JPS6088954A - Photoconductive member - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to optical 4-electromagnetic waves that are sensitive to electromagnetic waves such as light (here, light in a broad sense refers to ultraviolet light, visible light, infrared radiation, X-rays, gamma waves, etc.). Regarding parts.

Photoconductive materials that form photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the manufacturing field, and document reading devices have high sensitivity and low signal-to-noise ratio [photocurrent (IP)].
/dark current (Id)), has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has a desired dark resistance value, and is harmless to the human body during use. Furthermore, in solid-state imaging devices, characteristics such as being able to easily process afterimages within a predetermined time are important.In particular,
In the case of an electrophotographic imaging member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned harmlessness during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as a-8t) is a photoconductive material that has recently attracted attention, for example, German Publication No. 2746967 and German Publication No. 285.
It is described in Japanese Patent No. 5718 as an image forming member for electrophotography, and in German Publication No. 2933411 as an application to a photoelectric conversion/reading device.

According to Heigo et al., a photoconductive member having a photoconductive layer composed of conventional a-81 has excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are points that can be further improved in terms of use environment characteristics and stability over time in order to improve overall characteristics.

For example, when applied to an electrophotographic image forming member, when trying to achieve high light sensitivity and high dark resistance at the same time, in the past, residual potential often remained during use, and this type of light When a conductive member is used repeatedly for a long time, fatigue accumulates due to repeated use, resulting in so-called residue.

- Inconveniences often occur, such as a strike phenomenon occurring or a gradual decline in responsiveness when used repeatedly at high speeds.

Furthermore, a-8i has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, there is still room for improvement in the sense that it is not possible to effectively use light on the longer wavelength side when using commonly used halogen lamps or fluorescent lamps as a light source.

In addition, if the irradiated light is not sufficiently absorbed in the photoconductive layer and the amount of light reaching the support increases, the reflectance of the support itself to the light transmitted through the photoconductive layer will decrease. When it is high, interference due to multiple reflections occurs within one photoconductive layer, which is one of the causes of "blurring" of images.

Is this influence due to the irradiation to increase the resolution? The smaller the cut is, the larger the light becomes, which is a big problem especially when a semiconductor radar is used as a light source.

Furthermore, when forming a photoconductive layer using an a-8i material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and control of electrical conductivity are added. For this reason, boron atoms, phosphorus atoms, etc., and other atoms for improving properties are contained in the photoconductive layer as constituent atoms, but depending on how these constituent atoms are contained, However, problems may arise in the electrical or photoconductive properties 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 the injection of charge from the support side is not sufficiently prevented in a dark area, etc. There are quite a few.

Furthermore, when the thickness of one layer becomes more than 10 microns or more, the layer may be removed from the vacuum deposition chamber for layer formation, and as the time passes and the layer is left in the air, the layer may become trapped, lifted or peeled from the surface of the support, or the layer may This resulted in problems such as the formation of cracks. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and it is important to solve this problem in terms of stability over time. .

Therefore, while the characteristics of the a-8t material itself are improved, the above-mentioned considerations are made when designing the photoconductive member.

This invention has been made in view of the above points, and a-8i
As a result of comprehensive research and consideration from the viewpoint of applicability and applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we have found that silicon atoms are the base material. An amorphous material containing at least one of a hydrogen atom (b) or a halogen atom (1), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as these generic terms] as “a
-81 (using I(, This photoconductive material not only exhibits extremely superior properties in practical use, but also surpasses conventional photoconductive materials in all respects, especially as a photoconductive material for electrophotography. This invention is based on the discovery that the material has excellent absorption characteristics on the long wavelength side. It is an all-environment type with almost no restrictions on the usage environment, has a photosensitivity characteristic on the long wavelength side, is extremely resistant to light fatigue, does not cause deterioration even after repeated use, and has no or no residual potential. The main objective is to provide a photoconductive member that is hardly observed.

Another object of the present invention is to have high photosensitivity in the entire visible light range, especially with semiconductor radars! It is an object of the present invention to provide a photoconductive member which is excellent in tinging and has a fast photoresponse.

Another object of the present invention is to provide excellent adhesion between the eyebrows provided on the support and the support and between each of the laminated layers, to have a dense and stable structural arrangement, and to provide high layer quality. An object of the present invention is to provide a photoconductive member.

Another object of the present invention is to provide charge retention properties during charging processing for electrostatic image formation to such an extent that ordinary electrophotographic methods can be applied very effectively when used as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member which has excellent electrophotographic properties with sufficient electrophotographic properties and whose properties hardly deteriorate even in a humid atmosphere.

Still another object of the present invention is to provide a photoconductive member for electrophotography in which it is easy to obtain high-quality images with a high zero degree, clear halftones, and high resolution. .

Yet another object of the present invention is to provide a photoconductive member having high photosensitivity, high signal-to-noise ratio characteristics, and good electrical contact with the support.

The photoconductive member of the present invention is composed of a support for the photoconductive member, a first layer region (G) made of an amorphous material containing dalmanium atoms, and an amorphous material containing silicon atoms. A second 7 iV region (S) exhibiting photoconductivity was composed of a first layer of layers If'ff provided in order from the support side and an amorphous Hamura layer containing silicon atoms and oxygen atoms. and a light-receiving layer composed of a second layer, and the first layer contains carbon atoms. The photoconductive member of the present invention can solve all of the above-mentioned problems, and exhibits extremely excellent electrical, chemical, photoelectric properties, electrical pressure resistance, and use environment properties.

In particular, when applied as an electrophotographic imaging member,
It has no influence of residual potential on image formation, has stable electrical characteristics, high sensitivity, and a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and has high density.
It is possible to stably and repeatedly obtain high-quality images with clear halftones and high resolution.

In addition, the optical 6t member of the present invention has a strong light-receiving layer itself formed on the support and has excellent adhesion to the support, so that it can be repeatedly used continuously at high speed for a long time. be able to.

Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, particularly excellent matching with semiconductor radar, and fast photoresponse.

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

FIG. 1 shows an example of a first embodiment of the present invention.

The photoconductive member 100 shown in FIG. 1 has a first layer (1) 102 and a second layer (n) i 03 on a support 101 for the photoconductive member, and Layer (It) t
o a has a free surface 106 on one end face.

The first layer (1) 102 is made of an amorphous material containing germanium atoms and, if necessary, at least one silicon atom, one hydrogen atom, and one Halodan atom from the support i o i n+. Hereafter, j a -Ge(sl, u,
X) A first layer region (G) composed of (abbreviated as j)
10.4 and a second layer region (S) 105 composed of a-8t(H,X) and having photoconductivity are laminated in this order.

Dalmanium atoms contained in the first layer region side 104 are continuous and uniform in the layer thickness direction of the first layer region (G) 104 and in the in-plane direction parallel to the surface of the support 1010. The first layer region (G)
104.

In the present invention, a yc column 1-A? is provided on the first layer region (G). r nh Roni Q1 Yamatf I juice does not contain rumanium ltm-7-u, and by forming the first layer (1) in such a layered structure, it can be compared from relatively short wavelengths including the visible light region. The photoconductive member can be made into a photoconductive member that has excellent photosensitivity to light of wavelengths in the entire range up to short wavelengths.

Furthermore, the distribution state of germanium atoms in the first layer region (G) is such that dahmanium atoms are continuously distributed in the entire layer region, so that the distribution state of germanium atoms in the first layer region (G) and the second layer region (G) are different. Layer area ■
), and when a semiconductor laser or the like is used, the long-wavelength light that is almost completely absorbed by the second layer region @) is transferred to the first layer region (G). It is possible to substantially completely absorb the light and prevent interference due to reflection from the surface of the support.

Further, in the photoconductive member of the present invention, the first layer region (G
) contains silicon atoms, the first layer region (G
) and the second layer region (S) each have a common constituent element of silicon atoms, so that chemical gas stability can be sufficiently ensured at the laminated interface. has been done.

In the present invention, the content of rumanium atoms contained in the first layer region (G) is determined as desired so as to effectively achieve the object of the present invention. Preferably 1 to 10 X 10 a for the sum with atoms
tomlc pprfh More preferably 100 to 9.
5 X 105 atoms 1c ppm 5 optimally 50
0 to 8 x 10 atomic ppm - In the present invention, the layer thickness of the first layer region (G) and the second layer region (S) is determined to effectively achieve the object of the present invention. As this is one of the important factors, great care must be taken in the design of the photoconductive member to ensure that the desired properties are fully imparted to the photoconductive member formed.

In the present invention, the layer thickness T of the first layer region (G) is preferably I'130X to 50μ, more preferably 40μ to
40μ, optimally 50X to 30μ.

Further, the layer thickness T of the second layer region (S) is preferably 0.5
~90μ, preferably 1-80μ, optimally 2-5
It is assumed to be 0μ.

The sum (T, +T) of the layer thickness TB of the first layer region IG) and the layer thickness T of the second layer region 0) is determined by the characteristics required for both layer regions and the entire first layer (1). It is appropriately determined as desired when designing the layers of the photoconductive member, based on the organic relationship between the characteristics and the characteristics to be determined.

In the optoelectronic member of the present invention, the numerical range of the above (T, +T) is preferably 1 to 100μ, more preferably 1 to 100μ.
80μ, optimally 2 to 50μ.

In a more preferred embodiment of the present invention, the above-mentioned layer thickness TB and layer thickness T are preferably set to appropriate values so as to satisfy the relationship T, /T≦1. Preferably selected.

In selecting the layer thickness TB and the layer thickness T value in the above case, it is preferable that the relationship Tm/T≦0.9, optimally TB/T≦0.8, be satisfied. layer thickness TB
and the value of the layer thickness T is determined.

In the present invention, the content of germanium atoms contained in the first layer region (G) is I x 105 atomic
ppm or more, the layer thickness Tl of the first layer region 6)
is desirably as thin as possible, preferably 30μ
The following shall apply.

In the photoconductive member of the present invention, the first layer (1) is used for the purpose of increasing photosensitivity and dark resistance, as well as improving the adhesion between the support and the first layer (1). Layer (1) contains carbon atoms. The carbon atoms contained in the first layer (1) may be contained in the entire layer area of the first layer (1) without the blade side, or may be contained in a part of the first layer (1). It may be contained and unevenly distributed only in the layer region.

Further, the distribution state of carbon atoms may be such that the distribution concentration C (C) thereof may be uniform or non-uniform in the layer thickness direction of the first layer (1).

In the present invention, when the main purpose is to improve photosensitivity and dark resistance, the layer region (C) containing carbon atoms provided in the first layer (1) is (1), and when the main purpose is to strengthen the adhesion between the support and the first layer (1), the first layer (1) ) is provided so as to occupy the area of the support-side sealing layer.

In the former case, it is desirable that the carbon atoms contained in the layer region C) be reduced, while in the latter case, the carbon atoms contained in the layer region C) should be relatively increased in order to ensure enhanced adhesion to the support.

Also, for the purpose of achieving both the former and the latter at the same time,
The first layer (
Carbon atoms are distributed at a relatively low concentration on the second layer (n) side of 1), or carbon atoms are distributed in the interface layer region of the first layer (1) on the second layer (II) side. It is sufficient to form a distribution state of carbon atoms in the layer region (C) such that carbon atoms are not actively contained.

In the present invention, the layer region (
The content of carbon atoms contained in C) depends on the characteristics required for the layer region (C) itself, or when the layer region (C) is provided in direct contact with the support, the content of the carbon atoms in the support It can be selected as appropriate based on the organic relationship, such as the relationship with the properties at the contact interface with the material.

In addition, if another layer region is provided in direct contact with the layer region (Q), the relationship with the characteristics of the lumbosacral layer region and the characteristics at the contact interface with the lumbosacral layer region.・The amount of carbon atoms contained in the layer region (C) is determined as desired according to the characteristics required of the photoconductive member to be formed. The content is preferably o, ooi to 5° atomic%, more preferably 0.003 to 30 atomic%.

In the present invention, the layer region (C) occupies the entire area of the first layer (1), or even if it does not occupy the entire area of the first layer (1), the layer area (Q) of the layer thickness T0 Layer thickness T of first layer (I)
When the proportion of carbon atoms in the layer region (C) is large, it is desirable that the upper limit of the content of carbon atoms contained in the layer region (C) is sufficiently smaller than the above value.

In the case of the invention, the layer thickness T of the layer region (C). When the proportion of wood carbon atoms in the layer thickness T of the first layer (1) is two-fifths or more, the upper limit of the amount of wood carbon atoms contained in the layer region (C) is as follows: It is preferably 30 atomic% or less, more preferably 29 atomic% or less, and optimally 10 atomic% or less.

2 to 10 show typical examples of the distribution state of carbon atoms contained in the layer region (C) of the photoconductive member of the present invention in the layer thickness direction.

In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of carbon atoms, the vertical axis represents the layer thickness of the layer region (C), and tB represents the position of the end surface of the layer region (C) on the support side. , tT indicates the position of the end surface of the layer region (Q) on the side opposite to the support side.

That is, the layer region (C) containing carbon atoms is formed as a layer from the t8 side toward the tT side.

FIG. 2 shows a first typical example of the distribution state of carbon atoms contained in the layer region (Q) in the layer thickness direction.

In the example shown in FIG. 2, from the interface position tB where the surface of the support where the layer region (C) containing carbon atoms is formed and the surface of the layer region (C) contact, the carbon Carbon atoms are contained in the layer region (C) where carbon atoms are formed while the distribution concentration C (C) of atoms takes a constant value C1, and the carbon atoms are contained in the layer region (C) where the atoms are formed, and the position t1
The concentration is gradually and continuously decreased from C2 until reaching the interface position tTK. At the interface positions t and r, the distribution concentration C (C) of carbon atoms is C3.

In the example shown in FIG. 3, the distribution concentration C of the contained oxygen atoms is from position t to the concentration C4 up to position t7.
Gradually and continuously decreases from the position tf to the lagoon office Cμh
Formation of a ladder distribution pattern 1. In the case of Figure 4, the distribution concentration C (C) of glandular atoms at position t2t is set to a constant value of concentration C6 from position tB, and gradually and continuously between position t2 and position tT. The distributed concentration C (C'l) is substantially zero at the position tT (substantially zero here means less than the detection limit amount).

In the case of FIG. 5, the distribution concentration C of carbon atoms is continuously and gradually decreased from the concentration CB from position t to position tT, and becomes substantially zero at position tT.

In the example shown in FIG. 6, the distribution concentration C (C
) is a constant value of density C9 between position tB and position 13, and is set to be the density ate at position tT. Between the position t3 and the position tT, the distribution concentration C is linearly positioned from the position t3 and is decreased until it reaches T.

In the example shown in FIG. 7, the distribution concentration C is at the position tB.
The concentration C1l takes a constant value until position t4.
From 4 to position tT, the density is −2 to the performance CIS −
It is assumed that the distribution state decreases in number.

In the example shown in FIG. 8, from position tB to position tT, the distribution concentration C (C) of carbon atoms decreases linearly from the concentration C14 to substantially zero.

In FIG. 9, from position tB to position ts, the distribution concentration C (C) of carbon atoms is smaller than the concentration C15.
11l in a linear function, and the positions t5 and tT
An example is shown in which the concentration CtS is set to a constant value between .

In the example shown in FIG. 10, the distribution concentration c (C) of carbon atoms is the concentration CI? at position tB? The concentration C17 is initially slowly decreased until reaching the position t6, and then rapidly decreased in the vicinity of the position t6 to reach the concentration cis at the position t6.

Between position t6 and position t7, the concentration is decreased rapidly at first, and then gradually decreased until the concentration reaches 01G, and between position t7 and position ts, the concentration is extremely slowly and gradually decreased. The concentration C at position 1° is reduced.
It reaches 20. Between the position ta and the position tT, the concentration decreases from C20 to substantially zero according to a curve shaped as shown in the figure.

As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of carbon atoms contained in the layer region (C) in the layer thickness direction, in the present invention, on the support side , has a portion where the distribution concentration C (C) of carbon atoms is high, and the distribution state of carbon atoms has a portion where the distribution concentration C (C) is considerably lower on the interface tT side than on the support side. C).゛In the present invention, the layer region (C) containing carbon atoms constituting the first layer (1) is a region containing carbon atoms at a relatively high concentration on the side of the support as described above. Current area (
B) is desirable, and in this case, the adhesion between the support and the first layer (I) can be further improved.

The localized region (B) is desirably provided within 5 μm from the interface position tB, if explained using the symbols shown in FIGS. 2 to 10.

In the present invention, the localized region (B) is located at the interface position t
It may be the entire layer region (LT) up to a thickness of 5 μm from n, or it may be a part of the layer region (LT).

Whether the localized region is a part or all of the layer region (LT) is determined as appropriate depending on the characteristics required of the first layer (1) to be formed.

The localized region (J3) is defined as the distribution state of the carbon atoms contained therein in the layer thickness direction, with the maximum value cm of the distribution concentration of carbon atoms.
The layer is formed so that a distribution state can be obtained in which hx is preferably 500 atomic plx or more, more preferably 800 atomic ppm or more, and optimally 1000 at 1000 ato or more.

That is, in the present invention, the layer region (C) containing carbon atoms has a layer thickness of within 5 μm from the support side (5 μm from tB).
It is desirable to form the layer so that the maximum value Cm&X of the distribution concentration C (C) exists in the layer region of μ thickness.

In the present invention, the halogen atoms (3) contained as necessary in the first layer region (G) and the second layer region constituting the first layer (1) are specifically is fluorine,
Mention may be made of chlorine, bromine, iodine, especially fluorine-I-LPt.
4 - Momikuyashi^L1i acceptance and shi ≠; appearance.

In the present invention, in order to form a-Ge (in the first layer region composed of Sl, H, It is done by a deposition method. For example, a-Ge(St, a
In order to form the first layer region (G) composed of #x), for example, a raw material for supplying Go that can supply germanium atoms (Ge) and, if necessary, silicon atoms (Ge) are required.
) and the raw material gas for introducing hydrogen atoms or/and the raw material gas for introducing norodane atoms (3) into a deposition chamber whose interior can be made to have a reduced pressure with the desired gas. A glow discharge may be generated in the deposition chamber under pressure to form a layer on the surface of a predetermined support that has been placed in a predetermined position. When germanium atoms are contained in the first layer region (G) with a non-uniform concentration distribution, the distribution concentration of dalmanium atoms is controlled according to a desired rate of change curve, and the first layer region (G) is composed of @-Ga (St@H1X). It is sufficient to form a layer. In addition, when forming by a sputtering method, for example, a target composed of SL in an atmosphere of an inert gas such as Ar*He or a mixture of these with a space as a base, or a target composed of SL, or the target is formed of Ge. He5Ar can be used as needed using two sheets of the configured targut or using a mixed targut of si and Go.
The raw material for supplying Ge diluted with S and the gas for introducing hydrogen atoms (6) or/and halodane atoms (X) as necessary are added to the deposition chamber for sputtering. This is accomplished by introducing the desired gas into a plasma atmosphere.

At this time, by controlling the gas flow rate of the raw material for supplying Ge according to a desired rate of change curve, and by sagging or sagging the target, the distribution concentration of dalmanium atoms in the first layer region (G) can be adjusted as desired. can be controlled.

In the case of the ion grating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline dalmanium or single crystal germanium are housed in a deposition cart as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. (EB method), etc., and the flying evaporates are passed through the desired gas plasma atmosphere.
This can be done in the same manner as in the sputtering method.

Examples of substances that can be used as the raw material for supplying S1 in the present invention include 5iH41812H61813H8
Silicon hydrides (silanes) in a gaseous or gaseous state such as #5i4H1o can be used effectively.Especially, they are easy to handle when creating a single layer, have good Si supply efficiency, etc. In this respect, 5iH4t 5t2H6 is preferred.

GeH4 is a substance that can be formed with the raw material for supplying Ge.
5Ge2H6* Ge5H12Ge4H+ (1# Ge
5H12a Ge6H14yGe 7H16t Ge
Darmanium hydride in a gas-containing state or in a gas-containing state such as aH16s Qe 9H20 can be used effectively, especially in terms of ease of handling during one-layer production work and good Ge supply efficiency. s GeH4eGe 2H6t
Preferable examples include Ge and H8.

Many halogen compounds are effective as raw materials for introducing halodane atoms used in the present invention, including halogens, halogs/compounds, interhalodan compounds, halogen-substituted silane derivatives, etc. Preferable mention may be made of solid or gasifiable herodane compounds.

Further, silicon hydride compounds containing a herodane atom, which are in a gaseous state or can be gasified and have a silicon atom and a halogen atom as constituent arsenic atoms, can also be mentioned as effective in the present invention.

Specifically, the halogen compounds that can be suitably used in the present invention include ), halodane, chlorine, bromine, iodine, BrF, C1Fe, ClF3. BrF5°BrF3. Examples include interhalodan compounds such as IF55, IF75, IC1, and IBr.

Specifically, as a silicon compound containing a halogen atom, so-called a silane derivative substituted with a halodane atom, for example, 8
iF4t 5t2F6* 5ICt4s 5i13r4
etc.+7) Silicon halide can be mentioned as preferred.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, the raw material for supplying Ge is stf:
Even if the raw material that can be supplied is silicon hydride as a sulfur, a-5 containing halodane atoms on the desired support may be used.
A first layer region (G) made of iGe can be formed.

When creating the first layer region (2) containing halogen atoms according to the glow discharge method, for example, the raw materials for supplying S1 are silicon halide, which will be the gas, and dalmanium hydride, which will be the raw material gas for supplying Ge, and Ar. Gases such as a H2e He are introduced into the deposition chamber to form the first layer region (G) at a predetermined mixing ratio and gas flow particles, and a glow discharge is generated to remove these gases. The first layer region G) can be formed on the desired support by forming the plasma flJl gas, but in order to make it easier to control the ratio of hydrogen atoms introduced, A layer may be formed by mixing a desired amount of gas with hydrogen or a silicon compound gas containing hydrogen atoms.

In addition, Nagasu may be used not only as a single species, but also as a mixture of multiple species at a predetermined mixing ratio.

In both the sputtering method and the ion grating method, in order to introduce halogen atoms into the formed layer, a gas of the above-mentioned halodane compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere containing such gas.

In addition, when hydrogen atoms are introduced, a raw material gas for introducing hydrogen atoms, such as F2, or the above-mentioned silanes or/
A gas such as dalmanium hydride or the like may be introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas.

In the present invention, the above-mentioned herodane compounds or halodane-containing silicon compounds are effectively used as raw material gases for introducing halodane atoms, but HF, HC7! , ,IBr.

Hydrogen fluoride such as HI, SiF2F2# SL
H212mskH2CL2*5iHCt,, 5iH2
Halodane-substituted silicon hydrides such as Br2.5IHBr, and GeHF3s GeF2F2. GeHF3sGeH
Ct3sGeH2C12, GeH, C1a GeHBr
, s GeF2Br2t GeH,Br5GeHIs
s GeF212. Halodanide containing a hydrogen atom as one of its constituent elements, such as hydrogenated dalmanium halide such as GeH3I, GaF G5C24* GeBr4+ G
e14aGeF2m1 GeCL GeBr2* Halogenated group A such as GeI2
/ 7 Ni, 2#, etc., which are in a gaseous state or can be converted into gases, are also effective as primary materials.
can be mentioned as a starting material for forming the layer region (G).

Among these substances, a halide containing a hydrogen atom is a hydrogen atom that is extremely effective in controlling electrical or photoelectric properties at the same time as introducing halogen atoms into the layer when forming the first layer region (G). Since it also introduces halogen, it is used as a suitable raw material for halogen introduction in the present invention.

In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, F2 or 5iH4t 5t2H6t
Silicon hydride such as S13H8, 5i4H1o, etc. with dalmanium or a dalmanium compound for supplying Ge, or GeH4t Ge 2H6* Ge sHB * G
e 4H10# Qe 5H12t Ge6H14eQ
This can also be carried out by causing germanium hydride such as e 7H16# Ge 5H18e Qe 9H20 and silicon or a silicon compound for supplying St to coexist in the deposition chamber to generate a discharge.

In a preferred embodiment of the invention, the first layer (1
) The amount of hydrogen atoms (b), the amount of halodan atoms (3), or the sum of the amounts of hydrogen atoms and halodan atoms (H×X) contained in the first layer region (G) constituting 0.0
1-40 atomic%, more preferably 0.05-40 atomic%
30 atomic chips, optimally 0.1-25 atoms
ic%.

To control the amount of hydrogen atoms (b) and/or halodane atoms (3) contained in the first layer region (G), for example, the support temperature or/and the hydrogen atoms (b) or What is necessary is to control the amount of the starting material used to contain the rodan atoms (2) introduced into the deposition system, the discharge power, etc.

In the present invention, in order to form the second layer region (S) composed of a-st (He From inside, Go
A case where the first layer region (G) is formed using the starting material excluding the starting material that becomes the raw material gas for supply [starting material for forming the second layer region (S) (■)] It can be carried out according to similar methods and conditions.

That is, in the present invention, to form the second layer region 0) composed of a-8i (H = It is made by a vacuum deposition method.

For example, in order to form the second layer region (S) composed of a-8t (H, Along with the raw material gas for hydrogen atoms (b) and/or for the introduction of halogen atoms oO as necessary,
The mixture is introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber, thereby forming a layer consisting of a-8t(H-X) on the surface of a predetermined support that has been placed at a predetermined position in advance. Just let it happen. In addition, in the case of forming by sputtering, for example, when sputtering Tardat composed of St in an atmosphere of inert gas such as ArtHe or a mixture of gases such as these, hydrogen atoms (6
) or/and halodan atoms (3) in a deposition chamber for sputtering.

In the photoconductive member of the present invention, the second layer region (S), which is provided on the first layer region (G) containing r-rumanium atoms and does not contain dalmanium atoms, is conductive. By including characteristics that control the properties, the conductive properties of the layer region (S) can be controlled arbitrarily as desired.

Such substances include so-called impurities in the semiconductor field, and in the present invention, a-81(H,X) constituting the second layer region (S) to be formed.
For K, a p-type impurity that provides p-type conductivity characteristics and an n-type impurity that provides n-type conductivity characteristics can be mentioned.

Specifically, p-type impurities include atoms belonging to Group Ⅰ of the periodic table (Group Ⅰ atoms), such as B (boron), At (aluminum), Ga (gallium), and In (indium).
, Tt (thallium), etc., and B%G& is particularly preferably used. As an n-type impurity, the periodic table V
Atoms belonging to the group (Group V atoms), such as P (phosphorus), A@
(arsenic), sb (antimony), Bl (bismuth), etc., and P*As is particularly preferably used.

In the present invention, the content of the property controlling the conductive properties contained in the second layer region 0) depends on the conductive properties required for the layer region (S) or directly on the layer region (S). It can be selected as appropriate based on organic relationships such as the quality of other layer regions provided in contact with the lumbosacral layer region and the relationship with the characteristics of the fused interface with the lumbosacral layer region.

In the present invention, the content of the substance controlling conduction properties contained in the 20th notification area (S) is preferably 0.0
01-1000 atomic ppm, more preferably 0.05-500 atomic ppm, optimally 0
．． It is assumed to be 1 to 200 atomic ppm.

In order to structurally introduce a substance that controls the conduction properties into the second layer region (S), such as a group II atom or a group V atom, a group The starting material or the starting material used for Group V materials may be introduced in gaseous form into the deposition chamber together with other starting materials for forming the second layer region.

As a starting material for use exclusively with group (III) atoms, it is desirable to use a material that is in the form of a slag at room temperature and normal pressure, or that can be easily converted into a sulfur under at least layer-forming conditions. . Specifically, for introducing boron atoms, B2Hbs B4H1o is used as a W emitting material for Group II, B4H1o, etc.
s B5H9jB5Ht1 e B6■10 y B
6■12 eB6I■, 4 etc. boron hydride, BF3a
Boron halides such as BC15w BBr5y are available. This pond, ktct3°GaC13e cm (cu
, ), , Inch5#TtCt3, etc. Effectively used in the present invention as a starting material for the 4 group ■ atoms are PH, a for introducing phosphorus atoms.
Hydrogen incarnation of P2H4, PH4I# PF35 PF5
tPct, PC15e PBr5a PBr3* P
An example of this is the 0-Dan ratio, such as Is. In addition, AsH3
*AsF3. AaC63*AsBr5tAsF5.
SbH3* SbF, *SbF5* 5bCt5u
8bC15z BiH3yBiC4,t Blur3
etc. can also be mentioned as effective starting materials for use in Group V Hara Chihiro.

In the present invention, in order to provide the layer region (C) containing carbon atoms in the first layer (1), a starting material for introducing carbon atoms is added in addition to the formation of the first layer (1). The first layer (I
) may be used together with the starting material for forming the layer, and may be contained in the formed layer while controlling its amount. Layer area (C)
When a glow discharge method is used to form the first layer (1), a starting material for introducing carbon atoms is added to one selected as desired from among the starting materials for forming the first layer (1) described above. As starting materials for such carbon atom introduction,
Most gaseous substances containing at least carbon atoms or gasified substances that can be converted into gases can be used.

For example, a raw material gas containing silicon atoms (St) as a constituent atom, a raw material gas containing carbon atoms (C) as a constituent atom, and a hydrogen atom (B) or a halodane atom (3) as a constituent atom depending on your safety. The raw material to be used is a mixture of sulfur and sulfur at a desired mixing ratio, or the raw material to be silicon atoms (Si) and Th constituent atoms is sulfur, and carbon atoms (C) and hydrogen atoms (6) are used as constituent atoms. The raw material to be used for the Si
) and hydrogen atoms (6) can be used in combination.

Alternatively, a raw material having silicon atoms (St) and hydrogen atoms as constituent atoms may be mixed with a raw material having carbon atoms (C) and t- constituent atoms.

Examples of those having C and H as constituent atoms include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like.

Specifically, i1 methane (CH4) as a saturated hydrocarbon
, Ethane (C2H6), Zoofy (Cs)Ia
) s n-2tane (“4H10) #Pentane (C
5H12), ethylene hydrocarbons include ethylene (
02H4), propylene (C,H6), ften-1 (
C4H6)s 7" 77-2 (C4H6) isobutylene (C4H8)t pentene (C5H,.), examples of acetylene hydrocarbons include acetylene (02H2)s methylacetylene (C6■4), butyne (C4H6), etc. It will be done.

In these ponds, 5t(CH3)4. Alkyl silicides such as Si(C2H5)4 can be mentioned.

In the present invention, layer region C) may further contain oxygen atoms and/or nitrogen atoms in addition to carbon atoms in order to further enhance the effects obtained with carbon atoms. Examples of raw materials for introducing oxygen atoms into the layer region (C)K include oxygen (02), , tzoy(
o5) s-nitric oxide (No), nitrogen dioxide (No 2
) e-nitrogen dioxide (N2o), nitrogen sesquioxide (N2o)
03) e Trinitrogen tetraoxide (N204) #Nitrogen sesquioxide (N205), nitrogen trioxide (NO3), silicon atom (
Sl), oxygen atom (0), and hydrogen atom (6) as constituent atoms, for example, zosiloxa/(u3siostu,)
, Trisiloxane (H3SiO31H20SiH3)
It is possible to praise lower siloxanes such as

Starting materials that can be effectively used as raw materials for introducing the nitrogen atom axis used when forming the layer region (C) include N as a constituent atom, or N and H as constituent atoms. For example, nitrogen (N2), ammonia (NH3),
hydrazine (H2NNH2), hydrogen azide (HN3),
Mention may be made of gaseous or gasifiable nitrogen such as ammonium azide (NH4N3), nitrogen compounds such as nitrides and azides. In addition to this, in addition to the introduction of halogen atoms (a), nitrogen trifluoride (F, N) and nitrogen tetrafluoride (F4N2-long halodane nitrogen compounds) can be used. I can't help but mention it.

To form a layer region (C) containing carbon atoms by a sputtering method, a single crystal or polycrystalline Si wafer or a C wafer, or a wafer containing a mixture of sl and C is used as a target, These may be performed by sputtering in various gas atmospheres.

For example, if a tSi wafer is used as a target, the raw material for introducing carbon atoms and optionally hydrogen atoms and/or halogen atoms can be diluted with a diluting agent as necessary for sputtering deposition. The silicon wafer may be introduced into a chamber, and the Si wafer may be subjected to s/4'y starching by forming a ssolazma using these gases.

Alternatively, 81 and C can be used as separate targets, or by using a single piece of tardat that is a mixture of Sl and C, Suff4. dilution as a gas for tar
This can be done by sludge or shaving in an ambient atmosphere or in a gas atmosphere containing at least hydrogen atoms (6) and/or halodane atoms Q as constituent atoms. As the raw material gas for introducing carbon atoms, the raw material gas for introducing carbon atoms in the raw material gas shown in the example of glow discharge described above can be used as an effective gas also in the case of sputtering.

In the present invention, when a layer region (C) containing carbon atoms is provided when forming the first layer (1), the layer region (C) containing carbon atoms is provided.
By changing the distribution concentration C (C) of carbon atoms contained in C) in the layer thickness direction, a desired distribution state in the layer thickness direction (depth
In order to form a layer region (0) having a profile, a gas of the starting material for introducing carbon atoms whose distribution concentration C (C) is to be changed in the case of a glow discharge is introduced, and the gas flow rate is changed as desired. This is accomplished by introducing a predetermined needle in the middle of the gas flow path system into the deposition chamber, with appropriate changes according to the rate curve. It is sufficient to perform an operation to gradually change the opening of the pulp.At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a pre-designed change rate curve to achieve the desired content. You can also get a rate of 1.

When the layer region (0) is formed by the S&G method, the distribution concentration of carbon atoms in the layer thickness direction C(C)t is changed in the layer thickness direction to obtain the desired distribution state of carbon atoms in the layer thickness direction. (depth profile), firstly, as in the case of the glow discharge method, a starting material for introducing carbon atoms is used in a gas state, and when the gas is introduced into the deposition chamber. This is accomplished by appropriately changing the gas flow rate as desired.

Second, if a sputtering target is used, for example, a mixed target of Sl and C, the mixing ratio of 81 and C can be changed in advance in the layer thickness direction of the target. It is achieved by letting it happen.

In the present invention, the amount of hydrogen atoms (6) or the amount of halogen atoms (up to) or hydrogen atoms contained in the second layer region @) constituting the first layer (1)' to be formed The sum of the amount of halogen atoms (H+X) is preferably 1 to 40ato
mic %e more preferably 5 to 30 atomic %,
Optimally, it is 5 to 25 atomic%.

In the photoconductive member 100 shown in FIG. 1, a second layer (II) 103 is formed on a first layer (1) 102.
has a free surface 106 and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, electrical pressure resistance, usage environment characteristics, and durability.

Further, in the present invention, the first layer (1) 102 and the second layer (1) 102
Since each of the amorphous materials constituting the layer region 105 has a common constituent element of silicon atoms, chemical stability is sufficiently ensured at the laminated interface.

The second layer (II) in the present invention consists of silicon atoms (S
an amorphous material (hereinafter referred to as [*-(Si,0l-X)y(HJ) It is written as 1-yJ.However, it is composed of o (x ey < 1).

a − (8ixo, ++X)y (H#X),
The second layer (II) composed of -y is formed by a glow discharge method, a sputtering method, an electron beam method, an ion implantation method, an ion blating method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. The advantages include that it is relatively easy to control the manufacturing conditions for manufacturing the conductive member, and that it is easy to introduce oxygen atoms and halodan atoms together with silicon atoms into the second layer (1) to be manufactured. , glow discharge method or snow'? The Tuttering method is preferably employed.

Furthermore, in the present invention, the 20th layer (II) may be formed by using a glow discharge method and a sputtering method in the same apparatus system.

To form the second layer ω) by the glow discharge method a
-(S 1 xol-x)y (H@ When the introduced gas is caused to generate a glow discharge, it becomes a snolasma, and a-( Stxol-X), (
H, X), -.

All you have to do is deposit it.

In the present invention, a -(stXo, -y) (HpX
) The raw material for forming 1-y is silicon atoms (S
(t), gaseous substances whose constituent atoms are at least one of the following: oxygen atoms (0), hydrogen atoms (b), and rodan atoms (g), or gasified substances that can be turned into gases. Most can be used.

When using a raw material gas containing St as one of Si, O, H, and X, for example, St is used.

A raw material gas containing constituent atoms, Of, a raw material containing constituent atoms S, and a raw material containing H constituent atoms depending on the packaging.
and X t: ;in are used by mixing the raw material gas with constituent atoms at a desired mixing ratio, or the raw material gas with St as constituent atoms is mixed with O and Hfc! : A raw material gas containing O and X as constituent atoms and/or a raw material containing O and
A raw material gas having constituent atoms of St, 0, and I (or a raw material gas having three constituent atoms of 81.0 and X) is mixed. can be used.

Also, separately, raw materials containing Si and H as constituent atoms are SKO.
The raw material having t- constituent atoms may be mixed with s, or the raw material having 81 and X as constituent atoms may be mixed with s, and the raw material having O as constituent atoms may be mixed with good.

In the present invention, preferred halogen atoms (2) contained in the second layer (value) are F,' CL t Br,
I, and F e C1 is particularly preferred.

In the present invention, raw materials that can be effectively used to form the second layer ω) are those that are in a stale state at room temperature and normal pressure or that are easily oxidized. The substances obtained can be listed.

Further, when forming the second layer (II) by the suctioning method, for example, the following procedure is performed.

Firstly, when sputtering a target made of St in an atmosphere of an inert gas such as Ar or He or a mixed gas containing these gases, oxygen atoms (
0) Add hydrogen atoms σ() to the raw material gas for introduction as necessary.
It may be introduced into a vacuum deposition chamber where sputtering is performed together with a raw material gas for introduction and/or for introduction of halogen atoms (3).

Secondly, 5I is used as a target for Su-ya Tsutaring.
A second layer formed by using a target made of O2, or a target made of Si and a target made of SiO2, or a target made of Si and 5102. An oxygen atom (0) can be introduced into (1[). At this time, if the above-mentioned raw material gas for introducing oxygen atoms (0) is also used, the flow rate can be controlled to introduce atoms (0) into the second layer (b).
The content of oxygen atoms (0) introduced into the second layer (n) is determined by the amount of oxygen atoms (0) introduced into the deposition chamber. The flow rate at the time of introduction is controlled, or the proportion of oxygen atoms (0) contained in the target for introducing oxygen atoms (0) is adjusted when creating the target, or both. By doing this, it is possible to arbitrarily control as desired.

The starting materials used as raw material gas for supplying Si used in the present invention include 5iH4t 5i2H6r 5ix
Ha *5i4H,. Silicon hydride (silanes) in a gaseous state or which can be gasified such as SiH4, etc. can be effectively used. In particular, SiH4, 5t2)[6 is preferred.

If these starting materials are used, Si can be formed in the second layer (U) formed by appropriately selecting the layer forming conditions.
At the same time, H can also be introduced.

Effective starting materials that serve as raw material gas for supplying Si include:
In addition to the above-mentioned silicon hydride, silicon compounds containing a halogen atom (3), so-called silane derivatives substituted with a halogen atom, specifically, for example, SiF4゜S i F S 1C
tS IB r 4 etc./%Oj'n siliconide is preferred 2
61 4 It can be praised as something worthy.

Furthermore, SiH2F2.5iI (2t2.5IH2C2
2,5iHCt3゜5iH2Br2.5iHBr3, etc. (ff Dan-substituted silicon hydride, etc., which is in a gaseous state or can be gasified, and has a hydrogen atom as one of its constituent elements...Rhodanide is also an effective second layer (n ) can be mentioned as a starting material for supplying 81 for the formation of

Even when these silicon compounds containing rhodan atoms (3) are used, X can be introduced together with St into the formed second layer (II) by appropriately selecting the layer forming conditions as described above. You can.

Among the above-mentioned starting materials, the silicon rhodanide compound containing a hydrogen atom is used to simultaneously introduce a halogen atom (3) into the layer during the formation of the second layer (II), and to improve electrical or photoelectric properties. Since we also introduce hydrogen atoms (6), which are extremely effective for control,
In the present invention, it is used as a starting material for the introduction of a suitable nitrogen atom (3).

Used when forming the second layer (If) in the present invention
.

In addition to the above-mentioned materials, effective starting materials that can be used as raw material gases for introducing halogen atoms (3) include, for example, halogen gases such as Eva, fluorine, chlorine, bromine, and iodine, BrF,
C4F, CLF, , BrF5, BrF3
．． IF51 /% of IF, IICA, lBr etc.
0 interdan compounds, HF, HCt.

Examples include hydrogen halides such as HBr and I(I).

Oxygen atoms used in forming the second layer (II) (
0) A starting material that can be effectively used as a raw material gas for introduction is oxygen (02), which has 0 as its constituent atoms, or has N and 0 as its constituent atoms.
s-Nitrogen oxide (No), nitrogen dioxide (No2), -nitrogen dioxide (N20), nitrogen sesquioxide (N2o5) rnitrogen tetroxide (N2O4) +nitrogen sesquioxide (N2o5)
*Nitrogen trioxide (No3), silicon atom (St)
and an oxygen atom (0) and a hydrogen atom (6) as constituent atoms, for example, disiloxit 7 (H,5iO8iH,)
# )su'/o kisay(H3SiO8iH20Si
Examples include lower compounds such as H3).

In the present invention, the diluent gas used when forming the second layer (II) by a glow discharge method or a sputtering method is a so-called rare gas, such as TIe rNe,
Preferred examples include Ar.

The second layer ([) in the present invention is carefully formed on the punch to provide the required properties to the desired consistency.

That is, a substance whose constituent atoms are Sl, 0, and H or/and
In the present invention, a- (
In order to form S ixo , -ρa(H,X), □y, the creation conditions are strictly selected as desired. For example, in order to provide the second layer (II) with the main purpose of improving electrical voltage resistance, a −(S Z xo , −
x ) y (H'

In addition, when the second layer (II) is provided with the main purpose of improving the continuous edge-turning usage characteristics and the usage environment characteristics, the above-mentioned degree of electrical insulation is relaxed to a certain extent, and it has a certain degree of resistance to the irradiated light. As an amorphous material with a sensitivity of
”-(s'xo,-x)y (H*X)1-, l
rE is made fR.

a − (5txo, −x), (
n, x), -.

The second layer consisting of ω) imported wheat wJ\\\\\eagle%%S rat bond,
When forming a layer, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. It is desirable that the temperature of the support during layer formation be strictly controlled so that a-(slxO4-x)y(H,X)1□ having the desired properties can be formed as desired.

In the present invention, the formation of the second layer (It) is carried out by appropriately selecting an optimal temperature range in accordance with the method of forming the second layer (II) in order to effectively achieve the desired purpose. However,
Preferably 20 to 40°C, more preferably 50 to 350°C
°C, optimally between ioo and 300 °C. Second layer (I
For the formation of I), glow discharge method and sputtering method are used because delicate control of the composition ratio of atoms constituting the layer and control of layer thickness are relatively easy compared to other methods. Although it is advantageous to employ these layer formation methods, the second layer (II)
When forming a layer, the discharge power at the time of layer formation is set to a-(S t xo 1
- x ) y (H*

a having the characteristics that enable the object of the present invention to be achieved;
”' (S 1 xo 1- x )y (H*
) The discharge conditions for effectively creating 1-y with good productivity are preferably 1.0 to 300 W, more preferably 2.0 to 250 W, and optimally 5.0 to 200 W.
It is said that

The gas pressure in the deposition chamber is preferably 0.01 to ITorr.
More preferably, it is about 0.1-0.5 Torr.

In the present invention, the above-mentioned values are listed as the preferable numerical ranges of the support temperature and discharge power for forming the second layer (It), but these layer forming factors are determined independently and separately. The desired characteristics a-(S i , co 1-x )y (Hp X)
It is desirable that the optimum value of each layer creation factor be determined based on mutual organic relationship so that the second layer (I[) consisting of 1-y is formed.

The amount of oxygen atoms contained in the second layer (It) in the photoconductive member of the present invention is similar to the production conditions of the second layer Ql), so that the desired characteristics for achieving the object of the present invention can be obtained. This is an important factor in the formation of the second layer (n).

The amount of oxygen atoms contained in the second layer (If) in the present invention can be determined as desired depending on the type and characteristics of the amorphous material constituting the second layer ([1)]. It can be decided.

That is, the general formula a-(S i xO'1-x )y
The amorphous material represented by (H* ,0
(a (1), an amorphous material composed of silicon atoms, oxygen atoms, and hydrogen atoms (hereinafter r a −(Sl, O
,-,)cHl-8''.

However, 0<b, c<1), an amorphous material composed of silicon atoms, oxygen atoms, halodane atoms, and optionally hydrogen atoms (hereinafter referred to as "a - (s t , 01-.1 )" .

It is written as (H,X),-,J. However, it is classified as 0<dSe(1).

In the present invention, the second layer (I[) is a-St, Ol
-, the amount of oxygen atoms contained in the second layer (If) is represented by a of a -S i aO, -a, the a force (preferably 0.33 to 0.99999
, preferably 0.5 to 0.99, optimally 0.6 to 0
．． It is 9.

In the present invention, the second layer (n) is a −(s t ,
01-b) When composed of cHl-0, the second layer (
The amount of oxygen atoms contained in n) is '-(”'b01
-b) When expressed as cHl-c, b is preferably 0.3
3 to 0.99999, preferably 0.5 to 0.9, most preferably 0.6 to 09, C preferably 06 to 0.99,
More preferably 0.65-0.98, optimally 0.7-0
．． It is 95.

The second layer (ID is a − (st, o, −,) el (u
, x), -6, the second layer (II
) is the content of oxygen atoms contained in a −(S i
aO, -a). (HIX), d of -e, d is preferably 0.33 to 0.99999, more preferably 0.5 to 0.99, optimally 0.6 to 0.9
, e is preferably 0.8 to 0.99, more preferably 0.
82-0.99, optimally 0.85-0.98.

The number range of the layer thickness of the second layer (n) in the present invention is one of the important factors for effectively achieving the purpose of the present invention. It can be determined as desired depending on the intended purpose so as to achieve the desired goals.

In addition, the thickness of the second layer (It) is determined by the amount of oxygen atoms contained in the layer ω) and the thickness of the first layer (1), depending on the area of each layer. It is necessary to appropriately determine the desired characteristics based on the organic relationship depending on the characteristics required.

In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production.

The thickness of the second layer (II) in the present invention is preferably 0.003 to 30μ, more preferably 0.004 to 30μ.
The thickness is preferably 20μ, preferably 0.005 to 10μ.

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

Cr + Mo, Au, Nb, Tar
Examples of the electrically insulating support include polydiester, polyethylene, polycargonate, cellulose acetate, polypropylene, and JIJ vinyl chloride. Monovinylidene chloride,? Listyrene? Films or sheets of synthetic resins such as 1-noamide, glass, ceramics, paper, etc. are commonly used. These electrically insulating supports preferably have at least one surface conductively treated, and the conductively treated surface 0'I! Preferably, l is provided with other layers.

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

kA, Cr*Mo, Au, lr*
Nb, Ta, V, Ti + Pt rPd
, In2O3, SnO, ITO (In2O, +5n
Conductivity is imparted by providing a thin film consisting of O2), etc., and the synthesis of a polyester film etc.
ff(l]' If it is an ET film, NtCr, k
A*Ag*Pb, Zn, Ni, A
u.

Cr, Mo, Ir r Nb, Tar
A thin film of metal such as V + Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, star/ejector IJing, etc., or the surface is laminated with the metal, and conductive force is applied to the surface; Granted. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and as desired,
Although its shape is determined, for example, if the photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member, an endless belt or a cylindrical shape is recommended for continuous high-speed copying. desirable. The thickness of the support is appropriately determined so as to form a photoconductive member of the desired thickness, but if flexibility is required as a photoconductive member, the thickness of the support may be determined appropriately. (as thin as possible within the range). In such cases, the thickness is preferably 10μ or more from the viewpoints of manufacturing and handling of the support, mechanical strength, etc., according to Hyakuen et al.

Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained.

FIG. 11 shows an example of a photoconductive member manufacturing apparatus.

In the gas tempehs 1102 to 1106 in the figure, a thick phase gas for forming the photoconductive member of the present invention is sealed. 99994, hereinafter S i
H47'i (abbreviated as e) is gas, 1103 is Get (a gas (purity 99.999%, hereinafter referred to as Ge T (4/l) (abbreviated as e)) diluted with He, and 1104 is H
1105 is C
2H4f gas (purity 99.999 degrees) tempeh, 1106 is a H2 gas (purity 99.999 degrees) cylinder.

In order to flow these gases into the reaction chamber 1101, nozzles 1122 to 1126 of the gas temps 1102 to 1106 are used.
, check that the leak/J valve 1135 is closed, and also check the inlet valves (lubs 1112 to 1116, outflow valves 1117 to 1121, auxiliary) and the valves 1132 and 113.
Make sure that valve 3 is open, then open main valve 1 first.
134 is opened to exhaust the reaction chamber 1101 and each gas pipe. Next, the vacuum gauge 1136 reads 1/); about 5
When it reaches 10-' torr, turn on the auxiliary noggle 113.
2°1133, close the outflow nozzles 1117-1121.

Next, to give an example of forming the first layer (1) on the cylindrical substrate 1137, use s t H4Ae gas from Gas Temperature 1102,
GeH4/He is gas temperature 1105 p C2H
4 Open the valves 1.122, 1123.1125, adjust the outlet pressure 1127.1128.1130 to l kg 7 cm2, and inlet valve 1112.
1113 and 1115 are gradually opened to allow flow into mass flow controllers 1107, 1108, and 1110, respectively. Subsequently, the outflow knob 1117°1118.112
0. The auxiliary valve 1132 is gradually opened to allow each gas to flow back into the reaction chamber 1101. SiH4/1 at this time (
Adjust the outflow valves 1117, 1118, and 1120 so that the ratio of the e gas flow rate and the CH gas flow rate becomes the desired value, and also keep the pressure inside the reaction chamber 1101 at the desired value. Vacuum gauge 1 to match the value
Main while looking at the reading of 136/? Lube 1134-(7
) Adjust the aperture. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of approximately 50 to 400°C by the heating heater 1138, the power source 1140 is set to the desired power to cause glow discharge in the reaction chamber 1101. The first layer region (G) is formed on the substrate 1137 to a desired layer thickness by causing glow discharge and maintaining the glow discharge for a desired time. At the stage where the first layer region (G) has been formed to the desired layer thickness, the discharge valve 1118 is completely closed and the discharge conditions are changed as necessary for the desired time according to the same conditions and procedures. By maintaining the glow discharge, the first layer region (
G) a second material substantially free of germanium atoms thereon;
A layer region (S>) can be formed.

In order to make the second layer region (S) contain 4-marine which controls the conductivity, (fll
For example, a gas such as 82H6r PH5 may be added to the gas introduced into the deposition chamber 1101.

In order to form the second layer (II) on the first layer (1) formed to a predetermined layer thickness as described above, the same steps as in the case of forming the first layer (1) are carried out. By loop operation, the file is S
This is accomplished by diluting each of iH gas and NO with a diluent gas such as He as necessary to generate electricity in one of the gases according to desired conditions. In the second layer (II) -
- To contain Rodan atoms, f! If you are S I F
The second layer (II) is formed by adding SiH4 gas and C2H4 gas, or by adding SiH4 gas thereto and forming the second layer (II) in the same manner as above.

It goes without saying that all outflow valves other than the outflow valves and J/rev required when forming each layer are closed.
In addition, when forming each layer, in order to prevent the gas used to form the previous layer from remaining in the reaction chamber 1101 and in the gas piping leading from the outflow valves 1117 to 1121 to the reaction chamber 1101, Close Lubes 1117-1121,
Open auxiliary valves 1132 and 1133 and open main valve 1.
134 to fully open the system to temporarily evacuate the system to a high vacuum, if necessary.

The amount of oxygen atoms contained in the second layer (II) is, for example, 5iH4jf in the case of glow discharge, and the flow rate ratio of No gas into the reaction chamber 1101 is changed as desired, or, When forming a layer by four-step ring, when forming a targut, the silicon wafer and Si
It can be controlled as desired by changing the s/e and ta area ratio of the O2 plate or by changing the mixing ratio of silicon powder and SiO2 powder and molding the tardoubt. Halogen atoms (3) contained in the second layer (II)
The amount of raw material gas for introducing halodane atoms, for example, 5IF
Step 4 is achieved by adjusting the flow rate when the gas is introduced into the reaction chamber 1101.

Further, during layer formation, it is desirable that the base body 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation.

Examples will be described below.

Example 1 A cylinder-shaped AA was manufactured using the manufacturing apparatus shown in FIG.
Layers were formed on the substrate under the conditions shown in Table 1 to obtain an electrophotographic image forming member.

The image forming member thus obtained was placed in a charging exposure experiment apparatus and the image forming member was set at θ5. Perform corona charging for 0.3 aec at OkV,
A light image was immediately irradiated. A tungsten lamp light source was used as a light source, and a light amount of N21ux and aeC was irradiated through a transmission type test chart.

Immediately thereafter, a good toner surface image was obtained on the surface of the image forming member by cascading (1) a charging developer (containing toner and Φ year) onto the surface of the image forming member. When the toner image on the image forming member was transferred onto a transfer paper by corona charging at 05,000 kV, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 2 Layer formation was carried out in the same manner as in Example 1 except that the manufacturing apparatus shown in FIG. 11 was used and the conditions shown in Table 2 were used to obtain an electrophotographic image forming member. Example 1
An image was formed on a transfer paper under the same conditions and procedures as in Example 1, except that the conditions were reversed, and an extremely clear image quality was obtained.

Example 3 Layer formation was carried out in the same manner as in Example 1 except that the manufacturing apparatus shown in FIG. 11 was used and the conditions shown in Table 3 were used to obtain an electrophotographic image forming member.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 4 In Example 1, GeH4/1 (e gas and S i H
4/) An electrophotographic image forming member was prepared in the same manner as in Example 1, except that the content of germanium atoms contained in the first layer was changed as shown in Table 4 by changing the Ie gas flow rate ratio. Created each.

Using the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 4 were obtained.

Example 5 Electrophotographic image forming members were prepared in the same manner as in Example 1 except that the thickness of the first layer was changed as shown in Table 5.

For each image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 5 were obtained.

Example 6 A cylindrical kA was produced using the manufacturing apparatus shown in Fig. 11.
A layer was formed on the substrate under the conditions shown in Table 6 to obtain an electrophotographic image forming member.

The image forming member thus obtained was placed in a charging exposure experiment apparatus and the image forming member was set at θ5. Corona charging was performed at OkV for 0.3 seconds, and a light image was immediately irradiated. A tungsten lamp light source was used as a light source, and a light intensity of 2 tux, sec was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the imaging member by cascading (2) a charged developer (including toner and carrier) onto the surface of the imaging member. When the toner image on the image forming member was transferred onto a transfer paper by corona charging at 05,000 kV, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 7 In Example 1, the light source was replaced with a tungsten lamp.
An electrophotograph was created under the same toner image forming conditions as in Example 1, except that an electrostatic image was formed using a 10 nm GaAs-based semiconductor radar (10 mW). When the image quality of the toner-transferred image of the image forming member was evaluated, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained.

Example 8 Since the conditions for creating the layer (■) were set to the conditions shown in Table 7,
Otherwise, each of the electrophotographic image forming members (sample dust 8-201 to
8-2'08.8-301~8-308°8-601~
8-608) were created.

Each electrophotographic image forming member thus obtained was individually installed in a copying machine, and 05. 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. Olux, sec.

The latent image was developed with a charged developer (containing toner and carrier) and transferred to regular paper. The transferred image is
It was extremely good.

Toner remaining on the electrophotographic imaging member without being transferred was cleaned with a rubber blade. Even after repeating this process more than 100,000 times, no image deterioration was observed in any case. The results are shown in Table 7A.

Example 9 When forming layer (II), the target area ratio of Ar and NO mixed gas, silicon ribbon wafer, and 8102 was changed to form layer (II).
Each of the image forming members was produced in the same manner as in Example 1, except that the content ratio of silicon atoms and oxygen atoms in II) was changed. For each of the image forming members thus obtained, image formation, development, and
After repeating the cleaning process about 50,000 times, image evaluation was performed and the results shown in Table 8 were obtained.

Example 10 Same as Example 1 except that when forming the layer (II), the flow rate ratio of SiH4 gas and No gas was changed to change the content ratio of silicon atoms and oxygen atoms in the layer (■). Each of the imaging sections was made in exactly the same manner.

After repeating the steps up to transfer approximately 50,000 times using the method described in Example 1 for each image forming part thus obtained,
When image evaluation was performed, the results shown in Table 9 were obtained.

Example 11 When forming layer (II), SiH4 gas, 5IF4 gas, and N were used.

Example 1 except that the content ratio of silicon atoms and oxygen atoms in the layer (n) was changed by changing the gas flow rate ratio.
The second half of the image forming member was created in exactly the same manner as in the above. After repeating the steps of image formation, development, and printing approximately 50,000 times as described in Example 1 for each of the image forming members thus obtained, image evaluation was performed. I got similar results.

Example 12 Each of the imaging members was produced in exactly the same manner as in Example 1, except that the layer thickness of layer (II) was changed.

The steps of image formation, development, and noning as described in Example 1 were repeated to obtain the results shown in Table 11.

Common layer forming conditions in the embodiments of the present invention shown in Table 11 are shown below.

Substrate temperature: r Rumanium atom (Ge) containing layer: approx. 200°C Dalmanium atom (Ge) non-containing layer: approx. 250°C Discharge frequency: 13.56 M[(z Reaction chamber pressure during reaction: 0. 3 Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive wing of the present invention, and FIGS. 2 to 10 are respectively layer regions (C
), an explanatory diagram for explaining the distribution state of carbon atoms in
FIG. 1 is a schematic explanatory diagram illustrating the apparatus used for producing the photoconductive member of the present invention in FIG. 100... Photoconductive member 101... Support body 102.
...First layer (1) 103...Second layer (■) 104
...First layer area (G) 105...Second layer area (S) -111→-C Procedural amendment Showa (November 1970) - 9th Case of Manabu Shiga, Commissioner of the Patent Office Relationship with applicant (I' 1ilr (1&i'li) 3-cho Shimomaruko, Ota-ku, Tokyo!-1δ(J i(!'2υ・1”i: ,g
(f[;) (100) Canon Co., Ltd.? 1.4. Address of agent: 2-6-2 Marunouchi, Chiyoda-ku, Tokyo Marunouchi Shigesu Building 330 Column 8 of the detailed description of the invention in the specification. Contents of amendments: As shown in the attached document. We will correct the following matters. Note 1, page 52, line 10, it says "0.5-0.8" [0,5-0, . Correct it to 99 j.

Claims (3)

[Claims] (1) A support for a photoconductive member, a first layer region (G) made of an amorphous material containing dalmanium atoms on the support, and an amorphous material containing silicon atoms. A second layer region (S) which is composed of and exhibits photoconductivity is composed of a first layer of a layered structure provided in order from the support side, and an amorphous material containing silicon atoms and oxygen atoms. and a second layer containing carbon atoms in the first layer.
A photoconductive member having a t% characteristic. (2) The photoconductive member according to claim 1, wherein at least one of the first layer region (G) and the second layer region (S) contains hydrogen atoms. (3) A1 according to claim 1 or 2, wherein at least one of the first layer region ←) and the second layer region (S) contains a halodane atom, catfish
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