JPS58134644A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member which has excellent durability and moisture resistance and in which residual potential is not observed in an amorphous silicon (a-Si) photoconductive member of laminated type, by providing the specific 2nd amorphous layer on the specific 1st amorphous layer. CONSTITUTION:A substrate 101 and the 1st amorphous layer 102 which consists of an amorphous material consisting basically of Si atoms and contg. H atoms and/or halogen atoms and exhibits photoconductivity are provided. The layer 102 is composed of the 1st layer region 103 contg. atoms of O as constituting atoms and the 2nd layer region 104 contg. atoms of the group III as constituting atoms, both of which areas co-possess at least part thereof and exist internally near the substrate 101, and between which the relations of the euqation is estabilished if the thickness of the region 104 is defined as tB and the difference between the thickness of the layer 102 and the thickness tB of the 2nd layer region as T. The 2nd amorphous layer 107 contg. Si atoms, C atoms and H atoms is provided on the layer 102.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoconductive member that is sensitive to various electromagnetic waves of light (herein, light in a broad sense refers to light, visible light, infrared light, X-rays, gamma rays, etc.). Regarding.

As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an image forming member for electrophotography in the field of formation, or a document reading device, it is highly sensitive and has a photocurrent (Ip) of 8N ratio.
/ dark current (Id)), has absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, has the desired dark resistance value, and does not cause any pollution 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, amorphous silicon (hereinafter referred to as a-8i) is a photoconductive material that has recently attracted attention.
55718, as an electrophotographic image forming member,
German release No. 293341! The application to a photoelectric conversion/reading device is described in the publication.

A photoconductive member having a conventional photoconductive layer composed of 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 stability, stability over time, and durability, there is still room for further improvement in terms of improving overall properties. The reality is that.

For example, when applied to electrophotographic image forming members, when trying to achieve high photosensitivity, high dark resistance1, and cyclization at the same time, it has often been observed in the past that residual potential remains during use. When such photoconductive members are used repeatedly for a long period of 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, chlorine atoms, etc., and electrically conductive type Array 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. In this case, problems may arise in the electrical or photoconductive properties or voltage resistance of the formed layer.

That is, for example, if the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or if in a dark area, the charge on the side of the support ll' →, :i: luminescence that the prevention is not sufficient;
Or, it is commonly called "white spots" on the image transferred to the transfer paper. There were some image defects, such as cleaning defects, that were thought to be caused by local discharge breakdown phenomena.

In addition, if the image is used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time (the image is left in the air after being taken out of the vacuum deposition chamber) Along with this, lifting and peeling of the layer from the surface of the support 1,
Otherwise, phenomena such as cracks occurring in the layer may occur.

This phenomenon often occurs especially when the support is a drum-shaped support that is normally used in the electronic field, and there are issues that need to be resolved in terms of stability over time. be.

Therefore, while efforts are being made to improve the properties of the ASI material itself, 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-mentioned points, and is characterized by its applicability and applicability to a-8i as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of intensive comprehensive research from this perspective, we have discovered that amorphous materials containing silicon atoms as a matrix and at least one of hydrogen atoms σ■ or halogen atoms ■, so-called hydrogenated amorphous silicon and halogenated amorphous silicon, have been developed. or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as ra-8 as a generic term]
i(H, Arrival [
Not only does it exhibit 7 excellent properties, but it also surpasses conventional photoconductive materials in every respect.
Based on the findings 1 and 1, it has been found that it has particularly excellent properties as a photoconductive member for electrophotography.

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 that has excellent moisture resistance and has no or almost no residual potential observed.

Another object of the present invention is 1. provided on a support,
It is an object of the present invention to provide a photoconductive member with high layer weight.

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

Still another object of the present invention is to produce high-quality images with high density, clear halftones, and high resolution without image defects or blurring during long-term use. It is an object of the present invention to provide a photoconductive system for electrophotography that can be easily obtained.

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 support for the photoconductive member, and an amorphous material having silicon atoms as a matrix and containing at least one of hydrogen atoms (O) and halogen atoms (X) as constituent atoms. (a-8i(H, and a second layer region containing atoms belonging to Group 1 of the periodic table as constituent atoms, which share at least a portion of each other. The layer thickness of the surface rudder second layer region is tB.
Then, the difference between the layer thickness of the first amorphous layer and the layer thickness t13 of the second N4 region is 1tf to/(T+tB
) so, 4 relationships are established, and on the amorphous layer ≠, a second amorphous material made of an amorphous material containing silicon '1 atoms and carbon atoms as constituent atoms is formed. It is characterized by having a stratum layer.

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 high 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 the formation of both sides, its electrical characteristics are stable, and it has high sensitivity and a high 8N ratio. Therefore, it has excellent light fatigue resistance and repeated use characteristics, and has a high concentration.
It is possible to stably repeat high-quality images with high resolution and clear %/%-;l-.

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.

2-2～. ]]Lj, -1-f/ Hereinafter, the photoconductive member of the present invention will be described 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 a first amorphous layer (1 ) 102 and a second amorphous layer 107 formed on the amorphous layer (1) 102 and made of an amorphous material whose constituent atoms are silicon atoms, carbon atoms, and hydrogen atoms. .

Amorphous layer (1) 102 is a first layer region 0) containing oxygen atoms as a constituent atom; Area (I
ID 104, and on the second layer region Q[l 104,
It has a layer structure consisting of a ★ layer region 106 that does not contain oxygen atoms or group (Ⅰ) atoms.

The layer region 105 provided between the first layer region 0) 103 and the splitter layer region 106 contains group (I) atoms but does not contain oxygen atoms.

The oxygen atoms contained in the -0th layer region (o)ioa or the group Ⅰ atoms contained in the second layer region (l [1104) are continuous in the layer thickness direction in each layer region. Preferably, the particles are uniformly distributed, and are substantially uniformly distributed continuously in the direction of V in a plane substantially parallel to the surface of the support 1010.

In the photoconductive member of the present invention such as the example shown in FIG. 1, the surface side portion of the amorphous layer (1) 102 has a layer region ( ##corresponding to the single layer region 106 shown in FIG. 1), but contains Group Ⅰ atoms but does not contain oxygen atoms (layer region 105 shown in FIG. 1)vi does not necessarily have to be provided. Don't narrow it down.

That is, for example, in FIG. 1, the first layer region 103 (0
) and the 20th layer region (III 104) may be the same layer region, or the second layer region tllD 104 may be provided in the first layer region 0) 103. It is something.

In the photoconductive member of the present invention, by containing oxygen atoms in the first layer region (0), high dark resistance and amorphous
Emphasis has been placed on improving the adhesion between the X layer (I) and the support on which it is directly provided. Emphasis has been placed on further improving humidity and corona ion resistance and increasing sensitivity. .

In particular, as in the photoconductive member 100 shown in FIG. Knee layer area (
IID104, layer region 10 containing no oxygen atoms
5, and a layer region 106 containing no oxygen atoms and Group 11 atoms, the first no region <0) 103
In the optical voice guiding member of the present invention, better results are obtained in the case of a layer structure having a layer region shared by the second layer region tII() 104. ) forms a part of the first layer region (01
vx, for the purpose of improving the adhesion of the amorphous layer (1) with the support, and also constitutes a part of the amorphous layer (rm<1) (group 2 atoms). The second layer region (l [+) contained in the amorphous layer (1) is, for one thing, the charge treatment applied from the free surface side of the amorphous layer (■) to the support side. An amorphous layer (I
3 provided in a structure in which the support body and the amorphous layer (1) share at least a part of each other as a layer region where the support and the amorphous layer (1) join as a part of body and
Alternatively, in order to more effectively improve the adhesion with the L-region provided directly on the second layer region (G),
The first layer region is separated from the contact interface with the support, and the second layer region (provided so as to include IID, the first layer region 0 so as to have a layer structure) is an amorphous layer. B (boron), AI (aluminum), Ga (gallium), In (indium), Tl (thallium), etc. are used as the middle atoms, and ri B is particularly preferably used.
, Ga. .

The content of Group Ⅰ atoms in the group may be determined as desired so as to effectively achieve the purpose of the present invention, but #-
1 - Consists of 7 layers of quality - Rui: Sealicorn Ni Primat 0 Rose Hill Ko7 1,000 Normal vi 30 ~ 5 X 10 ''' a
tornic ppm.

Preferably rJ: so~/X/04atom
ic ppm, an optimal amount of oxygen atoms is also present in the formed photoconductive member.

In the photoconductive member of the present invention, the layer thickness ta of the layer region surface containing Group (1) atoms (11 layer region 10 in FIG.
4 layer thickness), layer region (2) provided on the layer region similar]
The layer thickness T of the layer region (layer region 106 in FIG. 1) except for It is desirable that the value of the relational expression shown in (1) be 0.3S or less, most preferably 0.3 or less.

In the present invention, the layer thickness tB of the layer region containing group (I) atoms is usually 3oX to 5μ, preferably 40A-
4)'1 It is desirable to set θA-, a, and x to be optimal.

Further, the sum of the layer thickness T and the layer thickness tB (T+tn) is usually 1 to 100μ, preferably 1 to 80μ.

The optimum thickness is preferably 2 to 50μ.

V as the layer thickness to of the layer region (0) containing oxygen atoms
It is preferable that the thickness be determined in accordance with a desired purpose in relation to the layer thickness tB of the layer region (to) that shares at least a part of the layer region. In other words, if the purpose is to strengthen the adhesion between the hanging layer region (e) and the support that is in direct/pin contact with the layer region (to), the layer region 0
) is only required to be provided at least in the layer region at the end of the layer region (2) on the side of the support. ) Also, if the aim is to strengthen the adhesion between the layer region [phase] and the layer region provided directly on the layer region (corresponding to the layer region 106 in FIG. 1), , it is sufficient that the layer region 0) is provided at least in the end layer region 11 opposite to the side where the support is provided in the layer region (to), so the layer thickness to of the layer region 0) is at most 1 The layer thickness tB of the vehicle region (2) is sufficient.

Furthermore, in order to satisfy the above two points, it is necessary to have a layered structure in which layer region (2) is provided in layer region (O).

In order to more effectively measure the relationship between the layer region (2) and the layer region provided directly on the layer region (2), 1.1. Above (the side with the support and vi
It is preferable to extend it in the opposite direction.

In the present invention, the layer thickness to is C1, taking into consideration the above-mentioned points.
10 μm per person, preferably 8 μm per person.

The optimum value is 30A to 5μ.

In the photoconductive member 100 shown in FIG.
) 107 has a free surface 108 and is provided to achieve the objectives of the present invention mainly in moisture resistance, continuous repeated use characteristics, pressure resistant toilet environment characteristics, and durability.

In the present invention, the first amorphous layer (1) 102 constituting the amorphous layer (1) 102 and the second amorphous layer (
n) Since each of the amorphous materials forming 107 has a common constituent element of silicon atoms, chemical stability is sufficiently ensured in the product l-field.

The second amorphous layer 1, ■) is an amorphous material [a-(Sixc
+-x) yHt-y +However, 0<x, y<1
) is formed.

The second amorphous layer (II) composed of a-(5izC+-x)y'H+'l is formed by glow discharge method, sputtering method, ion implantation method, ion blating method, and electron beam method. etc. 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 manufacturing conditions for manufacturing a photoconductive member having the following properties. A second amorphous layer that creates carbon and hydrogen atoms along with silicon atoms (
n) The glow discharge method or the sputtering method is preferably adopted because of the advantages such as ease of introduction.3 Furthermore, in the present invention, the glow discharge method and the sputtering method are used in the same equipment system. The second amorphous layer (II
) may be formed.

To form the second amorphous layer (■) by the glow discharge method, a-(SixC+-x)y :H1'! For forming o
The raw material gas is mixed with a dilution gas at a predetermined mixing ratio as necessary, and introduced into a deposition chamber for vacuum deposition where the support 101 is installed, and the introduced gas is caused to generate a glow discharge. is applied to the first amorphous layer (1) already formed on the support 101.
1xct-x) y: HI'I t may be deposited,) In the present invention, a-(8ixO1-x)y:H+-)
As the raw material gas for formation, most gaseous substances containing at least one constituent atom of 8i+o+H or gasified substances that can be gasified can be used.

8i, 0. When using a raw material gas containing 87 as one of the H atoms, for example, a raw material gas containing Si 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 also be mixed in a desired mixing ratio. , or a raw material gas having 8ii constituent atoms; 8. It is possible to mix and use a raw material gas having three constituent atoms: i, 0, and 1.
,,1. ．． 1. : Also, apart from that! A raw material gas containing C as constituent atoms may be mixed with a raw material gas containing lll□i and H as constituent atoms.

In the present invention, 8iH, 8i2H6, 81BHB 7814H containing Si and H as constituent atoms is effectively used as the raw material gas for forming the second amorphous layer (1).
Silicon hydride gas such as silanes (8i7ane) such as Io, saturated hydrocarbons containing C and H as constituent atoms, for example, 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, as a saturated hydrocarbon, methane (OH4)
, ethane (CaI(a), propy(OH,),
n-butane (n-0,H,.), pentane (O5Hs
t),, Ethylene hydrocarbons include ethylene (C2■'L), propylene (0sHa), butene-t (04Ha), butene-2 (04Ha),
Inbutylene (CaHa), benzone (0°Hl.

)1 Acetylene hydrocarbons include acetylene (Ct
Ht), methylacetylene (0sHa), butyne (04H11), and the like.

Si and 0. ! :H as a constituent atom include alkyl silicides such as 8 i (OH3)4.8 (OsHs)a. In addition to these raw material gases, H3 is of course also used as an effective raw material gas for introducing H.

To completely form the second amorphous layer (1) by sputtering method, single crystal or polycrystalline SI kneebar or C
Wafer or Sl and 0 are mixed γ and contain c7'L-
All of these can be performed by sputtering a wafer gold target in a variety of gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gases for introducing C and H are diluted with diluting gas as necessary and introduced into the deposition chamber for sputtering. Forming plasma and forming the above S = wafer? All you have to do is sputtering.

Alternatively, sputtering can be performed in a gas atmosphere containing at least hydrogen atoms by using separate targets for Si and C, or by using a single mixed target of 8i and C. Ru.

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

In the present invention, fL used when forming the second amorphous layer (1)' by a glow discharge method or a sputtering method.
The diluent gas used is so-called noble 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.

That is, depending on the preparation conditions, the substance containing the 5Il ('l and I) gold constituent atoms can have a structure ranging from crystalline to amorphous, and electrically conductive to semiconducting to semiconducting.
Since it shows properties between insulating properties of 1 and properties between photoconductive properties and non-photoconductive properties, Himi Oboro has the desired properties depending on the purpose +4 a-S
i
'C-tf) Creation and matter.

Choices are made rigorously.

For example, to provide the second amorphous layer (H) fr for the main purpose of improving pressure resistance, a (SlxC+ x)yI
(,, is made as an amorphous material with pronounced electrically insulating behavior under the conditions of use.

In addition, when the second amorphous layer (n) is provided with the primary purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the degree of acidity described in ``2'' will be relaxed to some extent. , an amorphous material H that has a certain degree of sensitivity to irradiated light.
a-(SixO+-x)yH+-y is created as follows.

a − (SI X □
+ −X ) yH,, the second amorphous rfj consisting of y
j(1)'e When forming a layer, the temperature of the support during layer formation is an important factor that influences the structure of the formed layer and the is a-(SixO
t-x)yHt-7 places: 1 so that it can be created as desired
- It is desirable that the temperature of the support during preparation be tightly controlled. □'・4・'11゜In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the second amorphous layer (1) is as follows: It is desirable to combine it with the formation method (1).

In forming the second amorphous layer (1), it is relatively easy to finely control the composition ratio of the atoms that make up the layer and control the layer thickness compared to other methods. It is advantageous to adopt the glow discharge method or the sputtering method, but when forming the second amorphous layer (Otori) using these layer forming methods, the layer temperature should be adjusted in the same manner as the above-mentioned support temperature. The discharge power and gas pressure during formation are one of the important factors that influence the characteristics of the a(8ixO+-x)y:H,7 that is created.

a- having the characteristics for achieving the object of the present invention;
(8iXO, -x)y:H, -y is normally produced as a discharge power condition of 10~
It is desirable that the power is 30 nW, preferably 20 to 200 W. It is desirable that the gas pressure in the deposition chamber is usually about 001 to ITOrr1, preferably about 0.1 to 0.5'T'orr.

In the present invention, the desirable numerical ranges of the support temperature and discharge power for creating the second amorphous layer (1) include the values in the above ranges, but these layer creation factors are , not something that can be determined independently and separately, but an FI
21 = −(S i x(3+ −x )
It is desirable that the optimum value of each layer forming factor be determined based on the mutual organic relationship so that a second amorphous layer consisting of yH+-y is formed.

The amounts of carbon atoms and hydrogen atoms contained in the second amorphous layer (1) in the light guide member of the present invention are similar to the manufacturing conditions of the second amorphous layer (1) according to the present invention. is an important factor in the formation of the second amorphous layer (1), which provides the desired properties to achieve the objective.

The amount of carbon atoms contained in the second amorphous 11j11 (11) in the present invention is usually I X L 973-90a
tomic level, preferably 1 to 90 atrni
c %, preferably 10 to 80 atomic %. The content of hydrogen atoms is usually 1 to 40 atomic%, preferably 2 to 3 atomic%.
5 atomic%, optimally 5-30 atomic
%, and photoconductive members formed when the hydrogen content is within these ranges are excellent and can be sufficiently applied in practical applications.

That is, if we use the above expression a - (SixOs-x)yH+-y, the father would normally be 0. IH, 99999, preferably 0.1 to 0.99, optimally 015 to 0, usually 0.
6 to 0.99, preferably 0.65 to 0.98, most preferably 07 to 0.95.

The numerical range of the layer thickness of the second amorphous layer 0) in the present invention is one of the important factors for effectively achieving the object of the present invention.
It is one.

The numerical range of the layer thickness of the second amorphous layer (1) 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.
:'',・ The layer thickness of the second amorphous layer (1) is determined by the amount of carbon atoms and hydrogen atoms contained in the layer (1), and the amount of the first amorphous layer (1).
) also needs to be appropriately determined as desired based on the organic relationship depending on the characteristics required for each layer region. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production.

In the present invention, the 1-thickness of the second amorphous layer (1) is usually ρθo, 3-. 30A preferably θ, θθ4~20
/A It is desirable that θ, θ(K-70) be optimal.

The support used in the present invention may be either electrically conductive or electrically insulating. Examples of the conductive support include N10r and stainless steel.

A/, Or, Mo, Au, Nb, Ta, V, Ti, P
Examples include metals such as T, Pd, and alloys thereof.

Polyester is used as the electrically insulating support.

Polyethylene, polycarbonate, cellulose (.

Acetate, polypropylene, polyvinyl chloride.

(Polyvinyl chloride) (2) Polystyrene (1) Polyamide (1).

Synthetic resin films or sheets, glass, etc.

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

For example, if it is glass, Ni0r is applied to its surface.

Al, (,!r, Mo, Au, Ir, Nb
, 'I''a, V, 'l'i, Pt, Pd.

In2(-,'l8,8n02, I',I'C1
Conductivity is imparted by providing a thin film made of (In, 03+ 5n02), etc., or if it is a synthetic resin film such as polyester film, Ni0r, Ae
, Ag, pb, Zn, Ni, Au.

Or, MO, Ir, Nl), Ta, V, Ti
, l', etc., on the surface by vacuum evaporation, steron beam evaporation, sputtering, or the like, or by laminating the surface with the metal described above, to impart conductivity to the surface. The shape of the support is cylindrical.

The photoconductive member 1 shown in FIG.
If 0 is used as an image forming part for electrophotography, it is desirable to have an endless belt shape or a cylindrical shape in the case of continuous high-speed copying. 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.

Hyakuen et al. In such cases, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is usually set to 10P or more.

In the present invention, the amorphous layer (+) composed of a-8i (H, done by law. for example,
In order to form the amorphous layer (1) composed of a-8i (H, , for introducing a hydrogen atom (H) or/and a halogen atom (X
) A raw material gas for introduction is introduced into a deposition chamber whose inside can be made to have a reduced pressure, and a glow discharge is generated in the deposition chamber, and a-8i
(f(rX)).Also, when forming by sputtering, for example Ar,)(e
When sputtering a target composed of Si in an atmosphere of an inert gas such as gas or a mixed gas based on these gases, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) is used. It may be introduced into a deposition chamber for sputtering.

In the present invention, the halogen atoms (X) contained in the amorphous layer (X) are specifically fluorine,
Examples include chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

The raw material gas for S1 supply used in the present invention is SiH, 5i2T(, 8i, H8, 5ijl,
. etc. (7) Silicon hydride in a scum state or capable of being gasified (
Silanes) are mentioned as those that can be used effectively, and S1) (4Is i, H6 are particularly preferred in terms of ease of handling in layer creation work, good 8i supply efficiency, etc.) .

Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogenated compounds having the following formula:

Furthermore, it can be obtained in a gaseous state or in a gasified state containing silicon atoms and halogen atoms as constituent elements.

Silicon compounds containing halogen atoms are also effective in the present invention.

The halogen compounds preferably used to obtain H2 in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, O/F, O, /F.

BrP, , BrF8. TF, , IP, ,
Examples include halogen compounds such as TCl and IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, 8
+F418+, H6, S+O/, , 8+Br4, etc. 17 are listed as preferable examples of rogenated silicon pot 1. "□" 1 When forming the characteristic light guide paper member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride is used as a raw material gas capable of supplying 8i. Even without using a gas, an amorphous layer (1) consisting of a-84 containing rogen atoms is formed on a predetermined support.
-Can be formed.

According to the glow discharge method, an amorphous layer containing halogen atoms (
1), basically, silicon halide gas, which is the raw material gas for supplying 81, and gases such as Ar, H2, He, etc. are mixed at a predetermined mixing ratio and gas flow rate to form an amorphous material. An amorphous layer (f) can be formed on a given support by introducing the amorphous layer (f) into a deposition chamber for forming layer 0) and generating a glow group 11 to form a plasma atmosphere of these gases. However, in order to introduce hydrogen atoms, a layer may be formed by mixing a predetermined amount of a silicon compound gas containing hydrogen atoms with these gases.

Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio.

Amorphous layer (1) f consisting of a-8i(H,X) by reactive sputtering method or ion blating method
For example, in the case of sputtering method, S
Sputtering is performed in a predetermined gas plasma atmosphere using a target consisting of i, 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 This can be done by heating and evaporating the source using a resistance heating method, an electron beam method (EB method), or the like, and passing the flying evaporated material through a tube in a predetermined gas plasma atmosphere.

At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion blasting method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to introduce the gas and completely form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H2 or a gas such as the nine silanes mentioned above, is introduced into a deposition chamber for sputtering and formed into a plasma atmosphere of the gas. bM.

Just do it.

In the present invention, the halogen compounds mentioned above or the silicon compounds containing halogen are used as effective raw material gases for introducing halogen atoms.
In addition, Kake', HCI.

Hydrogen halides such as HBr, HI, SiH, F,
, 8 iH, I 2°8iH, (J2.5iHCl
, , SiH, Br, 1.5i) I) 3r, etc., halogen-substituted silicon hydrides, etc., which are in a gaseous state or can be gasified, and halides as one of the total constituents of hydrogen atoms are also effective amorphous layers. (1) Can be mentioned as a starting material for formation.

These halogen compounds containing hydrogen atoms form an amorphous layer (
During the formation of 1), 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. 0 raw materials ″″::2;S:2;1. . 1,・□1.
6°. , 46°, in addition to the above, Hl or SiH
4, Si! H6.

8i, H8,5i4H,. S of silicon hydride gas such as
This can also be achieved by causing release of K by coexisting in the deposition chamber with a silicon compound for supplying i.

For example, in the case of the reactive sputtering method, an 8i target tray is used, and a gas for introducing halogen atoms, H, and gases are introduced into the deposition chamber, including an inert gas such as He I Ar as necessary, to generate a plasma. An atmosphere is formed, and the S
By sputtering on l targetera l-',
An amorphous layer (1) made of asi (ratio X) is formed on the support.

Furthermore, it is also possible to introduce a gas such as B, H, etc., which also serves as impurity doping.

In the present invention, an amorphous layer (1
), the amount of hydrogen atoms (H) or the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms, (H
(10X) is usually 1 to 40 atomic%, preferably 5 to 30 atomic%. Shi゛・□.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the amorphous layer (1), for example, the support temperature may be controlled by controlling the amount of hydrogen atoms (H) or halogen atoms (X). The amount of the starting material used to contain (X) introduced into the deposition system, the discharge force, etc. may be controlled.

A layer region (layer) containing a group atom in the amorphous layer (1)
In order to provide a layer region (0) containing oxygen atoms, an amorphous layer (0) is formed by a glow discharge method, a reactive sputtering method, etc.
In addition to the formation of 1), an amorphous layer (1) containing a large number of the starting materials for introducing the group atom and the starting material for introducing the oxygen atom.
Amorphous layer (1) is formed by using it together with a forming substance and controlling its amount in the layer to be formed. A layer region containing enzyme atoms (0) and a layer region containing No. 1 Otori group atoms (1
), the starting material that becomes the raw material gas for forming each layer region may be selected from the starting materials for forming the amorphous layer (1) described above or from among the starting materials as desired. The starting material for introducing oxygen atoms into the haze or/
and the starting material for the introduction of Group 1 atoms. Such a starting material for introducing an oxygen atom or a starting material for introducing a group atom may be a gaseous substance containing at least an oxygen atom or a constituent atom of a group atom, or a gaseous substance containing at least an oxygen atom or a constituent atom of a group atom. Most of them can be used.

For example, if layer region (0) is to be formed, a raw material gas containing silicon atoms (Si) and # elementary atoms (
A raw material gas containing 0) as constituent atoms and a raw material gas containing hydrogen atoms (, H) or/or halogen atoms (x) f as necessary in a desired mixing ratio are used. Or, the raw material gas containing silicon atoms (Si)e and the raw material gas containing oxygen atoms (0) and hydrogen atoms (H) are also mixed at a desired mixing ratio. , or a raw material gas whose constituent atoms are silicon atoms (8i), silicon atoms (Si), and oxygen atoms (0)
and a raw material gas having three constituent atoms of hydrogen atoms (H) can be mixed and used.

Alternatively, a raw material gas having silicon atoms (Sl) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas having oxygen atoms (0) as constituent atoms.

Specifically, starting materials for introducing oxygen atoms include, for example, oxygen (Cot), ozone (Oa), -nitrogen oxide (NO), nitrogen dioxide (Not), and -nitrogen dioxide (Nt).
O), nitrogen sesquioxide (NtOs), nitrogen tetroxide (N2
O4), nitrogen sesquioxide (N20.), nitrogen trioxide (
For example, disiloxane H, 5iO8iH3,) disiloxane H48i ('
) 81H20s iH, etc. can be mentioned. In the present invention, when forming a layer region using the total glow discharge method, B, H, B, H,
, B, H, tank, Bs1Ho, E3sl(t+, BI
IHI. .

11 Boron hydride such as B6H11 and B6H14%' Br3.
BOn8. BBr.

Examples include boron halides such as. In addition, klo
ll, Ga0l8. Ga(OHs)s, I n0
13. Tlo13 and the like can also be mentioned.

The content of the group atoms introduced into the 1-region (1) containing all group atoms is the amount of the group atoms introduced into the deposition chamber.
Gas flow rate, gas flow rate ratio, discharge power of starting material for human use,
It can be arbitrarily controlled by controlling the support temperature and the pressure in the deposition chamber.

To form the entire layer region (0) containing acid:A atoms by a sputtering method, a monocrystalline or polycrystalline Si wafer or Sin, wafer, y, is Si and S t
This can be carried out by sputtering a nine-needle ligation target containing a mixture of Ot in various gas atmospheres.

For example, if a Si wafer is used as a target, a raw material gas ', for introducing oxygen atoms and optionally hydrogen atoms or/and halide atoms.

may be diluted with 1" dilution gas if necessary and introduced into a deposition chamber for sputtering to form a gas plasma of these gases to sputter the St wafer.

Also, separately, 81 and 8i0. By using a single mixed target of Si and sio as a separate target from the d, at least hydrogen atoms (F(
) Father is / & H halogen atom (X) All constituent elements 2 F and 1. It is formed by sputtering in a gas atmosphere containing

As the raw material gas for introducing oxygen atoms, the oxygen in the raw material gas shown in the example of the 7ζ Glo Ichipoku mentioned above is used! Even if the raw material gas for Toko introduction is a sputter link, it will be a noisy gas (
2. Used and prayed.

In the present invention, the diluting gas used when forming the crystalline layer by glow radiation h'f, or the sputtering gas used in the past when forming it by the Oma sputtering method is used.゛In the case of standard rust gases such as He, Ne, A
It can be concluded that r etc. are good -14.

Next, a method of manufacturing the nine-piece electric wire formed by the glow discharge decomposition method will be described.

FIG. 2 shows an apparatus f for producing Gendou Kamebe printing using the glow discharge decomposition method.

202, 203, 204, 205, 206 in the diagram
The gas cylinders are sealed with raw material gases for each of the inventions.
9.999%, hereinafter abbreviated as Sin,/He. ) To the Hon.
The second area is ← Te, and the returned B 2) (, gas (purity 99.999%).

The following 1 (abbreviated as 2H6/He) cylinder 204 is a 5i2H,l gas (purity 99.99%, hereinafter 5i2H,/He) diluted with He.When introducing halogen atoms into the layer to be formed, 8 + Instead of H4 gas or Si, H6 gas, you can change the cylinder to use SiF4 gas, for example.

Koi 1. (I) The K to be injected into the reaction chamber 201 is the pulp 222-226 of the gas cylinders 202-206.
, the leak pulp 235 is closed, and the inflow pulps 212-216 and the outflow pulps 217-22
1. Confirm that Urasuke Pulp 232 and 233 are open, and first open the main valve 234 and open the reaction chamber 2.
011 Exhaust the inside of the gas pipe. Then, at time i when the vacuum 1236 reads approximately 5X] and 0-6 torr, the auxiliary valves 232, 233 and the outflow valves 217-212 are closed.

Base cylinder 2; (An example is given in which the first amorphous layer (1) is completely formed in 7 hours. From the gas cylinder 202, S
i t-i, / t-t e gas, gas cylinder 203
132H6/) (e gas, gas cylinder 2f)6. '
CBJo Kasuno Kehalup 222, 223, 22
6 and adjust the ratios of the outlet pressure gauges 227, 228 and 231 to 1 kg/crl K and H+4, respectively, and gradually open the inlet valves 212, 213 and 216 k,
Mass flow controller → 07, 208, 211 BiJ
to flow into. Subsequently, outflow pulp 217, 218
, the auxiliary pulses 7'' 232 , 233 'c are gradually opened and the respective gases are poured into the reaction chamber 201 .

bll at this time, (4/L (e gas flow meter, IJ2+l
, / lie gas, , , flow, , fence 2, N regas flow -
The outflow pulp 217 so that the ratio of
, 218° and 221', and vacuum tri 23 so that the pressure inside the reaction chamber 201 becomes 111 as desired by PJT.
Open the main valve 2:14 while reading 6.
adjust. After confirming that the temperature of the base cylinder 237 is set to a temperature in the range of 50 to 4 (10"0) by the heating heater 238,
Set to the '1 force of IJi Shen to generate anti-Lp, glow release zone in the + chamber 201.Base cylinder 2: (7-1-) First, form a 1m head containing IJi elements and oxygen. do.

At this time, when the time has elapsed, the gas or NO gas is introduced into the reaction chamber 20 by closing the valve of the corresponding gas introduction pipe A1. In particular, the layer thickness of the boron-containing J-region or the oxygen-containing layer region can be controlled as desired.

After the layer regions containing boron and oxygen, respectively, are formed in the ψ layer region as shown in [26], the outflow pulp 218, 22
1's husband closes the dinner party and continues to glow, 4(,,,-
JTψ time sequence 4: l (,, B j h layer region containing boron and boron, respectively - boron and oxygen are not contained) - region is formed to a desired layer thickness, Formation of the first amorphous layer (1) is completed.

When a halogen atom is contained in the first region 1-, the above gas is, for example, SrF4/Hek, 1! and sent into the reaction chamber.

A second amorphous layer J is formed on the first amorphous layer 1m (1) formed on the base cylinder 237 by an operation similar to that described above.
i! To form 4(++)i, the first amorphous 'ffl
For example, SiH4 gas and 02H4 gas are diluted with diluent residue such as He if necessary, and flowed into the reaction chamber 201 at a desired flow rate by the same valve operation as in the case of forming 1 m (1). , by generating a glow discharge according to desired conditions.

It is unnecessary to close all outflow valves other than the gas outflow valves necessary to form each layer completely, and when forming each layer, the gas used for forming the previous layer is not allowed to flow through the reaction chamber 201. Inside, from the outflow pulp 217 to 221 to the reaction chamber 20
In order to avoid remaining in the gas piping leading to 1,
Close the outflow pulp 217 to 221 and close the auxiliary valve 232,
If necessary, the main valve 233 is opened, the main valve 234 is fully opened, and the system is once evacuated to a high vacuum.

Father, while layer formation is taking place, I- uniformity of formation is 11”
To achieve this, the base cylinder 237 is rotated by the motor 239 at a desired speed.

/ Layer formation was performed on an aluminum substrate under the following conditions.

Table 1 Photosensitive drum thus obtained (image forming member for electrophotography)
It was installed in all copying machines, corona charging was performed at θ5 kV for 0.2 seconds, and a light image was irradiated. A tungsten lamp was used as the light source, and the light intensity was 1 Olux·sec. The latent image was developed using a charged developer (including toner and carrier) and transferred to ordinary paper, and the transferred image was extremely good. The toner remaining on the photosensitive drum without being transferred is cleaned by a rubber blade and transferred to the next copying process. Even when such steps were repeated over 150,000 times, no deterioration of the image was observed. Layer formation was carried out under the following conditions.

Other conditions were the same as in Example 1.

The photosensitive drum thus obtained was installed in a copying machine, and (g) corona charging was performed at 5 kV for 0.2 see, and a light image was irradiated. The light source uses a tungsten lamp, and the light intensity is 1
, Olux-see and *O latent image were developed with a developer (containing toner and carrier) and transferred to ordinary paper, and the transferred image was very good. Toner remaining on the photosensitive drum 10 without being transferred is cleaned by a rubber blade, and the toner is moved to the next copying process. Even after repeating this process more than 100,000 times, no deterioration of the image was observed.

Example 3 Using the apparatus shown in FIG. 2, layers were formed on an AJ substrate under the following conditions. Table 3 Other conditions were the same as in Example 1.

Install the photosensitive drum thus obtained in a copying machine, and
Corona charging was performed at kV for 0.2 sec, and a light image was irradiated. A tungsten lamp is used as the light source, and the light intensity is 1.
O1ux-t, ec. The latent image was developed with a θ-charged developer (containing toner and carrier) and transferred to ordinary paper5, but the transferred image was very good and had a high density.It remained on the photosensitive drum without being transferred. The toner is.

Even after repeating this procedure, which involves cleaning with a rubber blade and moving on to the first 0 copying process, over 150,000 times, no deterioration was observed in the first imager.

Layer formation was carried out in exactly the same manner as in Example 1 except that the content of atoms and carbon atoms was varied. The process up to transfer was repeated about 50,000 times using the method described in Example 1 for the thus obtained photosensitive drum, and then the image quality was evaluated, and the results shown in Table 4 were obtained.

Table 4: Layer formation was performed in the same manner as in Example 1, and the evaluation results are as shown in the table below.Table 5: Layer formation was performed in the same manner as in Example 1, and the evaluation results were good. The results were obtained.

Table 6 shows that layers were formed in the same manner as in Example 1, and good results were obtained when evaluated.

[Brief explanation of drawings]

FIG. 1 is a schematic layer configuration diagram schematically showing the layer structure of a preferred embodiment of the photoconductive member of the present invention, and FIG. 2 is an example of an apparatus for manufacturing the photoconductive member of the present invention. This is a schematic explanatory diagram showing ah.

Claims (1)

[Claims] (1) consisting of a support for a photoconductive member and an amorphous material having a silicon atom as a matrix and containing at least either a hydrogen atom or a hydrogen atom as a constituent atom;
In a photoconductive member having a first amorphous layer exhibiting photoconductivity, the first amorphous layer includes a first layer region containing oxygen atoms as constituent atoms, and a first layer region containing oxygen atoms as constituent atoms, and a first layer region containing oxygen atoms as constituent atoms. a second layer region containing atoms belonging to Group 1, which share at least a part of each other and are internalized toward the support side; The layer thickness is tB
If the difference between the layer thickness of the first amorphous layer and the layer thickness tB of the second layer region is T, then the relationship tB/(T+tB)≦0.4 is established, and the first A light guide 1; member comprising a second amorphous layer made of an amorphous material containing silicon atoms, carbon atoms, and hydrogen atoms as constituent atoms on the amorphous layer.