B! l N9, B5H11, Be)
ho, GaCl3, AlCl3, BFa,
BCl3, BBr3, BI3, etc. can be mentioned.

To form the first layer of a-9i (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.

In any case of this VA, sputtering method, or ion blating method, in order to introduce predetermined atoms into the first layer to be formed, hydrogen atoms (H) and/or halogen atoms (X) are introduced. The raw material gas for introducing nitrogen atoms (N) and the raw material gas for introducing atoms of group Ⅰ of the periodic table can be used as necessary depending on the atomic composition of the formation region.
It is sufficient to introduce an inert gas such as Ar into the sputtering or ion blating chamber to form a plasma atmosphere of the gas.

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 1 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 atoms of Group 1 of the periodic table introduced into the deposition system, the temperature of the support, the discharge power, and the like.

In the present invention, so-called gases such as He, He, At, and the like can be suitably used as the diluting gas used when forming the first layer by a glow discharge method or a sputtering method.

The second layer 105 formed on the photoconductive first layer 102 in the present invention has a free surface and is mainly characterized by moisture resistance, continuous cycling properties, electrical pressure resistance, and use. It is provided to achieve the objectives of the present invention in terms of environmental characteristics and durability.

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

The second layer 105 in the present invention is made of an amorphous material (hereinafter referred to as a-(Si
x c, -X ) y (H, X) ry, where O<x, y<1).

a-(Six C+ -x)y (H,X) +-y
The second layer is formed by a glow discharge method, a sputtering method, an ion implantation method, an ion blating method, an electron beam method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. Glow discharge has the advantages that it is relatively easy to control the conditions for manufacturing the component, and that it is easy to introduce carbon atoms and/\\rogen atoms together with silicon atoms into the second layer. The second layer may be formed by using the glow discharge method and the sputtering method in the same apparatus system.

To form the second layer by the glow discharge method, a-(
Six cl -X ) y (H, The gas is introduced into a deposition chamber for vacuum deposition in which a support is installed, and the introduced gas is turned into a gas plasma by generating a glow discharge, and is deposited on the photoconductive first layer on the support. a
-(Sjx c, -X)y (H,X)ly may be deposited.

According to the present invention, a-(SiXc, -X)y (H
, Most gas forest materials or gasified materials that can be gasified can be used.

When using a raw material gas having Si as a constituent atom as one of Si, 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, If necessary, a raw material gas containing H as a constituent atom and/or a raw material gas containing X 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 C and a raw material gas containing H as constituent atoms and/or C
and a raw material gas having constituent atoms of For example, a gas or a raw material gas containing Si, C, and X as constituent atoms may be 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 M constituent atoms may be used. A mixture of the gas and raw material waste containing C as a constituent atom may be used.

In the present invention, preferred halogen atoms (X) that may be contained in the second layer include F, C1, Br,
I, particularly F and CI are preferred.

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.
4, Si2H6, Si3 H'B, Si4 HIO
Silicon hydride gas such as; C and H as constituent atoms, for example, saturated hydrocarbons having 1 to 4 carbon atoms, 2 to 4 carbon atoms;
Ethylene hydrocarbons of 4, acetylene hydrocarbons having 2 to 4 carbon atoms; simple halogens; halogen'1 1,' hydrogen hydride: interhalogen compounds; silicon halides; halogen-substituted silicon hydrides, etc. .

In terms of size, saturated hydrocarbons include methane, ethane,
Propane, n-butane, pentane; ethylene hydrocarbons include ethylene, propylene, butene-1, butene-2, i-butylene, pentene; acetylene hydrocarbons include acetylene, methylacetylene, butyne;
＼As a single halogen, ＼halogen gases include fluorine, fluorine, bromine, and iodine; as hydrogen halides, HF, old,
HClHBr; Interhalogen compounds include CIF,
ClF3, GIFs, BrF, BrF3, BrF
5, IF5, IF7, [1, IBr; silicon halides include SiF4, Si2 F6.5i
CI4, 5iC13Br, 5iC12Br2.5
iCIBr3, Osomoto5iC131, SiBr4
; As the halogen-substituted silicon hydride, S i H2
F2.5iH2CI2.5iHCI3.5iH3C1,
Examples include 5iH3Br, 5iH2Br2.5iHBra, and the like.

In addition to these, CF4.0C14, (Br4, CHF3
, CH2F2, CH3F, CH3Cl,
Halogen-substituted paraffin hydrocarbons such as CH3tlr, CH31, C2H5Cl, SF4, SF6
Fluorinated sulfur compounds such as S i (CH3)4
.

Alkyl silicide such as 5i(C:2Hs)41; S i
Cl(CH3)3.5iC12(C)13)2,3
Silane rust conductors such as halogen-containing alkyl silicides such as iC13CM3 may also be mentioned as useful.

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, 5i can easily contain silicon atoms, carbon atoms, and hydrogen atoms and can form a layer with desired characteristics.
(C1(3)4 and 5iHC as containing a halogen atom: 13, SiH2012, 5iC14
Alternatively, a-(StXcl-X)y(H,
X) A second layer consisting of ly can be formed.

To form the second layer by the sputtering method, a single crystal or polycrystalline Si wafer and/or C wafer or a wafer containing a mixture of Si and C is targeted, and these are mixed as necessary. /
This can be done by sputtering in various gas atmospheres containing hydrogen atoms and/or hydrogen atoms as constituent elements.

For example, if Si wafer /\- is used as a target, the raw material gas for introducing C, H and/or However, the Si wafer /\- may be sputtered by forming a gas plasma of these gases.

In addition, Si and C are separate targets,
Alternatively, sputtering may be performed in a gas atmosphere containing hydrogen atoms and/or halogen atoms as necessary by using a single target containing a mixture of Si and C.

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:
So-called rare gases, such as He, Ne, Ar, etc., can be mentioned as preferred.

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

That is, a substance containing Si, (E, H and/or In the present invention, a-( Si%c, -X )y (H
, For example, when the second layer is provided with the main purpose of improving electrical voltage resistance.

'a-(Si, CI-x)y (H,
X) +-y is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

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
xC+ -x )y (H,X) +-y is created.

a-(Si, c, -X)y on the surface of the first layer
When forming the second layer consisting of (H, In the invention, a-(SiXc, -X) having the desired properties
It is desirable that the temperature of the support during layer formation be strictly controlled so that y (H,XL-y can be formed as desired6)
In the present invention, the formation of the second layer is carried out by appropriately selecting an optimal range according to the method of forming the second layer in order to effectively achieve the desired purpose.
~400°C, more preferably 50-350°C, optimally
It is desirable that the temperature be 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 way as the support temperature described above. H,X
) +-y (7) It can be mentioned as one of the important factors that influence the characteristics.

a-(Six CI-x)y (H,X) having the characteristics to effectively achieve the object of the present invention
The discharge power conditions for effectively creating ly with good productivity are preferably lO to 300W, more preferably 20 to 250W, and optimally 50 to 200W. .

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 a-(S
It is preferable that the optimum value of each layer creation factor is determined based on the mutual organic relationship so that a second layer consisting of txCs -* )y (H,X) ty is formed. The amount of carbon atoms contained in the second layer of the photoconductive member is the same as the conditions for forming the second layer, so that the second layer can obtain the desired characteristics that achieve the object of the present invention. This is one of the important factors for

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 calendar.

That is, the general formula a-(Si, 1C, -X)y (H
, X) ry can be broadly classified into
An amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as a-3ilG, -a, where 0 < a <
1) An amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as a-(Sib c, -b) e
Written as Hr-6, where 0 < b, c < 1)
, an amorphous material composed of silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms (hereinafter referred to as a-(
SiiCf-a) e(H, xL-0, where O<
d, e<1).

In the present invention, when the second layer is composed of a-3i, IC, -@, the amount of carbon atoms contained in the second layer is
Preferably, I x 10' to 90 atomic%,
More preferably 1 to 80 ata pusic%, optimally 1O to
It is desirable that it be 75 atomic%.

That is, if expressed as a in the above a-Si&C: , -, a is preferably 0.1 to 0.999i3!3, more preferably 0.2 to 0.99, and optimally 0. 25 to 0.9.

On the other hand, in the present invention, when the second layer is composed of a-(SibC+-t,)e(H,xL-1), the amount of carbon atoms contained in the second layer is preferably IX 10 ' ~80 atomic%, more preferably 1~90 atomic%.

The hydrogen atom content is preferably 1 to 40 atom
mic%, more preferably 2 to 356 atomic%, optimally 5 to 30 atomic%,
Photoconductive members formed with hydrogen contents within these ranges are well suited for practical applications.

That is, the first (7)a-(SibC'+-b)c(H,xL
-c, preferably b is 0.1 to 0. ! 3
99H1, more preferably 0.1 to 0.88, most preferably 0.
15-'0.9, C is preferably 0.6-0.89, more preferably 0.65-0.88, most preferably 0.7-0.
95 is desirable.

The second layer is a-(stc+-a)e(o, xL-0
In the case of the second layer, the content of carbon atoms contained in the second layer is preferably 1
atomic%, more preferably 1-90 atomic%
, the optimum value is preferably 10 to 80 atomic%. The content of halogen atoms is preferably 1 to 20 atomic%, more preferably 1 to 20 atomic%.
18 atomic%, optimally 2-15 atomic%
It is desirable that the halogen atom content be within these ranges, so that photoconductive members produced 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 llatomic
% or less, more preferably 13 atomic% or less.

That is, the first (7)a-(S1iC+-1)a(H,XL-
If expressed as d and e of s, d is preferably 0.1
-0.89998, more preferably 0.1-0.99, optimally 0.15-0.9, e preferably 0.8-0.9
9, more preferably C 0.82 to 0.89, optimally 0.
X is preferably 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 consider economic efficiency, which takes into account productivity and mass production.

The thickness of the second layer in the present invention is preferably 0.
．． 0.004 to 20 scales, more preferably 0.003 to 30-1;
The optimum value is 0.005 to 10 u).

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 to form the target. By doing so, it 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 photoconductive layer of the photoconductive member of the present invention.
H4 gas (purity 139.1119%) cylinder, 1103
is 82H6 gas diluted with H2 (911.99% purity)
, hereinafter referred to as B2) 16/H2 gas) cylinder, 1104
is NH3 gas (purity 913.99%) cylinder, 1105
is a CH4 gas (purity 99.99%) cylinder, and 110B is a SiF4 gas (purity 99.'39%) cylinder.0Although not shown in the figure, in addition to these, install additional cylinders of the desired gas type as necessary. Is possible.

In order to cause these dregs to flow into the reaction chamber 1101, each valve 1122 to 112 of the gas pump 1102 to 110B is
8 and leak valve 1135 are closed;
Make sure that valve 3 is open, then open main valve 1 first.
134 is opened to exhaust the reaction chamber 1101 and gas piping. Next, the reading on the vacuum gauge 1138 is approximately 5X 10' to
When rr is reached, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, SiH4 gas from gas cylinder 1102, gas cylinder 1103
B2 H6/H2 gas from the valve 11, NH3 gas from the gas cylinder 1104, CH4 gas from the gas cylinder 1105, and SiF4 gas from the gas cylinder 1106, respectively.
Open 22-112B and check the outlet pressure gauges 1127-113
Adjust the pressure of 1 to IKg/c+s2 and open the inlet valve 1
112 to 1118 are gradually opened to allow the flow into mass flow controllers 1107 to 1111. Subsequently the outflow valves 1117-1121 and the auxiliary valves 1132.1
133 is gradually opened to allow each gas to flow into the reaction chamber 1101. Adjust the outflow valves 1117 to 1121 so that the ratio of these gas flow rates at this time becomes a desired value,
Also, set the vacuum gauge 1 so that the pressure inside the reaction chamber reaches the desired value.
Adjust the opening of the main valve 1134 while checking the reading of 138.

Then, the temperature of the gas cylinder 1137 becomes the heating heater 1.
After confirming that the temperature is set at 50 to 400° C. by 138, *@11ao 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 B2 Ha/l (2 gas flow rate was changed appropriately, and the discharge, power, substrate Region A constituting the lower layer of the first 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 the gas operation system valves used and close the reaction chamber 1.
101 is evacuated to high vacuum. When the reading on the vacuum gauge 1136 reaches approximately 5X 10' torr, repeat the same operation as above to remove SiH4, SiF4,
Open the operation system valve of B2H6/H2, control the flow rate of each raw material waste to the desired value, and generate glow discharge in the same manner as above to form region B that constitutes the lower layer of the first layer. do.

The upper layer constituting the first layer also has a nitrogen atom and boron atom content distribution curve designed in advance by repeating the same operations as described above.

Next, close all the gas operation system valves used and close the reaction chamber 1.
Evacuate tot to high vacuum once. When the reading on the vacuum gauge 1138 reaches approximately 5X 10' torr, repeat the same operation as above, open the operation valves for diluent gases such as SiH4, CH, and He if necessary, and check each source gas. The second layer is formed by controlling the flow rate to a desired value and generating glow discharge in the same manner as in the case of the first 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, a photoconductive 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 drum-shaped photoconductive member was cut out, and the concentration of boron atoms and nitrogen atoms in the layer thickness direction was determined using a secondary ion quality analyzer, and the concentration distribution shown in Figure 4 was obtained. Got the results. Further, the remaining portion of the photoconductive member drum was set in an electrophotographic apparatus, and a latent image was formed using a charging corona voltage of +6 KV and an image exposure of 0.8 to 1.51 ux*see.

Subsequently, the development, transfer, and fixing processes were carried out using well-known methods, and the image evaluation was performed using A4 size paper under normal conditions. In a high-temperature, high-humidity environment, images equivalent to 10,000 sheets were produced, and the quality of each image, such as density, resolution, gradation reproducibility, and image defects, was determined for each 10,000-sheet sample. An evaluation was conducted, and extremely good evaluations were obtained for all of the above items, regardless of environmental conditions or 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 to a photoconductive layer with no treatment applied to the surface, the acceptance potential is improved by about 1.4 to 1.7 times. It was clarified that the effect of preventing charge injection from the surface by doping with nitrogen atoms and the effect of doping with boron atoms were sufficiently effective. This improvement in charge acceptance ability is not limited to just image density, but also allows for a wider latitude of corona conditions, expanding the range of image quality selection.
It has the great advantage of being able to

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 the second
This may be due to the effect of providing the upper layer with a nitrogen atom concentration distribution as shown in Figure 4, and there was a clear difference under high humidity conditions compared to a layer that did not have such a nitrogen atom concentration distribution.

Example 2.3 and Comparative Example 1.2 The same method as in Example 1 except that the thickness of the third layer (upper layer) was variously changed by changing the deposition time. A drum-shaped photoconductive member was produced.

When this photoconductive member was subjected to the same image evaluation as in Example 1, the results shown in Table 2 were obtained.

Example 4.5 and Comparative Examples 3 to 5 A drum-shaped light 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 conductive member was produced. When this photoconductive 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 photoconductive 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 photoconductive member were as shown in FIGS. 5 and 6, respectively. As a result of performing image evaluations on these photoconductive members 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 Examples 1, 6, and 7, respectively. 57-52179, the second layer was formed under the conditions shown in Table 6-1, and the second layer was formed under the conditions shown in Table 6-2. Fifteen types of samples (Samples 8-1-1 to 8-18. -1~8-8-8.8-
A total of 24 samples (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 1.01ux
*Second. 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 The same as Example 9 except that when forming the second layer by spacilling method, the target area ratio of 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 100,000 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 100,000 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, S+Fa gas, C2
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 created in exactly the same manner as in Example 1. For each of the image forming members thus obtained, the same image forming, developing, and cleaning steps as in Example 1 were repeated 100,000 times, and then image evaluation was performed, and the results shown in Table 10 were obtained. .

6-1 Table 6-2 Supplying 200 SCCM of Ar during sputtering
Table MI Si)+4/He=1, M2S1To/H
e=0.5, xsiF4/)Ie=0.5

[Brief explanation of 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. 2nd a
Figures 1 to 21 are diagrams schematically showing the concentration distribution of nitrogen atoms and atoms of group m 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: Lower layer 104: Upper layer 10
52 second layer + 101: Reaction chamber 1102-ll0EI: Gas cylinder 1107-1111: Mass flow controller 1.11
2 to 1118: Inflow valves 1117 to 1121: Outflow valves 1122 to 1128: Valve 1127 to 1131: Pressure regulator

Claims (1)

[Claims] 1, a support, and a conductive first layer 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 the thickness direction, from the support side, the layer is composed of a lower layer containing atoms of group Ⅰ of the periodic table throughout the layer thickness direction, and an upper layer containing atoms of group Ⅰ of the periodic table and nitrogen atoms. A photoconductive member.