JPS6029754A - Photoconductive material for electrophotography - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 that is incorporated into an electrophotographic apparatus used in an office as a business machine, pollution-free property 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.
German Publication No. 2,855,718 describes an application to an electrophotographic image forming member, and German Publication No. 2,933,411 describes an application to a photoelectric conversion/reading device.

However, a photoconductive member having a photoconductive layer composed of conventional a-5i 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 require 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, it has often been observed in the past 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.

Furthermore, according to many experiments by the inventors of wood, etc., it has been found that the material used for forming the photoconductive layer of an electrophotographic image forming member is the material (7).
A-5i has many advantages compared to conventional inorganic photoconductive materials such as SE, CAS, and ZnO, or organic photoconductive materials such as PVCz and TNF, but it has many advantages for use in conventional solar cells. a-5i with characteristics added
Even if the light-distributing conductive layer of an electrophotographic imaging member has a photoconductive layer of an intermediate layer Ml)k, which is composed of
ay) is extremely fast, and preferably electrophotography is difficult to apply, and in addition, the above tendency is remarkable in a humid atmosphere, and in some cases, the electrostatic charge may hardly be retained until the phenomenon time, etc. It turns out that there are many issues that need to be resolved.

Furthermore, when the photoconductive layer is composed of a-5i material,
In order to improve its electrical and photoconductive properties, hydrogen atoms, hydrogen atoms, halogen atoms such as elementary atoms and chlorine atoms, and boron atoms, phosphorus atoms, etc. to control the electrical conductivity type, or other Other atoms are contained in the photoconductive layer as constituent atoms in order to improve the properties, but depending on the manner in which these constituent atoms are included, problems may arise in the electrical and photoconductive properties of the formed layer. may occur.

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-9i photoconductive member is made by a generally known method, it may be necessary to use a photoconductive layer that is not sufficiently long because, for example, the lifespan of photocarriers generated in the photoconductive layer formed 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 unclear, perhaps because excessive optical carriers generated near the surface of the photoconductive layer flow in the lateral direction.

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-3i 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 from the viewpoint of applicability and applicability of a-3i 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 (H) and a halogen atom (X), that is, so-called hydrogenated a-Si
, halogenated a-Si or halogen-containing hydrogenated a-
In a photoconductive member having a photoconductive layer containing α-5i (hereinafter referred to generically as α-5i(H, This photoconductive material not only exhibits extremely superior properties in practical use, but also surpasses conventional photoconductive materials in all respects, especially as a photoconductive material for electrophotography. This is based on the fact that it has been found to have 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 ordinary electrophotographic methods can be applied extremely 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 in laminated living rooms.

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 layer contains at least one kind of atom selected from Group Ⅰ of the periodic table and a nitrogen atom, and the nitrogen atom is contained in the second layer from the part above the center of the layer in the thickness direction of the layer. For atoms of Group Ⅰ of the periodic table, the layer has a concentration distribution such that the concentration of atoms thereof increases toward It is characterized by having a concentration distribution having a maximum concentration.

The photoconductive member of the present invention, in which the photoconductive layer has the above-described layer structure, can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates the characteristics and 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 6i visual images with high image density, clear halftones, and high resolution, and has excellent light fatigue resistance, repeated use characteristics, and It has excellent characteristics for repeated use in humid atmospheres.

Hereinafter, one photoconductive member of the present invention will be explained in detail with reference 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 2i 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.

The photoconductive member 100 of the present invention comprises a-9i, preferably a-3t()1. A photoconductive first layer 102 containing X) as a main component is formed, and a second layer 103 containing silicon atoms and carbon atoms as essential components is further formed on this first layer 102. Formed and composed.

The photoconductive member 100 of the present invention has a-9i (
Amorphous layer 10 containing photoconductivity as main components
2 is formed and configured.

The nitrogen atoms doped (contained) in the first layer have a substantially uniform concentration distribution in the direction parallel to the support surface, but have a substantially uniform concentration distribution in the layer thickness direction. As shown in the figure (the vertical axis shows the distance from the support and the horizontal axis shows the atomic concentration), the nitrogen atomic concentration increases from the center of the layer toward the layer junction interface with the second layer. It has a concentration distribution. Note that the nitrogen atom concentration from the central portion of the layer toward the surface on the side where the support is provided may have a constant concentration distribution as typified by FIG. 2a, or It may have a concentration distribution in which the nitrogen atom concentration increases, as typified by FIG. 2b.

On the other hand, regarding the atoms of group Ⅰ of the periodic table doped into the first layer, the concentration distribution is almost uniform in the direction parallel to the support surface in the layer, similar to the concentration of nitrogen atoms. , regarding the layer thickness direction, Figures 28 to 2 are shown in Figure 28 (the periodic table group Ⅰ atoms are represented by boron, and the atomic concentration scale on the horizontal axis is not the same as that for nitrogen atoms). The maximum concentration is at or near the end face on the side where the support is provided. It should be noted that the concentration distribution of Group Ⅰ atoms of the periodic table from the central part of the layer toward the second layer increases as the nitrogen atom concentration increases, as typified by Figure 2a. It is preferable to have a concentration distribution.

In addition, the portion having the maximum nitrogen atom concentration or the portion having the maximum Group Ⅰ atom concentration of the periodic table within the layer is represented by the layer as shown in Fig. 2d and ffs2i, respectively. It may have a certain length in the thickness direction or it may be just one point, and furthermore, the manner in which the concentration of these atoms increases toward the edge of the layer must be continuous. Although it is more preferable, there is no problem even if the density distribution changes stepwise, and the type of density distribution to be provided should be appropriately selected depending on the functions required of the image forming member and the manufacturing equipment of the photoconductive member. belongs to.

In this way, the photoconductive member of the present invention has a first layer in which nitrogen atoms and atoms of group Ⅰ of the periodic table are formed so as to have the above-mentioned atomic concentration distribution with respect to the layer thickness. When used as a photoreceptor for photography, image smearing does not occur even when the image density is particularly high and the image exposure amount is high, halftones appear clearly, and the resolution is high.
The reason why high-quality visible images can be obtained is due to the high resistance effect of the first layer having a photoconductive layer due to nitrogen atom doping, and the nitrogen concentration near the layer interface between the first layer and the second layer. Extremely good charge-accepting ability is achieved due to the wide cap of the energy band of the part due to the high atomic concentration, and the effect of preventing charge injection from the support side due to doping with atoms of group Ⅰ 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, the excess carriers generated there will move anywhere when an electric field is applied, canceling out the charge in the dark part, and as a result, the image It is understood that flow occurs, but the wide gap described above increases the activation energy for carrier generation even if there is complex bending of the energy band at the layer junction interface, making it easier to generate carriers. does not occur. The reason why it is more preferable to have a concentration distribution in which the atoms of group Ⅰ of the periodic table from the central part of the layer toward the second layer increases in accordance with the increase in the concentration of nitrogen atoms is that As the concentration of nitrogen atoms increases toward the concentration of nitrogen atoms, the number of nitrogen atoms doped as a toner also increases, and in order to compensate for this, the number of atoms of group Ⅰ of the periodic table is also increased.

The concentration of nitrogen atoms doped in the first layer is preferably 0.1 to 57 atomic in the portion where the concentration is maximum, that is, in the vicinity of the layer junction interface with the layer of wS2.
%, more preferably 1-51-57ato%, optimally 5-5? atomic%, and in the part where the concentration is minimal, that is, in or near the central part of the layer, it is preferably 0.005 to 35 atomic%, more preferably 0.01 to 30 atomic%, optimally 0.
．． It is set at 5 to 25 atoaic%.

The maximum content concentration and the minimum content concentration of nitrogen atoms are determined within the above numerical range as appropriate according to the content concentration of group Ⅰ atoms of the periodic table, respectively. In order to more effectively achieve the object of the present invention, it is desirable to increase the concentration of each of them.

Further, the maximum concentration is preferably 1.05 times or more, more preferably 11 times or more, and most preferably 1.15 times or more, as compared to the minimum concentration.

In addition, the content of Group I atoms of the periodic table is usually 80-LX 1 in the part where the concentration is maximum, that is, in the end face of the layer on the side where the support is provided or in the vicinity thereof.
05105ato ppm, preferably 100-5X
104ato+nic ppm, optimally 150~I
XIO4 atomic ppm, while in the minimum part, i.e. the central part of the first layer, it is usually 1 to 4 atomic ppm.
1001000ato pp+o, preferably 5-70
0 atomic ppm, optimally 10-500ato
It is desirable that it be set to ic pp+1.

The above-mentioned maximum content concentration and minimum content concentration are respectively determined within the above numerical range according to the content concentration of nitrogen atoms, but in the present invention, each content concentration is increased in accordance with the content concentration of nitrogen atoms. Desirable for achieving objectives more effectively. In addition, the maximum concentration is preferably at least twice the minimum concentration, more preferably 3 times or more, and more preferably 3 times the minimum concentration.
It is desirable to double or more.

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.

Examples of the Group I atoms of the periodic table to be doped in the first layer include boron, aluminum, potassium, .thallium, and thallium, 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, No.
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.

That is, for example, if it is glass, NiC is applied to the surface of the glass.
r, Ai, Cr, No, Au, It, Nd,
Ta, V, Ti, Pt, Inz03.51102,
Conductivity is imparted by providing a thin film made of ITO (In203+5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr,
AI, Ag, Pb, Zn, Ni, Au, Cr,
A thin film of metal such as No., 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, and then Provides electrical conductivity.

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., the thickness 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-Si (H1x) by the glow discharge method, hydrogen atoms are basically used together with a raw material gas for supplying Si that can supply silicon atoms (Si). (H) Raw material gas for introduction and/or raw material gas for halogen atom (X) introduction, and raw material gas for nitrogen atom (N) introduction and atoms of group Ⅰ of the periodic table depending on the constituent atomic composition of the formation region. The raw material gas for introduction may be replaced with Ar if desired.
, , He and other inert gases are introduced into a deposition chamber whose interior can be reduced in pressure at a predetermined mixing ratio and maximum gas flow to generate a glow discharge in the deposition chamber and remove these gases. By forming a plasma atmosphere of , a-9i (
A layer consisting of H, X) is formed.

In addition, when forming the first layer by a sputtering method, a target made of Si is sputtered in an atmosphere of inert scum such as Ar or He, or a mixture of scum using these scum as a pace. At this time, depending on the scum for introducing hydrogen atoms (H) and/or halogen atoms (X), and the raw material gas for introducing nitrogen atoms (N) and for introducing atoms of group Ⅰ of the periodic table, depending on the constituent atomic composition of the formation area. All you have to do is deposit the raw material waste into a deposition chamber for sputtering.

The raw material scraps for supplying Si used to form the first layer include 5it14, Si2H6,5IsHs
, 5i4H+o and other silicon hydrides (silanes) in a scum state or capable of becoming scum are considered to be effectively used, especially in terms of ease of handling in layer creation work, good S1 supply efficiency, etc. Preferred examples include SiH4 and Si2H6.

In order to introduce hydrogen atoms into the first layer in the present invention,
Mainly B2 or the above SiH4,5i2) 16.5
This is carried out by supplying a silicon hydride gas such as i3HB or 5i4H+o 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 scum, halides, interhalogen compounds, and halogen-substituted silanes. Preferred examples include halogen compounds that are in a dregs state or can be dregs-formed, such as derivatives. Furthermore, a gaseous or dregs-forming compound containing silicon atoms and halogen atoms,
Silicon compounds containing halogen atoms can also be mentioned as effective.

In the present invention, the halogen compounds that can be suitably used for forming the first layer include fluorine,
Halogen gas such as chlorine, bromine, iodine; BrF,
CIF, ClF3, BrF3, BrF5, IF3,
Examples include interhalogen compounds such as 1F7, ICI, and far.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, SiF
4. Silicon halides such as Si2F6.5ill<, 5iBr+ can be mentioned as preferable ones. The raw material residue when introducing halogen atoms into the first layer includes the above-mentioned halogen compounds or halogen-containing silicon halides. Silicon compounds are used as effective ones, but in addition) IF, 8C1, HBr, old isohydrogen halide, 5rHzFz, 5iH212゜5iH
2C12, 5iHC13, 5iH2Br 2.5iHB
Gaseous or gasifiable halides having a hydrogen atom as one of their constituents, such as /\halogen-substituted silicon hydride such as r3, 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 the nitrogen atom.

In the present invention, the raw material gas for supplying nitrogen atoms used to form the first layer includes N as a constituent atom.
For example, nitrogen (N2), ammonia (NH3), hydrazine (H2NN)+2) hydrogen acyde (NH3).

Nitrogen compounds such as gaseous or gaseous nitrogen such as ammonium azide (N)14N3), nitrides, and azides can be mentioned. 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 gas for supplying atoms of group Ⅰ of the periodic table used to form the first layer is B2)1.
6, B4HIO1B5 B9, B5HII, B611
]0. GaCl3, AlCl3, 8F3.8CI3,
BBr3, BI3, etc. can be mentioned.

To form the first layer made of a-Si(H, Sputtering is performed in a predetermined gas plasma atmosphere, and in the case of the ion plate ink method, polycrystalline silicon or single crystal silicon is placed in a deposition boat as an evaporation source. This can be carried out by heating and evaporating the flying evaporated material using a beam method (EB method) or the like 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. and raw material gas for introducing nitrogen atoms (N) and raw material gas for introducing Group Ⅰ atoms of the periodic table according to the constituent atomic composition of the formation region, He, A as necessary.
It is sufficient to introduce an inert gas such as r into the sputtering or ion blating chamber to form a plasma atmosphere of the gas.

To control the amount of hydrogen atoms, /\rogen atoms, and nitrogen atoms contained in the first layer, for example, hydrogen atoms (H), /\rogen atoms (X), nitrogen atoms, One or more of the following may be controlled: the amount of the starting material used to contain atoms (N), atoms of group Ⅰ of the periodic table, introduced into the deposition system, the temperature of the support, the discharge power, and the like.

In the present invention, the diluting gas used when forming the first layer by the claw discharge method or sputtering method is 3i! Preferred examples include He, Ne, Ar, and the like.

The second layer 103 formed on the photoconductive first layer 102 in the present invention has a free surface and is mainly resistant to moisture, continuous repeated use characteristics, electrical pressure resistance, and usage environment. This is provided in order to achieve the object 1 of the present invention in terms of 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 103 in the present invention is made of an amorphous material (hereinafter referred to as a-(Si
x C+ −X )y 01. X) Written as ly,
However, O<x, y<1).

a-(1; 1xC+-x)y()1. The formation of the second layer composed of X)+-y is performed 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, equipment capital investment load, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. The glow discharge method has the advantages that it is relatively easy to control the conditions for manufacturing the conductive member, and it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the second layer to be produced. Alternatively, a sputtering method is preferably employed. Further, the second layer may be formed using a glow discharge method and a sputtering method in combination within the same device system.

To form the second layer by the claw 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 gas is introduced into a deposition chamber for vacuum deposition in which the body is installed, and the introduced gas is turned into a regas plasma by generating a glow discharge, and is deposited on the photoconductive first layer on the support. a-
(Sig c, -x)y ()1. X) ly
All you have to do is deposit it.

In the present invention, a-(Sjg C+ -X)y
(H, Most gaseous substances or gasified substances containing gaseous substances can be used.

When using a raw material gas having Sl as a constituent atom as one of Si, C, H, and X, for example, a raw material gas having Sl 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 whose constituent atoms are Si and X at a desired mixing ratio. Examples include mixing raw material scraps consisting of atoms or raw material scraps containing three constituent atoms of Si, C, and X at a desired mixing ratio.

Alternatively, as another method, a raw material gas containing Sl and H as constituent atoms and a raw material gas containing C as constituent atoms may be mixed, or a raw material gas containing Si and X as constituent atoms may be used. You may use a mixture of w, w, and dregs having C as a constituent atom.

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

In the present invention, SiH containing Si and H as constituent atoms is effectively used as the raw material waste for forming the second layer.
Silicon hydride scum such as 4,5izH6,Si:+Hs, 5i4H+o; C and H as constituent atoms, for example, saturated hydrocarbons with a1 to 4 carbon atoms, ethylene hydrocarbons with 2 to 4 carbon atoms, carbon Examples include acetylenic hydrocarbons having 2 to 4 atoms; simple halogens; hydrogen halides: interhalogen compounds; silicon halides; halogen-substituted silicon hydrides.

Specifically, saturated hydrocarbons include methane, ethane,
Propane, n-butane, pentane; ethylene hydrocarbons include ethylene, propylene, butene-1, butene-2, j-butylene, pentene; acetylene hydrocarbons include acetylene, methylacetylene, butyne; as a single halogen Ha, fluorine, a! Halogen residue of chlorine, bromine, and iodine; hydrogen halides include HF, old,
HClHBr; Interhalogen compounds include CIF,
ClF3, ClF5, BrF, BrF3, BrF
5, IF5, IF7, IC1, IBr; silicon halides include SiF4.5i2Fc+, 5iCI4
, 5iCI3Br, 5iC12Elr2, SiC:1
Br3. Mu every mu.

5iCI31. SiBr4; As the halogen-substituted silicon hydride, SiH2F2.5iH2CI2.5iH
C13,5it (3C:l, 5IH3Br, 5rH2B
Examples include r2.5IHBr3.

In addition to these, CF4, CCl4, CBr4, CHF3
, Cl2F2, CH3F, CHsCl, C)
I: +Br, (d131. Halogen-substituted paraffinic hydrocarbons such as C2H5Cl, fluorinated sulfur compounds such as SF4, SF6; 5i(C)I3)4, Si(C2
H5) alkyl silicide such as 4; 5iCI(tl:H
3) 3.5iCI□(CH3)2, 5iC13CH3
Silane derivatives such as halogen-containing alkyl silicides can 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 S as a substance containing a halogen atom: HCl3.5iH2CI2, 5iC14 or 5
A-(Six c, -X)y (H,XL
A second layer consisting of -y 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 used as a target, and these are mixed as necessary. Sputtering may be performed 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 forming a gas plasma of these residues.

Also, separately, Si and C are used as separate target feet.
Alternatively, this can be accomplished by using a single target sheet made of a mixture of Si and C, and performing sub-interisolation in a gas atmosphere containing hydrogen atoms and/or halogen atoms, if 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:
So-called rare gases, such as He, Me, ^r, etc., can be mentioned as suitable gases.

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

In other words, substances whose constituent atoms are Si, C, and optionally H and/or Properties between properties and insulation,
In addition, since each exhibits properties ranging from photoconductive properties to non-photoconductive properties, in the present invention, a-(SiXC,-1i)y (H,X
6) For example, when the second layer is provided with the main purpose of improving the electrical withstand voltage, a-
(Six C, ->l)y (H,

In addition, if a second layer is provided with the main purpose of improving the characteristics of continuous repeated use or the characteristics of the usage environment, the degree of electrical insulation described above will be relaxed to some extent, and the second layer will have a certain degree of sensitivity to the irradiated light. As the second amorphous material, a-(S
ix c, -X )y (H,X) +-y is created.

a-(Slx C+ -x) on the surface of the 117th) layer
When forming the second layer consisting of y (H, In the present invention, a-(St, c, -
It is desirable that the temperature of the support during layer formation be tightly controlled so that X )y (H,X) +-y can be formed as desired.

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, preferably 1
It is desirable that the temperature be 00 to 300°C. Second
For the formation of this layer, glow discharge and sputtering methods are advantageous because delicate control of the composition ratio of atoms constituting the layer is relatively easy compared to other methods. When forming the second calendar 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)+-y
It can be cited as one of the important factors that influence the characteristics of.

a-(SiXc, -X)y (H,X)I having the characteristics to effectively achieve the object of the present invention
The discharge power conditions for producing -y efficiently and efficiently are preferably 10 to 300 W, more preferably 20 to 250 W, and most preferably 50 to 200 W. It is.

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

In the present invention, the formation factors such as the desired numerical range of the support temperature and discharge power for creating the second layer cannot be determined independently and separately, but are , -X)y (H,X)'+-y
In the photoconductive member of the present invention, the optimum value of each layer formation factor is determined based on the mutual organic relationship so that the second layer is formed from □. The carbon atoms contained in the layer, as well as the conditions for forming the second layer, are important factors for forming the second layer that provides the desired properties that achieve the object of the present invention. There is one.

The amount of carbon atoms contained in the second layer according to the present invention is determined as desired depending on the characteristics of the amorphous material constituting the '*2O' layer.

That is, the general formula &'-(SIXC+ -X)y (
The amorphous material represented by Hl, x), -y can be roughly divided into silicon atoms and a-9ilCt-@, but
< a < 1), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as a-(Sib c,
-b)c Written as HI-e, provided that 0 < b,
c < 1), an amorphous material r(
Hereinafter, a-(Si, C+-, +)a()1. XL-a
It is written as However, it is classified as Q<d, a<1).

In the present invention, when the second layer is composed of a-5iaC+-, the amount of carbon atoms contained in the second layer is preferably I x 10' -90 atomic%, more preferably 1 -81-80ato%, optimally 10-
? It is desirable that it be 5 atomic%.

That is, if we represent a in the previous a-5i, C+-, then a
is preferably 0.1 to Q, 9!398! II, more preferably 0.2-0.89, optimally 0.25-0.9.

On the other hand, in the present invention, the second layer is a-(Sib C+ -b )e (H,X) I-0
In this case, the amount of carbon atoms contained in the second layer is preferably IX 10' -90 atomic%, more preferably 1 to 90 atoIIIic%.

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

That is, the previous a-(SibC+-b)c(H,X)+-0
b is preferably 0.1 to o, 5ss9
s, more preferably 0.1 to 0.99, j & suitably 0.1
5 to 0.9, C is preferably 0.6 to 0.99, more preferably 0.65 to 0.88, optimally 0.7 to 0.8
5 is desirable.

The second layer is a-(Si, +C+-,+)e(H,x)
+-e, the content of carbon atoms contained in the second layer is preferably l x 10-3
~906 toiic%, more preferably 1 to 90 atoms
ic%, preferably 10 to 80 atomic%. The content of halogen atoms is preferably 1 to 20 atomic%, more preferably 1-+8 atomic%, and optimally 2 to 15 atomic%.
It is preferable to set the halogen atom content to mic%, and photoconductive members prepared when the halogen atom content is within this range can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably +9ato
It is desirable that the content be mic% or less, more preferably 13 atomic% or less.

That is, the previous a-(Si4 c,-, ha (H,X)+
- If expressed as d and e of a, d is preferably 0.
1 to 0.8θ9θ8, more preferably 0.1 to 0.99, optimally 0.15 to 0.8, e is preferably 0.8 to 0.
99, more preferably 0.82 to 0.88, optimally 0.
It is desirable that it is 85 to 0.88.

The numerical range of the layer thickness of the second layer in the present invention is appropriately determined according to the desired 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 economic efficiency, taking into account productivity and souvenirs.

The thickness of the second layer in the present invention is preferably 0.
．． 003 to 30 tiles, more preferably 0.004 to 20 tiles,
The optimum range is preferably 0.005 to top.

In the case of the claw discharge method, the amount of carbon atoms contained in the second layer Φ can be controlled, for example, by adjusting the flow rate of gas introduced into the deposition chamber for introducing carbon atoms,
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 the Mne 1 sludge introduced into the deposition chamber for introducing halogen atoms.

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 pumps 1102 to 1106 in the figure are sealed with raw material waste for forming the amorphous layer of the photoconductive member of the present invention.
H4 gas (purity se, ss%) cylinder, 1103t B
B2H6 gas diluted with 2 (purity 9L99%, hereinafter B
2H6/B2 gas) cylinder, 1104 is NH3 gas (purity 99.99%) cylinder, 1105 is CH4 gas (purity 119.99%) cylinder, 1106 is SiF4
A gas (purity 99.1119%) cylinder is not shown, but other than these, desired gas types can be added as needed.

In order to flow these gases into the reaction chamber 1101, each valve 1122 to 112 of the gas pump 1102 to 110B is
Check that B and leak valves 1X35 are closed, and also check that inlet valves 1112 to 1116 and outlet valves
)Rev 1117-1121 and auxiliary valve 1132.1
Make sure that 133 is open, and then go to main/<
Lube 1134 is opened to exhaust the reaction chamber 1101 and gas piping. Next, the reading of vacuum gauge 1138 is about 5X 1G4
When the torr is reached, the auxiliary valve 1132, the valve 33 and the outflow loop 111? ~Close 1121. Next, from gas cylinder 1102, SiH4 cassette, gas cylinder 11
B2H6/)12 gas from 03, NH3 gas from gas pump 1104, CH4 gas from gas pump 1105, and SiF4 scum from gas pump 1105 by opening valves 1122 to 112B and outlet pressure gauges 1127 to 1.
131 is adjusted to IKg/0m2, and the inflow valves 1112 to 111B are gradually opened to flow into the mass flow controllers 91107 to 1111. Subsequently, outflow valve 111? ~1121 and auxiliary valve 1132.
1133 is gradually opened to supply each gas to the reaction chamber 1101.
to flow into. At this time, adjust the outflow valve tttv~1121 so that the ratio of the flow rates of each of these gases 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.

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 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, NH3 gas and B2H6/
By appropriately changing the B2 gas flow rate and correcting the plasma state that changes accordingly, the discharge power,
The first layer is formed by controlling the substrate 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 once evacuated to high vacuum. When the reading on the vacuum gauge 113fi reaches approximately 5X 104 torr, repeat the same operation as above, open the operating system valves for SiH4, CH4, and diluent gas such as He if necessary, and check the flow rate of each raw material gas. Control it to the desired value,
Glow discharge is generated in the same manner as in the case of the first layer, and the second layer is
layers are formed. When containing halogen atoms in the second layer, open the SiF4 operation valve at the same time,
All that is required is to generate a glow discharge.

Examples will be described below.

Example 1 Using the photoconductive member manufacturing apparatus shown in FIG. 3, a first photoconductive material was deposited on an AI cylinder according to the manufacturing conditions shown in Table 1 by the glow discharge decomposition method described in detail above. layer and a second layer were formed. 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 mass spectrometer, and the concentration distribution results shown in Figure 4 were obtained. I got it. In addition, the remaining part of the drum-shaped photoconductive member was set in an electrophotographic device, and the charging corona voltage was +6 KV, and the image j1 light was 0.8 to 1.51.
A latent image was formed using ux/sec, and then the development, transfer, and fixing processes were performed using well-known methods, and the image was evaluated. Images equivalent to 10,000 sheets were taken out, and images equivalent to 150,000 sheets were taken out in a high-temperature environment, and the [density] [resolution] of each image was determined for each sample of -
Evaluations were made based on the quality of gradation reproducibility, image defects, etc., and extremely good evaluations were obtained for all of the above items, regardless of environmental conditions or the number of durable sheets. In particular, the item [Em degree] is noteworthy, 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, it was found that the acceptance potential was improved by about 2 to 2.5 times compared to a product without nitrogen atoms added. It was inferred that the synergistic effect of increasing the resistance by doping and preventing charge injection by changing the boron atom content 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 the first
The fourth layer has a maximum portion near the bonding interface with the second layer.
This seems to be the effect of creating a nitrogen atom concentration distribution as shown in the figure.
The difference between these and those without such a nitrogen atom concentration distribution was obvious.

Example 2 A drum-shaped photoconductive member was produced in the same manner as in Example 1, except that the concentration distribution form of nitrogen atoms and boron atoms was changed. Details of the manufacturing conditions are shown in Table 1. Regarding this drum-shaped photoconductive member, the constituent atomic concentration analysis and image evaluation were carried out in exactly the same manner as in Example 1. As a result, the nitrogen atom and boron atom concentration distribution results shown in FIG. 5 were obtained. In addition, good results almost equivalent to those of Example 1 were obtained regarding image evaluation.

Comparative Example 1 and Examples 3 to 5 Concentration distribution form of nitrogen atoms and boron atoms.

A drum-shaped photoconductive member was produced in the same manner as in Example 1 except for the changes shown in FIG. 6 (Comparative Example 1) and FIGS. 7 to 9 (Examples 3 to 5). The same image evaluation as in Example 1 was performed on these drum-shaped photoconductive members. As a result, for the drum-shaped photoconductive member of Comparative Example 1, the image was good under normal conditions, but under high-temperature conditions, image deletion occurred after the 120,000th sheet. On the other hand, with respect to the drum-shaped photoconductive members of Examples 3 to 5, very excellent contrast images were obtained, and no image deletion occurred even under high temperature and high humidity conditions.

Example 6 The first layer was formed on a drum-shaped photoconductive member formed according to the same conditions and procedures as in Examples 1 and 2. Nine types of samples were formed using the sputtering method described in Table 771.3-1, and the same conditions as those shown in Table 3-2 were used. Fifteen types of samples (Samples 6-1-1 to 6-1-8, 6-2-1 to 8-8- 2
-8, e-3-1 to [1-3-8 total of 24 samples)
It was 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
・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 remaining on the electrophotographic imaging member without being transferred is
Cleaned with rubber blade. Even when this process was repeated over 10,000 times, no image deterioration was observed in any case.

Table 4 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 7 The same procedure was carried out except that when forming the second layer by sputtering 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 fiS5 were obtained.

Example 8 Completely the same method as 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 6 were obtained. .

Example 9 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,
The same steps of image formation, development, and cleaning as in Example 1 were repeated 10,000 times, and then image evaluation was performed, and the results shown in Table 7 were obtained.

3-1 During table sputtering, 200 SCCH of Ar was supplied.
-2 Table

[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. Second
Figures a to 2d 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. 4.5.7-9
The figure is a diagram showing the analysis results of the constituent atomic concentration distribution of a photoconductive member in an example of the present invention. FIG. 6 is a diagram showing the analysis results of the constituent atomic concentration distribution of a photoconductive member of a comparative example. 100: Photoconductive member 101: Support 102: First, Fj 103: Second layer 1101: Reaction chamber 1102~+10θ: Gas cylinder 1107~1111: Mass flow controller 1st, 2~
1118: Inflow valve 1117-1121: Outflow valve 1122-1128: Valve 1127-1131: Pressure regulator +132: Auxiliary valve 1133: Main valve 11
34: Gate 8 valve 1135: Leak valve 1136
: Vacuum gauge 1137 + base cylinder 113B : Heater 1139 : Motor 1140 : High frequency power supply (
Matching box) Fig. 29 ffi Zh Fig. 2j Fig. 2m Fig. 2n Fig. 21 Fig. 21 Fig. 20 Fig. 2p Fig. 2t Fig. 2r Fig. a , 11 (Ume radical θ ~) Fig. 4 Fig. 5 (K? A#542i1t (A, +, ,) Fig. 6 Fig. 7 Fig. 8 Fig. S Procedure Correction Divination (Method) % formula % 1. Indication of the case 1982 Patent Application No. 58348 2. Name of the invention Photoconductive member 3. Person making the amendment Relationship to the case Patent applicant (1 (to) Canon Co., Ltd. 4, Agent address Tokyo 5, 1-9-20 Akasaka, Miyakominato-ku, Date of amendment order: Date of dispatch: August 28, 1980 6. Column for a brief explanation of the drawings in the specification subject to amendment. 7. Contents of amendment.

Claims (1)

[Claims] l) a support and a photoconductive first layer disposed 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 has a layer according to the periodic table. Contains at least one type of atom selected from group (3) and a nitrogen atom, and the concentration of nitrogen atoms increases from the part above the center of the layer to the second layer in the thickness direction of the layer. For atoms of Group Ⅰ of the periodic table, the concentration distribution has an increasing concentration distribution and has a maximum concentration at or near the end face on the side where the support is provided in the layer thickness direction. A photoconductive member comprising: