JPS6057984A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain the photoconductive member of total environment type having stabilized electric, optical and photoconductive characteristics at all times and also having excellent photosensitive characteristics on the long wave side and optical fatigue resistance by a method wherein nitride atoms are contained in a photoreceptive layer and, at the same time, the distribution density in layer thickness direction is specified. CONSTITUTION:A photoconductive member 100 has a supporting member 101 to be used as a photoconductive member and a photoreceptive layer 102 consisting of a -SiGe(H, X), containing nitrogen atoms and having photoconductive property. A photoreceptive layer 102 has the first layer region (1) 104 having the value of C(1) for distribution density C(N) in layer thickness direction of the nitrogen atoms, the second layer region (2) 105 having the value of C(2), and the third layer region (3) 106 having the value of C(3). In the first, second and third layers, it is not always necesssary that nitrogen is contained in these layer regions, but the distribution density C(3) is to be larger than either of the distribution density C(1) and C(2), and at least either of the distribution density C(1) and C(2) is not zeroed, or the distribution density C(1) and C(2) are unequally formed.

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, R-rays, etc.). Regarding.

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 is highly sensitive and has a photocurrent (Ip) of 8N ratio.
/dark current (Id)), has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has the desired dark resistance value, and is non-polluting to the human body during use. In addition, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point.

Based on these points, Light Guide 1 has been attracting attention recently! The material is amorphous silicon (hereinafter referred to as 1a-8i), for example, German Publication No. 2746967, German Publication No. 2
Publication No. 855718 describes an image forming member for electrophotography,
DE 2933411 describes an application to a charging conversion reading device.

A photoconductive member having a conventional photoconductive layer composed of a-8i has excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and furthermore, stability over time, which requires comprehensive improvement of characteristics.

For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use, and this type of When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speeds, responsiveness gradually decreases, etc. There were many cases where problems occurred.

Historically, a-8i has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, making it difficult to match with semiconductor lasers currently in practical use. In this case, when a commonly used halogen lamp or fluorescent lamp is used as a light source, 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 absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases,
If the support itself has a high reflectance for light transmitted through the photoconductive layer, interference due to multiple reflections will occur within the photoconductive layer, which is one of the causes of "poke" in the image.

This effect becomes larger as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the 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 '1
Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms to control gas conduction type, or other atoms are included in order to improve other properties. Depending on the method, problems may arise 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 be shortened. There are many cases where it is not sufficient, or in the dark area, the injection of pollutants from the support side is not sufficiently prevented.

Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it caused the phenomenon that occurred most often. 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-8i 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 is characterized by its applicability and applicability to A-8I as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive research and consideration from this perspective, we have discovered an amorphous material that has silicon atoms (Si) and germanium atoms (Ge) as a matrix and contains at least either hydrogen atoms (H) or halogen atoms (X). , place jt
l Hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to as [a-8iGe (H,X)]
A photoconductive member designed and produced with a photoreceptive layer exhibiting photoconductivity consisting of a photoconductive layer (using J) as described below has a remarkable practical effect. It not only shows excellent properties, but also surpasses conventional photoconductive materials in every respect, especially as a photoconductive material for electrophotography. This is based on the discovery that the absorption 4y spectrum characteristics on the wavelength side are excellent.

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 main object of the present invention is to provide a photoconductive member that is durable, does not cause 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, is particularly compatible with semiconductor lasers, and has a 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 portion side that is dense and stable in terms of structural arrangement and has high layer quality.

Another object of the present invention is that when applied as an electrophotographic imaging member, the static Nf! 1! It is an object of the present invention to provide a photoconductive member which has sufficient charge retention ability during charging treatment for formation and has excellent electrophotographic properties in which almost no deterioration of the properties is 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 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 has a support for the photoconductive member and a photoconductive photoreceptive layer made of an amorphous material containing silicon atoms and germanium atoms, A first layer region (1) in which the layer contains nitrogen atoms and has a concentration distribution in the thickness direction of C(1), C(31, and 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(2), C(1), and C(1), C(2
) is not O or C(1)
, C(2) are not equal).

The photoconductive member of the present invention designed to have the above-described layer structure can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates pressure resistance and usage environment characteristics.

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. As a result, high-quality images with high density, clear halftones, and high resolution can be stably and repeatedly obtained with excellent light fatigue resistance and repeated use characteristics.

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

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

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. 1 includes a support 101 for the photoconductive member, and an a-8iG
The photoreceptive layer 102 is made of e(H,X), contains nitrogen atoms, and has photoconductivity.

The germanium atoms contained in the photoreceptive layer 102 may be uniformly distributed in the photoreceptive layer 102, or may be contained evenly 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. is necessary. In particular, it is uniformly contained in the layer thickness direction of the light-receiving layer 102, and the side opposite to the side on which the support 101 is provided (
Either the free surface 103 side of the photoreceptive layer 102 is distributed more toward the support side 101 (the interface side between the photoreceptive layer 102 and the supporter 101), or vice versa. It is contained in the photoreceptive layer 102 so as to have a distribution state of .

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

In the photoreceptive layer 102 of the photoconductive member 100 shown in FIG. 1, the distribution concentration C(N) of nitrogen atoms in the layer thickness direction is C(1).
A first layer region (1) 104 having a value of C(2), a second layer region (3) 106 having a value of +2+105°C(3).

In the present invention, the above-mentioned 1. Second. The third layer regions do not necessarily need to contain nitrogen atoms in any of these three layer regions, but the distribution concentration C
(3) is larger than both of the distribution concentrations C(1) and C(2), and at least one of the distribution concentrations C(1) and C(2) is not O or the distribution concentration C(
1) and C(2) must not be equal.

When either one of the distribution concentrations Cfl) and Cf2) is O, the photoreceptive layer 102 includes either the first layer region (1) 104 or the second layer region as a layer region that does not contain nitrogen atoms. +2) 105 with a third layer region (3) having a higher distribution concentration C(3).

In this case, if nitrogen 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 (1) 1
04 as a layer region containing no nitrogen atoms in the photoreceptive layer 1.
02, and conversely, prevention of charge injection from the support 101 side into the photoreceptive layer 102 and
In order to improve the adhesion between the photoreceptor M102 and the photoreceptor M102, it is necessary to design the photoreceptor M102 with the second layer region +21105 as a layer region that does not contain nitrogen atoms.

In the present invention, the maximum distribution concentration C(3) among the three
In order to improve the dark resistance of the photoreceptive layer 102 while maintaining good photosensitivity characteristics, the third layer region (3) 106 having It is desirable to set the layer thickness to a relatively low value and to have a sufficient thickness within the required range.

Furthermore, if the third layer region (3) 106 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 (3) 106 may be )
The layer thickness of layer 106 is made as thin as possible within the range where the effect of blocking charge injection is sufficiently obtained, and the layer thickness of photoreceptor M1 is
It is desirable to provide the third layer region (3) 106 as close as possible to the free surface 103 of 02 or to the support 101.

In this case, if the third layer region (3) 106 is provided closer to the support 101 side, the first layer region (1) The support 101 and the light-receiving layer 102 are
It is provided mainly to improve the adhesion between the

If the third layer region (3) 106 is provided closer to the free surface 103 side, the second layer region (2)
l05 is provided mainly for the purpose of preventing the third layer region (3) 106 from being exposed to a humid atmosphere.

In the present invention, the layer thicknesses of the first layer region (1) and the second layer region (2) are distribution concentrations C(1) and C(2).
), but is preferably 0.003 to 100μ, more preferably 0.0
It is desirable that the thickness be 04 to 80μ, most preferably o, oos 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 0.00.
It is desirable that the thickness be 3 to 80μ, more preferably 0.004 to 50μ, and optimally 0.005 to 40μ.

When the third layer region (3) is mainly provided with the function of a charge injection blocking layer, it is provided close to the support side or the free surface side of the photoreceptive layer, and the layer thickness is preferably 30 mm.
It is desirable that the thickness be less than μ, more preferably less than 20 μ, optimally less than 10 μ. At this time, the layer thickness of the first layer region (1) on the side of the support where the third layer region (3) is provided or the second layer region (2) on the free surface side is the same as that of the third layer region (3).
The distribution concentration C(3) of nitrogen atoms contained in the layer region (3) of
), but it is preferably set to 5μ or less, more preferably 3μ or less, and most preferably 1μ or less.

In the present invention, the maximum value of the distribution concentration C(3) of nitrogen atoms is preferably 67 atomic with respect to the sum of silicon atoms, germanium atoms, and nitrogen atoms (hereinafter referred to as [T (5iGeN ) J). %, more preferably 50 atomic%, optimally 40 atomic%
It is desirable that this is done.

Moreover, the minimum value of the distribution concentration C(3) is T (5iGeN
) preferably 10 atomic pprl'
preferably 1 s ato+nic ppm,
Optimally, it is desirable to set it to 20 atomicpprll.

When the distribution concentrations C(1) and C(2) are not 0, the minimum value is preferably 3 atomic ppm, preferably 5 atoms, for T (5iGeN).
It is desirable to set it to ic ppm.

2 to 10 show typical examples in which the distribution state of germanium atoms contained in the light-receiving layer of the leading redundant member in the present invention is non-uniform in the layer thickness direction.

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
T indicates the position of the surface of the photoreceptive layer opposite to the support side. That is, the photoreceptive layer containing germanium atoms has t
Layer formation is performed from the B side toward the tT 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, the surface on which the germanium atom-containing photoreceptive layer is formed and the surface of the photoreceptive layer are located 1.0 mm from the interface position tB. Up to the position t, germanium atoms are contained in the formed photoreceptive layer while the distribution concentration C of germanium atoms takes a constant value CI, and the distribution concentration C2 increases until the position It, or even the interface position tT. It has been gradually and continuously reduced. At the interface position tT, the distribution concentration C of germanium atoms is C8.

In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C4 from the position tB to the position tT, and reaches the concentration C1 at the position HtT. is formed.

In the case of FIG. 4, the distribution concentration C of germanium atoms is kept at a constant value C6 from position H1B to position t2, and gradually and continuously decreases between position [tz and position 1i1iftT, At tT, the distribution concentration C is substantially zero (substantially zero here means less than the detection limit).

In the case of FIG. 5, the distribution concentration C of germanium atoms is continuously gradually decreased from the concentration C8 from the position type A to the position type A, and becomes substantially zero at position (iitT).

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is a constant value of concentration C0 between position tB and position 18, and the concentration CIO is determined at position tT.

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

In the example shown in FIG. 7, the distribution concentration C is of order t! f
From tB to position t4, the concentration C1l takes a constant value, and from position Hb to position tT, the concentration decreases linearly from CI2 to C11l.

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 C14 to substantially zero.

In FIG. 9, from position tB to position t, the distribution concentration C of germanium atoms is C,! It is linearly decreased to the concentration CI6, and the position t and the position ItT
An example is shown in which the concentration CI6 is set to a constant value between .

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is at a concentration C, ? and
Until reaching position t6, the concentration C17 is slowly decreased at first, and near the position t6, it is rapidly decreased to the concentration Cl1l at position t6.

Between position t6 and position t7, the concentration is decreased rapidly at first, and then gradually decreased to a concentration C11 at position t7, and between position 17 and position tll,
very slowly and gradually decreased at position t8,
The concentration reaches C7°. Between position f1Mfa and position 1T, the concentration CtO is reduced 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, germanium atoms are The light-receiving layer is provided with a distribution state of germanium atoms having a portion where the distribution concentration C of atoms is high, and a portion where the distribution concentration C is considerably lower on the interface tT side than on the support side. is cited 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 μm from the interface position tB.

The localized region (A) may be the entire layer region (LT) up to 5 μm thick from the interface position tB, or may be a part of the layer region (LT).

Whether the localized region (A) is a part or all of the layer region (h'r) is determined as appropriate depending on 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 1000 atomic ppm or more with respect to the sum with silicon atoms, more preferably. 5000 atomic ppm or more, optimally I
It is desirable that the layer be formed in such a manner that a distribution state of at least X 10' atomic ppm can be achieved.

That is, in the present invention, the photoreceptive layer containing germanium atoms is formed such that the maximum value Cmax of the distribution concentration exists within 5 μm in layer thickness from the support side (layer region 5 μm thick from tn). It is preferable to

In the present invention, the content of germanium atoms contained in the photoreceptive layer is appropriately determined as desired so that the object of the present invention is effectively achieved, but Preferably 1 to 9.5 x 1051
05ato ppm, more preferably 100-8X
105105ato ppm, optimally 500-7
It is desirable that the amount is 105105 at ppm.

The distribution state of germanium atoms in the photoreceptive layer is such that germanium atoms are continuously distributed in the entire layer region, and once the distribution of germanium atoms in the layer thickness direction C is directed 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
On the support side, change in the distribution concentration C is sufficiently increased, and on the free surface side of the photoreceptive layer, the change in the distribution concentration C is suppressed as much as possible.
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, by extremely increasing the distribution concentration C of germanium atoms at the end of the photoreceptive layer on the support side, when a semiconductor laser is used, the side of the laser irradiation surface of the photoreceptor layer is Light on the long wavelength side that is not fully absorbed can be substantially completely absorbed in the end layer region of the support side of the photoreceptive layer, effectively eliminating interference due to reflection from the support surface. It can be prevented.

In the photoconductive member of the present invention, in order to increase photosensitivity and dark resistance, and to prevent charge injection from the free surface of the photoreceptive layer, the photoreceptor layer contains: Contains nitrogen atoms. The nitrogen atoms contained in the photoreceptive layer may be uniformly contained 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 nitrogen atoms is non-uniform in the layer thickness direction in the entire photoreceptive layer, as described above.
1st. 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 nitrogen atoms in the entire photoreceptive layer. Symbols used throughout the explanation of these figures are as shown in FIG. It has the same meaning as used in FIGS.

In the example shown in FIG. 11, the distribution concentration of nitrogen atoms is C(N) C□ from position t to position t, and the distribution concentration C(N) of nitrogen atoms from position [1* to position i11 is C.W.
t, and the distribution concentration C(N) of nitrogen atoms is C21 from position tll to position tT.

In the example shown in FIG. 12, the distribution concentration C(N) of nitrogen atoms from position tB to position 111 is C2, and position t
From 12 to position 1lls, the distribution concentration of nitrogen atoms C(N
) is increased stepwise to C2, from position t13 to position 1T.
Up to this point, the distribution concentration C(N) of nitrogen atoms was reduced to 025.

In the example of FIG. 13, the distribution concentration C(N) of nitrogen atoms from position tB to position t14 is C76, and from position t14 to position 11. The distribution concentration of nitrogen atoms C(N) up to C,? and stepwise increase at position t8. The distribution concentration C(N) of nitrogen atoms in the empty position fttT is set to a concentration 02 lower than the initial concentration.
It is set at 8.

In the example shown in FIG. 14, the distribution concentration C(N) of nitrogen atoms from position tB to position t16 is C2°, and position t
From □ to position t, 7, the distribution concentration of nitrogen atoms C(N) is decreased to CSO, and from position 117 to position ii￥1□, the distribution concentration of nitrogen atoms C(N) is increased stepwise to Cl1l. , the distribution concentration C(N) of nitrogen atoms is reduced to Coo from position tea to position tB.

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

In the former case, the content of nitrogen atoms contained in the layer region (N) is relatively small in order to maintain high photosensitivity;
In the second case, it is desirable to increase the amount relatively to prevent charge injection from the free surface of the photoreceptive layer, and in the latter case, it is desirable to increase the amount relatively to ensure enhanced adhesion to the support.

In addition, in order to achieve all three simultaneously, it is necessary to distribute the concentration at a relatively high concentration on the support side, to distribute at a relatively low concentration at the center of the photoreceptive layer, and to distribute it at a relatively low concentration on the free surface side of the photoreceptor layer. In the surface layer region (N), a distribution state of nitrogen atoms may be formed in the layer region (N) such that the number of nitrogen atoms is increased.

In order to prevent charge injection from the free surface, a layer region (
It is desirable to form N).

In the present invention, the content of nitrogen atoms contained in the layer region (N) provided in the photoreceptive layer depends on the characteristics required for the layer region (N) itself, or when the layer region (N) is attached to the support. When provided in direct 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 (N), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region The nitrogen atom content is appropriately selected with consideration given to the following.

The magnetism of the nitrogen atoms contained in the layer region (N) can be adjusted as desired depending on the properties required of the photoconductive member to be formed, but it is preferably 0. 001-50 atomic%, more preferably 0.002-40 atomic%, optimally o, o
It is desirable that the content be oa to 30 atomic%.

In the present invention, even if the layer region (N) occupies the entire area of the photoreceptive layer or does not occupy the entire area of the photoreceptor layer, the layer thickness T of the photoreceptor layer is equal to the layer thickness To of the layer area (N). When the proportion of nitrogen atoms in the layer region (N) is sufficiently large, it is desirable that the upper limit of the content of nitrogen atoms contained in the layer region (N) is sufficiently smaller than the above value.

In the case of the present invention, when the ratio of the layer thickness To of the method M (N) to the layer thickness T of the photoreceptive layer is two-fifths or more, The upper limit of the amount of nitrogen atoms contained is preferably 30 atomic% or less, more preferably 2 atomic% or less, based on T (Si GcN).
0 atomic% or less, optimally 10 atomic%
The following is desirable.

In the present invention, the layer region (N) containing nitrogen atoms that enhances the photoreceptive layer contains nitrogen atoms at a relatively high concentration on the support side and near the free surface, as described above. In the former case, it is desirable to further improve the adhesion between the support and the photoreceptive layer and to improve the receptive potential. I can do it.

The localized region (B), explained using the symbols shown in FIGS. 11 to 14, is preferably provided within 5 μm from the interface position l&tB or the free surface tT.

In the present invention, the localized region (B) is located at the interface position t.
B or the entire layer area up to 5μ thick from the free surface IT (LT
), or as part of the layer region (L'r).

Whether the localized region is a part or all of the layer region (L〒) is determined as appropriate depending on the characteristics required of the light-receiving layer to be formed.

The localized region (B) has a distribution state of nitrogen atoms contained therein in the layer thickness direction, such that the maximum value Cmax of the distribution concentration C(N) of nitrogen atoms is preferably 500 atomic ppm.
It is desirable that the layer be formed in such a manner that the distribution of -El is more preferably 800 atomic ppm or more, most preferably 1000 atomic ppm or more.

That is, in the present invention, the layer region N containing nitrogen atoms has a layer thickness within 5 μm from the support side or free surface (
It is desirable to form the layer so that the maximum value Cmax of the distribution concentration exists in the layer region from 1B or t7 to 5μ.

In the present invention, specific examples of the halogen atoms contained in the photoreceptive layer as 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 conduction characteristics of the photoreceptor layer can be controlled as desired by containing a substance that controls the conduction characteristics in the photoreceptor layer.

Examples of such substances include so-called I9r impurities in the field of semiconductor materials, and in the present invention, a-8iGe (H,
On the other hand, n-type impurities that provide p-type conductivity and n-type impurities that provide n-type conductivity can be mentioned. Specifically, the n-type impurities include atoms belonging to Group M of the periodic table (Group 1 atoms), such as B (boron), Ae (aluminum), Ga (gallium), and In (indium).

Among them, B and Ga are particularly preferably used.

As n-type impurities, atoms belonging to Group V of the periodic table (Group V atoms), such as P (phosphorus), A8 (arsenic), sb
(antimony), Bi (bismuth), etc., especially,
P is preferably used.

It is As.

In the present invention, the content of the substance that controls conduction customization contained in the photoreceptive layer is determined based on the conductivity properties required of the photoreceptor layer or whether the photoreceptor layer directly meets the requirements of the conduction characteristics. It can be appropriately selected depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support provided.

In addition, when the substance controlling the conduction properties is incorporated into the photoreceptor layer and is locally incorporated in the desired layer region of the photoreceptor layer, it is particularly possible to When containing it in the body side end layer region, consider the characteristics of other layer regions provided in direct contact with this layer region and the relationship with the characteristics at the contact interface with the other layer region. The content of the substance controlling the conduction properties is selected accordingly.

In the present invention, the content of the substance that controls conduction properties contained in the photoreceptive layer is preferably 0.01 to
5 x 10' atomic ppm, more preferably 0.5-1 x 10' atomic ppm
, @suitably 1 to 5 X 103 atomic ppm
It is desirable that this is the case.

In the present invention, the content of the substance controlling conduction properties in the layer region containing the substance is preferably 30ato
mic ppm or more, more preferably 50 atomic
c ppm or more, optimally 100 atomic ppm
m or more, it is preferable that the substance is locally impregnated in a part of the light-receiving layer, particularly in the case where the light-receiving layer is 1 m or more.
It is preferable that the particles be unevenly distributed in the support side end layer region.

Among the above, by containing the substance controlling the conduction characteristics in the support-side end layer region tEl of the photoreceptive layer in a content equal to or higher than the above value, for example, the substance controlling the conduction characteristics can be In the case of n-type impurities, while the free surface of the photoreceptive layer is charged to ω polarity, injection of electrons from the support side into the photoreceptor layer can be effectively prevented.
In addition, when the substance to be contained is the n-type impurity described above, the free surface of the photoreceptive layer is charged to θ polarity, but the injection of holes from the support side into the photoreceptor layer is effectively suppressed. can be effectively prevented.

In this way, when the end layer region tEl contains a substance that controls the conduction characteristics of one polarity, the remaining non-region of the photoreceptive layer, that is, the end layer region + El except for the gold. The layer region (Zl 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 contained in the layer region 1!, l at the end f. It is also good to use a lid that is one step smaller than the amount of shavings that can be used.

In such a lifting platform, the content of the substance controlling the conduction characteristics contained in the n1JH old region tZl is determined according to the polarity and content of the substance contained in the end layer region fE). It is determined appropriately according to the above, but preferably 0.001 to 1000 atomic ppm
The optimum content is preferably 0.1 to 200 atomic ppm.

In the present invention, the end layer region (LL) and the layer region tZl
When containing a substance that controls the same type of conductivity,
Preferably, the number of Miyaarui in the layer region tZl is 3.
It is desirable to set it to 0 atOnlie ppm or less. In addition to the above-mentioned case, in the present invention, there is a layer region containing a substance that controls conductivity with one polarity in the photoreceptive layer, and a layer region that controls conductivity with the other polarity. A so-called depletion layer can also be provided in the contact region by directly contacting the layer region containing the substance.

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. Thus, a depletion layer can be provided.

In the present invention, the photoreceptive layer composed of a-8iGe (H, be done. For example, in order to form a photoreceptive layer composed of a-8iGe (H, The raw material gas for Ge supply that can supply (Ge) and the raw material gas for introducing hydrogen atoms (H) as needed/and the raw material gas for introducing hydrogen atoms (X) are kept under reduced pressure inside. a-8iGe (H
, X) may be formed. Further, in order to contain germanium atoms in a non-uniform distribution state, a layer consisting of a-8iGe (H,X) may be formed while controlling the distribution concentration of germanium atoms according to a desired rate of change curve. In addition, when forming by sputtering method, for example, a target made of St, or a target made of St in an atmosphere of an inert gas such as Ar or He, or a mixed gas based on these gases, or a combination of the target and Ge. Using two targets composed of Si and Ge, or using a mixed target of Si and Ge, as necessary,
A raw material gas for supplying Ge diluted with a diluent gas such as Ar is introduced into a deposition chamber for sputtering, and a gas for introducing hydrogen atoms (H) and/or hydrogen atoms (X) is introduced as necessary. , by creating a plasma atmosphere of the desired gas. In order to make the distribution of germanium atoms 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 vapor deposition board 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.

A substance that can be used as a raw material gas for supplying St used in the present invention is SiH4,5itHs.

Silicon hydride (silanes) in a gaseous state or that can be gasified, such as Si, Hs + Si + Hto, can be effectively used, and in particular, ease of handling during layer creation work,
S I H4eSi2Hs in terms of St supply efficiency etc.
are listed as preferred.

GeH is a material that can be used as a material gas for supplying Ge.
4, G6JI6, Ge, H,, Ge4H1os Ge
5Hu, Gem HI3, Ge7H1a, Ge6H+a
Germanium hydride in a gaseous state or which can be gasified, such as Ge4H1o, is mentioned as one that can be effectively used.
In particular, %GeH45ced (6, Ge5H@) is preferred in terms of ease of handling during layer formation work, good Ge supply efficiency, and the like.

Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into

Further, 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 mentioned as effective in the present invention.0 Suitable in the present invention Specifically, halogen compounds that can be used include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, ClF5 C1F, BrF5,
Interhalogen compounds such as BrF5, IF3, IF7, ICZ s I Br, etc. can be added.

Silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms.

Specifically, for example, SiF, 5i2Fa s 5iCt
Preferred examples include silicon halides such as a s SiBr4.

When a photoconductive member, which is characteristic of the present invention, is formed by a glow release 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. Even without using silicon oxide gas, a-8iGe containing rogen atoms can be deposited on a desired support.
It is possible to form a photoreceptive layer consisting of.

When manufacturing a light-receiving layer containing halogen atoms according to the glow release method, basically, for example, silicon halide is used as a raw material gas for supplying St, germanium hydride is used as a raw material gas for supplying Ge, and Ar%H2 , He, etc., at a predetermined mixing ratio and gas flow rate, are introduced into the deposition chamber where the photoreceptive layer is formed, and a glow discharge is generated 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 halogen atoms into the layer formed by either the sputtering method or the ion blating method,
What is necessary is to introduce a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms into the deposition chamber to form a plasma atmosphere of the gas.

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

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but hydrogen halides such as HFs HC'5HBr1HI, etc. 5iHtFt, 5iHtI*, SiH, C1
2, Si ICZ8, SiH, Br2.5iHBr1
halogen-substituted silicon hydrides such as, and Ga HFs s
Ge Hz F2, GeHaF, GeHCl5s
GeH,Cz, ,GeH5C1%GeHBr,,G
eH2Br2, GeHs13r 1GeHI5, Ge
Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides such as H212 and GeHsr, GcF, GeC1a, GeBr4% GeI
4% GeFt % GeCtt, GeBr2, Ge
Germanium halides such as L, and other gaseous or gasifiable substances may also be mentioned as effective starting materials for forming the photoreceptive layer.

Among these substances, rogenides (containing hydrogen atoms) are
When forming the photoreceptive layer, hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer at the same time as halogen atoms are introduced into the layer. Ru.

In order to structurally introduce hydrogen atoms into the photoreceptive layer, in addition to the above, L, S i H4, S 12 H6, Si,
H,, S 54 Ho or other silicon hydride with germanium or a germanium compound for supplying Ge, or
GeH<s Ge! Ha, Ge, l-18, Ge, H
,,,Ge,H,,,Ge6 H,4,GGtH+e,
Ge6H, B, Geg H2o and other germanium hydride and silicon or silicon compound for supplying Si;
This can also be done by coexisting in the deposition chamber and causing discharge.

In a preferred example of the present invention, the amount of hydrogen atoms ttnO, the amount of halogen atom heads, or the sum of the amounts of hydrogen atoms and halogen atoms (H
+X) is preferably 0, 01 to 40 atomic
%, preferably 0.05-30 atomic%
Optimally, 3 is preferably 0.1 to 25 atomic %.

In order to control the amount of hydrogen atoms (11) and/or halogen atoms (2) contained in the light-receiving layer, for example, the temperature of the support may be varied/and the amount of hydrogen atoms (11) or (3) may be controlled. In the present invention, in order to provide the layer region N containing nitrogen atoms in the photoreceptive layer, the amount of the starting material introduced into the deposition apparatus system, the discharge force, etc. In this case, the starting material for introducing nitrogen atoms may be used together with the above-mentioned starting material for forming the photoreceptive layer, and the amount thereof may be controlled and contained in the layer to be formed.

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

For example, a raw material gas whose constituent atoms are silicon atoms (St), a raw material gas whose constituent atoms are nitrogen atoms (H), and a raw material gas whose constituent atoms are hydrogen atoms (0 or 2), and hydrogen atoms (2) as necessary. or use a raw material gas whose constituent atoms are silicon atoms (St) and raw material gases whose constituent atoms are nitrogen atoms (he) and hydrogen atoms σl. Alternatively, a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing three constituent atoms: silicon atoms (St), nitrogen atoms N, and hydrogen atoms (0) may be mixed at a desired mixing ratio. It can be used in combination with.

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

Nitrogen atoms (he) used in forming the layer region (he)
Starting materials that can be effectively used as raw material gases for introduction include nitrogen (N2), ammonia (NT(
), hydrazine (H7NNH7).

Hydrogen azide (HN, ), ammonium azide (NH,N
, ), etc., and nitrogen compounds such as nitrides and azides. In addition to this, halogenated nitrogen compounds such as nitrogen trifluoride (FAN) and nitrogen tetrafluoride (F4Nt) can be mentioned, since in addition to introducing nitrogen atoms (■), halogen atoms (■) can also be introduced. I can do it.

In the present invention, in order to enhance the effect obtained by nitrogen atoms in the layer region, oxygen atoms can be further contained in addition to nitrogen atoms. The raw material gas for introducing oxygen atoms into the layer region is as follows:
For example, oxygen (0,>, oxy7(03)l-nitrogen oxide (
NO), nitrogen dioxide (Nov), -nitrogen dioxide (N
20), nitrogen sesquioxide (NtOs), trinitrogen tetraoxide (Nt04), nitrogen sesquioxide (NyOs), nitrogen trioxide (No, ), silicon atom (Si), oxygen atom (0), and hydrogen atom■ For example, lower siloxanes such as disiloxane (T(,5iO8iHs) + trisiloxane (Hs SiO8t Hz O8+ ) I3) having these as constituent atoms can be mentioned.

To form layer region (1) by sputtering method, a single crystal or polycrystalline Si wafer or Si sN wafer is used for forming the photoreceptive layer.
Sputtering may be performed using a wafer containing a mixture of N4 as a target in various gas atmospheres.

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

Alternatively, by using Si and SiS N4 as separate targets, or by using a single target containing a mixture of Si, Si, and N4, it is possible to perform sputtering in a dilution gas atmosphere as a sputtering gas. or at least 0 hydrogen atoms
This is accomplished by sputtering in a gas atmosphere containing straddle/and halogen atoms (3) as constituent atoms.

As the raw material gas for introducing oxygen atoms, the raw material gas for introducing nitrogen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, when a layer region (N) containing nitrogen atoms is provided when forming a photoreceptive layer, the distribution concentration of nitrogen atoms contained in the layer region (N) is set to 0 (N). By changing stepwise in the layer thickness direction, the desired distribution state (de
To form a layer region (N) with a distribution density 0 (N
) is introduced into the deposition chamber while the gas flow rate of the starting material for introduction of nitrogen atoms is suitably changed according to a desired rate of change curve.

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 forming the layer region (N) by a sputtering method, the distribution concentration 0 (N) of nitrogen atoms in the layer thickness direction is changed stepwise in the layer thickness direction to obtain a desired distribution state (N) of nitrogen atoms in the layer thickness direction. In order to form a depth profile ), first, as in the case of the glow discharge method, a starting material 'K for introducing nitrogen atoms is used in a gaseous state, and when the gas is introduced into the deposition chamber, This is accomplished by appropriately changing the gas flow rate as desired.

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

In the photoreceptive layer, there is a substance that controls the conductivity, such as No.
To structurally introduce group atoms or group V atoms, during layer formation, a starting material for introducing group (I) atoms or a starting material for introducing group V atoms is introduced in a gaseous state into a deposition chamber. It may be introduced together with other starting materials for forming the photoreceptive layer.

As a starting material for the introduction of such group (III) atoms, it is desirable to use a material that is gaseous under normal pressure or at least easily gasified under the layer forming process. . Specifically, starting materials for introducing Group 10 atoms include B2H,, B, )I,
. , B, 11. , I3. [(,,,I(61-1,
. .

B, 14. , , B, I-J, , etc., Bli'', , , 80g3.
, Ga(37t3, Ga((3H,)s, 1
nO1s, Tl07I, and Temple can also be mentioned.

In the present invention, starting materials for introducing Group V atoms that are effectively used include PH,
, P, H, etc., I) i-I, T, PI
', .

PF, , P(Jl, , PC&, PBr, ,
Examples include halogen ratios such as PBr, PI3, etc. In addition, A, 5l13. AsF, .

As07! s, AsBr3, Asl', , S
bH,, SbF, , SbF, , 5bOAs.

5bOj! s, B+l-1s, Brols,
B+Brs and the like can also be mentioned as effective starting materials for introducing group V 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 30λ or more, and more preferably 40A.
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 10 μm or less, more preferably 10 μm or less. is desirably 8μ or less, preferably 5μ or less.

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

A6, Or, Mn, An, Nb, Ta,
Examples include metals such as V, Ti, Pt, and Pb, and alloys thereof.

Polyester is used as an electrically insulating support.

Polyethylene, polycarbonate, cellulose.

Acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are commonly used. 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 glass, s N (Gr+k
l, Or, Mo, Au, Ir, Nh, Ta
, V, Tj, Pt, Pd.

In203 + SnO, + ITO (IntOs +
Conductivity 1 is imparted by providing a thin film made of Ni0r, AI, Ag, P, etc., or if it is a synthetic resin film such as polyester film.
d, Zn, Ni, Au.

Or, Mo, Ir, Nb, Ta, V, Ti
, thin films of metals such as Pi are deposited by vacuum evaporation, electron beam evaporation,
Conductivity is imparted to the surface by sputtering or the like, or by laminating the surface with the metal. The shape of the support may be any shape, such as a cylinder, a belt, or a one-plate shape, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If used as a member for continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is appropriately determined so as to form the desired oil-immersed photoconductive member, but if the photoconductive member requires courage, the thickness of the support may be sufficient. It is made as thin as possible within the range that can be achieved. In such cases, the thickness is preferably 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc.

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

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 photovoltaic member of the present invention. For example, 1102 and 1106 are 5il14 gases diluted with lle (purity 99. 999%.

Hereinafter, it will be abbreviated as 5i114/He. ) cylinder, 1103 is H
Ge) 14 gas (pure +199.999%
, hereinafter abbreviated as Ge1-44/1]e. ) cylinder, 110
4 is S i F gas diluted with He (purity 99.9
99r (hereinafter abbreviated as 5ili'', /Ile) cylinder, 1105 is an NH gas (purity 99.999%) cylinder, and 1106 is an H2 gas (purity 99.999X) cylinder.

In order to flow these gases into the reaction chamber 1101, valves 1122 to 1126 of gas cylinders 1102 to 106 are used.
Check that the leak valve 1135 is closed 1
~, also, inflow pulps 1112 to 1116, outflow pulp 1
117-112], auxiliary pulp I 132° 1133 are open, first open the main valve 11.
34 is opened to exhaust the inside of the reaction chamber 11-01 and each gas pipe. Next, the reading of the vacuum gauge 1136 is about 5 X H)
When it becomes torr, auxiliary pulp 1132, 1133
, close the outflow pulps 1117-1121.

Next, to give an example of a platform for forming a light receiving area on the cylindrical base 1137, 5i from the gas cylinder 1102 is used.
ll, /He gas, GeH4/ from gas cylinder 1103
I le gas, NH gas from gas cylinder 1105, open pulp 1122.1123.1124 and check the pressure of outlet pressure gauge 1127.1128.1129 to IKti/ca
Adjust to 1~, inflow pulp 1112.1113.1114
Gradually increase l3i1, mass flow controller 1107
．． 1108 and 1109 respectively. Is it tied up? + output valves 1117, 1118.1119. Auxiliary valve l] 32'i gradually opens to supply each gas to the reaction chamber 11.
01. At this time, adjust the outflow pulps 1117, 1118, and 1119 so that the ratio of S i H, / He gas bV, IXi to ( ) eH, / l 4e gas flow rate and N113 gas flow h1 becomes the desired value. ~, Father, adjust the opening of the main valve 1134 by checking the reading of the pressure gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value.

After confirming that the temperature of the substrate l]37(m degree) is set in the range of 50 to 400°C by the heating heater 1138, the power supply 1140 is set to the desired power and the temperature is set in the reaction chamber 1101. It is contained in a layer formed by generating a glow discharge and at the same time appropriately changing the opening of the valve 1118 by adjusting the flow rate of NH and gas manually or by using an external drive motor or the like according to a pre-designed rate of change curve. control the distribution concentration of nitrogen atoms.

Father, 1-During formation, in order to ensure uniform layer formation, the base body 137 is rotated at a constant speed by a motor 1139, which is heavy.

Examples will be described below.

Example 1 As shown in FIG.
Electrophotographic imaging members and samples 1 to 1 (sample 46111 to f/113-4) were prepared on substrate A according to the conditions shown in Table 1 (Table 2).

The content distribution concentration of germanium atoms in each sample is the first
6, and the distribution concentration d of nitrogen atoms is shown in FIG. 17.

Each sample obtained in this way was placed in a charging exposure experimental device α
■5. Perform corona charging for 0.3 (8) with OKV,
A light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light intensity of 21 ux-(8) was irradiated through a transmission type test chart.

A good toner image was obtained on the surface of the imaging member by immediately cascading a θ-chargeable developer (including toner and carrier) over the surface of the imaging member. Toner image on image forming member-F ■5. The corona charging of OKV transfers onto the transfer paper, and even if the sample contains Ir≧, it has excellent resolution and clear gradation with good gradation reproducibility.
A tf+i image was obtained.

''2, the same toner image was obtained except that an 81 Q nm (Q GaA, S-based semiconductor laser (LOMW)) was used instead of the tungsten lamp as the light source, and an electrostatic single image was formed. When the image quality of the toner transfer image was evaluated using 9 samples for each sample under the forming conditions, it was found that all samples had excellent M power and a clear, high-quality image with good gradation reproducibility.

Example 2 Samples (Samples-1621-1 to 23-4) as electrophotographic forming members were prepared on a cylindrical At substrate under the conditions shown in Table 3 using the manufacturing apparatus shown in FIG. 15. (Table 4).

The distribution concentration of germanium atoms in each sample is the first
The distribution concentration of vehicle heavy atoms is shown in FIG. 6, and in FIG. 17.

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. In addition, each sample was heated at 38°C and 80% l.
-4l-1 was tested for repeated use 200,000 times, and no deterioration in image quality was observed in any of the samples.

5(3) Common layer forming conditions in the examples of the present invention shown in Table 2 and Table 4 are shown below.

Substrate temperature: germanium atom (()e) containing layer...
...About 200℃ discharge frequency: 13.56Mf4z 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 member of the present invention, and FIGS.
11 to 14 are explanatory diagrams for explaining the distribution state of nitrogen atoms in the photoreceptive layer, and FIG. 15 is an explanatory diagram for explaining the distribution state of nitrogen atoms in the photoreceptive layer, respectively. FIG. 16 is a schematic explanatory diagram of the device used in the invention. FIG. 17 is a distribution diagram showing the distribution of each atom in the embodiments of the present invention. lOO...Photoconductive member 101...Support 102.
・Photoreception! -1! -Riii...di4 C --m-→-C -1--→-C □C

Claims (8)

[Claims] (1) It has a support for a photoconductive member and a photoreceptive layer that exhibits photoconductivity and is made of an amorphous material containing silicon atoms and germanium atoms, and the photoreceptor layer contains nitrogen atoms. contain, and the distribution concentration in the layer thickness direction is c
(i). C(3), C(2) first layer region (1), third layer region
A photoconductive member characterized by having a layer region (3) of C(3) and a second layer region (2) in this order from the support side (However, C(3)
)> C(2), C(1), and C(1),
At least one of C(2) is not O, or C(1). C(2) are not equal). (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 halogen atoms. (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 governing conductivity is an atom belonging to Group 1 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.