JPS60140249A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member superior in photosensitivity, etc., by forming a layer composed of a layer region made of amorphous Ge and a photoconductive layer region made of amorphous Si, and contg. N in a nonuniform concn. distribution in the layer thickness direction, and an amorphous layer made of Si and O in succession on a substrate. CONSTITUTION:The objective photoconductive member 100 is obtained by successively forming on a substrate 101 the first layer 102 composed of an amorphous layer region 105 made of Ge and a photoconductive layer region 106 made of amorphous Si, and the second amorphous layer 103 made of Si and O. The first layer 102 contains N in a concn. distribution in the layer thickness direction having concn. C1 in the first region C3 in the third region, and C2 in the second region formed in this order from the side of the substrate 101, and C3> C2, C1, and one of C1 and C2 is not 0 or C1 is not equal to C2.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a method that is sensitive to electromagnetic waves such as light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.). It relates to a certain photoconductive member.

[Prior Art] As a photoconductive material for 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 recommended to use photoconductive materials that have high sensitivity and a high signal-to-noise ratio [photocurrent (Ip)].
/dark current (Id)), have absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, have fast photoresponsiveness, have a desired dark resistance value, and be harmless to the human body during use. Furthermore, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point.

Based on this point, amorphous silicon (denoted as 1; l&a-9i) is a photoconductive member that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion/reading device is described in DE 2933411.

A photoconductive member having a conventional photoconductive layer composed of a-Sf has a high dark resistance value and a high light sensitivity.

Electrical, optical, and photoconductive properties such as photoresponsiveness.

The reality is that there are points that can be further improved in terms of use environment characteristics such as temperature resistance and stability over time, and it is necessary to improve overall 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 due to repeated use may accumulate, resulting in so-called ghost development, which causes afterimages, or when used repeatedly at high speeds, responsiveness gradually decreases. There were many cases where spots appeared.

Furthermore, a-St 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 a commonly used halogen lamp or fluorescent lamp is used as a light source, there remains room for improvement in that the light on the longer 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-St material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, However, problems may arise in the electrical or photoconductive properties of the formed layer.

That is, 1. For example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer may not be sufficient, or the injection of charge from the support side may not be sufficiently prevented in dark areas. There are many cases.

Furthermore, if the layer thickness exceeds 10 or more layers, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes after it is left in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs particularly when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that need to be solved in terms of stability over time.

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.

[Objective] The present invention has been made in view of the above points, and includes: a, -3i
As a result of comprehensive research and consideration from the viewpoint of applicability and applicability as photoconductive members used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms and germanium an amorphous material containing at least either a hydrogen atom or a halogen atom, so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to as a generic term for these] As a notation r a-
5iGe (H, Conductive materials not only exhibit outstanding practical properties, but also
Compared to conventional photoconductive materials, it is superior in all respects, especially as a photoconductive material for electrophotography, and has excellent absorption spectrum characteristics on the long wavelength side. The present invention is based on this finding.

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 have high photosensitivity in the entire visible light range;
In particular, it is an object of the present invention to provide a photoconductive member that is excellent in matching with a semiconductor laser and has a fast optical response.

Still another object of the present invention is to provide excellent adhesion between a layer provided on a support and a support, and between each laminated layer, and to provide a dense and stable structural arrangement. It is an object of the present invention to provide a high-quality photoconductive member.

Still another object of the present invention is to provide a charge control system for electrostatic image formation to the extent that ordinary electrophotography can be applied very effectively when applied as an image 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 have high density, clear halftones, and high resolution.

It is an object of the present invention to provide a photoconductive member for electrophotography which allows high quality images to be easily obtained.

Still 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 a support.

[Structure of the Invention] The photoconductive member of the present invention is composed of a support for the photoconductive member and an amorphous material containing germanium atoms, and a first layer region (G) provided on the support. and the first layer region (
G) a photoconductive second layer region (S) provided thereon;
and a second layer provided on the second layer and made of an amorphous material containing silicon atoms and oxygen atoms; The layer includes a first region (1) and a third region that contain nitrogen atoms and have nitrogen atom distribution concentrations of C(1), C(3), and C(2) in the layer thickness direction, respectively. (3), second area (2
) in this order from the support side.

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 the photoconductive member of the present invention is applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical properties are stable, and it has high sensitivity and high sensitivity. It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

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

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.

[Example] Hereinafter, the photoconductive member of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a schematic configuration diagram for explaining the layer configuration of a photoconductive member according to a first embodiment of the present invention.

The photoconductive member 100 shown in FIG. and a second layer (II) 103 provided thereon. First layer (I
) 102 and the second layer (II) 103 constitute a light-receiving layer 104.

The first layer (I) 102 is an amorphous material (hereinafter referred to as ra-Ge) containing germanium atoms and, if necessary, at least one of silicon atoms, hydrogen atoms, and halogen atoms.
(Si, H, (hereinafter ra-Si (H,
) J), and is provided on the first layer region (G) 105 and exhibits photoconductivity (S) 10
6.

The germanium atoms are distributed evenly and uniformly in the first layer region (G) 105.
It may be contained in the layer, or it may be contained evenly in the layer thickness direction, but the distribution concentration may be non-uniform.

In each case, in the first layer region (G) 105, with respect to the in-plane direction parallel to the surface of the support,
It is necessary for germanium atoms to be contained evenly and uniformly in order to make the properties uniform in the in-plane direction.

In particular, it is contained evenly in the layer thickness direction of the first layer (I) 102, and on the side opposite to the side where the support 101 is provided (the free surface 107 of the photoreceptive layer 104). side)
The support 101 side (the photoreceptive layer and the support 1
The germanium atoms are contained in the first layer region (G) 105 so that they are distributed more toward the interface side with the first layer region (G) 105 or vice versa.

In the photoconductive member of the present invention, as described above, the distribution state of germanium atoms contained in the first layer region (G) 105 is as described above in the layer thickness direction, and the distribution state of the germanium atoms is as described above. In the in-plane direction parallel to the surface of 101, it is desirable to have a uniform distribution state.

In the present invention, germanium atoms are not contained in the second layer region (S) 106 provided on the first layer region (G) 105, and the first layer region (G) 105 does not contain germanium atoms. By forming the layer (I) 102, a photoconductive member is obtained that has excellent photosensitivity to light in the entire range of wavelengths from relatively short and long wavelengths to relatively long wavelengths, including the visible tapered range. be able to.

Further, in one of the preferred embodiments, the distribution state of germanium atoms in the first layer region (G) 105 is such that germanium atoms are continuously and evenly distributed throughout the entire layer region, and germanium atoms are evenly distributed throughout the layer region. Since the distribution concentration C of atoms in the layer thickness direction decreases from the support 101 side toward the second layer region (S) 106, the first layer region (G) 1
05 and the second layer region (S) 106, and by extremely increasing the distribution concentration C of germanium atoms at the side edge of the support 101 as described later, When a semiconductor laser or the like is used, the light on the long wavelength side that is almost completely absorbed by the second layer region (S) 106 is substantially completely absorbed in the first layer region (G) 105. can be absorbed,
Interference due to reflection from the surface of the support 101 can be prevented.

2 to 10 show typical examples in which the distribution state of germanium atoms contained in the first layer region (G, ) 105 in the layer thickness direction is non-uniform.

In FIGS. 2 to 1O, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer region (G) 105 exhibiting photoconductivity, and t represents the support 101. t□ indicates the position of the surface of the first layer region (G) 105 on the side opposite to the support side. That is, in the first layer region (G) 105 containing germanium atoms, layers are formed from the t side to the tT side.

FIG. 2 shows the first typical plastic state in which the distribution of germanium atoms contained in the first layer region (G) 105 in the layer thickness direction is #11.

In the example shown in FIG. 2, from the interface position t, where the surface where the first layer region (G) 105 containing germanium atoms is formed and the surface of the support 101 are in contact, to the position t, The distribution concentration C of germanium atoms is contained in the first layer (I) while taking a constant value of 01, and the distribution concentration gradually and continuously decreases from C2 from the position t1 to the interface position t1. has been done. At the interface position tT, the distribution concentration C of germanium atoms is C1.

In the example shown in FIG. 3, the first layer region (G) 1
The distribution concentration C of germanium atoms contained in 05 gradually and continuously decreases from the concentration C4 from the position 1B to the position tT, forming a distribution state in which the concentration C5 is reached at the position 0.

In the case of FIG. 4, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 is constant at a concentration C4 from position t8 to position t2, and from position t2 to position t
□ is gradually and continuously decreased until position t7
In this case, the distribution concentration C is substantially zero (substantially zero here means that it is less than the detection limit amount).

In the case of FIG. 5, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 is continuously and gradually decreased from the concentration C1 from the position t8 to the position ta. It is substantially zero at tT.

In the example shown in FIG. 6, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in the position t
, and the position t1, the concentration Cte is a constant value,
At the position tT, the concentration C10 is 0. Between the 0 position upper 3 and the position tT, the distribution concentration C is reduced from the position t3 to the position tT.

In the example shown in FIG. 7, the first layer region (G) 1
The distribution concentration C of germanium atoms contained in 05 takes a constant value of concentration C11 from position t to position t, and decreases linearly from concentration CI2 to concentration CI3 from position t to position tT. It is said that

In the example shown in FIG. 8, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in is at the position t,
From there, up to position 1T, the concentration decreases linearly from CI4 to substantially zero.

In the diagram f39, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 is linearly decreased from the concentration C1° to the concentration C16 from the position t to the position t9, Position t! .

An example is shown in which the concentration CI4 is kept at a constant value between and the position E0.

In the example shown in FIG. 10, the first layer region (G)
The distribution concentration C of germanium atoms contained in 105 is a concentration C1° at position t, and this concentration C,7J: at the beginning, it decreases slowly until it reaches position t.
Near position 6, the concentration CI? decreases rapidly and at position t6, the concentration CI? “It will be done.

Between position t and position t7, the concentration decreases rapidly at first, and then decreases slowly and gradually to reach the concentration CI at position t7, and between position t7 and position pass, it decreases extremely slowly. The concentration is gradually decreased to reach "so" at position t. Between position t and position 0, the concentration is decreased from C20 to substantially zero according to a curve shaped as shown in the figure. ing.

As described above, from FIGS. 2 to 10, the first layer region (G)
As described in some of the typical examples of the distribution state of the germanium atoms contained in the support 105 in the layer thickness direction, in the present invention, the support 101 has a portion with a high distribution concentration C of germanium atoms. , it is preferable that the first layer region (G) 105 is provided with a distribution state of germanium atoms having a portion where the distribution concentration C is considerably lower on the interface tT side than on the support 101 side. Example 1
It is mentioned as one of the

The first layer region (G
) 105 is preferably a localized region (A
) is desirable.

For example, if the localized region (A) is explained using the symbols shown in FIGS. 2 to 1O, it is preferable that the localized region (A) be provided within 5 l in the layer thickness direction from the interface position t8.

The localized region (A) may be the entire layer region (LT) from the interface position t to a thickness of 5 IL, or may be a part of the layer region (LT).

Whether the localized region (A) should be part or all of the layer region (LT) is determined as appropriate depending on the characteristics required of the first layer region (G) 105 to be formed.

In the localized region (A), the distribution state of the germanium atoms contained therein in the layer thickness direction is such that the maximum value Cmax of the distribution concentration of germanium atoms is the sum of the distribution concentration of germanium atoms and silicon atoms.
Preferably 1000 atomic ppm or more, more preferably 50
It is desirable that the layer be formed in such a manner that a distribution state of 00 atomic ppm or more, optimally 1X10 atomic ppm or more, can be obtained.

That is, in the present invention, the first layer region (G) 105 containing germanium atoms is distributed within 5 JL in layer thickness from the support 101 side (layer region from 1.3 to 5 #L thick). It is preferable that it is formed so that a maximum concentration value Cwax exists.

In the present invention, the content of germanium atoms contained in the first layer region (G) 105 is appropriately determined as desired so as to effectively achieve the object of the present invention. Preferably 1 to 10
X I Os atomic ppm more preferably 100 to 9.
5X10' atomic ppm, optimally 500-8X10
Preferably, it is expressed in atomic ppm.

The distribution state of germanium atoms in the first layer region (G) 105 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 small when exposed to light from the support 101 side. If a decreasing change is given toward the free surface 107 side of the receptor layer 104 or vice versa, the rate of change curve of the distribution concentration C can be arbitrarily designed as desired. Accordingly, the first layer region (G) 105 having the required characteristics can be realized as desired.

For example, the distribution concentration C of germanium atoms in the first layer region (G) 105 is sufficiently increased on the support 101 side, and as low as possible on the free surface 107 side of the photoreceptive layer 104. By giving a change in the distribution concentration C to the distribution concentration curve of germanium atoms, high photosensitivity can be achieved for light of all wavelengths from relatively short wavelengths to relatively short wavelengths, including the visible light region. In addition to being able to achieve
It is possible to effectively prevent interference with coherent light such as laser light.

In the present invention, the layer thickness of the first layer region (G) 105 and the second layer region (G) 105 are
The layer thickness of the layer region (S) 106 is one of the important factors for effectively achieving the object of the present invention. , due care must be taken in designing the photoconductive member.

In the present invention, the layer thickness TE of the first layer region (G) 105
+ is preferably 30A to SO=, more preferably 40
It is desirable that the number of people is 40 people, and optimally 50 people to 30 people.

Further, the layer thickness T of the $2 layer region (S) 106 is preferably 0.5 to 90 p, more preferably 1 to 80 JL, and most preferably 2 to 50 JL.

The layer thickness of the first layer region (G) 105 and the second layer region (S
) 106, the sum of the layer thicknesses T (TB + T) of the photoconductive member is determined based on the organic relationship between the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. It is appropriately determined according to the requirements during layer laying.

In the photoconductive member of the present invention, the above (T, n+T)
The numerical range of is preferably 1 to 100 g, more preferably 1 to 80 g, most preferably 2 to 50 p.

In a more preferred embodiment of the present invention, the above layer thickness T
, i+, and layer thickness T, it is desirable that appropriate numerical values be selected for each, preferably so as to satisfy the relationship TB/T≦1.

In selecting the numerical values of layer thickness Tn and layer thickness T in the above case, more preferably the relationship TB/T≦0.9, optimally T n /T≦0.8 is satisfied. It is desirable that the values of layer thickness TB and layer thickness T be determined in the same manner.

In the present invention, when the content of germanium atoms contained in the first layer region (G) 105 is 1X10 atoms ppm or more, the layer thickness TB of the first layer region (G) 105 is It is desirable to make it fairly thin, preferably 3011
．． The amount is more preferably 25 g or less, most preferably 20 liters or less.

In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the first layer (1) 102, In the first layer (I) 102, a layer region (N) containing nitrogen atoms is provided.

As shown in FIG. 11, the first layer (I) 102 includes a first region (1) 108 in which the distribution concentration C(N) of nitrogen atoms in the layer thickness direction has a value of C(1), A second region (2) 109. having a value of C(2). and a third region (3) 110 having a value of C(3).

In the present invention, the above-mentioned 1. Second. Each of the third regions does not necessarily need to contain nitrogen atoms in any of these three 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 0 or the distribution concentration C(1) ,
C(2) must not be equal.

When either the distribution concentration c (B or C(2) is 0, the first layer (I) 102 is a region that does not contain nitrogen atoms, and is either the first region (1) 108 or It has a second region (2) 109 and a third 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 107 into the first layer (I) 102, the first region (1)
108 in the first layer (
I) It is necessary to design the support 102, and conversely, the support 10
If the purpose is to prevent charge injection from the first side into the photoreceptive layer 104 and to improve the adhesion between the support 101 and the photoreceptive layer 104, the second region (2) 109 should contain nitrogen atoms. It is necessary to design the first layer (I) 102 as a region where no oxidation occurs. In the present invention, among the three, the maximum distribution concentration C
In order to improve the dark resistance of the first (1) 102 while maintaining good photosensitivity characteristics, the third region (3) lto having the distribution concentration C(3) It is desirable to set the value to a relatively low value and to set the layer thickness to a sufficient thickness within the necessary range.

Furthermore, if the third region (3) 110 is expected to have a charge injection prevention effect by setting the value of the distribution concentration C(3) to a relatively high value, the layer of the third region (3) 110 The thickness of the second layer (II) 103 should be as thin as possible within a range where a sufficient effect of blocking charge injection can be obtained.
It is desirable to provide the third region (3) 110 at a position as close as possible to the free surface 107 side or the support body 101 side.

In this case, the third region (3) ltO is the support 1
If it is installed closer to the 01 side,
The region (1) 108 is made sufficiently thin within a necessary range, and is provided mainly to improve the adhesion between the support 101 and the light-receiving layer 104.

When the third region j * (3) llo is provided closer to the free surface 107 side, the second region (2) 10
9 is provided mainly for the purpose of preventing the third region (3) 110 from being exposed to a humid atmosphere.

In the present invention, the first region (1) and the second region (2
) is determined as desired in relation to the uniform distribution concentrations C(1) and C(2), but is preferably 0.003 to 100IL, more preferably 0.004IL.
~80IL, optimally 0.005~50IL.

Further, the layer thickness of the third region (3) 110 is the distribution concentration C(3
), but preferably 0.
003 to 80 wells, more preferably 0.004 to 50 wells,
The optimum range is 0.005 to 40 liters.

When the third region (3) 110 mainly functions as a charge injection blocking layer, it is provided close to the support 101 side or the free surface 107 side of the first layer (I) 102, and The layer thickness is preferably 30μ or less, more preferably 2
It is desirable to set it to 0IL or less, optimally 1OIL or less.

At this time, the layer thickness of the first region (1) 108 on the side of the support 101 where the third region (3) 110 is provided or the second region (2) 109 on the free surface 107 is ,
It is determined as appropriate depending on the value of the distribution concentration C(3) of nitrogen atoms contained in the third region (3) 110 and the point of productive efficiency, but it is preferably 5μ or less, more preferably 3μ.
Hereinafter, it is optimally desirable to set it to tp or less.

In the present invention, the maximum value of the distribution concentration C(3) of nitrogen atoms is preferably 67JN for the sum of silicon atoms, germanium atoms, and nitrogen atoms (hereinafter referred to as "T(SiGeN)J"). 5o atom%, more preferably 5o atom%
, the optimum value is preferably 40 atomic %.

Moreover, the minimum value of the distribution concentration C(3) is T(SiGeN)
It is preferable that 1O atoms ppm, more preferably 15 atoms ppm, and most preferably 20 atoms ppm. When the distribution concentrations C(1) and C(2) are not O, the minimum value is preferably 1 atom ppm, more preferably 3 atoms ppm, optimally 5 atoms ppm, for T(SiGeN). It is desirable to set it as ppm.

In the present invention, the distribution state of nitrogen atoms is determined in the first layer (I
) 102 as a whole is non-uniform in the layer thickness direction as described above; In each of the second and third regions, the thickness is uniform in the layer thickness direction.

12 to 15 show typical examples of the distribution of nitrogen atoms in the entire first layer (I) 102. FIG.

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

In the example shown in FIG. 12, the distribution concentration C(N
) from position tB to position t is C2, and position t9
to position tII is 5□, and from position tII to position t
C21 is used up to T.

In the example shown in FIG. 13, the distribution concentration C(N
) is a demon from position tB to position t12, and position t12
The force increases stepwise to C2 from position t13 to position t13, and decreases to C force from position t18 to position t.

In the example of the fJ14 diagram, the distribution concentration C(N) of nitrogen atoms is set to - from position tB to position t1+* and increases stepwise as % from position t to position tIf. Is the concentration 02 lower than the initial concentration? It's happening.

In the example shown in FIG. 15, the distribution concentration C(N
) from position 1B to position t1. Until 9. position t16
From position t17 to position t17, it decreases to C7°, and from position t17 to position t18, it increases stepwise to 91°, and from position t1
．． The distance from position t to position t is decreased in 9 meters.

In the present invention, the nitrogen atom-containing layer region (N) provided in the first layer (I) 102 (the first layer region (N) described above) is provided in the first layer (I) 102.
Second. (composed of at least two third regions) is provided so as to occupy the entire layer area of the first layer (I) 102 when the main purpose is to improve photosensitivity and dark resistance. In order to prevent charge injection from the free surface 107 of the first (I) 102, a layer is provided near the free surface to strengthen the adhesion between the support 101 and the photoreceptive layer 104. When the main purpose is to measure, the photoreceptive layer 1
It is provided so as to occupy the support side end layer region of 04.

In the first case, the content of nitrogen atoms contained in the layer region (N) is relatively low to maintain high photosensitivity, and in the second case the free surface of the first layer (I) 102 107
In the third case, the nitrogen atom content is relatively high in order to prevent charge injection from the support 101. It is desirable that it be done more often.

In addition, for the purpose of achieving the former champion at the same time, support 10
Nitrogen atoms are distributed at a relatively high concentration on the 1 side, relatively low concentration at the center of the first layer (I) 102, and nitrogen atoms are distributed at a relatively low concentration on the free surface 107 side of the first layer (I) 102. 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 107,
It is desirable to form a layer region (N) in which the distribution concentration C(N) of nitrogen atoms is increased on the free surface 107 side.

In the present invention, the nitrogen atom content in the nitrogen atom-containing layer region (N) provided in the first layer (I) 102 depends on the characteristics required for the layer region (N) itself or the layer region (N). When the region (N) is provided in direct contact with the support 101, the region (N) may be appropriately selected depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support 101. I can do it.

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 may also be determined. The nitrogen atom content is appropriately selected in consideration of the above.

The amount of nitrogen atoms contained in the layer region (N) can be determined as desired depending on the properties required of the photoconductive member to be formed, but it is determined that the amount of nitrogen atoms contained in the layer region (N) is the sum of silicon atoms, germanium atoms, and nitrogen atoms ( Preferably 0.001 to 50 at%, more preferably 0.002 to 40 at%, optimally 0.003 to 40 at%, relative to rT (SiGeN)).
It is desirable that the content be 30 atomic %.

In the present invention, the layer region (N) is the first layer (1) 102
Or, even if it does not occupy the entire area of the first layer (I) 102, the ratio of the layer thickness TO of the layer region (N) to the layer thickness T of the first layer (I) 102 is sufficient. If the amount of nitrogen atoms is large, it is desirable that the upper limit of the content of nitrogen atoms contained in the layer region (N) is set to be sufficiently larger than the above value.

In the present invention, when the ratio of the layer thickness TO of the layer region (N) to the layer thickness T of the first layer (I) 102 is two-fifths or more, the layer region (N) ) The upper limit of the amount of nitrogen atoms contained in T (SiGeN) is preferably 30 at % or less, more preferably 20 at % or less, and optimally 10 at % or less. is desirable.

In the present invention, the layer region (N) containing nitrogen atoms is formed on the support 101 side or/and the second layer (I) as described above.
I) It is preferable to provide a localized region (B) in which nitrogen atoms are contained at a relatively high concentration near the 103 side, and in this case, the support 101 and the first layer (I ) 102 and the acceptance potential can be further improved.

The localized region (B) is preferably provided within 5w from the surface of the first layer (I) 102 on the support 101 side and the second layer (II) 103 side.

In the present invention, the localized region CB) is the first layer (
I) 102, the support 101 or the second layer (II
) 103 side surface to a thickness of 5JL (sometimes it is the entire layer region (Lv), and sometimes it is a part of the layer region (LT).

Whether the localized region (B) is a part or all of the layer region (Lv) is determined as appropriate depending on the characteristics required of the light-receiving layer 104 to be formed.

In the localized region CB), the maximum value Cmax of the distribution concentration C(N) of nitrogen atoms as the distribution state of the nitrogen atoms contained therein in the layer thickness direction is preferably 500 atoms PPM or more, more preferably 800 atoms PPM. ppm or more, optimally 1000
It is desirable that the layer be formed in such a manner that a distribution state of atomic ppm or more can be achieved.

That is, in the present invention, in the first layer (I) 102,
The layer region (N) containing nitrogen atoms has a layer thickness of 5IL from the support 101 side or the surface of the second layer (n) 103.
It is desirable that the distribution density be formed such that the maximum value Cmax of the distribution concentration exists within the range Cmax.

In the present invention, the halogen atoms contained in the first layer (I) 102 as necessary include fluorine,
Examples include chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

In the photoconductive member of the present invention, the first layer region (G) 105 that contains germanium atoms and/or the second layer region (S) 106 that does not contain germanium atoms has a dominant conductive property. By containing the substance (D), the conductive properties of the layer region (G) and/or layer region (S) can be arbitrarily controlled as desired. In the present invention, the layer region (PN) containing the substance CD controlling the conduction properties may be provided in part or all of the first layer (I) 102. Alternatively, the layer region (PN) may be provided in part or all of the layer region (G) or (S).

Substances (D) that control such conductive properties include so-called impurities in the semiconductor field, and in the present invention, P-type conductive properties are used for silicon atoms or germanium atoms. Examples include a p-type impurity that provides a conductive property, and an n-type impurity that provides an n-type conductivity. Specifically, p-type impurities include atoms belonging to Group ■ of the periodic table (Group ■ atoms), such as boron (B), aluminum (AA), gallium (Ga), indium (In), and thallium ( There are TJD, etc., and those that are particularly suitable are:
B, Ga. In addition, - as an n-type impurity is an atom belonging to Group V of the periodic table (Group V atom), for example, phosphorus (
P), arsenic (As), antimony (sb), bismuth (Bi), etc., and particularly preferably used is P.
, As.

In the present invention, the content of the substance (D) that controls the conductive properties contained in the first layer (I) 102 is determined by the conductive properties required for the second layer (I) 102 or The layer can be appropriately selected depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support 101 in which the second layer (I) 102 is provided in direct contact.

In addition, the substance (D) that controls the conduction characteristics described above is included in the first layer (
I) 102, the second layer (I) 10
When it is contained locally in a desired layer region of 2, particularly when it is contained in a layer region at the end of the support side of the first layer (I) 102, it is in direct contact with the layer region. The properties of other layer regions to be provided and the relationship with the properties at one contact interface with the other layer regions are also considered, and the substance (
The content of D) is selected as appropriate.

In the present invention, the content of the substance (D) that controls conduction properties contained in the first layer (I) 102 is preferably o, oi to 5 x 104 atoms ppI11, more preferably is 0.5 to 1xlo4 atom ppm, optimally 1 to
Desirably, the amount is 5×10 atoms ppm.

In the present invention, the content of the substance (D) that controls conduction characteristics in the layer region (PN) containing the substance (D) is preferably 30 atomic ppm or more, more preferably 50 atomic ppm or more. ppm or more, optimally 100 atoms ppm or more, the substance (D) governing the conduction properties is preferably contained locally in a part of the layer region of the first layer (I) 102. It is desirable that it is unevenly distributed, particularly in the support side end layer region (E) of the first layer (I) 102.

Among the above, by containing the substance (D) that controls the conductive characteristics in the support side end layer region (E) of the first layer (I) 102 in a content equal to or higher than the above value. , for example, if the substance CD) is the p-type impurity described above, it is injected into the photoreceptive layer 104 from the support 101 side when the free surface 105 of the photoreceptive layer 104 is subjected to polar charging treatment. When the substance that can effectively block the movement of electrons and controls the conduction characteristics is the n-type impurity, the free surface 105 of the photoreceptive layer 104 is charged to θ polarity. At this time, the movement of holes injected into the light-receiving layer 104 from the support 101 side can be effectively prevented.

In this way, when the support side end layer region (E) contains the substance (D) that controls the conductivity of one polarity, the remaining layer region of the first layer (I) 102, i.e. The layer region (Z) excluding the support side end layer region (E) may contain a substance that controls the conduction characteristics of the other polarity, or may contain a substance that controls the conduction characteristics of the same polarity. The substance that controls
It may be contained in an amount much smaller than the actual amount contained in the support side end layer region (E).

In such a case, the content of the substance 1) that controls the conductive properties contained in the layer region (Z) depends on the polarity and content of the substance contained in the support side end layer region (E). It is determined as desired depending on the amount, but preferably 0.001 to 1000 w, ppffl, preferably 0.05 to 500 atomic ppm, optimally 0.1
It is desirable that PPff1 be 200 atoms.

In the present invention, when the support side end layer region (E) and the layer region (Z) contain the same type of substance that controls conductivity, the content of the substance in the layer region (Z) The content is preferably 30 atomic ppm or less. In addition to the above-mentioned cases, in the present invention, the first layer (
I) In 102, a layer region containing a substance controlling conductivity having one polarity and a layer region containing a substance controlling conductivity having the other polarity are brought into direct contact. It is also possible to provide a so-called depletion layer in the contact layer region. For example, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in the first layer (I) 102 so as to be in direct contact with each other, so that the so-called p-n A junction can be formed to provide a depletion layer.

In the present invention, the first layer region (G) 105 composed of a-Ge (S i , H, It is formed by a vacuum deposition method. For example, by glow discharge method, a-Ge(
First layer region (G) 1 composed of Si, H, X)
To form 05, basically a raw material gas for supplying germanium atoms that can supply germanium atoms, a raw material gas for supplying silicon atoms that can supply silicon atoms, and a raw material for introducing hydrogen atoms as necessary. A gas and/or a raw material gas for introducing halogen atoms is introduced at a desired gas pressure into a deposition chamber whose interior can be depressurized to generate a glow discharge within the deposition chamber, which is installed in a predetermined position in advance. , a layer made of a-Ge (S i , H, X) may be formed on the surface of a predetermined support. Further, in order to contain germanium atoms in the first layer region (G) 105 in a non-uniform distribution state, the distribution concentration of germanium atoms is controlled according to a desired rate of change curve, and a-Ge (Si, H, What is necessary is to form a layer consisting of X). In addition, in the sputtering method, a target composed of silicon atoms, or a target composed of the target and germanium atoms is used in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases. Using two targets or a mixed target of silicon atoms and germanium atoms, source gas for supplying germanium atoms diluted with a diluent gas such as He or Ar as needed. The first layer region (G) 105 is formed by introducing a gas for introducing hydrogen atoms and/or halogen atoms into a deposition chamber for sputtering as necessary to form a plasma atmosphere of a desired gas. In this sputtering method, if the distribution of germanium atoms is to be made non-uniform, the target may be sputtered while controlling the gas flow rate of the raw material gas for supplying germanium atoms 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,
The first layer region (G) 105 can be formed in the same manner as in the sputtering method.

Substances that can be used as raw material gas for supplying silicon atoms used in the present invention include S I H+, S s, H
a, Si, H,, Si, H, Silicon hydride (silanes) in a gaseous state or which can be gasified is mentioned as one that can be effectively used, especially for ease of handling during layer preparation work. S i H4, in terms of good silicon atom supply efficiency, etc.
Preferred examples include S i, H,.

Examples of substances that can be used as raw material gas for supplying germanium atoms include G e H,, G e2H, and G eJH.

G e,H,,,G ekH,2,Ge,H,,,G
Germanium hydride in a gaseous state or capable of being gasified, such as e7H, . In terms of germanium atom supply efficiency, etc.
Preferred examples include GeH9, Ge2H, Ge, and H.

Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, and halogen-substituted silane derivatives. Or a halogen compound that can be gasified is preferably mentioned. Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CJIF, CfLF, BrF,
, B r F, , IFJ, I I7, ICI, and IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
tyuF4. S i2F, , SiCζ, S i B r
Silicon halides such as No. 4 are preferred.

When a photoconductive member characteristic of the present invention is formed by a glow discharge method using such a silicon compound containing halogen atoms, a raw material gas capable of supplying silicon atoms together with a raw material gas for supplying germanium atoms is used. The first layer region (G) made of a-3iGe containing halogen atoms can be formed on the desired support 101 without using silicon hydride gas.
105 can be formed.

When manufacturing the first layer region (G) 105 containing halogen atoms according to the glow discharge method, basically, for example, silicon halide is used as a raw material gas for supplying silicon atoms, and raw material gas for supplying germanium atoms. Germanium hydride and gases such as Ar, I2, He, etc. are mixed at a predetermined mixing ratio and gas flow rate to form a first layer region (G) 105.
The first layer region (G) 105 can be formed on the desired support 101 by introducing the gas into a deposition chamber for forming a gas and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to more easily control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be further mixed with these gases to form a layer.

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 first layer region (G) 105 formed by either the sputtering method or the ion blating method, the above-mentioned halogen compound or the above-mentioned halogen atom-containing silicon compound gas is used. It is sufficient to introduce the gas into the deposition chamber to form a plasma atmosphere of the gas.

Further, when introducing hydrogen atoms into the first layer region (G) 105, a raw material gas for introducing hydrogen atoms, for example, I2,
Alternatively, gases such as the above-mentioned silanes and/or germanium hydride 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 HF, HCl, HBr, and HI are also used. , S i H, IF, , S i H, I, , S i I
20 sentences 2.5iHC, S i H, B r,, 5iH
Brj, etc. (1) ha'o-substituted silicon hydride, and G e
HF,,G e H,F,G e H,F,G e
HCQ,, G e H, Cl,, G e H, CfL,
G e HB r,, G e H, B r,, G e
H,Br,G e HI,,G e H,I,,G
Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides such as e H3I, G e F
,,GeC,GeB r4. G e I4, G
eF4. Gaseous or gasifiable substances such as kermanium halides such as GeC12, GeBr, GeI, etc. can also be mentioned as useful starting materials for forming the first layer region (G) 105.

Among these substances, halides containing hydrogen atoms are hydrogen atoms that are extremely effective for controlling electrical or photoelectric properties at the same time as introducing halogen atoms into the layer when forming the first layer region (G) 105. Since atoms are also introduced, it is used as a suitable raw material for halogen introduction in the present invention.

In order to structurally introduce hydrogen atoms into the first layer region (G) 105, in addition to the above, H2 or .'S i H4,
si, H,, Si, H,, Si, H, Hiroc7) Silicon hydride with germanium or a germanium compound for supplying germanium atoms, or G e H,, G
e,H,,GeJH,,Ge,H,,,Ge,H
,,,Ge,H,,),Ge,H,,,Ge,H,
,,G e,H,'f' (7) This can also be carried out by causing germanium hydride and silicon or a silicon compound for supplying silicon atoms to coexist in a deposition chamber to generate a discharge.

In a preferred example of the present invention, the amount of hydrogen atoms, the amount of halogen atoms, or the sum of the amounts of hydrogen atoms and halogen atoms (H
+X) is preferably 0. O1-401-40 atoms, preferably 0.05-30 at%, most preferably 0.1-25 at%.

In order to control the amount of hydrogen atoms and/or halogen atoms contained in the first layer region (G) 105, for example, the support temperature or/and the amount of hydrogen atoms or halogen atoms used to contain them can be controlled. The amount of starting material introduced into the deposition system, the discharge force, etc. may be controlled.

In the present invention, the second
The layer region (S) 106 is the first layer region (G) described above.
Starting material (II) for forming the second layer region (S) 106 excluding the starting material that becomes the raw material gas for supplying germanium atoms from the starting material (I) for forming the second layer region (S)
) can be formed according to the same method and conditions as when forming the first layer region (S) 106.

That is, in the present invention, the second layer region (G) 105 composed of a-3i (H, Formed by law. For example, in order to form the second layer region (S) 106 composed of a-5i (H, Along with the raw material gas, a raw material gas for introducing hydrogen atoms and/or for introducing halogen atoms as necessary is introduced into a deposition chamber whose interior can be depressurized, and a glow discharge is generated in the deposition chamber to generate a predetermined amount. A layer consisting of a-3i(H,X) may be formed on the surface of a predetermined support. In addition, when forming by sputtering method,
For example, when sputtering a target composed of silicon atoms in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, a gas for introducing hydrogen atoms and/or halogen atoms is used for sputtering. It is sufficient to introduce it into the deposition chamber.

In the present invention, the second layer region (S) 106 formed
The amount of hydrogen atoms or the amount of halogen atoms contained in
Or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 1 to 40 at%, more preferably 5 to 30 at%
The optimum content is preferably 5 to 25 atomic %.

In the present invention, in order to provide the layer region (N) containing nitrogen atoms in the first layer (I) 102, the first layer (I) 1
When forming 02, the starting material for introducing nitrogen atoms is used together with the starting material for forming the first layer (I) 102 described above, and the amount thereof is controlled and contained in the layer to be formed. good.

When a glow discharge method is used to form the layer region (N), a starting material for introducing nitrogen atoms is added to a material selected as desired from among the starting materials for forming the first layer CI) 102 described above. is added. 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 containing silicon atoms, a raw material gas containing nitrogen atoms, and a raw material gas containing hydrogen atoms and/or halogen atoms as necessary are mixed at a desired mixing ratio. Alternatively, a raw material gas containing silicon atoms and a raw material gas containing nitrogen atoms and hydrogen atoms may be mixed at a desired mixing ratio, or A raw material gas having constituent atoms and a raw material gas having three constituent atoms, silicon atoms, nitrogen atoms, and hydrogen atoms, can be mixed and used.

Alternatively, a raw material gas having nitrogen atoms as constituent atoms may be mixed with a raw material gas having silicon atoms and hydrogen atoms as constituent atoms.

A starting material that can be effectively used as a raw material gas for introducing nitrogen atoms used when forming the layer region (N) has nitrogen as a constituent atom, or has nitrogen and hydrogen as constituent atoms. For example, nitrogen (N2), ammonia (NHJ)
), hydrazine (H, N N N2), hydrogen azide (
Mention may be made of gaseous or gasifiable nitrogen, such as HNρ, ammonium azide (NH4N, ), and nitrogen compounds such as nitrides and azides. In addition, halogenated nitrogen compounds such as nitrogen trifluoride (F3N) and nitrogen tetrafluoride (F, N2) can be mentioned because they can introduce halogen atoms in addition to nitrogen atoms. .

In the present invention, the layer region (N) may further contain oxygen atoms in addition to nitrogen atoms in order to further enhance the effect obtained by nitrogen atoms.

As the raw material gas for introducing oxygen atoms into the layer region (N), for example, oxygen (0,), ozone (0,
, ), -nitrogen oxide (NO), nitrogen dioxide (NO2),
-Nitrogen dioxide (NyuO), nitrogen sesquioxide (N, O,)
, trinitrogen tetraoxide (N304), nitrogen sesquioxide (N, O,
), nitrogen trioxide (NO,) whose constituent atoms are silicon atoms, oxygen atoms, and hydrogen atoms, such as disiloxane (
H,5iOSiH,), trisiloxane (H,S i
Examples include lower siloxanes such as OS i H, OS i H, ).

To form the layer region (N) by the sputtering method, when forming the first layer (I) 102, a single crystal or polycrystalline silicon wafer or St, N, wafer, or silicon atoms and S ia% Sputtering may be carried out by using a wafer containing a mixture of as a target and sputtering them in various gas atmospheres.

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

Alternatively, silicon atoms and Si3N+ can be used as separate targets, or by using a single target that is a mixture of silicon atoms and Si, N4, in an atmosphere of dilution gas as a sputtering gas. Alternatively, sputtering may be performed in a gas atmosphere containing at least hydrogen atoms and/or halogen atoms as constituent atoms.

As the raw material gas for introducing nitrogen 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 forming the first layer (I) 102,
When providing a layer region (N) containing nitrogen atoms, the distribution concentration C(N) of nitrogen atoms contained in the layer region (N) is changed in the layer thickness direction to obtain a desired distribution in the layer thickness direction. state (d
In order to form a layer region (N) having an epth profile), in the case of a glow discharge, a starting material gas for introducing nitrogen atoms whose distribution concentration C(N) is to be changed is adjusted by adjusting the gas flow rate to a desired rate of change. It may be introduced into the deposition chamber while changing it appropriately according to the curve. For example, the opening of a predetermined needle valve provided in the coating 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. At this time,
For example, a desired content rate curve can be obtained by controlling the flow rate using a microcomputer or the like according to a rate of change curve designed in advance.

When forming a layer region (N) by a sputtering method, the distribution concentration C(N) of nitrogen atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (d) of nitrogen atoms in the layer thickness direction.
epth profile), first, as in the case of the glow discharge method, a starting material for introducing nitrogen atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is This can be done by appropriately changing as desired.

Second, if a mixed target of silicon atoms and Si3N4 is used as a sputtering target, for example, silicon atoms and Si3N+
This is achieved by changing the mixing ratio with the target in the layer thickness direction of the target in advance.

In the first layer (I) 102, a substance that controls the conduction properties;
For example, in order to structurally introduce a group II atom or a group V atom, a starting material for introducing a group II atom or a starting material for introducing a group V atom is deposited in a gaseous state during layer formation. Examples of starting materials that can be introduced into the chamber together with other starting materials for forming the second region (S) 106 are those that can be used at room temperature and pressure. It is desirable to use a gaseous material, or at least one that can be easily gasified under the layer forming conditions. Specifically, starting materials for the introduction of group Ⅰ atoms include B2H,, B4H, , B&H, , B, Hll, B.
,H,. ,B6H,,,B.

Boron hydride such as H14, BF3. BCl,,BBr,
Examples include boron halides. In addition, A.I.
Cl,,G e Cl,,Ge (OH,),I nc
i,, TlC1,, etc. can also be mentioned.

In the present invention, the starting materials for introducing Group V atoms that are effectively used for introducing phosphorus atoms are PH,
Hydrogenated phosphorus such as P, H4, P H41, P H3, PF
,,PCIJ,PCl,,PBr,,PBr,,P I
Examples include halogenated phosphorus such as No. 3. In addition, A s H
j, A s FJ, A s Cl,, A s B
r,,A s'F,,S bH,,S bF,,S
b thickness S bcJl,, S bci,, B i H,
, BiCJl, , B i Br, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

In the present invention, the layer thickness of the layer region (PN) that constitutes the first layer (I) 102 and is unevenly distributed on the support 101 and contains a substance that controls conduction characteristics is as follows. , which is appropriately determined as desired depending on the characteristics required of the layer region (PN) and other layer regions forming the first layer (I) 102 formed on the layer region (PN). In Although,
The lower limit is preferably 30A or more, more preferably 40λ or more, and optimally 50λ or more. When the content is 30 atomic ppm or more, the upper limit of the layer thickness of the layer region (PN) is preferably 10 g or less, preferably 8 μm or less, and optimally 5 μm or less. is desirable.

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

Furthermore, in the present invention, since each of the amorphous materials constituting the first layer (I) 102 and the second layer (II) 103 has a common constituent element of silicon atoms, both Chemical stability is sufficiently ensured at the laminated interface of layers (I) 102 and (II) 103.

The second layer (n) 103 in the present invention is an amorphous material (hereinafter referred to as r a -(Si
xo+ -x) y(H,X) +-yJ, provided that 0<x, y<1. ).

The second layer (I) 103 composed of a-(SixO+-x)y(H,X)+-y can be formed by glow discharge method, sputtering method, electron beam method, ion plantation method, or ion blating method. , etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be produced. The second layer (II) 103 is relatively easy to control the manufacturing conditions for manufacturing the conductive member and contains oxygen atoms and halogen atoms together with silicon atoms.
A glow discharge method or a sputtering method is preferably employed since they have the advantage of being easy to introduce into the interior.

Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same system to generate the second M(n)to3
may be formed.

To form the second layer (II) 103 by the glow discharge method, a-(S ixo+-x) y(H,X)
The raw material gas for l-7 formation is mixed with dilution gas at a predetermined mixing ratio as necessary, and introduced into the deposition chamber where the support 101 is installed, and the introduced gas is used to cause glow discharge. A gas plasma is generated by generating a gas, and a −(S ixO+−x ) y(H,X) +− is applied to the first layer (I) 102 already formed on the support 101
It is sufficient to deposit y.

In the present invention, a-(S 1xOrx)y (H,
)+-y The raw material gas for forming y is silicon atoms,
Most gaseous substances or gasified substances containing at least one of oxygen atoms, hydrogen atoms, and halogen atoms can be used.

When using a raw material gas that has a silicon atom as one of silicon atoms, oxygen atoms, hydrogen atoms, and halogen atoms, for example, a raw material gas that has silicon atoms as a constituent atom and an oxygen atom as a constituent atom. If necessary, a raw material gas containing hydrogen atoms and/or a raw material gas containing halogen atoms may be mixed at a desired mixing ratio, or silicon atoms may be used as constituent atoms. The raw material gas and the raw material gas containing oxygen atoms and hydrogen atoms or/and the raw material gas containing oxygen atoms and halogen atoms as M constituent atoms are also combined in a 4-tail mixture at a given mixing ratio. Alternatively, a raw material gas containing silicon atoms as mF# atoms and a raw material gas containing silicon atoms, oxygen atoms, and hydrogen atoms, or three constituent atoms: silicon atoms, # elementary atoms, and halogen atoms. It can be used by mixing it with the raw material gas as the constituent atoms.

Alternatively, a raw material gas containing silicon atoms and hydrogen atoms as constituent atoms may be mixed with a raw material gas containing oxygen atoms as constituent atoms, or a raw material gas containing silicon atoms and halogen atoms as constituent atoms may be used. A raw material gas containing oxygen atoms as a constituent atom may be combined with the raw material gas and used.

In the present invention, fluorine, chlorine, bromine, and iodine are preferred as halogen atoms contained in the second layer (]l)'103, with fluorine and chlorine being particularly preferred.

In the present invention, raw material gases that can be effectively used to form the second layer (1) 103 include gaseous substances or substances that can be easily gasified at normal temperature and normal pressure. I can do it.

When forming the second layer (I) 103 by sputtering, the process is performed as follows, for example.

Firstly, when sputtering a target made of silicon atoms in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, a raw material gas for introducing oxygen atoms is used. If necessary, it may be introduced into a vacuum deposition chamber in which sputtering is performed together with a source gas for introducing hydrogen atoms and/or for introducing halogen atoms.

Secondly, S i as a target for sputtering
A target composed of Ox, or a target composed of silicon atoms and a target composed of S i O2)+7) Two pieces, or a target composed of silicon atoms and S i 0
Oxygen atoms can be introduced into the second layer (II) 103 formed by using a target composed of 2 and 2. At this time, if the aforementioned raw material gas for introducing oxygen atoms is also used, the flow rate can be controlled to form the second layer (
II) It is easy to arbitrarily control the amount of oxygen atoms introduced into 103.

The content of oxygen atoms introduced into the second layer (II) 103 can be determined by controlling the flow rate when the raw material gas for introducing oxygen atoms is introduced into the deposition chamber, or by controlling the flow rate when the raw material gas for introducing oxygen atoms is introduced into the deposition chamber, or by controlling the flow rate of the raw material gas for introducing oxygen atoms. The proportion of oxygen atoms contained therein can be arbitrarily controlled as desired by adjusting the proportion of oxygen atoms contained therein when the target is produced, or by both.

The starting materials used as the raw material gas for supplying silicon atoms used in the present invention include SiH4, Si, H,...
Silicon hydride (silanes) in a gaseous state or that can be gasified, such as Si, H, Si4H+o, etc., can be used effectively, especially because of the ease of layer creation work and silicon atom supply efficiency. S i H4, S
i2H,2 is preferred.

If these starting materials are used, the second layer (II) 103 can be formed by appropriately selecting the layer forming conditions.
Hydrogen atoms may also be introduced in addition to silicon atoms.

In addition to the above-mentioned silicon hydride, effective starting materials that serve as raw material gas for supplying silicon atoms include silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, SiF, ,5i2F,,Si(
,Q,,5iBr+.

Preferred examples include silicon halides such as the following. Furthermore, S i H, F2. S i H,I
.

, S i H2CM2. S i HCM,, S i
H2B r,.

For supplying silicon atoms for forming the second layer (II) 103, gaseous or gasifiable halides having hydrogen atoms as one of their constituents, such as halogen-substituted silicon hydride such as 5iHBr, are also effective. It can be mentioned as a starting material.

Even when these silicon compounds containing halogen atoms are used, halogen atoms can be introduced together with silicon atoms into the second layer (II) 103 to be formed by appropriately selecting the layer forming conditions as described above. I can do it.

Among the above-mentioned starting materials, silicon halide compounds containing hydrogen atoms are extremely effective for controlling electrical or photoelectric properties at the same time as introducing halogen atoms into the layer when forming the second layer (11) 103. Since a hydrogen atom can also be introduced, it is used as a suitable starting material for introducing a halogen atom in the present invention.

In addition to the above-mentioned materials, effective starting materials that serve as raw material gases for introducing halogen atoms used in forming the second layer (II) 103 in the present invention include, for example, fluorine, chlorine, bromine, and iodine. Halogen gas, BrF, CfL
F.C.I.F.

BrF,,BrF,,IF,,IF,,I(,Q,I
Interhalogen compounds such as Br, HF, HC, HBr.

Examples include hydrogen halides such as HI.

The starting material that can be effectively used as a raw material gas for introducing oxygen atoms used when forming the second layer (n) 103 has oxygen atoms as a constituent atom or a mixture of nitrogen atoms and oxygen atoms. For example, oxygen (0,2
), ozone (OJ), -nitrogen oxide (NC)), nitrogen dioxide (No2), -nitrogen dioxide (N, O), nitrogen sesquioxide (N, 0.), nitrogen tetroxide (N, 04),
Nitrogen sesquioxide (N, o,), Nitrogen trioxide (NO,),
For example, disiloxane (H
YoS iOS t H3) + Trisiloxane (H,
Lower siloxanes such as S i OSH, O3i H, etc. can be mentioned.

In the present invention, so-called rare gases such as He, Ne, Ar, etc. are preferably used as the diluting gas used when forming the second layer (n) 103 by a glow discharge method or a sputtering method. I can do it.

The second layer (II) 103 in the present invention is carefully formed so that its required properties are imparted as desired.

In other words, substances whose constituent atoms are silicon atoms, oxygen atoms, and optionally hydrogen atoms and/or halogen atoms have structural forms ranging from crystalline to amorphous depending on the conditions for their creation, and in terms of electrical properties, From conductive to semiconducting,
Furthermore, it exhibits properties ranging from insulating to photoconductive to non-photoconductive. Therefore, in the present invention, a −(S ix
o+-x) y (H,X)ry is formed,
The selection of the production conditions is made strictly according to desire. For example, in order to provide the second layer (II) 103 with the main purpose of improving electrical withstand voltage, a−(Sixo+ −x
)y (H,

In addition, when the second layer (■) 103 is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to some extent, and it becomes less resistant to the irradiated light. As an amorphous material with a certain degree of sensitivity, a −(S 1xo1− x ) y(H, X)+−
y is created.

On the surface of the first layer (I) 102 (7), a-(SixO+
-x)y Second layer (n)1 consisting of (H,X)+-y
The temperature of the support 101 during layer formation is an important factor that influences the structure and properties of the formed layer. In the present invention, it is desirable that the temperature of the support during layer formation be strictly controlled so that a(SixOl-x)y (H,X)ry having the desired properties can be created as desired. . In the present invention, the support temperature is appropriately selected in the optimum range in accordance with the method of forming the second layer (■) 103 in order to effectively achieve the desired purpose, and the second layer (II) 103 The temperature of the support during layer formation is preferably 20 to 400°C, more preferably 50 to 350°C, most preferably 100 to 300°C. .

To form the second layer (II) 103, glow discharge is used to form the second layer (II) 103, since delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. When forming the second layer (II) 103 using these layer forming methods, it is advantageous to adopt a sputtering method or a sputtering method. a to be done
-(S 1xcl -x )yX+ - It is one of the important factors that influences the characteristics of -y.

a having the characteristics for achieving the object of the present invention;
The discharge power conditions for effectively creating -(S 1xo1- x )y It is desirable that the

The gas pressure in the deposition chamber is preferably between 0.01 and I Torr.
, more preferably about 0.1 to 0.5 Torr.

In the present invention, the support temperature and discharge power for forming the second layer (n) 103 are preferably within the ranges described above, but these layer formation factors are determined independently and separately. It is not determined based on the mutual organic relationship so that the second layer (■) 103 consisting of a-(SixOl-x)y (H,X)+-y with desired characteristics is formed. It is desirable that the optimum value of each layer creation factor be determined by

The amount of oxygen atoms contained in the second layer (U) 103 in the photoconductive member of the present invention is determined to have the desired characteristics to achieve the object of the present invention, similar to the conditions for forming the second layer (Ir) to3. This is an important factor for forming the resulting second layer (II) 103.

The amount of oxygen atoms contained in the second layer (II) 103 in the present invention is determined as desired depending on the type and characteristics of the amorphous material constituting the second layer (II) 103. It is something that can be done.

That is, the general formula a-(SixO+-X)V(H,X)
The amorphous material denoted by ry can be broadly classified as an amorphous material composed of silicon atoms and oxygen atoms (hereinafter referred to as ra
-SiaO+-a".

However, 0<a<1), an amorphous material composed of silicon atoms, oxygen atoms, and hydrogen atoms (hereinafter referred to as r a -(S
Written as ibo +-b)c Hl-CJ. However, 0<b
, cal), and an amorphous material composed of silicon atoms, oxygen atoms, halogen atoms, and optionally hydrogen atoms (hereinafter ra-(SidOrd) e (H,X) r
It is written as "e". However, it is classified as 0<d, e<1).

In the present invention, the second layer (II) 103 is a-3ia
When composed of O+-a, the amount of oxygen atoms contained in the second layer (II) 103 is expressed as a in a-Siao+-a, where a is preferably 0.33 to 0. 9999
9, more preferably 0.5 to 0.99, optimally 0.6 to
It is 0.9.

In the present invention, the second layer (II) 103 is a-(S
ibo + - b) c Hrc, the amount of oxygen atoms contained in the second layer (II) 103 is a -
(S 1boI-b)c When expressed as b and C in Hl-c, b is preferably 0.33 to 0.99999, more preferably 0.5 to 0.99, optimally 0.6 to 0.9
, C is preferably 0.6 to 0°99, more preferably 0.
65 to 0.98, most preferably 0.7 to 0.95.

The second layer (II) 103 is a −(S idO+−d
)e(H,X)+-e, the content of oxygen atoms contained in the second layer (II) 103 is a-(S 1dO1-d) ,X)i-
If expressed as d of e and e, d is preferably 0.3
3-0.999-99, more preferably 0.5-0.99
, is optimally between 0.6 and 0.9, and e is preferably 0.
The range from 8 to 0.99 is one of the important factors for effectively achieving the purpose of the present invention. This layer thickness is
In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose. Furthermore, this layer thickness also depends on the characteristics required for each layer region, in relation to the amount of oxygen atoms contained in the layer (n) 103 and the layer thickness of the first layer (I) 102. It is necessary to decide as appropriate based on the organic relationship depending on the desired situation.

In addition, it is desirable that this layer thickness is also taken into consideration from the economical point of view, taking into account productivity and mass production.

The layer thickness of the second layer (II) 103 in the present invention is preferably 0.003 to 30, more preferably 0.0
04 to 20IL, optimally 0.005 to top.

Further, in the present invention, in order to further enhance the effect obtained by oxygen atoms, carbon atoms may be included in the second layer (II) 103 together with oxygen atoms. The raw material gas for introducing carbon atoms into the second layer (II) 103 includes, for example, saturated hydrocarbons having 1 to 5 carbon atoms, carbon atoms having carbon atoms and hydrogen atoms; 2~
Examples include ethylene hydrocarbons having 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like. Specifically, saturated hydrocarbons include methane (CU+), ethane (C,H,), propane (C3Hρ, n-butane (n -C,H,,)
, pentane (crtt-), ethylene hydrocarbons include ethylene (C, H4), propylene (C, H,)
, butene-1 (C, Hρ , butene-2 (C4H,)
, inbutylene (C4Hρ, pentene (CtH+ρ)
, acetylene hydrocarbons include acetylene (for C), methylacetylene (C,H,), butyne (C4),
H6) and the like. In addition to these, as a raw material gas whose constituent atoms are silicon atoms, carbon atoms, and hydrogen atoms,
Examples include alkyl silicides such as 5t (containing CF2), S i (c, and λ).

The support 101 used in the present invention may be electrically conductive or electrically insulating.

Examples of the conductive support include NiCr, stainless steel, AM, C'r, Mo, Au, Nb, Ta, V, Ti,
Examples include metals such as Pt and Pd, and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are usually used. Ru.

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, NiCr1. A
4Q, Cr, Mo, Au, Ir, Nb, T
a, V, Ti, Pt, Pd, Injo,, S
noL, I To (I n20j+S no,)
Conductivity is imparted by providing a thin film consisting of NiCr, AJl, Ag, Pb, Zn, Ni, etc., or in the case of a synthetic resin film such as a polyester film.
Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt
Conductivity is imparted to the surface by providing a thin film of metal such as by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal.

The support lO1 can be obtained in any shape such as a cylinder, a belt, or a plate, and its shape is determined as desired. For example, the photoconductive member lOO shown in FIG. If used as a member for continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support 101 is determined as appropriate so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the thickness of the support 101 may be determined so that it can sufficiently function as a support. It is made as thin as possible within the range. In such a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness of the support lO1 is preferably 1.
01L or more.

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

FIG. 16 shows an example of a photoconductive member manufacturing apparatus.

In the figure, gas cylinders 1102 to 1106 are sealed with raw material gases for forming the photoconductive member of the present invention. 99.999%, hereinafter S
i Abbreviated as H4/He. ) cylinder, 1103 is He
G e H, gas (purity 99.999%,
Hereinafter, it will be abbreviated as G e H4/He. ) cylinder, 1104
is NH, gas (99.99% purity) cylinder, 1105
1106 is a He gas (purity 99.999%) cylinder, and 1106 is a H2 gas (purity 99.999%) cylinder.

In order to flow these gases into the reaction chamber 1101, valves 1122 to 1126 of gas pumps 1102 to 11o6,
Make sure the leak valve 1135 is closed,
In addition, inflow valves 1112 to 1116 and outflow valve 111
After confirming that 7 to 1121 and auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, when the vacuum gauge 1136 reads approximately 5X10 Torr, the auxiliary valves 1132, 1133. Outflow valve 11
71-1121 are closed.

Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137 as a support, Si H+/He gas from the gas cylinder 1102,
(y) G e Hv/He gas from gas pump 1103, NH Yogas from gas pump 1104, valve 1
122, 1123, 1124 open and outlet pressure gauge 11
By adjusting the pressure at 27.1128°1129 to 1 kg/crn' and gradually opening the inlet valves 1112, 1113, and 1114, the mass flow controller 110
71108 and 1110, respectively. Subsequently, the outflow valves 1117, 1118, 1119, and auxiliary valve 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101.

At this time (1) S i H4/He gas flow rate and G
e Adjust the outflow valves 1117, 1118 and 1119 so that the ratio of the H+/He gas flow rate to the NH gas flow rate becomes the desired value -, and also so that the pressure inside the reaction chamber 1101 becomes the desired value. Adjust the opening of main valve 1134 while checking the reading on vacuum gauge 1136. and the base 113
7 temperature is 50-400℃ by heating heater 1138
After confirming that the temperature is set in the range of Valve 1l1 by applying methods such as gas and manual or external drive motor
8 to 1120 by appropriately changing the apertures of NH
, the distribution concentration of germanium atoms and nitrogen atoms contained in the formed layer C(N
).

In the manner described above, the first layer region (G) 105 is formed on the base 1137 to a desired layer thickness by maintaining glow discharge for a desired period of time. At the stage where the first layer region (G) 105 has been formed to the desired layer thickness, the outflow valve 111B is completely closed and the desired layer is formed according to the same conditions and procedures, except for changing the discharge conditions as necessary. By maintaining the glow discharge for a period of time, a second layer region (S) 106 substantially free of germanium atoms can be formed on the first layer region (G) 105.

First layer region (G) 105 and second layer region (S) 1
In order to contain the substance (D) that controls conductivity in 06, the first layer region (G) 105 and the second layer region (S
) 106, for example, a gas such as BLH, PH3, etc. may be added to the gas introduced into the deposition chamber 1101.

In this way, the first layer (I) 102 is formed on the base 1137.

First layer (I) 1 formed to a desired layer thickness as described above
To form the second layer (II) 103 on the 02, for example, each of S i H4 gas and No gas is added as necessary by the same valve operation as in the formation of the first layer 102 (I). The diluent may be diluted with a diluent gas such as He and supplied into the reaction chamber 1101 to cause glow discharge according to desired conditions.

In order to contain a halogen atom in the second layer (II) 103, for example, add S i F gas and No gas, or add S i H gas to this and form the second layer (II) in the same manner as above. ) 103 may be formed.

It goes without saying that all outflow valves other than the gas outflow/<lub required when forming each layer are closed, and when forming each layer, the gas used to form the previous layer is not released into the reaction chamber 1101. In order to avoid gas remaining in the gas piping leading from the outflow valves 1117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary valves 1132 and 1133 are opened, and the main valve 1134 is closed.
If necessary, fully open the system and evacuate the system to high vacuum.

The amount of oxygen atoms contained in the second layer (n) 103 can be determined by, for example, changing the flow rate ratio of Si H4 gas and No gas introduced into the reaction chamber 1101 in the case of glow discharge, or When forming a layer by sputtering, the target is formed by changing the sputtering area ratio of the silicon wafer and the SiO wafer, or by changing the mixing ratio of the silicon powder and the SiO powder. It can be controlled as desired. The amount of halogen atoms contained in the second layer (II) 103 is determined by the raw material gas for introducing halogen atoms,
For example, this can be done by adjusting the flow rate when SiF4 gas is introduced into the reaction chamber 1101.

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

Examples will be described below.

Example 1 Using the manufacturing apparatus shown in FIG. 16, samples (sample Nos. 1-1 to 17-
6) were created respectively (MS2 table).

The content distribution concentration of germanium atoms in each sample is the first
The distribution concentration of nitrogen atoms is shown in FIG. 7, and in FIG. 18.

Each sample thus obtained was placed in a charging exposure experimental device (15), corona charged with OKV for 0.3 seconds (sec), and immediately irradiated with a light image.

The light image uses a tungsten lamp light source, 2ILux-8
A light amount of eC was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the sample (imaging member) by cascading the surface of the sample (imaging member) with a developer (containing toner and carrier) having a positive charge. The toner image on the sample is
When transferred onto transfer paper using OKV's corona charging, clear, high-density images with excellent resolution and good gradation reproducibility were obtained in all samples.

In the above, each sample was subjected to the same toner image forming conditions except that an 810 nm GaAs semiconductor laser (10 mW) was used instead of a tungsten lamp as a light source to form an electrostatic image. When the image quality of the toner transfer images was evaluated, it was found that in all samples, clear, high-quality images with excellent resolution and good gradation reproducibility were obtained.

Example 2 Samples (sample Nos. 21-1 to 27-8) as electrophotographic image forming members were prepared on a cylindrical An substrate-L using the manufacturing apparatus shown in FIG. 16 under the conditions shown in Table 3. were created for each (Table 4).

The content distribution concentration of germanium atoms in each sample is the first
FIG. 7 shows the distribution concentration of nitrogen atoms, and FIG. 18 shows the nitrogen 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. In addition, for each sample, 38℃, 8
When a repeated use test was conducted 200,000 times in an environment of 0% RH, no deterioration in image quality was observed in any of the samples.

Example 3 A cylindrical AJI was manufactured using the manufacturing equipment shown in Fig. 16.
Samples (sample teeth, 31-1 to 37-8) as electrophotographic image forming members were prepared on the substrate under the conditions shown in Table 5 (Table 6).

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

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, for each sample, 38℃, 8
When a repeated use test was conducted 200,000 times in an environment of 0% RH, no deterioration in image quality was observed in any of the samples.

Example 4 A cylinder-shaped Al
Samples (sample rb, 41-1 to 47-8) as electrophotographic image forming members were prepared on the substrate under the conditions shown in Table 7 (Table 8).

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

When each of these samples was subjected to image evaluation tests similar to those in Example 1, all samples provided high quality toner transfer images. Also, for each sample, 38°C5
When a repeated use test was conducted 200,000 times in an environment of 80% RH, no deterioration in image quality was observed in any of the samples.

Example 5 Sample work 11-1.12-1.13 of Example 1 except that the preparation conditions for layer (II) 103 were as shown in Table 8.
-1, respectively (sample positive, 11-1-1-11-1-8.1).
2-1-1~12-1-8.13-1-1~13-1-
24 samples of 8) were created.

Each of the electrophotographic image forming members thus obtained was individually installed in a copying machine, and under the same conditions as described in each example, each of the electrophotographic image forming members corresponding to each example was We evaluated the overall image quality of the transferred image and evaluated its durability through repeated continuous use.

Table 10 shows the results of the overall image quality evaluation of the transferred image of each sample and the durability evaluation after repeated and continuous use.

Example 8 When forming layer (II) 103, silicon wafer and S
i By changing the target area ratio of the O2 wafer, the layer (II
) Image forming members were prepared in exactly the same manner as Sample No. 11-1 of Example 1, except that the content ratio of silicon atoms to oxygen atoms in Sample No. 103 was changed. For each of the image forming members thus obtained, the steps of image formation, development, and cleaning as described in Example 1 were repeated approximately 50,000 times, and then image evaluation was performed.
The results shown in Table 1 were obtained.

Example 7 Example 1 except that when forming layer (11) 103, the flow rate ratio of SiH+ gas and NO gas was changed to change the content ratio of silicon atoms and oxygen atoms in layer (II) 103.
Each of the imaging members was made in exactly the same manner as Sample rllo, 12-1.

After repeating the steps up to transfer approximately 50,000 times using the method described in Example 1 for each image forming member thus obtained,
When image evaluation was performed, the results shown in Table 12 were obtained.

Example 8 Layer (II) When forming the layer 103, SiH4 gas, Si
Layer (II) 10 by changing the flow rate ratio of F, gas, and NO gas.
Each of the image forming members was created in exactly the same manner as Sample No. 13-1 of Example 1, except that the content ratio of silicon atoms and oxygen atoms in Sample No. 3 was changed. After repeating the image forming, developing and cleaning steps as described in Example 1 approximately 50,000 times for each of the image forming members thus obtained, image evaluation was performed, and the results shown in Table 13 were obtained.

Example 8 Image forming members were produced in exactly the same manner as in Samples No. 11-1 of Example 1, except that the layer thickness of layer (II) 103 was changed. Imaging as described in Example 1;
The development and cleaning steps were repeated to obtain the results shown in Table 14.

Table 14 The layer forming conditions in the embodiments of the present invention shown in Table 14 and above are shown below.

Substrate temperature: germanium atom (Ge) containing layer...approximately 2
00℃ Germanium atom (Ge)-free layer...approx. 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of the drawing]

FIG. 1 is a schematic layer configuration diagram for explaining the layer configuration of the light guide member of the present invention, and FIGS. 2 to 1θ diagrams each illustrate the distribution state of germanium atoms in the first layer (I). An explanatory diagram for explaining, FIG. 11 is a configuration diagram of a layer region containing nitrogen atoms, and FIGS. 12 to 15 respectively explain the distribution state of nitrogen atoms in the first layer (I). Explanatory diagram for doing so, No. 16
Figure 17 is a schematic explanatory diagram of the device used in the present invention.
18 are distribution state diagrams showing the content distribution concentration state of each atom in the example of the present invention. 100... Photoconductive member 101... Support 102... First layer (I) 103... Second layer (n) 104... Photoreceptive layer FIG. 1 C C C 11th Figure 12 Figure 13 C (N) Figure 17 (170I) (ITO2) (1703) (IY0
4) Germanium-containing π-containing Kahor coal (11% scrap)

Claims (1)

[Scope of Claims] (1) A support for a photoconductive member, a first layer region (G) made of an amorphous material containing germanium atoms, and provided on the support, and a silicon atom. a first layer comprising an amorphous material comprising a photoconductive second layer region (S) provided on the first layer region (G), and the second layer; A photoreceptive layer is provided thereon and is composed of a second layer made of an amorphous material containing silicon atoms and oxygen atoms, and the first layer contains nitrogen atoms and has a layer thickness of A first region (1) in which the distribution concentrations of nitrogen atoms in the directions are C(1), C(3), and C(2), respectively.
, a third region (3), and a second region (2) in this order from the support side (however,
C(3) > C(2), H(1), and c, (i)
, , c(2) is not 0, or C(1) and C(2) are not equal). (2) The photoconductive member according to claim 1, wherein at least one of the first layer region (G) and the second layer region (S) contains hydrogen atoms. (3) The photoconductor according to claims 1 and 2, wherein at least one of the first layer region (G) and the second layer region (S) contains a halogen atom. Element. (4) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is non-uniform. (5) The photoconductive member according to claim 1, wherein the germanium atoms are uniformly distributed in the first layer region (G). (7) The photoconductive member according to claim 6, wherein the substance that controls conductivity is an atom belonging to Group Ⅰ 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.