JPS59184358A - 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 N atom and an element of group III in a nonuniform concn. distribution in the layer thickness direction with respect with the element of group III.

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 ('I
p) / (Id) ], has absorption spectrum characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has the desired dark resistance value, and is non-polluting to the human body during use. In addition, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages within a predetermined time. Particularly, 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-9i) is a photoconductive material that has recently attracted attention. The application to a photo-electric conversion/reading device is described in DE 2933411, respectively.

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 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.

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).
Although a-9i has many advantages compared to conventional inorganic photoconductive materials such as Se, IEdS, and Zr+0, or organic photoconductive materials such as PVCz and TNF, it does not have the characteristics necessary for use in conventional solar cells. 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; Tsutomu's electrophotography method is difficult to apply;
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-9i material,
In order to improve its electrical and photoconductive properties, hydrogen atoms or halogen atoms such as fluorine atoms and chlorine atoms are added, and boron atoms and phosphorus atoms are added to control the electrical conductivity type, or other properties are improved. Therefore, other atoms are contained in the photoconductive layer as constituent atoms, 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. There are cases.

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 the energy band may occur.

For this reason, the various changes in charge behavior and structural stability issues are particularly important, and in order to exhibit photoconductive properties and desired functions, it is necessary to control these parts.
When you hold the key to success or failure, you have to use a lot of power.

In addition, when the a-3i photoconductive member is made by a generally known method, the formed photoconductive property may be insufficient due to the fact that the lifetime of photocarriers generated by light irradiation in the layer is not sufficient. You may not be able to obtain a good image density, or
Or, when the image exposure amount is large, the image tends to become blurred due to the fact that excess light carriers generated near the surface of the photoconductive layer flow in the lateral direction. Insufficient prevention of charge injection,
%, which often causes problems. Therefore.

While efforts are being made to improve the properties of the a-3i material itself,
When designing a photoconductive member, it is necessary to take measures to obtain the desired electrical and optical properties as described above.

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 comprehensively neglecting thorough research consideration, a-
9i, especially an amorphous material having a silicon atom as a matrix and containing at least one of a hydrogen atom (H) and a halogen atom (X), that is, so-called hydrogenated a-Si
, /\ halogenated a-9i or halogen-containing hydrogenated a
-9i (hereinafter these will be collectively referred to as a-9i(l(,X)
In a photoconductive member having a photoconductive layer containing a photoconductive layer containing: This is based on the discovery that it is superior in all respects to conventional photoconductive materials, and that it has particularly excellent properties as a photoconductive material for electrophotography. .

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.
From the support side, a lower layer containing atoms of group (I) of the periodic table; a lower layer containing nitrogen atoms and atoms of group (I) of the periodic table; and an upper layer containing a concentration distribution that is non-uniform with respect to the direction.

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.

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

FIG. 1 is a diagram schematically showing a layer structure for explaining an embodiment of the structure of a photoconductive member of the present invention. 2nd-
Figures 1 to 2-15 are diagrams schematically showing the degree distribution of atoms of Group Ⅰ of the periodic table in the lower layer of the first layer of the photoconductive member of the present invention, and Figures 3-1 to 3 Figure 38 shows nitrogen and elemental atoms in the upper layer of the first layer of the photoconductive member of the present invention, and
FIG. 2 is a diagram schematically showing a group atom concentration distribution.

As shown in FIG. 1, the photoconductive member 100 of the present invention has a photoconductive material containing a-3i, preferably a-9i (H, A first layer 102 is formed, and the first layer 1
A second layer 105 containing silicon atoms and carbon atoms as essential components is formed on 02.

The first layer 102 is formed from the support side to the lower layer (103) due to the difference in the constituent atomic composition in the layer thickness direction.
and an upper layer (104).

The atoms of group Ⅰ of the periodic table doped (contained) in the lower layer (103) have a nearly uniform concentration distribution state in the layer in the direction parallel to the support surface, but in the layer thickness direction. It assumes a non-uniform concentration distribution state. Such non-uniform concentration distribution states are shown in Figures 2-1 to 2-15.
Figure (vertical axis shows distance from support, horizontal axis shows atomic concentration,
(Illustrated with boron atoms representing Group Ⅰ atoms of the periodic table), the maximum concentration is at or near the end surface on the side where the support is provided, and the concentration is higher toward the upper layer. It is preferable that the concentration distribution is such that the contained atomic density is reduced. In this case, the manner in which the atomic concentration decreases toward the upper layer may be continuous, as typically shown in Figure 2-2, or as typically shown in Figure 2-2. It is okay even if it changes in a step-like manner. Further, the portion near the support having the maximum concentration of Group I elements of the periodic table may have a certain length in the layer thickness direction as representatively shown in Figure 2-1. , even if it is just one point as shown in Figure 2-2. Furthermore, it is not necessary that the elements belonging to Group 1 of the periodic table are contained throughout the entire lower layer; (2) There may be a region that does not contain group members.

The thickness of the lower layer ('103) in the layer thickness direction may be determined as desired, but is preferably between 1 scale and 1 scale.
100JLI11, more preferably Igm~80 decoys, optimally 2μ·~50 decoys.

In the present invention, the content of Group I elements of the periodic table contained in the lower layer (103) is determined by the characteristics required for the lower layer, its film thickness, and the amount of the element provided directly on the upper part of the layer. It is determined as appropriate and desired in terms of the organic relationship with the properties required for the upper layer and the efficiency of mass production. From this point of view, the content of Group I elements of the periodic table contained in the lower layer is preferably 0.01 to 5X 10
'atomic ppm, more preferably 0.5-I
X 10' atomic ppm, optimally 1-5X
It is desirable that the content be 103103 at ppm.

In addition, if the Group Ⅰ elements of the periodic table are contained unevenly in the layer thickness direction in the lower layer, a high concentration may occur at or near the end face of the layer on the side where the support is provided. The maximum value of the concentration distribution of Group I elements of the periodic table in the layer thickness direction is preferably 80 to lx1.
05atomic ppn+, more preferably 100
~5X105 atomic ppm, optimally 150~
IX 10' atomic ppm is desirable. When a layer region containing a high concentration of Group I elements of the periodic table is provided at the end of the lower layer on the side of the support, the layer thickness of the region is preferably 20A to 20A, more preferably 20A to 20A. is 30A to 15mm, optimally 40A -10u
It is said that

Nitrogen atoms and Group Ⅰ elements of the periodic table doped into the upper layer (104) have a substantially uniform concentration distribution state in the direction parallel to the support surface, but in a preferred embodiment, 1 Regarding the layer thickness direction, see Figures 3-1 to 3-36.
Figure (vertical axis shows distance from support, horizontal axis shows atomic concentration,
Group II elements of the periodic table are represented by boron atoms, but the atomic concentration scale is not the same for both groups. It has a concentration distribution such that the concentration of contained atoms increases from the side toward the second layer. The pattern of increase in the atomic concentration toward the second layer may be continuous or stepwise; The part with the maximum concentration is
It may have a certain length in the layer thickness direction as shown in FIG. 3-6, or it may be just one point as shown in FIG. 3-1.

On the other hand, nitrogen atoms may have a uniform concentration distribution within the layer, or may have a non-uniform (continuously or stepwise changing) concentration distribution. However, it is preferable that nitrogen atoms also have a concentration distribution such that the concentration of nitrogen atoms increases from the lower layer toward the second layer, as in the case of Group I elements of the periodic table.

The thickness of the upper layer is preferably 20A to 15μ, more preferably 30A-104, and optimally 40A to 5 tiles.

The concentration of Group I elements of the periodic table in the upper layer is preferably 30 to 5X 104104a in the portion where the concentration is maximum, that is, in the vicinity of the layer interface between the first layer and the second layer.
to ppm, more preferably 50 to 1×1O'ato
mic ppm, optimally 100-5X 103ato
+iic ppm, and in the part where the concentration is minimal, that is, in the boundary part with the lower layer, it is preferably O-1
0-1O00ato pP+1, more preferably 0-8
00 atomic ppm, optimally O~800ato
It is desirable to set it to mic ppm.

On the other hand, the concentration of nitrogen atoms in the upper layer is determined as desired when forming the upper layer, but is preferably IX 10-" to 57 atomic%.
, more preferably 1 to 50 atomic%, most preferably 5 to 45 atomic%. When nitrogen atoms have a content moisture distribution, the concentration is preferably 0.1 to 57 atomic%,
More preferably 1 to 57 atomic%, optimally 5 to 57 atomic%
57 atomic%, and in the part where the concentration is minimal, preferably 0 to 35 atomic%, more preferably 0 to 30 atomic%, optimally 0 to 20-2
It is assumed to be 5ato%.

The photoconductive member of the present invention has a first layer formed in such a manner that the concentration of nitrogen atoms and atoms of group Ⅰ of the periodic table has the above-mentioned atomic concentration distribution in the layer thickness direction. When used as an image forming member for electrophotography, image blurring does not occur even when the image density is particularly high and the image exposure amount is high, halftones appear clearly, and high resolution and high resolution are achieved. The reason why you can get quality visible images is
The effect of increasing the resistance of the first layer by doping with nitrogen atoms and the
Due to the high concentration of λ nitrogen atoms on the surface near the layer interface with the second layer of the layer, the energy band of this part becomes wide-gap, and an extremely good charge-accepting ability is achieved. This is believed to be based on the effect of preventing charge injection from the support side by doping with group atoms. In other words, if there is a layer junction interface between the -L part layer of the first layer and the lower layer, excess carriers generated here will move anywhere when an electric field is applied, causing an effect that cancels out the charges in the dark part. However, in the first layer of the present invention, the wide gap described above prevents carrier generation even if complex bending of the energy band occurs at the layer bonding interface. The activation energy for this increases, and carrier generation does not occur easily. This is desirable in order to achieve the object of the present invention more effectively. Further, it is desirable that the maximum content concentration is preferably twice or more, more preferably three times or more, as compared to the minimum content concentration.

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 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 conductive support include N1Gr, stainless steel, and AI.

Cr, Mo, Au, Nb, Ta, V, Ti,
Examples include metals such as PL and Pd, and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinyl chloride 7, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. 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, 1. For example, if it is glass, NiC is applied to the surface of the glass.
r, A1. Or, No, Au, Ir, Nd, Ta,
V,? i, Pt, l11203, 5nOz, I
Conductivity is imparted by providing a thin film made of TO (In203+ 5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr,
AI, Ag, Pb, Zn, Ni, Au, Or,
Mo, Ir, Nb, Ta, V, Ti, P
Conductivity is imparted to the surface by providing a thin film of metal such as T on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal.

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 cases, from the viewpoint of manufacturing and handling of the support, as well as mechanical strength, etc., it is usual.

It is said to be more than 10 scales.

In the present invention, a-Si()1. To form the first layer composed of X), 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-8i (H, Depending on the raw material gas for introducing hydrogen atoms (H) and/or the raw material gas for introducing halogen atoms (X), and the raw material gas for introducing nitrogen atoms (N) according to the constituent atomic composition of the formation region, the raw material gas for introducing nitrogen atoms (N) and the periodic table No. The raw material gas for introducing group atoms may be Ar 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 gas flow rate, and a glow discharge is generated in the deposition chamber to generate a plasma of these gases. By forming an atmosphere, a-3i (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 supplying Si used to form the first layer includes SiH4, S! 2H6, S! 3Hg, S
Silicon hydrides (silanes) in a gaseous state or that can be gasified, such as i 4 Hto, can be effectively used, especially in terms of ease of handling in one-layer production work and good Si supply efficiency. Preferred examples include SiH4 and Si2H6.

In order to introduce hydrogen atoms into the first layer in the present invention,
Mainly N2 or the above SiH4, Si2H6,5i
This is carried out by supplying a silicon hydride gas such as 3Hs, 5i4H1o, etc. into the deposition chamber to generate an electric discharge.

In the present invention, many halides are effective as the raw material gas for introducing halogen atoms that can be used to form the first layer, such as halogen scum, halides, interhalogen compounds, and halogen-substituted silanes. Preferred examples include gaseous or gasifiable halogen compounds such as 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, CI
F, ClF3, BrF3, BrF5, IF3, IF
7, ICI, IBr, and other interhalogen compounds.

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, 5iC14, and SiBr4.

As a 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, IF, HCI, HBr, Old hydrogen halides, SiH2F2.5iH212, 5iH2C
1z, 5iHCla, 5iHzBr2.5iHBr3
Halogen-substituted silicon hydrides such as halogen-substituted silicon hydrides, etc., gaseous or gasifiable halides having hydrogen atoms as one of their constituents, such as halogen-substituted silicon hydrides, etc., can also be mentioned as effective starting materials for forming the first layer.

These halides containing hydrogen atoms can be used to introduce halogen atoms 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 N as a constituent atom.
For example, nitrogen compounds such as nitrogen (N2), ammonia (NH3), hydrazine (H2NNH2), hydrogen azide (HN3), ammonium azide (NH4N3), gaseous or gasifiable nitrogen, nitrides, azides, etc. be able to. In addition to this, nitrogen trifluoride (F3
N) Halogenated nitrogen compounds such as nitrogen tetrafluoride (F4 N2 ) can be mentioned.

In the present invention, the raw material gas for supplying atoms of group Ⅰ of the periodic table used to form the first layer includes B2H,
B4) 1to, B5 B9, B5) 111.86
HIOlGaC13, AlCl3, 8F3, 8C
I3, BBr3, BI3, etc. can be mentioned.

In order to form the first layer made of a-5i(H, Sputtering is carried out in a predetermined gas plasma atmosphere, and in the case of the ion blating method, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is used by a resistance heating method or an electron beam method ( EB method)
This can be carried out by heating and evaporating the flying evaporated material by, for example, passing through a predetermined gas plasma atmosphere.

At this time, in both the sputtering method and the ion blating method, in order to introduce predetermined atoms into the first layer to be formed, hydrogen atoms (H) and/or halogen atoms (X) must be introduced. Depending on the constituent atomic composition of the formation region, the raw material gas for introducing nitrogen atoms (N) and the raw material gas for introducing atoms of group Ⅰ of the periodic table may be used as necessary.
It is sufficient to introduce an inert gas such as r 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, 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 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, so-called rare gases such as He, Ne, Ar, etc. 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 repeated use characteristics, electrical pressure resistance, and usage environment. It is provided in order to achieve the object of the present invention in terms of characteristics and durability.

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
,, written as C+ -X)y (H,X) +-y,
However, 0 < x, y < 1).

The formation of the second layer composed of a-(Sixc, -x)y (H, Implemented by. 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 method or A sputtering method is preferably employed. Further, the second layer may be formed by using both the glow discharge method and the sputtering method within the same apparatus system.

To form the second layer by the glow discharge method, a-(
A raw material gas for forming SiXc, -X)y (HlX)ry is mixed with a diluent gas at a predetermined mixing ratio as necessary, and the support on which the photoconductive first layer is formed is prepared. The introduced gas is introduced into a deposition chamber for vacuum deposition, and the introduced gas is converted into a regas plasma by generating a glow discharge, and a-
(SiXc, -%)y (H,X)ly may be deposited.

In the present invention, a-(Six CI-X)y (H
, Most gaseous substances or gasified substances that can be gasified may be used.

When using a raw material gas containing Si as one of Si, C, H, and X, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing 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 H) and/or a raw material gas containing C and X as constituent atoms at a desired mixing ratio, or alternatively, a raw material gas containing Si as constituent atoms, S
Raw material gas or S containing three constituent atoms: i, G and H
An example is given in which a raw material gas having three constituent atoms, i, C, and X, is mixed at a desired mixing ratio.

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

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

In the present invention, Si, whose constituent atoms are Si and :H, is effectively used as the raw material gas for forming the second layer.
Silicon hydride gas such as H4, Si2H6, 5i3HB, 5i4H1o, etc. - saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and carbon atoms having 〇 and H as constituent atoms Examples include acetylenic hydrocarbons having a number of 2 to 4; 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, i-butylene, and pentene; acetylene hydrocarbons include acetylene, methylacetylene, butyne; are halogen gases such as fluorine, chlorine, bromine, and iodine; hydrogen halides include HF, Hl,
IClHBr; Interhalogen compounds include CIF,
ClF3, ClF5, BrF, BrF3, BrF
5, IF5. IF7. ICI, IBr; As silicon halide, SiF4, Si2F6.5iG
14, 5iC13Br, 5iC14Br2.5i
CIBr3, Ushihisha, 5iC131, 5iBz;
As the halogen-substituted silicon hydride, 5iHzFz, 5
iH2CI2.5iHC13, SiH3Cl, 5jJ(
3Br-, 5iH2Br2.5iHBr3, etc. can be mentioned.

In addition to these, CF4. GO+4, CBr4, CHF
3, CH2F2, CH3F, Cl5CI,
()+3Br, CI+31. C2) Halogen-substituted paraffinic hydrocarbons such as 1sc1, SF4, SF6
Fluorinated sulfur-poor compounds such as; ! 1ii(CH3)4.
5i(CzHs)4. Alkyl silicide such as; 5iC1
(CH3)3, SiC+2 (CH3)2, 5iC13
Silane derivatives such as halogen-containing alkyl silicides such as CH3 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 5iHC13, 5iH2C12, 5iC14 or Si as containing a halogen atom
A-(StXC,-11)y (H,X) +-y is produced by introducing HC1 etc. in a predetermined mixing ratio into the second layer forming apparatus in a gas state to generate a glow discharge.
A second layer consisting of:

In order to form the second layer by the sputtering method, a medium-crystalline or polycrystalline Sl wafer and/or a C wafer or a wafer containing a mixture of Si and C is targeted, 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 -'S i wafer is used as a target, the raw material scraps for introducing C, and/or However, the S1 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 using a single target containing a mixture of Si and C in a gas atmosphere containing a hydrogen atom or/and a halogen atom, 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 dilution residue 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.

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-(Six cl -X )y (H,
X) The formation conditions are strictly selected according to the desired conditions so that I-y is formed.6 For example, when the second layer is provided with the main purpose of improving electrical withstand voltage, a
-(SiXc, -X)y (H,

In addition, when a second layer is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the degree of electrical insulation mentioned above is relaxed to a certain extent, and the layer has a certain degree of sensitivity to the irradiated light. As an amorphous material, a-(Si
Xc, -X)y ()1. X) ly is created.

a−(Sixc, −X)y(
When forming the second layer consisting of H, In,
a, -(StXC, -X)y having the desired properties
It is desirable that the temperature of the support during layer formation be tightly controlled so that (H,X)ry 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, 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.

Similar to the support temperature described above, the discharge power during layer formation is created by a-(SjxC:+-x)y(H,xL-y
(7) It can be mentioned as one of the important factors that influence the characteristics.

6 a-(Six C+ -x)y (H,X) having the characteristics to effectively achieve the object of the present invention
The discharge power conditions for effectively creating +-y with good productivity are preferably 10 to 300 W, more preferably 20 to 250 W, and optimally 50 to 200 W. .

The gas pressure in the deposition chamber is preferably 0. O1~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
Preferably, the optimum value of each layer creation factor is determined based on the mutual organic relationship so that a second layer consisting of tXc, -X)y (H,X)ly is formed. The amount of carbon atoms contained in the second layer of the photoconductive member of the present invention 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. It is one of the important factors for formation.

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

That is, the general formula a-(Six c, -X)y (H,
X) The amorphous material represented by ly can be broadly classified as an amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as
It is written as a-S l@C1-a. However, 0 < a <
1) An amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as a-(Slb (+ -b)
c Written as H+-e, however, 0 < b, c < 1
), an amorphous material composed of silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms (hereinafter a-l
Si4Ct-a). ()1. It is written as XL-0.

However, it is classified as O < d, e < 1).

In the present invention, when the second layer is composed of a-9ilG, -@, the amount of carbon atoms contained in the second layer is
Preferably, I x 10' to 90 atomic%,
More preferably 1 to 80 ato+wic%, optimally 10
It is desirable that the content be 75 atomic%. That is, if a is expressed as a-9i, IC, -, a is preferably 0.1 to 0.99999, more preferably 0.2 to 0.99, and optimally 0.25. ~0.9.

On the other hand, in the present invention, the second layer is a-(Sib cl -b )e (H,X) t-0
In this case, the amount of carbon atoms contained in the second layer is preferably IX 10' to 80 atomic%, more preferably 1 to 90 atomic%.

The content of hydrogen atoms is - preferably 1 to 40 at
omic%, more preferably 2 to 35 atomic%,
Optimally, it is desirable that the hydrogen content be 5 to 30%, and photoconductive members formed when the hydrogen content is in this range are excellent in practical applications and can be fully applied. .

That is, the previous a-(Sib Ct -b). (H,X)
, -cl 17) b is preferably o, t
~0.913999, more preferably 0.1-0.99,
Optimally 0.15-0.9, C preferably 0.6-0
．． 99, more preferably 0.65-0.98, optimally 0
．． It is desirable that it is 7-0.95.

The second layer is a-(Sib cl-d)@(H,X
) When the second layer is composed of l-s, the content of carbon atoms contained in the second layer is preferably lXl0
-3 to 90 atomic%, more preferably 1 to 90 at
It is desirable that the optimum omic% is 10 to 80 atomic%. The content of halogen atoms is preferably 1 to 20 atomic%, more preferably 1 to 18 atomic%, most preferably 2 to 15 atomic%.
It is preferable that the content be atomic%, and photoconductive members prepared when the halogen atom content is within these ranges can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably 1
9 atomic% or less, more preferably 13 atomic%
% or less (desirable).

That is, the first (7)a-(Si4Ct-a)a(H-x)t
−6(7) d, e 17) If expressed as
t ~ 0.88, optimally 0.15-0.8, e preferably 0.8-0.9B, more preferably 0.82-0.9
8. The optimum value is 0.85 to 0.98.

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

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

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

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

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

FIG. 4 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.
iH4 gas (99.99% purity) cylinder, 1103 is H
82 H6 gas (purity 99.99%, hereinafter abbreviated as B2 H6/H2 gas) diluted with 2, 1104 is N
H3 gas (purity 99, H%) cylinder, 1105 is CH4
Gas (purity 99.89%) cylinder, 110B is a SiF gas (purity 99.99%) cylinder 0 Although not shown, it is possible to add other desired gas types as necessary. .

In order to flow these gases into the reaction chamber 1101, the valves 1122 to 112 of the gas cylinders 1102 to 110θ are
B and leak valves 1135 are closed, and inlet valves 1112 to 1l16. Outflow valves 1117-1121 and auxiliary valves 1132.113
Make sure that valve 3 is open, then open main valve 1 first.
134 is opened to evacuate the reaction chamber 1101 and gas piping. Next, the vacuum gauge 1138 reads 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, B2)+6/H2 gas from gas cylinder 1103, and N from gas cylinder 1104.
H3 gas, from the gas cylinder 1105 (H4 gas, SiF4 gas from the gas cylinder 110B, respectively) Lube 11
Open 22-112B and check the outlet pressure gauges 1127-113
Adjust the pressure of 1 to IKg/c 2, and reduce the inflow pressure to 111
Gradually open 2-111B and install mass flow controller 1.
107 to 1111. Continuing to leak luku rube! 117~(121 and auxiliary valve 1132.11
33 is gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the outflow valves 1117 to 1121 are adjusted so that the ratio of these gas flow rates becomes the desired value, and the vacuum gauge 11 is adjusted so that the pressure inside the reaction chamber becomes the desired value.
Adjust the opening of the main valve 1134 while checking the reading of 38.

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, in order to obtain a pre-designed boron atom content curve, the 82 H6/H2 gas flow rate is changed appropriately, and the discharge, etc. to form the lower layer of the first layer.

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 1138 reaches approximately 5X 10-@torr, repeat the same operation as above to remove SiH4, SiF4, N
Open the operation system valve of H3, 8286/H2, control the flow rate of each raw material gas to the desired value, generate a glow discharge in the same manner as above, and adjust the content of nitrogen atoms and boron atoms designed in advance. forming an upper layer of the first layer having a distribution curve;

Next, close all the gas operation system valves used and close the reaction chamber 1.
101 is once evacuated to high vacuum. When the reading on the vacuum gauge 1138 reaches approximately 5X 1G' torr, repeat the same operation as above, open the operation system valves for SiH4, CH4, and diluent gases such as He if necessary, and adjust the flow rate of each raw material gas. is controlled to a desired value, and a glow discharge is generated in the same manner as in the case of the first layer to form the second layer. When a halogen atom is contained in the second layer, the 5iF4 (7) operating system 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. 4, 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 mass spectrometer, and the concentration distribution results shown in Figure 5 were obtained. I got it.

In addition, the remaining part of the photoconductive member was set in an electrophotographic device, and the charging corona voltage was +6 KV, and the image exposure was 0.8 to 1.5.
A latent image is formed by 1ux* sec, followed by development,
The transfer and fixing processes were carried out using well-known methods, and image evaluation was performed using A4 size paper in a normal environment, with a total of 150,000 sheets of image output, and in a high-temperature environment. Below, two more images equivalent to 150,000 sheets were taken, and each image was evaluated based on the quality of [density] [resolution] [tone reproducibility] [image defects] etc. However, 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.1For example, it was found that the acceptance potential was improved by about 2 to 2.5 times compared to the one without nitrogen atoms, indicating that high resistance due to nitrogen atom doping. It was inferred that the synergistic effect of preventing charge injection due to the change in the amount and the content thereof was sufficiently effective. This improvement in charge acceptance ability has the great advantage of not only increasing image density but also widening the latitude of corona conditions and expanding the range of image quality selection.

Another item worth mentioning is resolution, and this series of tests showed that extremely clear images can be maintained under any environmental conditions. This seems to be the effect of having a nitrogen atom concentration distribution as shown in Figure 5, where the maximum portion is near the surface of the amorphous layer, and the difference from that without such a nitrogen atom concentration distribution is obvious. Ta.

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. 6 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 The distribution forms of the concentration of nitrogen atoms and the concentration of boron atoms were
Figure 7 (Comparative Example 1) and Figures 8 to 10 (Examples 3 to 5)
A drum-shaped photoconductive member was produced in the same manner as in Example 1 except for the following changes. Image evaluation exactly the same as in Example 1 was performed on these photoconductive members. As a result, for the photoconductive member of Comparative Example 1, the image was good under normal conditions, but under high temperature and high humidity conditions, image deletion occurred after the 120,000th sheet. On the other hand, with respect to the 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.

Examples 6 to 10 Constituent concentration carbon distribution similar to that in Figure 5, except that the boron atom concentration in the portion of the lower layer in Figure 5 corresponding to the distance from the support from 3 to 18 tiles was set to 0. (Example 6), the boron atom concentration in the portion corresponding to the distance from the support in FIG. 6 from 3 to 18.5 μm was 0.
A drum-shaped photoconductive member (Example 7) with a distance of 2 to 18 mm from the support shown in FIG. 9th drum-shaped photoconductive member (Example 8) in which the boron atom concentration in the portion corresponding to 0 was reduced to 0
The distance from the support shown in the figure is 2 to 18. A drum-shaped photoconductive member with a boron atom concentration of 0 in the portion corresponding to (Example 9)
) and drum-shaped photoconductive members (Example 10) were prepared in which the boron atom concentration was reduced to 0 in the portion corresponding to the distance from the support of 5 to 18.5 scales in Figure 1o, and these photoconductive members Image evaluation was conducted in exactly the same manner as in Example 1. As a result, good results almost equivalent to those of Example 1 were obtained.

Example 1 The first layer was formed on a drum-shaped photoconductive member formed according to the same conditions and procedures as in Example 1.2.3, as described in detail in JP-A-57-52178 and JP-A-57-521711. Sample 9 in which the second layer was formed according to the conditions shown in Table 3-1 by the disclosed swarming method.
Example 1 except that the seeds and conditions shown in Table 3-2 were changed.
15 kinds of samples (Samples 11-1-1 to 11-1-8, 11-2-1 to 11 −
A total of 24 samples (2-8.11-3-1 to 11-3-8°) 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
*See. 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 such steps were repeated over 100,000 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 12 When forming the second layer by the spar and ring method,
Each of the imaging members was prepared in exactly the same manner as in Example 1, except that the target area ratio of silicon wafer and graphite was changed and the content ratio of silicon atoms to carbon atoms in the second layer was changed. 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 5 were obtained. .

Example 13 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 6 were obtained. .

Example 14 When forming the second layer, 5rHa gas, SiF4 gas, (:
2) Each of the image forming members was produced in the same manner as in 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 the No. 14 gas. 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 7 were obtained. .

Table 3-1 2009CCM of Ar is supplied during sputtering.
- 2 Table N' S+H4/He= 1, xzsiH4/He=
0.5, xsiF4/He=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-
Figures 1 to 2-15 are diagrams schematically showing the concentration distribution of atoms of Group Ⅰ of the periodic table in the lower layer of the first layer of the photoconductive member of the present invention, and Figures 3-1 to 3-3- FIG. 38 is a diagram schematically showing the concentration distribution of nitrogen atoms and Group Ⅰ atoms of the periodic table in the upper layer of the first layer of the photoconductive member of the present invention. FIG. 4 is a diagram showing an apparatus for manufacturing a photoconductive member using a glow discharge decomposition method. Figures 5.6.8 to 10 are diagrams showing the analysis results of the constituent atomic concentration distribution of the photoconductive member in the example of the present invention. FIG. 7 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 layer 103: Lower layer 104: Upper layer 105
: Second layer 1101 : Reaction chambers 1102 to 1108 : Gas cylinders 1107 to 1111 : Mass flow controller 1112
~1118: Inflow valve 1117-1121: Outflow valve 1122-112θ: Valve 1127-1131: Pressure regulator 1132: Auxiliary valve 1133: Main valve 11
34: Gate valve 1135: Leak valve 113
6: Vacuum gauge 1137: Base cylinder 113
8: Heater 1139: Motor 1140: High frequency power supply (matching box) II 2-7
Figure 11 2-8 Figure IIK2-10
m Building 211 Figure II Figure 2-13 @
2-14 Figure 498- Ill 2-9 Figure III 2-12 Whistle 2-15 Figure 3-1 Figure 3-2 Interval 3-
4 Figures 3-5 and 3-7
Tube 3-8 Figure Down 3-10 Figure 3-11 Interval 3-3 Figure 6% Figure M 3-9 Figure Catfish 3-12 Figure II 313 tl! ! I Flute 3-14
WiIII 3-16 Figure Flute 3-
17 Figure II 3-191m Figure 3-20 $
Figure 3-22 Figure II 3-23 Figure 499- Figure 3-15 Figure Ill Figure 3-18 Figure III 3-21 Figure II Figure 3-24 Figure II Figure 3-26 Figure 113-28 Figure 3-29 Figure II 3 Figure -31 Figure II Figure 3-32 Figure 3-34 Figure II 3-35 Figure 113-27 Figure II 3-30 Figure III 3-33 Figure Ill Figure 3-36 5 Zujokan 41\Danso 11 (ta) 116! ! ! Figure 7 Figure 118

Claims (1)

[Claims] 1) a support, a photoconductive first layer provided on this support and containing an amorphous material having silicon atoms as a host, and provided on this first layer, In the photoconductive member having a second layer containing silicon atoms and carbon atoms as essential components, the first layer includes, from the support side, a lower layer containing atoms of group m of the periodic table; , an upper layer containing nitrogen atoms and atoms of group Ⅰ of the periodic table, and an upper layer containing atoms of group m of the periodic table in a non-uniform concentration distribution in the layer thickness direction. A photoconductive member.