JPS58150963A - Photoconductive material - Google Patents

Abstract

PURPOSE:To obtain a photoconductive material stabilized in electrical and optical properties, not causing deterioration even after repeated uses, and enhanced in durability and moisture resistance, by laminating specified layers composed of amorphous silicon (a-Si). CONSTITUTION:A photoconductive material 100 is formed by laminating on a substrate 101 an amorphous auxiliary layer and the first amorphous layer 102 composed of a-Si having the first layer region 104 composed of a-Si contg. O and the second layer region 105 composed of a-Si contg. an element of group V, such as P or As, both located on the side of the substrate 101, and satisfying the shown equation and inequality, where tB is thickness of the region 105, and T is the difference between thickness of the layer 103 and tB, and further, a second amorphous laye composed of a-Si contg. C and H.

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 rays, visible rays, infrared rays, 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 SN ratio (photocurrent (Ip)).
/dark current (Id)'), has absorption spectrum characteristics that match the spectral characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, has a desired dark resistance value, and is resistant to the human body during use. In addition, solid-state imaging devices are required to have characteristics such as being able to easily dispose of afterimages within a predetermined time. In particular, the pollution-free nature during use is important for the assembly of electrophotographic image forming members incorporated into electrophotographic apparatuses used in business machines and offices.

Based on this point, amorphous silicon (hereinafter referred to as a-8i) is a photoconductive material that has recently attracted attention.
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

According to Heigo et al., a photoconductive member having a photoconductive layer composed of conventional a-8i has excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as use environment characteristics. Although individual improvements have been made in terms of economic stability and durability, the reality is that there is still room for further improvement in terms of improving overall properties. .

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. When used repeatedly for a long time, fatigue accumulates due to repeated use, resulting in a so-called ghost phenomenon in which an afterimage occurs.

In addition, when forming a photoconductive layer using a-8i material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, However, problems may arise in the electrical or photoconductive properties or voltage resistance of the formed layer.

That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, the injection of charge from the support side is not sufficiently prevented in dark areas, or the transfer For example, there are image defects commonly called "white spots" on images transferred to paper, which are thought to be caused by local discharge breakdown phenomena, and defects that are thought to be caused by abrasion when a blade is used for cleaning. A so-called image defect called "white stripe" sometimes occurred.

Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs.

Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. You can win by causing phenomena such as ``happening''. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. .

Therefore, while efforts are being made to improve the characteristics of each A-8i material, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the above points, and a-S
As a result of intensive research and study on i from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc.,
An amorphous material having a silicon atom as its base material and containing at least one of a hydrogen atom (2) or (2) or a rogen atom (3), so-called hydrogenated amorphous silicon, (2) hydrogenated amorphous silicon, or (2) hydrogenated amorphous silicon containing a (2) halogenated amorphous silicon. [Hereinafter, a-8i (H, The photoconductive members designed and produced not only show extremely superior properties in practical use, but also surpass in every respect when compared with conventional photoconductive members. This is based on the discovery that it has extremely excellent properties as a member.

The electrical, optical, and photoconductive properties of the present invention are virtually always stable regardless of the environment in which it is used, and it is extremely resistant to light fatigue and does not deteriorate even after repeated use, making it durable. The main object of the present invention is to provide a photoconductive member which has excellent surface wettability and has no or almost no residual potential observed.

Another object of the present invention is to provide excellent layer density between a layer provided on a support and a support, and between each layer of laminated layers.
It is an object of the present invention to provide a photoconductive member that is dense and stable in terms of structural arrangement and has high layer weight.

Another object of the present invention is that when applied as an image forming member for electrophotography, the present invention has sufficient charge retention ability during the charging process for electrostatic image formation, and that ordinary electrophotographic methods can be applied very effectively. It is an object of the present invention to provide a photoconductive member having excellent table photographic properties.

Still another object of the present invention is to easily obtain high-quality images with no image defects or image blurring, high density, clear halftones, and high resolution during long-term use. An object of the present invention is to provide a photoconductive member for use in electrophotography.

Yet another object of the present invention is high photosensitivity.

Another object of the present invention is to provide a photoconductive member having high signal-to-noise ratio characteristics and high voltage resistance.

The photoconductive member of the present invention comprises a supporting film for a light guide member, and an auxiliary layer made of an amorphous material having silicon atoms (Si) as a matrix and containing nitrogen atoms (N) as constituent atoms. , an amorphous material [a-8i
(H, and a second 1@ area, which share at least a part of each other,
If the layer thickness of the second layer region is tB, and the difference between the layer thickness of the first amorphous layer and the second layer region tB is T, then ti+/(T+tB')≦0. A second amorphous layer is formed on the first amorphous layer, the second amorphous layer being made of an amorphous material containing silicon atoms, carbon atoms, and hydrogen atoms as constituent atoms. characterized by things.

The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems and has extremely excellent electrical and optical properties.

Indicates photoconductive properties, pressure resistance, and usage environment characteristics.

In particular, when applied as an image forming member for electrophotography, there is no influence of residual potential on image formation, its cage characteristics are stable, it is highly sensitive, and it has a high signal-to-noise ratio. Therefore, it has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

In addition, the photoconductive member of the present invention has a strong layer structure and excellent adhesion to the support, so that the amorphous layer formed on the support can be used continuously at high speed for a long time. Can be used repeatedly.

Hereinafter, the light 4 of the present invention will be explained in detail with reference to the drawings.

FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention.

The photoconductive member 100 shown in FIG. 1 has an auxiliary layer 102 a -8i (H
, X) and exhibits photoconductivity.
103 and a second amorphous layer (IIHos).The auxiliary layer 102 is provided mainly for the purpose of measuring the adhesion between the support 101 and the amorphous layer 103. It is made of a material having characteristics described later so that it has affinity with both of the crystalline layers 103.

The auxiliary layer in the photoconductive member of the present invention includes silicon atoms (
St) as a matrix, nitrogen atoms (N) as constituent atoms,
An amorphous material containing a hydrogen atom σ-force and a halogen atom (3) as necessary (hereinafter referred to as “a-8i N(H,X)
).

a-8iN(f(,X4) is a silicon atom (S
i) as a matrix and nitrogen atoms as constituent atoms (hereinafter referred to as -a-8tar'L-3J); ) as constituent atoms (hereinafter referred to as [a-(Si
bN+ -b ) cHI-C]), an amorphous material (denoted as "cHI-C") whose constituent atoms are a silicon atom (Sl) and a nitrogen atom N, a nitrogen atom prisoner, and optionally a hydrogen atom (11). Hereafter 1- a-(SidN, -d) e(H,
X) 1-eJ).

In the present invention, specific examples of the halogen atom prisoner contained in the auxiliary layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. .

Layer forming methods when the auxiliary layer is composed of the above-mentioned amorphous material include a glow discharge method, a sputtering method, an ion implantation method, an ion blating method, an electron beam method, and the like. These manufacturing methods are manufacturing conditions.

It is selected and adopted as appropriate depending on factors such as the level of equipment capital investment and the desired characteristics of the photoconductive member to be manufactured. The glow discharge method or the sputtering method is preferable because of the advantages that control is relatively easy and that nitrogen atoms and, if necessary, hydrogen atoms and halogen atoms can be easily introduced into the auxiliary layer to be prepared along with silicon atoms. will be adopted.

Furthermore, in the present invention, the auxiliary layer may be formed by using a glow discharge method and a sputtering method in the same apparatus system.

To form an auxiliary layer composed of a-8iN(H, ) A raw material gas for introduction and, if necessary, a raw material gas for hydrogen atom σ force introduction and/or a halogen atom (3) introduction, into a deposition chamber whose interior can be reduced in pressure, and into the deposition chamber. A glue discharge is generated and a S'N
It is sufficient to form an auxiliary layer consisting of ()T + X).

Further, when forming the auxiliary layer by sputtering, for example, the following method is used.

Firstly, in an atmosphere of an inert gas such as A, r, l-Te or a mixed gas based on these gases,
When sputtering a target made of
It may be introduced into a vacuum deposition chamber in which sputtering is performed together with a raw material gas for introducing η and/or for four halogen atoms (X).

゛Secondly, Si is used as a target for sputtering.
It is formed by using a target composed of 3N4, a target composed of SL and a target composed of Si3N, or a target composed of Sl and Si, N. Nitrogen atoms (p) can be introduced into the auxiliary layer. At this time, if the above-mentioned raw material gas for introducing nitrogen atoms N is also used, it is easy to control the flow rate and arbitrarily control the amount of nitrogen atoms introduced into the auxiliary layer.

The content of nitrogen atoms (P) introduced into the auxiliary layer can be determined by controlling the flow rate when the raw material gas for introducing nitrogen atoms (N) is introduced into the deposition chamber, or by controlling the flow rate when the raw material gas for introducing nitrogen atoms (N) is introduced into the deposition chamber. target,
) can be arbitrarily controlled as desired by adjusting the proportion of nitrogen atoms N contained in the target when preparing the target, or by doing both.

The starting materials used as the raw material gas for supplying S+ used in the present invention include 5iF1. ,8i2H,,Si.

Silicon hydride (silanes), which can be gasified into gas, such as I-1, Si, H, and o, can be used effectively. , S
5it-(4,5i2)J in terms of I supply efficiency, etc.
are listed as preferred.

By using these starting materials, it is possible to introduce H as well as 3t into the auxiliary layer formed by appropriately selecting the layer forming conditions.

In addition to the above-mentioned silicon hydride, effective starting materials that serve as raw material gas for supplying Si include silicon compounds containing a halogen atom (3), so-called... silane derivatives substituted with a halogen atom, specifically, for example, SiF,.

Preferable examples include silicon halides such as 5i2F, , 5icl, , 5iBr, and SiH, , F'2.5i)I, , T2. Si
H, Cl, , 8iHC113, 8iH, Br, .

Halogenated silicon hydrides such as S+HBr, etc., which are in a gaseous state or can be gasified, and have hydrogen atoms as one of their constituents can also be mentioned as starting materials for supplying Si for forming an effective auxiliary layer. I can do it.

Even when these silicon compounds containing halogen atoms (3) are used, X can be introduced together with Si into the auxiliary layer formed by appropriately selecting the layer forming conditions 1, as described above.

Up+iF 1. The silicon halide compound containing hydrogen atoms in the starting material contains hydrogen atoms (lI), which are extremely effective in controlling electrical or photoelectric properties, at the same time as introducing halogen atoms into the layer during the formation of the auxiliary layer. Therefore, in the present invention, it is used as a suitable starting material for introducing a halogen atom (X).

In addition to the above-mentioned materials, effective starting materials as raw material gases for halogen interatomic introduction used in forming the auxiliary layer in the present invention include, for example, halogen gases such as fluorine, chlorine, bromine, and iodine, 13rF, J!
F, ClF,, BrF,, Brf'
3. IF”,,TP,.

Interhalogen compounds such as ICl and IHr,
H(J.

Examples include hydrogen halides such as HBr and I■I.

A starting material that is effectively used as a raw material gas for introducing ♀ elementary atoms N used in forming the auxiliary layer is a starting material that has N as a constituent atom, or has N and [■] as constituent atoms. For example, nitrogen (N2).

Ammonia (NH,), hydrazine (T-J2NNH
, , ), hydrogen azide (HN3), ammonium azide (NU, N, ), etc., gaseous or gasifiable nitrogen, nitrides, azides, and other nine element compounds can be mentioned.

In addition to this, nitrogen trifluoride (F
3N), nitrogen tetrafluoride (F4N2), and other halogenated nitrogen compounds.

In the present invention, the diluting gas used when forming the auxiliary layer by the glow discharge method or sputtering method is as follows:
So-called rare gases, such as IIe.

Suitable examples include Ne, A, r, and the like.

The amorphous material a-8iN (H, Since the auxiliary layer is intended to make electrical contact uniform between the layers, the conditions for its formation are strictly selected and carefully prepared so that the desired properties are given to the auxiliary layer.

a-8iN(H,X
) The temperature of the support during layer formation can be cited as an important element in the layer formation conditions for forming the auxiliary layer consisting of (2).

That is, when forming an auxiliary layer consisting of a-8iN (H, ,
In the present invention, a-8iN having the desired characteristics
The temperature of the support during layer formation is strictly controlled so that (H,X) can be formed as desired.

In order to effectively achieve the purpose of the present invention, the optimal range of the support temperature when forming the auxiliary layer is selected as appropriate in accordance with the method of forming the auxiliary layer, and the formation of the auxiliary layer is carried out. However, in normal cases, the temperature is 50°C to 350°C, preferably 1
It is desirable that the temperature is between 00°C and 250°C. For forming the auxiliary layer, the auxiliary layer, the amorphous layer (I),
Other methods allow delicate control of the composition ratio of atoms constituting each layer and control of the layer thickness, allowing continuous formation of layers from the amorphous layer (■) to other layers as needed. Glow discharge method and sputtering method are advantageous because they are relatively easy to use, but when forming the auxiliary layer using these layer forming methods, the above-mentioned support temperature and Similarly, discharge power and gas pressure during layer formation can be cited as important factors that influence the characteristics of the auxiliary layer formed.

The discharge power conditions for effectively producing the auxiliary j- with the characteristics for achieving the purpose of the present invention with good productivity are usually 1 to 300 W, preferably 2 to 150 W.
It is. Also, the gas pressure inside the deposition chamber is usually 3 x 10~5 T.
orr, preferably 8×10 to 0.51. 'o It is desirable to set it to about 1r.

The amount of nitrogen atoms contained in the auxiliary layer in the photoconductive member of the present invention and the amount of hydrogen atoms and halogen atoms contained as necessary achieve the purpose of the present invention, as do the conditions for producing the auxiliary layer. This is an important factor in forming an auxiliary layer that provides the desired properties.

The amount of nitrogen atoms (N, the amount of hydrogen atoms, and the amount of halogen atoms contained in the auxiliary layer) are determined according to the above-mentioned layer formation conditions so that the object of the present invention can be effectively achieved. It is arbitrarily determined according to T et al.'s wishes.

When the auxiliary layer is composed of a b 13 NH-a, the content of nitrogen atoms in the auxiliary layer is preferably 1 x 10-
3-60 atomic%, more preferably 1-5 oat
In the representation of omic%, a, preferably d, 0.4 to 0.9
9999, preferably 5 to 099.

In the case of a-(SibN, -b)cH, -o, the nitrogen atom content is preferably 1×
10-3 to 55 atomic%, more preferably 1 to 5
5 atomic%, the hydrogen atom content is preferably 2 to 35 atomic%, more preferably 5 to 30 atomic%.
When expressed as atomic% and expressed as b and c, b is usually 0.43 to 0.99999, more preferably 0.
43 to 0.99, C is usually 0.65 to 098, preferably 0.7 to 095, and a(S'dN1-d
) e(H+
%, more preferably 1 to 60 atomic%, and the content of the halogen atom-containing acid or the combined content of halogen atoms and hydrogen atoms is preferably 1 to 20 atomic%, more preferably 2 to 15 atomic%. In this case, the content of hydrogen atoms is preferably 193 tomic% or less,
More preferably, it is 13 atomic% or less.

When expressed as d and e, d is preferably 0.
43-0.99999, more preferably 0.43-0
．． 99, C is preferably 0.8 to 0.99, more preferably 085 to 0.98.

The thickness of the auxiliary layer constituting the light guide member in the present invention is appropriately determined as desired depending on the thickness of the amorphous layer provided on the auxiliary layer and the characteristics of the amorphous layer. Ru.

In the present invention, the thickness of the auxiliary layer is usually 30
It is desirable that the range is λ to 2μ, preferably 40 to 15μ, optimally 50 to 1.5μ.

The first amorphous layer (1) 103 in the photoconductive member shown in FIG. Second layer region M105 containing atoms belonging to the group (group V atoms)
, and a layer region 107 containing no oxygen atoms and group (I) atoms on the second layer region (V) 105.

The layer region 106 provided between the first layer region Io) 104 and the layer region 107 contains group (I) atoms but does not contain oxygen atoms.

The oxygen atoms contained in the first layer region (0) 104 or the group V atoms contained in the second layer region M 105 are continuously uniform in the layer thickness direction in each layer region. Preferably, the particles are distributed continuously and substantially uniformly in a plane substantially parallel to the surface of the support 101.

In the various photoconductive members of the present invention shown in FIG. 1, the upper surface side portion of the amorphous layer (1) 103 includes:
It has a layer region (corresponding to the surface layer region 107 shown in FIG. 1) that does not contain oxygen atoms and Group Ⅰ atoms, but contains a layer region that contains Group V atoms but does not contain oxygen atoms (the first The layer region 106) shown in the figure does not necessarily have to be provided.

Alternatively, a second layer region (V) 105 may be provided within the first layer region (0) 104.

In the photoconductive member of the present invention, the first layer region 1o) contains oxygen atoms to provide a high dark resistance and a gap between the auxiliary layer on which the first amorphous layer mark is directly provided. The focus was on improving the adhesion of the film, and the layer region on the upper surface side was focused on increasing sensitivity by not containing oxygen atoms.

In particular, as in the photoconductive member 100 shown in FIG. 1, the amorphous layer (1) 103 has a first layer region containing oxygen atoms (
0) 104, second layer region containing group V atoms (V
) 105, layer region 106 containing no oxygen atoms,
and a layer region 107 that does not contain oxygen atoms or group (I) atoms, and has a layer region shared by the first layer region (0) 104 and the second layer region (Vl) 05. Better results are obtained in this case.

Light 4v of the present invention! , in the member, the first amorphous In)
The first layer region (Q
One is the amorphous layer (1) which forms part of the amorphous layer (1) for the purpose of improving the adhesion with the auxiliary layer (11).
- The second layer region containing Group V atoms is formed, for one thing, when the amorphous layer (If) is subjected to charging treatment from the free surface side. For the purpose of preventing charge from being injected into the inside of I), the support and the amorphous layer (1) are bonded as part of the amorphous layer (1), respectively 7! The area is provided in a structure in which at least a part of the loaf is shared.

In addition, in order to more effectively improve the adhesion between the second layer region (■ indicates the auxiliary layer and the layer region provided directly on the second layer region M, First layer area (0)
From the contact interface with the auxiliary layer, the second layer region (■) is provided so as to include the second layer region (■), and from the contact interface with the auxiliary layer, the second layer region is extended upwardly from the second layer region (■). The first layer region (0) is placed in the amorphous layer (1
) is preferable.

In the present invention, atoms belonging to Group Ⅰ of the periodic table contained between the second layer regions constituting the first amorphous layer (Il) are P (phosphorus), As ( arsenic), Sb
(antimony), Bi (bismuth), etc., and P and As are particularly preferably used.

In the present invention, the second layer region (the
The content of group atoms can be determined as desired so as to effectively achieve the object of the present invention, but it is usually 30 to 5 x 10 atomic pp in layer region V.
m, preferred [2〈is 50-1×104a joml Cp
l""soptimally 1. OO~5 X l Oato
It is preferable to set it to mic ppm.

The amount of oxygen atoms contained in the first layer region (0) is determined as desired depending on the properties required of the photoconductive member to be formed, but in the usual case, it is 0.001. ~
50 atomic%, preferably 0.002-4
0 atomic%, optimally 0.003-30 at
It is desirable to set it to omic%.

In the photoconductive member of the present invention, the layer thickness tB of the layer region (to) containing Group (1) atoms (in FIG. 1, the layer region 1
04 layer thickness), layer area (layer area (provided on ■), layer area (
The layer thickness T of the layer region (layer region 106 in FIG. 1) excluding (2) is determined so that the relationship satisfies the relationship shown above, but more preferably, It is desirable that the value of the relational expression shown above be 0.35 or more, and optimally 0.3 or less.

In the present invention, the layer thickness tB of the layer region M containing group V atoms is usually 30λ to 5μ, preferably 40λ.
It is desirable that the thickness be ~4μ, optimally 50λ~3μ.

Further, it is desirable that the sum (T+tn) of the layer thickness T and the layer thickness tB is usually 1 to 100μ, preferably 1 to 80μ, and optimally 2 to 50μ.

The layer thickness t of the layer region (O) containing oxygen atoms. In this case, it is desirable that the thickness be determined in accordance with the desired purpose in relation to the layer thickness 1B of the layer regions that share at least some of the layer regions. That is, if the purpose is to strengthen the adhesion between the layer region and the auxiliary layer that is in direct contact with the layer region (■), the layer region (0) is the end layer region on the support side between the layer regions. It suffices if it is provided at least in the layer area O)
j-thickness t. At most, the layer thickness tB of the layer layer M is sufficient for this purpose.

In addition, 1 region M (Vl and 1- provided directly on the layer region M)
If you want to strengthen the adhesion between the layer region (corresponding to the layer region 107 in Figure 1), the layer region (0) should be placed opposite the layer region (■, where the support is provided). Since it is sufficient that the layer be provided at least in the end layer region of the layer region (0), the layer thickness t of the layer region (0) may be at most the no thickness tB of manual sterilization.

Furthermore, considering the case where the above two points are satisfied, the layer thickness t of the layer region (0). Finally, at least layer area ■) 1
- It is necessary to have a thickness tB, and in this case, it is necessary to have a layered structure in which a length jt(V) is provided in the layer region (01).

To more effectively measure the adhesion between the layer region (■) and the layer region provided directly on the layer region M, place the layer region (P) above the layer region (■ (on the side with the support) It is preferable to extend in the opposite direction).

In the present invention, a portion containing no oxygen atoms is provided in the end layer region of the amorphous layer (fil) side of the amorphous layer (f), and the layer region (0) is replaced with the amorphous layer (11). When locally unevenly distributed on the opposite side, the layer thickness t. When closing, consider the above points 1
Although it can be determined as necessary according to your needs, usually 10
λ~10μ, preferably 20λ~8μ, optimally 30λ~
In the photoconductive member 100 shown in FIG. 1, the second amorphous layer (1103) formed on the first amorphous layer (1103)
I) 108 has free blush 109 [7, mainly moisture resistant,
It is provided in order to achieve the objectives of the present invention in terms of continuous repeated use characteristics, pressure resistance, use environment characteristics, and durability.

In the present invention, each of the amorphous materials forming the first amorphous layer (1) and the second amorphous layer (II) has a common constituent element of silicon atoms. Therefore, chemical stability is sufficiently ensured at the laminated interface.

The second amorphous layer (n) is an amorphous material [a-(S 1 xC
1-x)YHI-y+O<x, y<11.

The second amorphous layer (11) composed of a-(SixC1-x), H, can be formed by glow discharge method, sputtering method, ion implantation method, ion blating method, electron beam method, etc. done by.

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. It is relatively easy to control the manufacturing conditions for manufacturing the photoconductive member. A glow discharge method or a sputtering method is preferably employed because the second amorphous layer in which carbon atoms and hydrogen atoms are formed together with silicon atoms can be easily introduced into the layer.

Furthermore, in the present invention, the second amorphous layer (11
) may be formed.

To form the second amorphous layer (It) by the glow discharge method, a-(SixCI-,), H,-, for formation. The raw material gas is mixed with dilution gas at a predetermined mixing ratio if necessary, and introduced into a deposition chamber for vacuum deposition where a support is installed, and the introduced gas is caused to generate a glow discharge. a (S IxC+ -x ) on the first amorphous layer m already formed on the support before gas plasma conversion.
In the present invention, as the raw material gas for forming a-(SixC,x), H, -y, at least one of Si, C, and H is used as a constituent atom. Most gaseous substances or gasified substances that can be gasified can be used.

When using a raw material gas containing Si as one of Si, C, and H, for example, a raw material gas containing 8i as a constituent atom, a raw material gas containing C as a constituent atom, and a raw material gas containing H as a constituent atom. Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing C and H as constituent atoms may be mixed at a desired mixing ratio. Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing three constituent atoms, 8i, C, and H, can be mixed and used.

Separately, C is added to the source gas containing Sl and H as constituent atoms.
A mixture of raw material gases having constituent atoms may be used.

In the present invention, eight gases (Si, H,... Si, H,, Si,
H.

Silicon hydride gas such as silanes, C
and H as constituent atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and 2 to 4 carbon atoms.
-3 acetylenic hydrocarbons and the like.

Specifically, the saturated hydrocarbon 7 is methane (Cf(
, ), eta7 (C2H6), propy (CH8),
n-buta/(n C4H1O), penta/(C5H
I2), Etele/(
02 days, ), propylene (C, f(,), butene-1,
(04H8) I-butene-2(C(H8).

Inbutylene (C4Hs), pentene (C,H,.)
, As the acetylenic hydrocarbon, acetylene (C2H
2).

Methylacetylene (C,8G), butyne (C4H,l
'1 etc. are mentioned.

As a raw material gas containing Sr, C, and H as constituent atoms, 5
Examples include alkyl silicides such as iCCHs')<+8' (CtHI+)4. In addition to these raw material gases, H2 is of course also used as an effective raw material gas for H introduction.

Second amorphous layer (II) by sputtering/ligation method
In order to form this, sputtering is performed in various gas atmospheres using single crystal or polycrystalline 81 wafers, C wafers, or wafers containing a mixture of Sr and C as targets. good.

For example, if Si Ueno-- is used as a target, the raw material gas for introducing C and L() is diluted with diluting gas as necessary and introduced into the deposition chamber for sputtering. The Sr wafer may be sputtered by forming gas plasma.

Alternatively, sputtering can be performed in a gas atmosphere containing at least hydrogen atoms by using Si and C as separate targets or by using a single mixed target of S and C. Ru.

As the raw material gas for introducing C or H, the raw material gas shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, the diluent gas used when forming the second amorphous layer (II) by a glow discharge method or a sputtering method is a so-called rare gas.

For example, He, Ne, Ar, etc. can be mentioned as suitable materials.

The second amorphous layer (1) in the present invention is carefully formed so as to provide the desired properties.

In other words, materials whose constituent atoms are Si, C, and H can have structural forms ranging from crystalline to amorphous depending on the conditions of their creation, and electrical properties ranging from conductive to semiconductive to insulating. , and exhibit properties ranging from photoconductive properties to non-photoconductive properties, so in the present invention,
3-81XCI-X with desired characteristics according to purpose
The formation conditions are strictly selected according to the desired conditions so that the formation of the .

For example, in order to provide the second amorphous layer (1-1) with the main purpose of improving pressure resistance, a-(SixC+-x)'
IH+y is made as an amorphous material with pronounced electrically insulating behavior under conditions of use.

Father, when the second amorphous layer σD is provided for the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment,
The degree of electrical insulation described above is relaxed to some extent, and a-(SixC1-x)yHt 3' is created as an amorphous material having a certain degree of sensitivity to irradiated light.

a − (SixCt x
), yHl-y (when forming a mark, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer, and the present invention In , a→ixC+-x)yL Y having the desired properties
It is desirable that the temperature of the support during layer formation be controlled to a constant level so that the layer can be formed as desired.

In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the second amorphous layer σD should be set in an appropriate range in accordance with the method of forming the second amorphous layer surface. selected,
The formation of the second amorphous layer σD is carried out at a temperature of 50n-350°C, preferably between 100°C and 250°C. For the formation of the second amorphous layer surface, delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods.
It is advantageous to employ the glow discharge method or the sputtering method, but when forming the second amorphous layer (b) using these layer forming methods, the temperature of the layer formation as well as the support temperature described above must be adjusted. a − (SixCt −
x))'Ht-y is one of the important factors that influence the characteristics of a.
-(SixCs
-300W, preferably 20 to 200W. The gas pressure inside the deposition chamber is usually 0.01 to I Tor.
r, preferably about 0.1 to 0.5 Torr.

In the present invention, the desired value ranges of the support temperature and discharge power for creating the second amorphous layer surface and 1. However, these layer creation factors are not determined independently and separately, but are based on the desired characteristics a - (SixC+-x)yT.
(It is desirable that the optimum value of each layer formation factor be determined based on the mutual organic relationship when the second amorphous layer (5) consisting of V is formed. However, the carbon atoms contained in and the violets of hydrogen atoms are formed under the same conditions as the second amorphous layer 0]) to obtain the desired properties that achieve the object of the present invention. It is a pleasant factor.

The amount of carbon atoms contained in the second amorphous layer surface in the present invention is usually 1×10 to 90atOmiCcIb, preferably 1 to 90 atomic%, optimally 10 to 90%.
It is desirable that it be 80 atomic%.

The content of hydrogen atoms is usually 1 to 40ato
mic%, preferably! d 2-35 atomic%
The optimum hydrogen content is preferably 5 to 30 atomic%, and photoconductive members formed when the hydrogen content is in this range are excellent and can be fully applied in practice. be.

That is, if expressed as a-(SixC+x)YHt-y, 0.
6 to 099, preferably 0.65 to 098, optimally 0.
It is desirable that it is 7-0.95.

The numerical range of the layer thickness of the second amorphous layer in the present invention is one of the important factors for effectively achieving the object of the present invention.

The numerical range of the layer thickness of the second amorphous layer (b) 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 layer thickness of the second amorphous layer σD depends on the amount of carbon atoms and hydrogen atoms contained in the layer, the first amorphous layer (I)
The relationship with the layer thickness, etc., also needs to be determined as desired based on the organic relationship depending on the characteristics required for each layer region. In addition, it is desirable to be considered as economics considering productivity and mass production. , usually 0.003-30μ, preferably 0.004-20μ, most preferably 0.005-10μ.

The support used in the present invention (f) may be electrically conductive or electrically conductive. As the electrically conductive support,
For example, NiCr, stainless steel.

At, Cr, Mo + -Aa, h”b
, Ta, V, Tit, Pt+Pd, or alloys thereof.

Polyester is used as the electrically cyclic support.

Polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, etc., and glass.

Ceramic, paper, etc. are commonly used. Preferably, at least one surface of these electro-abrasive supports is subjected to conductive treatment, and another layer is preferably provided on the conductive-treated surface side.

For example, if it is glass, apply N1cr to its surface.

At, C r Mo * Au t Ir p
Nb t Tap V r TLPt r , Pd
r Tnz03r 5n02, ITOr (InzO
Conductivity can be imparted by providing four films consisting of NjCr + At+
AILPb + Zn + Ni + Au, Cr,
Mo*Ir+Nb, Ta, V+Ti
, thin films of metals such as Pt are deposited by vacuum evaporation, electron beam evaporation,
Conductivity is imparted to the surface by sputtering or the like, or by laminating the surface with the metal. The support can be formed into any shape such as a cylinder, a belt, or a plate, and the shape is determined depending on the need. For example, the photoconductive member 100 shown in FIG. If used as a member for continuous high-speed copying, it is desirable to have an endless 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 thickness of the support may be determined as necessary. It is made as thin as possible as long as it is within the range of sufficient performance. In such cases, the thickness is usually set to 10μ or more from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.

In the present invention, the first amorphous layer (I) composed of a 5t (H + It is done by a deposition method.

For example, by glow discharge method, a -5t(HLX)
In order to form the amorphous layer (I), basically, in addition to a raw material gas for supplying Si that can supply silicon source ((S i ), hydrogen atoms and/or halogen for introducing A raw material gas for introducing atoms (3) is introduced into a deposition chamber whose interior can be made to have a reduced pressure, and a glow discharge is generated in the deposition chamber, and the material gas is placed on a predetermined support surface that has been placed at a predetermined position in advance. A-8i (
A layer consisting of H, X) may be formed. In addition, when forming by a sputtering method, when sputtering a target made of St in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms ) or/and halogen atom (
3) All you have to do is introduce the introduction gas into the Q-temple for sputtering.

8. In the present invention, the halogen atoms contained in the amorphous layer (1) if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine atoms being particularly preferred. It can be mentioned as something.

The raw material gas for supplying Si used in the present invention is 5il(ip SL+Ha*5islHs r
Silicon hydride (silanes) in a dust state or which can be gasified, such as 5t4Hto, can be effectively used. In particular, 5N-I4 .5LzHe is preferred.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas.

Gaseous or gasifiable halogen compounds such as halides, interhalogen compounds, and halogen-substituted silane fatty conductors are preferably mentioned. Silicon compounds containing gaseous or gasifiable halogen atoms as an element can also be mentioned in this 'J Nishimei as effective.

Specifically, the halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine.
+ Br, F3+ IF* r IF7 + ICJ
Interhalogen compounds such as t IBr can be mentioned.

Preferred examples of silicon compounds containing halogen atoms, so-called 7-ranium derivatives substituted with halogen atoms, include silicon halides such as 5iFi, 5izFa+ 5iCt4+SiBr4, and the like.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using a silicon compound containing such a hydrogen atom, silicon hydride gas is used as a raw material gas capable of supplying Si. Even if this is not done, the amorphous layer (I) made of a-Si containing halogen atoms can be formed on the auxiliary layer already provided on a predetermined support.

According to the glow discharge method, an amorphous layer containing halogen atoms (
When forming I), basically silicon halide gas, which is a raw material gas for supplying Si, and Ar are used.

Gases such as Hz = He are introduced into the deposition chamber for forming the amorphous layer (I) at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to create a plasma atmosphere of these gases. By forming an amorphous layer on a predetermined support, a predetermined amount of silicon compound gas containing hydrogen atoms is also mixed with these gases in order to introduce hydrogen atoms. A layer may be formed by doing so.

In addition, each gas may be used not only as a single type but also as a mixture of multiple types at a predetermined mixing ratio.

An amorphous layer (I
), for example, in the case of the sputtering method, a target made of Si is used and sputtered in a predetermined gas plasma atmosphere, and in the case of the ion blasting method, polycrystalline silicon or single crystal silicon is formed. Silicon is housed in a deposition boat as an evaporation source, and the silicon evaporation source is heated by resistance heating method or electron beam method (EB method).
This is done by heating and evaporating the evaporated material using a method such as the method (method), etc., and passing the flying evaporated material through a predetermined gas plasma atmosphere).

At this time, in order to introduce the no-rogen atoms into the layer formed by either the sputtering method or the ion-blating method, it is necessary to use the above-mentioned no-rogen compounds or the silicon compounds containing the above-mentioned no-rogen atoms. It is sufficient to introduce a gas into the deposition chamber to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H2 or a gas such as the above-mentioned silanes, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas in step 1. Just do it.

In the present invention, the raw material gas for introducing halogen atoms and i
The above-mentioned halogen compounds or halogen-containing silicon compounds are used as effective ones,
In addition, HF, IICt.

)IBr, hydrogen halides such as HI, 5IH2F2
15tHzIzpSiHpC42+ 5iHCts,
Halides such as 5iHJrz+ 5iHBrs2 can also be mentioned as effective starting materials for forming the amorphous layer (I).

These hydrogen atom-containing compounds have an amorphous layer (
I) Hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer at the same time as halogen atoms are introduced into the layer during formation. used.

To structurally introduce hydrogen atoms into the amorphous layer <I),
In addition to 811, ■■2, or 5IH4* 512H6
This can also be achieved by causing a discharge by causing a silicon hydride gas such as +SisHg+ 5i4H+o to coexist with a silicon compound for supplying Si in the deposition chamber.

For example, D1: In the case of the reactive sputtering method, Sj metal is used, and a gas for introducing halogen atoms and F (
2 gases (as necessary) (including inert gases such as e and Ar) are introduced into the chamber to form a plasma atmosphere,
By sputtering the St metal,
An amorphous layer (I
) is formed.

Furthermore, it is also possible to introduce a gas such as B t Hs to also serve as impurity doping.

In the present invention, the total amount of hydrogen atoms contained in the first amorphous layer (I) of the photoconductive member to be formed, or the amount of V↓halogen atoms, or the relationship between hydrogen atoms and halogen atoms. sum (H
+X) is usually 1 to 40 atomic%, preferably 5 to 30 atomic%.

In order to control the amount of hydrogen atoms and/or halogen atoms contained in the first amorphous layer (I), for example, the support temperature and/or hydrogen atoms or halogen atoms can be controlled. The amount of the starting material used to contain (3) introduced into the deposition system, the discharge force, etc. may be controlled.

In order to provide the layer region M containing group V atoms and the layer region 0) containing oxygen atoms in the amorphous layer (I), the amorphous layer (I) is formed by a glow discharge method, a reactive sputtering method, etc. In the formation of the amorphous layer (I), a starting material for introducing group (III) atoms and a starting material for introducing oxygen atoms are used together with the starting material for forming the amorphous layer (I), respectively. This is achieved by controlling the amount and containing it.

When a glow discharge method is used to form the layer region 0) containing oxygen atoms and the layer region M containing group (III) atoms, which constitute the first amorphous layer (I), each layer The starting material to be the raw material gas for forming the region is selected as desired from among the starting materials for forming the amorphous layer (I) described above, and the starting material for introducing oxygen atoms and/or the starting material for introducing oxygen atoms and/or Starting materials for the introduction of group atoms are added. Such starting materials for introducing oxygen atoms or starting materials for introducing Group V atoms include gaseous substances or gasified substances containing at least oxygen atoms or Group V atoms as constituent atoms. Most of them can be used.

For example, to form a layer region), a raw material gas containing silicon atoms (St) and oxygen atoms (0) are used.
A raw material gas having constituent atoms and hydrogen atoms 0 as necessary.
or/and a raw material gas whose constituent atoms are halogen atoms are mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (St) and a raw material gas whose constituent atoms are zero oxygen atoms are used.
) and a raw material gas whose constituent atoms are hydrogen atoms σ◇ are mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (St) and silicon atoms (St), It is possible to use a mixture of a raw material gas having three constituent atoms: oxygen atom (0) and hydrogen atom (0).

Alternatively, a raw material gas containing oxygen atoms (0) as constituent atoms may be mixed with a raw material gas containing silicon atoms (Si) and hydrogen atoms (2) as constituent atoms. Specifically, examples of substances include oxygen (Ox), ozone (Os), -
Nitric oxide (NO), nitrogen dioxide (NO2), -nitrogen dioxide (N,0), nitrogen sesquioxide (NtOs)! ! ! a
Crab dioxide (N204) - Nitrogen sesquioxide (NtOe
), nitrogen trioxide (NO, ), and lower siloxanes whose constituent atoms are silicon atoms (Si), oxygen atoms (0), and hydrogen atoms, such as disiloxane HsSiO8iH3p trisiloxane HsSiO8iH*08iHs, etc. I can do it.

When the layer region M is formed using the glow discharge method, the starting materials for introducing Group Ⅰ atoms that are effectively used in the present invention are PHa, P, etc. for introducing phosphorus atoms.
Hydrogen north neighbor of 2H4, etc.-PHnIpPF3. pF,
PCt8. PClsy PBr*p PBr+
Examples include halogen ratios such as PIi. In addition, AsH
spAsF″3゜h侃iiAsC41ASBr3HAsF
5 # 5bHs H5bFs psbFipSbC4
s e 5bC4i + BiHs t B1C45+
B1Br5 and the like can also be mentioned as effective starting materials for introducing Group V atoms.

The content of Group V atoms introduced into the layer region M containing Group V atoms is determined by the gas flow rate of the starting material for introducing Group V atoms introduced into the deposition chamber, the gas flow rate ratio, the discharge power, It can be arbitrarily controlled by controlling the support temperature, the pressure inside the deposition chamber, etc.

To form the layer region 0) containing oxygen atoms by the sputtering method, a monocrystalline or polycrystalline Si wafer or a 5in2 wafer or St and 8i0. Sputtering may be carried out by using a wafer containing a mixture of as a target and sputtering them in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gas for introducing oxygen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary, and the material gas is diluted with a diluent gas as necessary to create a deposition chamber for sputtering. The Si wafer may be sputtered by introducing the gas into the Si wafer and forming a gas plasma of these gases.

Alternatively, by using Si and Si as separate targets or by using a single mixed target of Si and SiOz, at least hydrogen atoms can be removed in an atmosphere of dilution gas as a sputtering gas. ) or/and by sputtering in a gas atmosphere containing halogen atoms as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the example of glow discharge described above can be used as an effective gas also in the case of spatz ring.

In the present invention, a so-called rare gas, such as He, Preferred examples include Ne, Ar, and the like.

FIG. 2 shows the layer structure of another preferred embodiment of the photoconductive member of the present invention. The photoconductive member 200 shown in FIG. 21 is different from the photoconductive member 100 shown in FIG. Upper auxiliary layer 20 which performs the same function as
2-2.

That is, the photoconductive member 200 has a support body 2011
The lower auxiliary layer 202-1, the first amorphous + @ (I) 203 and the second amorphous layer (
II) 208 and wo JL4 L, amorphous layer (■) 20
3 C. First layer region containing oxygen atoms (Q)
204, a second layer region (V') 205 containing group V j11 children, and an upper auxiliary layer 202-2 between the layer region 206 and the one-layer region 207.

The upper auxiliary layer 202-2 has a layer region M2O3 and a layer region 20.
7 and uniform electrical contact at the contact interface between the two, and at the same time, by providing directly on the layer region M2O3, the layer quality of the layer region M2O3 is made strong. .

The lower auxiliary layer 202-1 and the upper auxiliary layer 202-2 constituting the photoconductive member 200 shown in FIG. Crystalline materials are used and formed by similar layering procedures and conditions to provide similar properties.

The amorphous layer (i) 203 and the amorphous layer 208 are also
Amorphous layer (J) 103 and amorphous layer (J) 1 shown in the figure
In the photoconductive member of the present invention, which has the same characteristics and functions as 08 and the same layer forming procedure and conditions as in the case of FIG. A layer region (
B) (corresponding to the layer region 106 in FIG. 1) contains a substance that controls the conduction properties, so that the conduction properties of the layer region (B) can be controlled as desired.

Examples of such substances include so-called impurities in the semiconductor field. In the present invention, for a-Si(H,X) constituting the amorphous layer me to be formed,
There are P-type impurities that provide P-type conduction characteristics, specifically, dium (Group 1 of the periodic table), Tl (thallium), etc., and B and Qa are particularly preferably used.

In the present invention, the content of the substance that controls all the conduction characteristics contained in the first layer region (B) is determined by the conduction characteristics required for the layer region (B) or the amount of the substance that directly contacts the layer region CB). It can be selected as appropriate based on the organic relationship, such as the characteristics of other layer regions provided therein and the characteristics of the contact interface with the other layer regions.

In the present invention, the content of the substance controlling the conduction characteristics contained in the layer region fBl is usually 0.0
01-1000 atomic plm, preferably 0,
It is desirable to set it to 05-500 atomic 1111111, optimally 0.1-200 atomic ppII.

In the layer region fBl there is a substance controlling the conduction properties, e.g.
In order to introduce the group atoms structurally, during the I-formation, the starting material jx for the introduction of the group I atom is placed in a gaseous state in a deposition chamber together with other starting materials for forming the amorphous layer. It would be good to introduce it. As the starting material for such introduction of Group (I) atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for the introduction of group Ⅰ atoms include BzHI and -BA.
so + BJ(9t BJ(11, BJ(to +
Boron hydride, BF” such as BaHxt-BJISa,
, BCez, BBr, and other boron halides. In addition, AlCl! ,.

G”CG + Ga (CHs)s + InCl3
+ TICeH etc. can also be mentioned.

In the photoconductive member of the present invention, as explained in the example shown in FIGS. 1 and 2, the layer region +01 constituting the amorphous layer (1) is ) is locally incorporated on the support side, but the present invention is not limited to this, and for example, the layer region (0) is formed into an amorphous layer. The amorphous layer (1) may be formed as the entire layer region of (1).

In this case, since the amorphous layer (1) must be made to exhibit photoconductivity, the upper limit of the amount of oxygen atoms contained in the layer region (0) is usually 30 atoms.
c%, preferably 10 atomic%, optimally 5 a
It is desirable to set it to tomic%. In this case as well, the lower limit is, of course, set to the above value 0.Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained.

FIG. 3 shows an example of a photoconductive member manufacturing apparatus.

302.303.304.305.306 in the diagram. The raw material waste for forming each layer region of the present invention is sealed in the gas cylinder of 3.
02 is SiH4 gas diluted with He (purity 99.9
99%, hereinafter abbreviated as S i I-1,/He. ) cylinder, 303 contains PH, gas (purity 99.
999%, hereinafter abbreviated as P/He. ) Cylinder, 304 is a Ci residual gas (purity 99.99%) cylinder, 306 C■.

It is a gas cylinder (99.999% purity).

In order to allow these gases to flow into the reaction chamber 301, make sure that the pulps of the gas cylinders 302-306, 322-326° leak pulp 335 are closed, and also the inflow pulps 312-316, outflow pulps 317-321, After confirming that the auxiliary pulp 332 is opened, the main pulp 334 is first opened to exhaust the reaction chamber 301 and gas piping. Next, when the vacuum gauge 336 reads approximately 5X10 torr, the auxiliary pulp 332.333. Inflow pulp 3
22-326. Close outflow pulps 317-321. Thereafter, a desired gas is introduced into the reaction chamber 301 by operating the valve of the gas pipe connected to the cylinder of the gas to be introduced into the reaction chamber 301 as prescribed.

Next, an example of producing a photoconductive member having a structure similar to that shown in FIG. 1 will be outlined.

First, to take an example of forming an auxiliary layer on the cylindrical support 337, Si
Open the valves 322 and 326 to remove NH and scum from the H4/He scum and scum cylinder 306 to the outlet pressure cage 327° 33
Adjust the pressure of 1 to 1 kg/d, and open the inlet valve 312゜3.
Gradually open 16 and install mass flow controller 307゜3.
31. Outflow valve 317°3
21. The auxiliary valve 322 is gradually opened to allow each gas to flow into the reaction chamber 301. At this time, the outflow valves 317 and 321 are adjusted so that the SiH, /He gas flow rate T (and the ratio to the dregs flow rate becomes a desired value), and the reaction chamber 30
While checking the reading on the vacuum gauge 336, adjust the opening of the main valve 334 so that the pressure inside the main valve 334 reaches the desired value. Then, the temperature of the support body 337 is raised to 50℃ by the heating heater 338.
After confirming that the temperature is set in the range of ~400°C, set the power source 340 to the desired power and turn on the reaction chamber 30.
The auxiliary layer is formed on the support 337 by generating a glow discharge in the auxiliary layer 337 . In order to introduce rogen atoms (into the auxiliary layer to be formed), for example, in all the explanations for creating the auxiliary layer above, SiF4 gas is used instead of SiH4 gas, or SiF4 gas is used in place of SiH4 gas. This is done by adding gas to form a no.

The lid containing nitrogen atoms, hydrogen atoms, and halogen atoms contained in the auxiliary tank is used to adjust the flow rate when introducing the starting material for forming the auxiliary layer containing these atoms into the reaction chamber 301. controlled by

For example, to control the nitrogen atom content, control the gas flow rate, and control the nitrogen atom content (1) to control the nitrogen atom content (1).
This is accomplished by adjusting the flow rates of each of the four gases.

Next, an example of forming the first amorphous layer (1) on the support 337J will be given. The shutter 342 is closed and connected to be supplied with high voltage power from a power source 340. 5iLz4 (e gas from the gas cylinder 302, PH and /He gas from the gas cylinder 303, and No gas from the gas cylinder 305 through valves 322 and 323, respectively.
, 325, outlet pressure gauges 327, 328, respectively.
, 330 is adjusted to 1 kg/c11, and the inflow valves 312 , 313 , 315 are gradually opened to allow the mass 70 to flow into the controllers 307 , 308 , 310 . Subsequently, the outflow valves 317, 318, 3
20. Gradually open the auxiliary valve 332 to allow each waste to flow into the reaction chamber 301. At this time, SiH, /He
The outflow valves 317 and 318 are adjusted so that the ratios of the waste flow rate, PHJHe gas flow rate, and No gas flow rate are set to desired values.
, 320, and adjust the opening of the main valve 334 while checking the reading on the vacuum gauge 336 so that the pressure inside the reaction chamber 301 reaches a desired value. Then, the temperature of the support body 337 is raised to 50 to 40 degrees by the heating heater 338.
After confirming that the desired temperature in the range of 0'O is set, the power supply 340 is set to the desired power and the reaction chamber 3 is heated.
First, a layer region containing phosphorus and oxygen is formed on the support 337 by causing a claw discharge in the 01.

At this time, by blocking the introduction of PI (3/He gas or No gas into the reaction chamber 301 by closing the valves of the corresponding gas introduction pipes), the layer region containing phosphorus or the oxygen The layer thickness of the layer region containing can be arbitrarily controlled as desired.

After the layer regions containing phosphorus and oxygen have been formed to the desired thickness as described above, each of the outflow valves 318 and 320 is closed and glow discharge is continued for a desired period of time to remove phosphorus and oxygen. A layer region that does not contain phosphorus and oxygen is formed to a desired layer thickness on the layer region that contains phosphorus and oxygen, respectively, and
Formation of the first amorphous layer (1) is completed.

In the photoconductive member of the present invention, as described above, the layer region (0) and the layer region (■) that constitute the amorphous layer (I) are those that share at least a part of the layer region. Therefore, when forming the amorphous layer (I), it is necessary to provide a desired length of time for simultaneously introducing, for example, PH gas and No gas into the reaction chamber 301 at desired flow rates.

For example, as described above, PH gas and NO gas are introduced into the reaction chamber 301 for a desired period of time from the start of formation of the amorphous layer (1), and after the diaphragm for the specified period of time, either gas is reacted. Room 3
layer area (0) by stopping introducing into 01
Alternatively, another layer region can be provided in either one of the layer regions (V).

Alternatively, when forming the amorphous layer (1), PH, gas or NO
After introducing either one of the scum into the reaction chamber 301 for a desired time, the other is further introduced into the reaction chamber 301 to perform one-carrier formation for a desired time, so that either phosphorus or oxygen is contained. A layer region containing both phosphorus and oxygen can be formed on the layer region.

Also, at this time, by stopping the introduction of only one of PH, gas, or NO gas into the reaction chamber 301 and continuing to introduce the other, the layer region containing both phosphorus and oxygen can be removed. A layer region containing either phosphorus or oxygen can be formed thereon.

In the case of a photoconductive member having an upper auxiliary layer 202-2 in the first amorphous layer (1) 203, as in the case of 2000 photoconductive members shown in FIG. ) 203, an upper auxiliary layer is provided in the amorphous layer 202-1 by performing the same layer formation as the lower auxiliary layer 202-1 formed according to the method described above. I can do it.

K, which forms the second amorphous layer (n) on the first amorphous layer (1) formed on the support 337 by the above operation, is the first amorphous layer. For example, 5il14 scum, C2I(4
This is accomplished by diluting each of the gases with a diluent gas such as 1-Ie as needed, flowing them into the reaction chamber 201 at a desired flow rate, and generating glow discharge according to desired conditions.

It goes without saying that all outflow valves other than those required for forming each layer must be closed, and when forming each layer, the gas used to form the previous layer may leak into the reaction chamber 301. , reaction chamber 301 from outflow valves 317 to 321
In order to avoid gas remaining in the gas piping leading to the inside, the outflow valves 317 to 321 are closed and the auxiliary valves 332 and 3
33 and fully open the main valve 334 to temporarily evacuate the system to a high vacuum, as necessary.

Further, during layer formation, the cylindrical support 337 is constantly rotated at a desired speed by a motor 339 in order to ensure uniform layer formation.Example 1 The manufacturing apparatus shown in FIG. , a layer was formed on a drum-shaped aluminum substrate under the following conditions: 1. The image forming member thus obtained was placed in a charging, exposing and developing device. Corona charging was performed at 05KV for 0.2 seconds,
A light image was immediately irradiated. A tungsten lamp is used as the light source.1. A light intensity of Olux, sec was irradiated using a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (containing toner and carrier) over the surface of the member.

The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No deterioration of the image was observed even after repeating the test more than 150,000 times.

67 Example 2 A layer was formed on a drum-shaped Al substrate under the conditions shown in Table 2 below using the manufacturing apparatus shown in Figure 3. I did it.

Other conditions were the same as in Example 1.

The image forming member thus obtained was placed in a charging, exposing and developing device, corona charging was performed at 05 KV for 0.2 sec, and a light image was immediately irradiated. A tungsten lamp is used as the light source.1. O1ux6. A light intensity of sec was irradiated using a transmission type test chart.

Immediately thereafter, a charged developer (containing toner and carrier) was cascaded over the surface of the member to obtain a good toner image on the surface of the member.

The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No deterioration of the image was observed even after repeating the test over 100,000 times.

8 9 Example 3 Using the apparatus shown in FIG. 3, a drum-shaped A/! A layer was formed on the substrate under the conditions shown in Table 3 below.

Other conditions were the same as in Example 1.

The image forming member thus obtained was placed in a charging, exposure and developing device, corona discharge was performed at 05 Kv for 0.2 sec, and a light image was immediately irradiated. A tungsten lamp was used as a light source, and a light intensity of 1.0.6 ux, sec was irradiated using a transmission type test chart.

Immediately thereafter, a charged developer (containing toner and carrier) was cascaded over the surface of the member to obtain a good toner image with extremely high density on the surface of the member.

The toner image thus obtained is once cleaned with a rubber blade, and the above image forming and cleaning steps are repeated again. Even when repeated over 150,000 times, no image deterioration was observed.Example 4 When forming the second amorphous layer (n), the area ratio of the silicon wafer and graphite was changed. An image forming member was prepared using L in exactly the same manner as in Example 3, except that the content ratio of silicon atoms and carbon atoms in the amorphous layer (n) was changed.

The image forming member thus obtained was subjected to image formation, development, and cleaning steps as described in Example 1 about 50,000 times, and then image evaluation was performed. Example 5 The second amorphous layer (If An imaging member was produced in exactly the same manner as in Example 1, except that the layer thickness of () was changed. The steps of image formation, development, and printing as described in Example 1 were repeated to obtain the following results.

Table 5 75 Example 6 An image forming member was prepared in the same manner as in Example 1, except that the methods for forming the auxiliary layer and the amorphous layer (1) were changed as shown in the table below.
When evaluation was performed in the same manner as in Example 1, good results were obtained.

・7・7 Example 7 Image-shaped member 1 was created in the same manner as in Example 1, except that the method for forming the auxiliary layer and the amorphous layer (I) was changed from the method shown in the table below. When evaluation was performed in the same manner as in Example 1, good results were obtained.

79 Example 8 Using the manufacturing apparatus shown in FIG. 3, a layer was formed on a drum Al substrate in the same manner as in Example 1, except that the conditions shown in Table 8 below were applied.

Example 2 was applied to the electrophotographic image forming member thus obtained.
A similar evaluation was performed and good results were obtained.

Example 9 The fr-1 layer was formed using the manufacturing equipment shown in FIG. I went.

When the thus obtained image forming member was evaluated in the same manner as in Example 3, it was found that a high quality image was obtained and it was excellent in durability.

88 Example 10 The layer creation conditions in the 34th layer creation stage of Example 8 were set to the conditions shown in Table 10 below. When each of the image forming members was produced and evaluated in the same manner as in Example 1, good results were obtained for each of them, particularly in terms of image quality and durability.

5

[Brief explanation of drawings]

1 and 2 schematically show layer structures of preferred embodiments of the photoconductive member of the present invention, respectively. FIG. 1 is a schematic explanatory diagram showing an example of an apparatus for manufacturing a conductive member. 1.00,200... Photoconductive member 101.201
... Support body 102.202-1.202-2 ... Auxiliary layer 10
3.203 ・First amorphous layer (1) 104.204
...First layer area (0) 105.205...
・Second layer region (■108.208...Second amorphous layer (1) 109.209...Free surface milf 6

Claims (1)

[Claims] (1) A support for a photoconductive member, an auxiliary layer made of an amorphous material containing silicon atoms as a matrix and nitrogen atoms as constituent atoms, and an amorphous material containing silicon atoms as a matrix. and a first amorphous substance exhibiting photoconductivity.
, the first amorphous layer contains a first layer region containing oxygen atoms and atoms belonging to Group V of the periodic table as constituent atoms, and is internalized toward the support side. and a second layer region, which share at least a part of each other, and the layer thickness of the second layer region is tB, and the layer thickness of the first amorphous layer is tB. If the difference from the 1-thickness tn of the second layer region is T, then the relationship ts/(T-1-tn)≦04 is established, and silicon atoms and A photoconductive member comprising a second amorphous layer made of an amorphous material containing carbon atoms and hydrogen atoms as constituent atoms.