JPS6045073A - 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 relates to a photoconductive member that is sensitive to electromagnetic waves such as light (here, light in a broad sense refers to ultraviolet rays, visible rays, infrared rays, X-rays, 2 gamma rays, etc.). 0 As a photoconductive material forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it has a high sensitivity and a high signal-to-noise ratio [photocurrent (Ip)
/ 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 these points, amorphous silicon (hereinafter referred to as aBi) is a photoconductive material that has recently attracted attention.
For example, German Publication No. 2746967, German Publication No. 285
No. 5718 describes its application as an image forming member for electrophotography, and German Published Publication No. 2933411 describes its application to a line photoelectric conversion/reading device.

In the same year, et al., a photoconductive member having a photoconductive layer composed of conventional a-8i has improved electrical, optical, photoelectric properties such as dark resistance value, photosensitivity, and photoresponsiveness, as well as moisture resistance, etc. The reality is that there are points that need to be further improved in terms of usage environment characteristics and stability over time, which require comprehensive improvement of characteristics.

For example, when applied to electrophotographic image forming members, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use. If a photoconductive member is used repeatedly for a long period of time, fatigue due to repeated use will accumulate, resulting in the so-called ghost phenomenon that causes an afterimage, or if it is used for high-speed green reversal, the responsiveness will gradually decrease. In many cases, these disadvantages arise.

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, when using normally used log lamps and fluorescent lamps as light sources, there is still room for improvement in that the light on the long wavelength side cannot be used effectively.

In addition, if the irradiated light is not sufficiently absorbed in the photoconductive layer and more of the light reaches the support,
When the support itself has a high reflectance for light transmitted through the photoconductive layer, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images.

This influence is j81I! In order to increase the image resolution, the smaller the irradiation spot is, the larger the irradiation spot becomes, which is a big problem especially when a semiconductor laser is used as the light beam.

Furthermore, when forming a photoconductive layer using a-8t material, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, , problems may occur in the electrical or photoconductive properties of the formed layer. That is, for example, the lifetime of photocarriers generated in the formed photoconductive layer by light irradiation may not be sufficient; Alternatively, in dark areas, there are many cases where the injection of charges from the side of the support is not sufficiently prevented.

Furthermore, if the layer thickness exceeds 10-odd microns, the layer may lift or peel off from the surface of the support, or it may crack as the time passes after it is left in the air after being removed from the vacuum deposition chamber for no-formation. It was a victory because it brought about phenomena such as this. This phenomenon is
In particular, there are issues that need to be resolved in terms of stability over time, as this often occurs when the support is a drum-shaped support commonly used in the field of electrophotography.

Therefore, while efforts are being made to improve the properties of the a-Si 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 points, and has applicability and applicability to a-8i as a photoconductive part side used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive research and consideration from this perspective, we have discovered an amorphous material that has a silicon atom (8i) and a germanium atom (Ge) as a matrix and contains at least either a hydrogen atom (n) or a halogen atom (X). The material is composed of so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter, [a-8iGe (H,X) J] will be used as a generic term for these). A photoconductive member designed and produced by specifying the structure of a photoconductive member having a photoreceptive layer exhibiting photoconductivity as explained hereinafter not only exhibits extremely excellent properties in practical use. , it is superior in all respects to conventional photoconductive materials, has particularly excellent properties as a photoconductive material for electrophotography, and has absorption spectrum characteristics on the long wavelength side. It is based on the points that have been found to be superior to

The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The primary object of the present invention is to provide a photoconductive member that is durable, does not exhibit deterioration even after repeated use, and has no or almost no residual potential observed.

Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponse.

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

Another object of the present invention is to provide an electric charge during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image or forming member for electrophotography. It is an object of the present invention to provide a photoconductive member which has sufficient retention ability and excellent electrophotographic properties with almost no deterioration in its properties observed even in a humid atmosphere.

Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution.

Yet another object of the present invention is high photosensitivity.

It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics and good electrical contact with the support.

The optical 4'N member of the present invention includes a support for the optical 4' electric member,
It has a photoconductive photoreceptive layer made of an amorphous material containing silicon atoms and germanium atoms, and the photoreceptor layer contains oxygen atoms and has a distribution in the layer thickness direction. A first layer region (1) whose concentrations are C(ll, C(31, C(2+), respectively.

It is characterized by having a third layer region (3) and a second layer region (2) in this order from the support side (however, C(3)>C
(21, C(1), and at least one of C(11, CF2+ is not O or C(11, Cf21
are not equal).

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

Shows photoconductive properties, electrical pressure resistance, and usage environment properties.

In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, it is highly sensitive, and it has a high signal-to-noise ratio. Therefore, it has excellent light fatigue resistance and repeated use characteristics, has high density, clearly displays No.-7 tones, and can stably and repeatedly produce high-quality images regardless of resolution.

In addition, the photoconductive member of the present invention has a photoreceptive layer formed on a support, which is strong and has excellent adhesion to the support, and can be continuously repeated at high speed for a long time. can be used.

vinegar! In addition, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, and is particularly excellent in matching with semicircular body lasers.
Moreover, the light response is fast.

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

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

The photoconductive member 100 shown in FIG. A-8i Ge (H,
X), contains oxygen atoms and gold, and has a photoreceptor 1fi102 having photoconductivity.

The germanium atoms contained in the light-receiving layer 102 may be distributed uniformly in the light-receiving layer 102, or may be uniformly contained in the layer thickness direction. However, the distribution concentration may be non-uniform. Hyakunen et al. In any case, in the in-plane direction parallel to the surface of the support, it is uniformly distributed and evenly contained from the point of view of uniformizing the properties in the in-plane direction. It's necessary. In particular, it is uniformly contained in the layer thickness direction of the light-receiving layer 102, and on the side opposite to the side where the support 101 is provided (the free surface 103 side of the light-receiving layer 102). so that it is distributed more toward the support side 101 (the interface f'I between the photoreceptive layer 102 and the support 101), or
Alternatively, the photoreceptive layer 102 may be distributed in the opposite manner.
contained within.

In the photoconductive member of the present invention, the germanium atoms contained in the photoreceptive layer have a distribution state of 1-1 in the layer thickness direction, as described above, and a distribution state of germanium atoms on the surface of the support. It is desirable that the distribution be uniform in the in-plane direction parallel to the direction.

The light guide 'i [light-receiving layer 10 of member 100] shown in FIG.
2 is a first layer region il+ 1.04, C(2
second layer region with a value of 1 + 2) 1.05,
The third layer region has a value of Ct31 (3+106).

In the present invention, the above-mentioned item 1. Second. Each of the third layer regions is always exposed to acid (
Although it is not necessary that atoms be contained, the distribution concentration C (
3) is the distribution concentration C(1).

C(2), and the distribution concentration C(1
1, C(21 must be non-zero or the distribution concentrations C(Fl, C(21i) must not be equal.

When either the distribution concentration C(11 or Cf21 is 0), the photoreceptive layer 102 has either the first layer region +1) 104 or the second layer region (2+) as a layer region that does not contain oxygen atoms. 105 and higher distribution concentration C
(3) having a third layer region (3).

In this case, if the enzyme atoms are contained in a relatively high concentration to obtain the effect of preventing charge injection from the free surface 103 into the photoreceptive layer 102, the first layer region (1110
4 as a layer region containing no oxygen atoms for light reception/@10
2, and conversely, it is necessary to design the support body 101 (t4
In order to prevent the injection of charges from 11 into the photoreceptive layer 102 and to improve the adhesion between the support 101 and the photoreceptive layer 102, the second layer region (2+ 105 should not contain oxygen atoms). It is necessary to design the photoreceptive layer 102 depending on the layer area.

In the present invention, the third layer region f31106 having the highest distribution concentration C(3) among the three is used to improve the dark resistance of the photoreceptive layer 102 while maintaining good photosensitivity characteristics. In this case, it is desirable to set the value of the distribution concentration C(3) to a relatively low value, and to set the layer thickness to a sufficient thickness within the necessary range.

In addition, if the third layer region (31106K) is expected to mainly prevent charge injection by setting the value of the distribution concentration C(3) to a relatively high value, the third layer region (31106K)
The layer thickness of the photoreceptive layer 102 is made as thin as possible within a range that can sufficiently obtain the effect of blocking charge injection.
It is desirable to provide the third layer region (31106) as close as possible to the free surface 103 side or the support 101 side.

In this case, if the third layer area (31106 is provided closer to the support special holiday 101 side)
The layer region +11104 is sufficiently thinned within a necessary range, and is provided mainly to improve the adhesion between the support 101 and the light-receiving layer 102.

If the third layer region (3+ 106 is provided closer to the free surface 103 side), the second layer region (21
105 is the third layer region (31106 is mainly provided for the purpose of preventing exposure to a humid atmosphere). In the present invention, the first layer region + 11 and the second layer region (2) The thickness is determined as desired in relation to the distribution concentration CTl) and C(21), but is preferably 0.
003-100μ, more preferably 0.004-80μ
, the optimum thickness is preferably 0.005 to 50μ.

Further, the layer thickness of the third layer region (3) is appropriately determined in relation to the distribution concentration C(3), but is preferably 0.003.
It is desirable that the thickness be ~80μ, more preferably 0.004~50μ, optimally 0.005~40μ.

If the third layer region (3) is to primarily function as a charge injection blocking layer, it should be provided close to the support side or the free surface side of the photoreceptive layer, and the layer thickness should preferably be adjusted. ,3
It is desirable that the thickness be 0μ or less, more preferably 20μ or less, and optimally 10μ or less. At this time, the first no region (1
) or the layer thickness of the second layer region (2) on the free surface side:
Distribution concentration C of oxygen atoms contained in the third layer region (3)
Although it is determined as appropriate from the point of view of the value of (3) and productive efficiency, it is preferably 5μ or less, more preferably 3μ or less, and optimally 1μ or less.

In the present invention, the maximum value of the distribution concentration C(3) of oxygen atoms is preferably 67 atomic%.

More preferably, it is 50 atomic%, most preferably 4° atomic%.

Further, the minimum value of the distribution concentration C(3) is preferably set to 10 atomic, more preferably 15 atomic, and suitably 20 atomic to T(5iGeO). .

If the distribution concentration CFl), C(21) is not 0, its minimum value is preferably 1 atomic P%+, more preferably 3 with respect to T(SiGeO).
Atomic familiar, optimally 5 atomic l11
It is desirable to set it to m.

FIGS. 2 to 10 show typical examples in which the distribution state of germanium atoms contained in the photoreceptive layer of the photoconductive member of the present invention in the layer thickness direction is non-uniform.

In Figures 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the photoreceptive layer exhibiting photoconductivity, and tB represents the position of the surface of the photoreceptive layer on the support side. ,t
, r indicates the position of the surface of the photoreceptive layer on the side opposite to the support side. That is, the photoreceptive layer containing germanium atoms has t
Layers are formed from the B side toward the 1T side.

FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the photoreceptive layer in the layer thickness direction.

In the example shown in FIG. 2, up to the interface position tB where the surface on which the photoreceptive layer containing germanium atoms is formed and the surface of the photoreceptor layer are in contact, the distribution concentration of germanium atoms is Germanium atoms are contained in the formed photoreceptive layer while C takes a constant value of C0, and the position vit+ is gradually and continuously decreased from the distribution concentration C1 up to the interface position 1T. At the interface position tT, the distribution concentration C of germanium atoms is C3.

In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms is from the position tB to the position t? A distribution state is formed in which the concentration gradually and continuously decreases from C4 until the concentration reaches C3 at position tT.

In the case of Fig. 4, the germanium atom distribution #[C is set at a constant value C6 from position tB to position t, and gradually and continuously decreases between position t and position tT. , at position tT, the distribution concentration C is substantially zero (substantially zero means that it is less than the detection limit amount).

In the case of FIG. 5, the distribution concentration C of germanium atoms is continuously and gradually reduced from the concentration C8 from the position tB to the position tT, and becomes substantially zero at the position 1T.

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is a constant value of concentration C9 between position tB and position t8, and is the concentration CtO at position tT.

Between position t3 and positions t and r, the distribution concentration C is linearly decreased from position t3 to position t.

In the example shown in FIG. 7, the distribution concentration C takes a constant value of concentration C11 from position t to position t, and
From t to position ta, the distribution state is such that the concentration decreases linearly from the concentration C+t to the concentration C1s.

In the example shown in FIG. 8, from position tB to position tT, the distribution concentration C of germanium atoms decreases linearly from the concentration CI4 to substantially zero.

In FIG. 9, from position tB to position t, the distribution concentration C of germanium atoms decreases linearly from concentration CII+ to concentration CI6, and from position t to position t.
An example is shown in which the concentration Cl1l is set to a constant value between (a) and (a).

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is CI7 at position tB, and this concentration CI? until position t6. At first, the concentration is decreased slowly, and around the position t6, it is rapidly decreased, and the concentration becomes C at the position t6.

Between position t6 and position t, the concentration is first rapidly decreased, and then gradually decreased to reach CIO at position t, and between position t and position t8, the concentration is extremely low. It is slowly and gradually reduced to a concentration C1° at position t. Between position 'It t and position 1T, the concentration is reduced from C7° 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 germanium atoms contained in the photoreceptive layer in the layer thickness direction, in the present invention, the support 11
In the photoreceptor layer, the germanium atom distribution state has a portion where the distribution concentration C of germanium atoms is high, and a portion where the distribution concentration C is considerably lower on the interface 1T side than on the support side. If provided,
This is listed as one of the preferred examples.

The photoreceptive layer constituting the photoconductive member of the present invention preferably contains germanium atoms at a relatively high concentration on the support side or, conversely, on the free surface side, as described above. It is desirable to have a localized area (A) where

For example, if the localized region (A) is explained using the symbols shown in FIGS. 2 to 10, it is desirable that the localized region (A) be provided within 5 μ from the interface position tB.

The above-mentioned localized region (A) may be the entire layer region (LA) up to 5μ thick from the interface position tB, or the layer region (
LT).

Whether the localized region (A) is a part or all of the layer region (LT) is appropriately determined according to the characteristics required of the photoreceptive layer to be formed.

The localized region (A) has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of germanium atoms is preferably 1001000 atoms or more relative to the sum with silicon atoms, and more. Preferably 5000 atomic pi1m or more, optimally I
X It is desirable that the layer is formed in such a manner that a distribution state such as 10' atomic ppph or more can be obtained. It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists within 5 μm (a layer region with a thickness of 5 μm from tB).

In the present invention, the content of germanium atoms contained in the photoreceptive layer is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably is 1~9.5 x 105a
tomic P, more preferably 100-8 X 10
5 atomic Wa, optimally 500-7
105 atomic pH 1 is desirable.

The distribution state of germanium atoms in the photoreceptive layer is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration C of germanium atoms in the layer thickness direction is from the support side to the free surface side of the photoreceptor layer. If a decreasing change or the opposite change is given, light with the required characteristics can be obtained by arbitrarily designing the change rate curve of the distribution concentration C as desired. The receiving layer can be realized as desired.

For example, the distribution concentration C of germanium in the photoreceptive layer
Change the distribution concentration C such that it is sufficiently high on the support side and as low as possible on the free surface side of the photoreceptive layer.
By applying this to the distribution concentration curve of germanium atoms, it is possible to achieve photosensitivity to light in the entire range of wavelengths from relatively short wavelengths to relatively short wavelengths, including the visible light region, and it is also possible to increase the photosensitivity to light in the entire wavelength range from relatively short wavelengths to relatively short wavelengths, including the visible light region. It is possible to effectively prevent interference with coherent light.

Furthermore, as will be described later in V, by extremely increasing the distribution concentration C of germanium atoms at the end of the photoreceptive layer on the side of the support, the laser irradiation surface of the photoreceptor layer is improved when a semiconductor laser is used. It is possible to substantially completely absorb light on the long wavelength side that is not fully absorbed by the support side end layer region of the photoreceptive layer, effectively eliminating interference due to reflection from the support surface. can be prevented.

In the photoconductive member of the present invention, in order to increase photosensitivity and dark resistance, and furthermore to prevent charge injection from the free surface of the photoreceptive layer, oxygen is contained in the photoreceptive layer. Contains atoms. The oxygen atoms contained in the photoreceptive layer may be contained evenly in the entire layer area of the photoreceptive layer satisfying the above conditions, or may be contained only in a part of the layer area of the photoreceptive layer. It is also possible to make it ubiquitous.

In the present invention, the distribution state of oxygen atoms is non-uniform in the layer thickness direction in the entire photoreceptive layer as described above. Second. In each third layer region, the thickness is uniform in the layer thickness direction.

11 to 14 show typical examples of the distribution of oxygen atoms in the entire photoreceptive layer.

Symbols used throughout the description of these figures have the same meanings as used in FIGS. 2 through 10.

In the example shown in FIG. 11, the oxygen atom distribution concentration Ct is set from position tB to position t, and from position t.

The oxygen atom distribution concentration C22 is set from the position t11 to the position t1, and the oxygen atom distribution concentration C1l is set from the position tt to the position tT.

In the example shown in FIG. 12, the oxygen atom distribution concentration Cu is set from position t8 to position tit, and from position tn to position tllll.
The oxygen atom distribution concentration is increased in a stepwise manner to c,4 until the point tt's to position 1T, and the oxygen atom distribution concentration is decreased to c.

In the example of FIG. 13, the oxygen atom distribution concentration C2° is stopped from the position tB to the position t14, and the oxygen atom distribution concentration is increased stepwise as Ct'r from the position t14 to the position till, and the oxygen atom distribution concentration is increased stepwise from the position t□ to the position t7. The distribution density is set to a density C□ which is lower than the initial density.

In the example shown in FIG. 14, the oxygen atom distribution concentration from position tB to position t18 is C2@, and from position tea to position tl? The oxygen atom distribution concentration is decreased to Cゎ until the position t
The oxygen atom distribution concentration CU is increased stepwise from position 17 to position till, and from position t18 to position t.

In the present invention, the oxygen atom-containing layer region 0) provided in the photoreceptive layer (the above-mentioned first, second, third (consisting of at least two layer regions) is provided so as to occupy the entire layer area of the photoreceptive layer when the main purpose is to improve photosensitivity and dark resistance. In order to prevent charge injection from the surface, a photoreceptor layer is provided near the free surface, and if the main purpose is to strengthen the adhesion between the support and the photoreceptor layer, the photoreceptor layer is provided near the free surface. It is provided so as to occupy the end layer region of the layer on the side of the support.

In the first case, the content of oxygen atoms contained in the layer region 0) is relatively low in order to maintain a high photosensitivity, in the second case in order to prevent charge injection from the free surface of the photoreceptor layer. In the latter case, it is desirable to use a relatively large amount in order to ensure enhanced adhesion to the support.

In addition, in order to simultaneously achieve the king, the concentration should be distributed at a relatively high concentration on the support side, the concentration should be distributed at a relatively low concentration at the center of the photoreceptive layer, and the concentration should be distributed at the free surface side of the photoreceptor layer. In the surface layer region, it is sufficient to form a distribution state of oxygen atoms such that the number of oxygen atoms is increased in the layer region (0).

In order to prevent charge injection from the free surface, a layer region (0) in which the distribution concentration of oxygen atoms is increased is entirely formed on the free surface side. However, when a layer region with a high distribution concentration of oxygen atoms comes into contact with the atmosphere, in the case of electrophotography, it may adsorb moisture in the air, causing image blurring. Therefore, it is desirable that the distribution concentration of oxygen atoms is low in the immediate vicinity of the free surface.

In the present invention, the content of oxygen atoms contained in the layer region 0) provided in the photoreceptive layer depends on the characteristics required for the layer region (1) itself or the layer region (0) is directly attached to the support. When provided in contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the support.

In addition, when another layer region is provided in direct contact with the layer region (0), the characteristics of the nucleon layer region and the relationship with the characteristics at the contact interface with the nucleon layer region are also considered. and the content of oxygen atoms is appropriately selected.

The amount of oxygen atoms contained in the layer region 0) is determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably 0.001 with respect to T (SiGeO). ~50 a, tomie% 1, preferably 0.002 to 40 atomic%, most preferably 0.0 (13 to 30 atomic%).

In the present invention, even if the layer region (0) occupies the entire area of the photoreceptive layer or does not occupy the entire area of the photoreceptive layer, the layer thickness of the photoreceptor layer of 1v thickness TO in the j-region (0) When the proportion of T is sufficiently large, the upper limit of the content of oxygen atoms in the layer region (0) is preferably set to be sufficiently larger than the above value.

In the case of the present invention, if the ratio of the layer thickness TO of the layer region 0) to the one end thickness T of the photoreceptive layer is two-fifths or more, in the layer region (0) The upper limit of the amount of oxygen atoms contained is preferably 30 atc! with respect to T (SiGeO). *ic% or less, more preferably
20 atomic or less, optimally 10 atomic
% or less.

In the present invention, the layer region (0) containing oxygen atoms constituting Mu of the photoreceptive layer is a layer region (0) containing oxygen atoms in a relatively planar concentration on the support side and near the free surface, as described above. In the former case, it is desirable to improve the adhesion between the support and the photoreceptive layer and to improve the receptive potential. I can do it.

The above localized region 0) can be explained using the symbols shown in FIGS. 11 to 14 as the interface position tB or the free surface tT.
It is more desirable that the distance be within 5μ.

In the present invention, the localized region (B) is the interface position @t
B or the entire layer area (Ll
), or may be part of the layer region (Ll).

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

Localized area CB)! -1: Enzymegen contained therein,
The maximum distribution concentration of oxygen atoms (if'j Cmax is preferably 5 (I Q a
tomic ppn or more, more preferably 800 at
omic ppm or more, optimally 1000 atomic
Distribution pattern '8' that seems to be more than c ppm? It is desirable to form a layer so that it can form a layer.

That is, in the present invention, one region (0) containing oxygen atoms has the maximum distribution concentration Cmax within 5 μm in layer thickness from the support side or free surface (layer region 5 μ thick from tB or tT). It is desirable that the structure be formed in such a way that it exists.

In the present invention, specific examples of the halogen atom (3) contained in the light-receiving layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can do it.

In the photoconductive member of the present invention, the conductive properties of the photoreceptive layer can be arbitrarily controlled as desired by containing a substance that controls the conductive properties in the photoreceptive layer L*.

Examples of such substances include impurities referred to in the semiconductor field, and in the present invention, a-8iGe (H,
), P-type impurities and n
Type conduction characteristics fr: The n-type impurity that gives it can be mentioned. Specifically, P-type impurities include atoms belonging to Group Ⅰ of the periodic table (Group 1 atoms), such as B (boron),
Al (aluminum), Ga (gallium), In
(Injiu!,).

Examples include Tl (thallium), among which B and Ga are particularly preferably used.

Examples of n-type impurities include atoms belonging to Group Ⅰ of the periodic table (Group Ⅰ atoms), such as P (phosphorus)-Aa (arsenic), sb
(antimony), Bi (bismuth), etc., especially,
P is preferably used.

It is 88.

In the present invention, the content of the substance that controls the conduction properties contained in the photoreceptive layer is determined by the conduction properties required for the first layer I, or the content of the substance that controls the conduction properties contained in the photoreceptive layer. It can be selected as appropriate depending on the organic properties, such as the relationship with the characteristics of the contact interface with the support to be used.

In addition, when the substance for controlling the conduction properties is contained locally in a desired layer region of the light-receiving layer, especially on the support side of the amorphous layer. When it is contained in the end layer region, the characteristics of other layer regions provided in direct contact with the one region and the relationship with the characteristics at the contact interface with one region of the nucleon are also taken into consideration. The content of the substance controlling the conduction properties is selected appropriately.

In the present invention, the content of the substance that controls conduction properties contained in the photoreceptor is preferably 0.0.
1-5 X 10' atomic ppm, more preferably 0,5-I X 10' atomic ppm
m, optimally rril ~5 x 10 satomic
It is desirable to set it as ppm.

In the present invention, the content of the substance controlling conduction properties in the layer region containing the substance is preferably 30 at.
omic ppm or more, more preferably 50 atoms
ic ppm or more, optimally 100 atomjcpp
m or more, the substance is a part of the photoreceptive layer.
It is preferable to contain it locally in the # region, and it is particularly desirable to make it unevenly distributed in the support-side end layer region of the photoreceptive layer.

Among the above, the end layer region of the photoreceptive layer on the side of the support (for example, by containing a substance that controls the conduction characteristics so that the content is greater than or equal to the above-mentioned value, the substance to be contained is 1). In the case of the P-type impurity described in item 1, when the free surface of the photoreceptive layer is subjected to polar charging treatment, injection of electrons from the support side into the photoreceptor can be effectively prevented. In addition, if the substance to be contained is the n-type impurity, when the free surface of the photoreceptive layer is charged to the Pore injection can be effectively prevented.

In this way, when the end layer region (5) contains a substance that controls the conduction characteristics of the polarity of the force, the remaining layer region of the photoreceptive layer, that is, the end layer region The layer region excluding (2) may contain a substance that controls the conduction characteristics of the other polarity, or the material that controls the conduction characteristics of the same polarity may be added to the end layer region (2). It is also possible to contain even less amount of the end of the fruit contained in the.

In such a case, the content of the substance that governs the conductive properties contained in the layer region (8) is as follows:
It is determined as desired depending on the polarity of the substance contained in g) and the content R1, but preferably,
o, ooi to 1000 atomic ppm, preferably 0.05 to 500 atomic ppm + optimally 0.1 to 200 atomic T) l) m.

In the present invention, when the end layer region (g) and the layer region 2) contain the same kind of substance governing conductivity, the content in the layer region (8) is preferably as follows: :(O
It is desirable that the amount be atomic ppm or less. In addition to the above-mentioned case, in the present invention, G2, a layer region containing a substance controlling conductivity having one polarity in the photoreceptive layer, and a layer region containing a substance controlling conductivity having one polarity; It is also possible to provide a layer region containing a substance in direct contact and to provide a so-called depletion layer in this contact region.

For example, the layer region containing the P-type impurity and the layer region containing the N-type impurity are provided in the photoreceptive layer so as to be in direct contact with each other to form a so-called p-n junction. , a depletion layer can be provided.

In the present invention, the photoreceptive layer composed of a 5iGe (H+ For example, a -8iGe (H,X)
In order to form a photoreceptive layer composed of, basically, a raw material gas for supplying Si that can supply silicon atoms (Si), a raw material gas for supplying Ge that can supply germanium atoms (Ge), If necessary, a raw material gas for introducing hydrogen atoms α () and/or a raw material gas for 4 halogen atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to perform the deposition. A-8 is generated on the surface of a predetermined support body, which is placed in a predetermined position in advance, by causing a glow discharge in the room.
A layer consisting of iGe (H,X) may be formed. or,
In order to contain germanium atoms in a non-uniform distribution state, a layer consisting of a-8iGe (H9X) may be formed while controlling the distribution concentration of germanium atoms according to a desired rate of change curve. In addition, when forming by a sputtering method, Si is formed in an atmosphere of an inert gas such as Ar, L(6) or a mixed gas based on these gases.
or the target and Ge
Using two targets made up of or St.
Using a mixed target of Ge and hydrogen atoms, if necessary, a source gas for supplying Ge diluted with a diluent gas such as He + Ar, etc. This is accomplished by introducing a gas for introducing atoms (3) into a deposition chamber for sputtering to form a plasma atmosphere of a desired gas. In order to make the distribution of germanium atoms non-uniform, the target may be sputtered while controlling the gas flow rate of the raw material gas for supplying Ge according to a desired rate of change curve.

In the case of the ion blating method, for example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition port as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. Except for heating and evaporating by method (EB method) etc. and passing the flying evaporated material through the desired gas plasma atmosphere,
This can be done in the same manner as in the sputtering method.

Substances that can be used as raw material gas for supplying Si used in the present invention include 5iI (4,5iyHe, 5ts
Silicon hydride (silanes) in a gaseous state or that can be gasified, such as HaSi+H+o, can be effectively used. In particular, 5IH4 is easy to handle during layer creation work, and has good St supply efficiency. *5ltHe is preferred.

As a material that can be a source gas for supplying Ge, GeH
,,Ge2H0+ Ge5t(s r Ge4H+o
*Ge5H1'21 GeqH,4TGeyH+e
, Ge5HI8. Germanium hydride in a gaseous state or that can be gasified, such as Geo) [to, can be effectively used. In particular, GeH+ + Get
Preferred examples include H6 and Ge3Hs.

Effective raw material gases for the introduction of 10-gen atoms (used in the present invention) include many non-rogen compounds, such as non-rogen gas, non-rogen compounds, inter-rogen compounds, and non-rogen substituted compounds. Preferred examples include gaseous or gasifiable halogen compounds such as silane derivatives.

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

Specifically, the metal halides that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CIF, and CA'Fs.

BrF5, BrF5, HF3, IF7,
Icl! , IBr, and other interhalogen compounds.

Examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include, for example, SiF4+ 5i2Fa, SiC/+ + 5iB
Preferred examples include silicon halides such as r+.

When a photoconductive member characteristic of the present invention is formed by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying St together with a raw material gas for supplying Ge. A light-receiving layer made of a 5iGe containing halogen atoms can be formed on a desired support without using silicon oxide gas.

When manufacturing a light-receiving layer containing halogen atoms according to the glow discharge method, basically, for example, silicon halide as a raw material gas for supplying St, germanium hydride as a raw material gas for supplying Ge, and Ar + Ht. *By introducing a gas such as He into the deposition chamber where the photoreceptive layer is to be formed at a predetermined mixing ratio and gas flow rate, and generating a glow discharge to form a plasma atmosphere of these gases, A light-receiving layer can be formed on a desired support, but in order to more easily control the introduction ratio of hydrogen atoms, hydrogen gas or a silicon compound containing hydrogen atoms may be added to these gases. A layer may also be formed by mixing a desired amount of 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.

In order to introduce 7-halogen atoms into the layer formed by either the sputtering method or the ion-blating method, a gas of the above-mentioned 7-halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient if a plasma atmosphere of the gas is formed by introducing the gas into the atmosphere.

In addition, when introducing hydrogen atoms, a raw material gas for hydrogen atom introduction, such as F2, or the above-mentioned silanes or/
A gas such as germanium hydride or the like may be introduced into a sputtering deposition chamber for 1° to form a plasma atmosphere of the gas.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for introducing halogen atoms.
In addition, HF, HC1! .

Hydrogen halides such as HBr, HI, SiH2F2.
5iH-dz.

5iH2CA'z, 5iHCls, 5iHd3r
2,5iHBr3@/%tffgen-substituted silicon hydride, and GeHF3, GeHBr3゜GeH3F
+ GeHCl5, GeH2C17, GeHBr3
．． GeHBr3゜GeF2Br21 GeHBr3,
Hydrogenated germanium halides such as GeHI, , GeF2I2, GeH,1, etc., which have a hydrogen atom as one of their constituents, GeF'' + lGeC
1h, GeBr+, GeI4, GeF2.
GeClt, GeBr,.

Gaseous or gasifiable substances such as germanium halides such as Ge I 2 can also be mentioned as useful starting materials for forming the photoreceptive layer.

Among these substances, non-halogenated substances containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming the photoreceptive layer. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen.

In order to structurally introduce hydrogen atoms into the photoreceptive layer, in addition to the above, 2H2, 5iHL, 5izH6, 5isH
s.

5i-4I (Io, etc.) with germanium or a germanium compound for supplying Ge, or with Ge
H4, Ge21(6, Ce3Ha, Ge41], I
o , Ge5H, +t , Ge5H14゜Gewl(1
6. Ges■■18+ This can also be carried out by causing germanium hydride such as GeaHto and silicon or a silicon compound for supplying Si to coexist in a deposition chamber to generate a discharge.

In a preferred embodiment of the present invention, the amount of hydrogen atoms (6) or the amount of halogen atoms (6) or the sum of hydrogen atoms and halogen atoms (H+X) contained in the photoreceptive til of the photoconductive member to be formed is preferably 0,01-40 ato
mic%, more preferably 0.05-30 atoms
c%, preferably 0.1 to 25 atomic.

In order to control the needles of hydrogen atoms α and/or halogen atoms (3) contained in the photoreceptive layer, for example, the temperature of the support and/or the hydrogen atoms ω◇ or the halogen atoms (3) can be controlled. It is only necessary to control the introduction of the starting material used for this purpose into the deposition apparatus system, the discharge power, etc.

In the present invention, in order to provide a layer region (containing oxygen atoms) in the photoreceptive layer, the starting material for introducing oxygen atoms is added to the starting material for forming the photoreceptive layer as described above. It may be used in conjunction with a substance to control the amount and contain it in the formed layer.

When the glow discharge method is used to form the layer region (0), a starting material for introducing oxygen atoms is added to one selected as desired from among the starting materials for forming the photoreceptive layer described above. As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used.

For example, a raw material gas whose constituent atoms are silicon atoms (Si), a raw material gas whose constituent atoms are oxygen atoms (0), and a raw material gas whose constituent atoms are hydrogen atoms (goods) or halogen atoms (2) as necessary. Either a raw material gas containing silicon atoms (Si) and a raw material gas containing 0 oxygen atoms and 0 hydrogen atoms can be used by mixing them at a desired mixing ratio. Alternatively, a raw material gas containing silicon atoms (St) as constituent atoms and a raw material containing three constituent atoms: silicon atoms (St), oxygen atoms (0), and hydrogen atoms (0) may be mixed at a desired mixing ratio. Can be used in combination with gas.

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

Specifically, for example, oxygen (01), ozone (0,), -
Nitrogen oxide (No), nitrogen dioxide (NO2), -nitrogen dioxide (N, 0), nitrogen sesquioxide (Ntos), trinitrogen tetraoxide (N, 0.), nitrogen sesquioxide (Nzoe), nitrogen trioxide ( NO, ), silicon atoms (Si) and oxygen atoms (0
) and hydrogen atoms as constituent atoms, for example, disiloxane (H3SiO8iH3), ) disiloxane (Hs
Examples include lower siloxanes such as S i OS i L OS i Hs).

To form the layer region (0) by the sputtering method, when forming the photoreceptive layer, target a single crystal or polycrystalline Si wafer, a Sin wafer, or a wafer containing a mixture of St and Stow. These may be performed by sputtering in various gas atmospheres.

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

Alternatively, by using St and Sin as separate targets or a single mixed target of St and 5iOz, at least hydrogen atoms or This is accomplished by sputtering in a gas atmosphere containing / and halogen atoms as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms in the raw material gas shown in the glow discharge example mentioned above is
It can also be used as an effective gas in sputtering.

In the present invention, when a layer region containing oxygen atoms is provided when forming a photoreceptive layer, the distribution concentration C(0) of oxygen atoms contained in the layer region (0) is determined by the layer thickness. The desired distribution state in the layer thickness direction (depth
To form a layer region (0) having a profile ), in the case of a glow discharge, a starting material gas for introducing oxygen atoms whose distribution concentration Cto) is to be changed is introduced, and the gas flow rate is adjusted to a desired rate of change curve. While changing it accordingly,
This is accomplished by introducing it into the deposition chamber.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be appropriately changed by any commonly used method such as manually or by using an externally driven motor.

When the layer region (0) is formed by sputtering, the distribution concentration C of oxygen atoms in the layer thickness direction is changed stepwise in the layer thickness direction to obtain the desired distribution state of acid MW molecules in the layer thickness direction ( depth profile).
First, as in the case of the glow discharge method, oxygen atoms can be introduced by using a starting material in a gaseous state and changing the gas flow rate when introducing the gas into the deposition chamber as desired. be done.

Second, the target for sputtering is, for example, S
If a target containing a mixture of i and Stow is used, this can be done by changing the mixing ratio of Si and 5i02 in advance in the layer thickness direction of the target.

In order to structurally introduce a substance that controls conduction properties into the photoreceptive layer, such as a group 1 atom or a group V atom, a starting material for introducing a group 1 atom or The starting material for introducing group V atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the photoreceptive layer.

As a starting material for such introduction of Group 1 atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such Group 1 atoms include B*Hs, B4) 11
01B s Ha,B5H,,,BeH+o -BeH
, 2, boron hydride such as B6HI4, BF, , Bcts
Examples include boron halides such as sBBrj. In addition, Atcts s c a Cts, Ga(CL)s
s InC45, Tocus, etc. can also be mentioned.

As a starting material for introducing a group V atom, the starting materials effectively used in the present invention for introducing a phosphorus atom are
, hydrogen north neighbor such as H4, PH4I, PFs s PFx,
pcz,, P C1s, PBr35 PBr35 PI
Examples include halogenated phosphorus such as s. In addition, A-sH,
, AsF, , A3Cl3 % AsBr5, AIIFB
, 5bHs, Sb F3, sbrg, 5bct8.5
bC1B, B1H8, BiCz, B1Br5 etc. are also No. V
It can be mentioned as an effective starting material for introducing group atoms.

In the present invention, the layer thickness of the layer region constituting the light-receiving layer and containing a substance that controls conduction properties and provided unevenly on the support side is defined as the thickness of the layer region formed on the layer region and the layer region formed on the layer region. The lower limit is preferably 30 λ or more, more preferably 40 Å.
As mentioned above, the optimum thickness is preferably 50 Å or more.

Further, when the content of the substance controlling the conductive properties contained in the layer region is 30 atomic ppm or more, the upper limit of the layer thickness of the layer region is preferably 1.
It is desirable that the thickness be 0μ or less, more preferably 8μ or less, and optimally 5μ or less.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include %NtCr+stainless steel, At, Cr%Mo,
Au, Nb, Tat V% Ti, Pt, Pd
Metals such as these or alloys thereof can be mentioned.

As the electrically insulating support, polyester, λ polyethylene, polycarbonate, cellulose Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is made of glass, %NxCr5A is added to its surface.
ts Cr, Mos Au, Irb Nb, Ta
, V% Tin Pt% Pdmln=0a s Sn
Conductivity can be imparted by providing a thin film made of O, ITO (IntOs +5nO7), etc., or if it is a synthetic resin film such as a polyester film, sN
iCr%At, AgN pci% Znb Nis A
utCr, Mo, Ir, Nb, Ta, Vs
Conductivity is imparted to the surface by providing a thin film of a metal such as Ti) Pt on the surface by vacuum evaporation, electron beam evaporation, sputtering, or the like, or by laminate-treating the surface with the metal. The shape of the support may be any shape such as cylindrical, belt-like, or plate-like, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. In the case of continuous high-speed copying, it is desirable to use an endless belt or a cylindrical shape. 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. It is made as thin as possible within the range. Hyakunen et al.
In such a case, an outline of an example of the method for manufacturing the photoconductive member of the present invention will be explained next.

FIG. 15 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the figure are sealed with raw material gases for forming the photoconductive member of the present invention. For example, 1102 is 5i) L4 gas diluted with He (99.999% purity).

Hereinafter, it will be abbreviated as SiH, /He. ) cylinder, 1103 is He
GeH diluted with gas (purity 99.999%, hereinafter referred to as GeH).

/He is abbreviated. ) cylinder, 1104 is 5iFi gas diluted with He3 (purity 99.99%, hereinafter S i F4
/ Abbreviated as He. ) cylinder, 1105 is a NO gas (purity 99.999q6) cylinder, and 1106 is a H2 gas (purity 99.999%) cylinder.

In order to flow these gases into the reaction chamber 1101, pulps 1122 to 1126 of gas cylinders 1102 to 1106,
Leak pulp 1] Check that 35 is closed,
In addition, inflow pulps 1112 to 1116, outflow pulp 111
7-1121, confirm that the auxiliary pulps 1132 and 1133 are open, first open the main pulp 1134 and open the reaction chamber 1101. and exhaust the inside of each gas pipe. Next, the reading on the vacuum gauge 1136 is approximately 5 X 10' torr.
At this point, the auxiliary pulps 1132 and 1133 and the outflow pulps 1117 to 1121 are closed.

Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137, the gas cylinder 1102 and the SO
L/He gas, GeH4/He from gas cylinder 1103
Gas, NO gas from gas cylinder 1105 to pulp 112
2.112:l, open 1124 and outlet pressure gauge 112
7.Adjust the pressure of 112B and 1129 to 1/-, gradually open the inlet valves 1112, 1113, and 1114,
into mass 70 controllers 51107, 1108, and 1109, respectively. Subsequently the outflow valve 1117.1
118.1119, the auxiliary valve 1132 is gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the outflow valves 1117, 111B and 1119 are adjusted so that the ratio of the L/He gas flow rate to GeH, /He gas flow rate and He gas flow rate becomes the desired value for J5i, and the reaction chamber 1101 While checking the reading on the vacuum gauge 1136, adjust the opening of the main valve 1134 so that the internal pressure reaches the desired value.

After confirming that the temperature of the substrate 1137 is set to a temperature in the range of 50 to 400°C by the heater 1138, the power source 1140 is set to the desired power to generate a glow discharge in the reaction chamber 1101. At the same time, the flow rate of No. gas is controlled manually or by an external drive motor, etc. at valve 1 according to a pre-designed rate of change curve.
In order to control the distribution concentration of oxygen atoms contained in the layer to be formed by appropriately changing the openings of the substrate 118, and to make the layer formation uniform while forming five layers,
37 is preferably rotated by a motor 1139 at a constant speed.

Examples will be described below.

Example 1 Samples (Samples Nnl 1-1 to 13-4) as electrophotographic image forming members were prepared on a cylindrical LT substrate under the conditions shown in Table 1 using the manufacturing apparatus shown in FIG. (Table 2) 0 The content distribution concentration of germanium atoms in each sample is
Sixthly, the distribution concentration of oxygen atoms is shown in FIG.

Place each sample obtained in this way in a charging exposure experiment device.■5. Corona charging was performed at OkV for 0.3 r&, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light intensity of 21 ux-sv was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading an O-charged developer (including toner and carrier) over the imaging member surface. The toner image on the image forming member is processed by 5. When transferred onto transfer paper using OkV corona charging, clear, high-density images with excellent resolution and good gradation reproducibility were obtained in all samples.

In the above, the light source is replaced by a tungsten lamp81
Using a 0 nm GaAs semiconductor laser (10 mW), n1! We evaluated the image quality of the toner transfer images for each sample under the same toner image formation conditions except for the image formation, and found that all samples had excellent resolution and clearness with good gradation reproducibility. A high-quality image was obtained.

Example 2 Samples (Samples Na21-1 to 23-4) as electrophotographic image forming members were prepared on a cylindrical At substrate under the conditions shown in Table 3 using the manufacturing apparatus shown in FIG. Table 4).

The content distribution degree of germanium atoms in each sample is the first
FIG. 6 shows the content distribution concentration of oxygen atoms, and FIG. 17 shows the oxygen atom content distribution concentration.

When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. Also, for each sample, 38°C 180%
When a repeated use test was conducted 200,000 times in an RH environment, no deterioration in image quality was observed in any of the samples.

Table 2 Common layer forming conditions in the examples of the present invention shown in Table 4 and above are shown below.

Substrate temperature: germanium atom (Ge) containing layer...approximately 2
00″C discharge frequency: 13.56 MHz Reaction chamber pressure during reaction: 0.3 Torr

[Brief explanation of the drawing]

Section 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are explanations for explaining the distribution state of germanium atoms in the photoreceptive layer, respectively. figure,
FIGS. 11 to 14 are explanatory diagrams for explaining the distribution state of oxygen atoms in the photoreceptive layer, respectively, FIG. 15 is a schematic explanatory diagram of the apparatus used in the present invention, and FIG. Figure, No. 17
Each figure is a distribution state diagram showing the distribution state of each atom in each example of the present invention. ioo...Photoconductive member 101...Support 102...Photoreceptive layer 1---→-C OtsuC--C-11111□□-- e

Claims (8)

[Claims] (1) It has a support for a photoconductive member and a photoconductive photoreceptive layer made of an amorphous material containing silicon atoms and germanium atoms, and the photoreceptor layer contains oxygen atoms. In addition to containing, the distribution concentration in the layer thickness direction is
C(ll. C(31, C(21), which is characterized by having a first layer region (1), a third layer region (3), and a second layer region (2) in this order from the support side. photoconductive member (however, C(31>
C(21, C(1) and C(11, C(at least one of 21 is not 0 or CFll. C(2) is not equal) 0 (2) The photoconductive member according to claim 1, wherein the photoreceptive layer contains hydrogen atoms. (3) The photoconductive member according to Claims 1 and 2, wherein the photoreceptive layer contains a norogen atom. (4) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the photoreceptive layer is non-uniform in the layer thickness direction. (5) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the photoreceptive layer is uniform in the layer thickness direction. (6) The photoconductive member according to claim 1, wherein the photoreceptive layer contains a substance that controls conductivity. (7) The photoconductive member according to claim 6, wherein the substance that controls conductivity is an atom belonging to Group 11 of the periodic table. (8) The photoconductive member according to claim 6, wherein the substance that controls conductivity is an atom belonging to Group V of the periodic table.