JPS60138559A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member having excellent characteristics by incorporating N at a specific distribution into three regions in the 1st amorphous layer formed with a region G contg. Si and Ge and a region S contg. Si in this order on a conductive base and providing the 2nd amorphous layer contg. Si and C on said layer. CONSTITUTION:A region 105 contg. Si and Ge is formed on a conductive base 101 in such a way that the Si and Ge are distributed uniformly over the entire region or are incorporated at a high concn. on the base 101 side and in the smaller concn. on the opposite side thereof. A region 106 contg. Si is then formed thereon and the 1st amorphous layer 102 is formed of the regions 105 and 106. N is incorporated in the layer 102 at different distribution concns. in such a way that the region 108 of a concn. C(1), region 110 of concn. C(3) and region 109 of concn. C(2) are successively formed from the base 105 side. The N is incorporated in such a way that C(3)>C(2), C(1) and either of C(1) or C(2) is not ''0'' and C(1), C(2) are not equal. The 2nd amorphous layer 103 contg. Si and C is formed on the layer 102 and a photoreceptive layer 104 is formed of the layers 102 and 103. The photoconductive member having an excellent electromagnetic conversion characteristic, durability etc. is thus obtd.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to electromagnetic waves that are sensitive to electromagnetic waves such as light (here, light in a broad sense, ultraviolet rays, visible rays, red light (indicating light rays, X-rays, gamma rays, etc.)). This invention relates to a 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, non-pollution during use is an important point.

Based on these points, light has recently been attracting attention! The mold member is made of amorphous silicon (denoted as ltmA-3i), for example, German Publication No. 2746967, German Publication No. 2
Publication No. 855718 describes an image forming member for electrophotography,
DE 2933411-A describes an application to a photoelectric conversion reader.

On the other hand, a photoconductive member having a conventional photoconductive layer composed of A-3I has a low dark resistance value and a low 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 If the conductive member is repeatedly used for a period of 11ν, fatigue will accumulate due to the repeated use, and so-called ghost development, in which an afterimage will occur, will occur. Alternatively, when used repeatedly at high speeds, inconveniences such as a gradual decrease in responsiveness often occur.

Furthermore, a-5i 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, if the halogen lamps and fluorescent lamps used in hallways are set to 0 (0), there is still room for improvement in that the long wavelength side light cannot be used effectively. .

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

This 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 a-3i material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Bottle atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms for control purposes, or other atoms for the purpose of improving other properties. Otherwise, problems may arise in the electrical or photoconductive properties of the formed layer.

That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or in a dark area, 11 of the male brush barrel from the support side:
There are many cases where human deterrence is not sufficient.

Furthermore, when the layer thickness reaches more than 10 hiro or more, the layer may lift off from the surface of the support, or the phase 1 or This resulted in problems such as the formation of cracks. 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 the characteristics of the A-3i material itself can be improved by 1.DELTA., when designing a photoconductive member, it is necessary to take measures to solve all of the above-mentioned problems.

[Objective] The present invention has been made in view of the above points, and a-3i
As a result of comprehensive research and consideration from the viewpoint of its applicability as a photoconductive member used in image forming members for electronic photography, solid-state imaging devices, reading devices, etc., we found that silicon An amorphous material having a matrix of atoms and germanium atoms and containing at least either a hydrogen atom or a halogen atom, so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogenated amorphous silicon germanium containing water (hereinafter referred to as amorphous silicon germanium) ra-5iGe(H, The photoconductive member prepared under the following conditions not only shows extremely superior properties in practical use, but also has 11 ffi in all respects compared to conventional photoconductive members. The present invention is based on the discovery that it has extremely excellent characteristics as a photoconductive member for photography and that it has excellent absorption spectrum characteristics on the long wavelength side.

The present invention has stable electrical, optical, and photoconductive properties at all times, and is a fully enclosed type with almost no restrictions on usage environments.It has excellent photosensitivity characteristics on the long wavelength side and is resistant to photofatigue. The main object of the present invention is to provide a photoconductive member which is extremely durable, shows no deterioration phenomenon even after repeated use, and exhibits no or almost no residual potential.

Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire IIf optical field, is particularly good in munching with a semiconductor laser, and has a fast photoresponse.

Still another object of the present invention is to improve the electrodepositivity between the layer provided on the support and the support and between the laminated layers, so that the structure is dense and stable in terms of structural arrangement. The object of the present invention is to provide a photoconductive member with high layer quality.

Still another feature of the present invention is that when applied as an image forming member for electrophotography, the charging process for electrostatic image formation can be performed to such an extent that ordinary electrophotography can be applied very effectively. It is an object of the present invention to provide a photoconductive member having sufficient charge retention ability and excellent electrophotographic properties in which almost no deterioration in the properties is observed even in a humid atmosphere.

Still another object of the present invention is to provide high density, clear halftones, and high resolution. Still another object of the present invention is to provide high photosensitivity, high signal-to-noise ratio characteristics, and good relationship with the support. An object of the present invention is to provide a photoconductive member having excellent electrical contact properties.

[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 a second layer region (G) exhibiting photoconductivity, which is composed of an amorphous material N1 containing silicon atoms and is provided on the first layer region (G).
S) a photoreceptive layer comprising a first layer having an upper layer and a second layer provided on the second layer and made of an amorphous material containing silicon atoms and carbon atoms; , the first layer is
The present invention is designed to have a layer structure as described above, which contains nitrogen atoms and is characterized by a list in which the distribution concentration of nitrogen atoms in the layer thickness direction is shown in this order from the support side. The photoconductive member can solve all of the above-mentioned problems and has 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 (1
) 102 and the second layer (II) 103 form the photoreceptive layer 10. ．． 4.

The first layer (I) 102 is made of an amorphous material (hereinafter ra-Ge) containing germanium and, if necessary, at least one of silicon atoms, hydrogen atoms, and halogen atoms.
(Si, H, (hereinafter ra-3i# (H,
)”), and the first layer region (G) 105J
, : a second layer region (S) exhibiting photoconductivity provided in
'106.

The germanium atoms are distributed uniformly in the first layer region (G) 105 without cutting edges.
It may be contained inside.

Alternatively, the distribution concentration may be non-uniform, although the content is uniform in the layer thickness direction. In any case, in the first layer region (G) 105, germanium atoms are contained uniformly and without any sharp edges in the in-plane direction parallel to the surface of the support. This is necessary from the point of view of making the characteristics uniform in the in-plane direction.

In particular, it is contained in the layer thickness direction of the first layer (I) 102 without cutting edges, and on the side opposite to the side where the support 101 is provided (the free surface 107 side of the photoreceptive layer 4104). ), or the distribution state is the opposite. Germanium atoms are contained in the first layer region (G) 105.

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. It is desirable to have a uniform distribution in the in-plane direction parallel to the surface of the lot.

In the present invention, the second layer region (S) provided in the first layer region (G) 105-L is as follows:
It does not contain germanium atoms, and by forming the first layer (I) 102 in such a layered structure, wavelengths in the entire range from relatively short and long wavelengths to relatively short wavelengths, including the visible light region, can be produced. A photoconductive member having low photosensitivity to light can be obtained.

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 distributed in the entire layer region without any number of million atoms, Since the distribution concentration C of germanium atoms in the layer thickness direction decreases from the support 101 side toward the second layer region (S) 106, the first layer region (G)
105 and the second layer region (S) 106, 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 first layer region (G) 105 substantially completely absorbs light on the long wavelength side, which is almost completely absorbed by the second layer region (S) 106. It can be absorbed into
Interference due to reflection from the surface of the support 101 can be prevented.

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

In FIG. 2 to FIG. 1O, the horizontal axis shows the distribution concentration C of germanium atoms, the vertical axis shows the layer thickness of the first layer region (G) 105 exhibiting photoconductivity, and the number indicates the support lot side. The position of the surface of the first layer region (G) 105 of 1. indicates the position of the surface of the first layer region (G) 105 on the side opposite to the support side. That is, the i- layer region (G) 105 containing germanium atoms is the first layer region (G) 105 of the gel manila 1, which is present from the t side to the t1 side, and the distribution pattern 11 in the layer thickness direction of the original r- layer.
A typical array of is shown.

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 with each other, to the position tl, germanium is The distributed concentration of atoms C is contained in the first layer (I) while taking a constant value of 01, and the distributed concentration gradually and continuously decreases from C2 from position 1 to interface position t. There is. At the interface position t□, the distribution concentration C of germanium atoms is C3.

In the example shown in FIG. 3, the first layer region (G) 1
The distribution concentration C of germanium atoms contained in 05 is from position 8 to position 1. A distribution state is formed in which the concentration gradually and continuously decreases from C4 until reaching position tT) and reaches the concentration C1.

In the case of FIG. 4, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 is constant at the concentration C0 from position tBJ to position t2, and from position t2 to position t
□ is gradually and continuously decreased until position t7
In the above, the distribution concentration CI'l 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 gradually and continuously decreased from the concentration C8 from position t to position t.
It is substantially zero at position tT.

In the example shown in FIG. 6, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in is at position 1
Between B and position 15, the concentration is constant at C9,
At position Kt, the concentration C8° is applied. Between the positions 1 and 1T, the distribution concentration C decreases in a monomodal manner from position t to position t.

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 C4° from position L5 to position tt□, and decreases numerically from concentration C52 to concentration C1 from position t4 to position tt□. It is said that the distribution state is as follows.

In the example shown in FIG. 8, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in is located,
From the position ta, the concentration decreases in a linear manner from CI4 to substantially zero.

In FIG. 9, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 decreases linearly from position t8 to position 1E with concentration c and from 5 to concentration CIG. , an example is shown in which the density CI4 is kept at a constant value between position t5 and position 1.

In the example shown in FIG. 10, the first layer region CG)
The distribution concentration C of germanium atoms contained in 105 is a concentration CI7 at the position t8, and is initially slowly decreased from this concentration C1□ until reaching the position t.
In the vicinity of position t6, the concentration decreases rapidly, and at position t6, the concentration c1? be done.

Between position t6 and position t7, the concentration is first rapidly decreased, and then gradually decreased to reach c1 at position LA, and between position E7 and position t&, it is extremely slowly decreased. and gradually decreases at position t, the concentration c2. leading to. Between position Eo and position t□,
Concentration c2. It is decreased according to a curve shaped as shown in the figure so that it becomes more substantially zero.

1: According to FIGS. 2 to 10, the first layer region (G
) As described above, some typical examples of the distribution state of germanium atoms in the thickness direction of the germanium atoms contained in the substrate 105 are explained. The first layer region (G) 105 is provided with a distribution state of germanium atoms having a portion where the above-mentioned portion 1fj If:2 degrees C is considerably lower on the interface tT side than on the support 101 side. One suitable example is the case where:

The first layer region (G
) 105 is preferably a localized region (A
, ), it is desirable that the interface be provided within 5IL in the layer thickness direction from the interface position.

”-2 The localized region (A) may be the entire layer region (L, ) from the interface position t8 to a thickness of 5 mm, or it may be a part of the layer region (L). In some cases.

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

The localized region (A) is defined as the distribution state of the germanium atoms contained therein in the layer thickness direction.
The maximum value Cmax of the ri concentration is preferably 1,000 atomic ppm or more, more preferably 5,000 atomic ppm or more, and optimally l×10 atomic ppm with respect to the sum of silicon atoms.
It is desirable that the layers be formed so that the distribution state described above can be obtained.

That is, in the present invention, the first layer region (G) 105 containing germanium atoms has a distributed concentration within 5 pL in layer thickness from the support 101 side (layer region from 1 to 5 pL thick). It is preferable to form the maximum value Cn+ax.

In the present invention, the content of germanium atoms contained in the first layer region (G) 105 may be determined as desired so as to effectively achieve the object of the present invention, but silicon atoms and Preferably 1 to 10
X 10 atomic ppm more preferably lOO~9,5
X I O' original-T-ppfil, optimally from 500 to
Preferably, the amount is 8XIO atoms ppm.

The distribution pattern m) of germanium atoms in the -th layer region ('G) 105 is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration of germanium atoms in the layer thickness direction C
is the free surface 107 of the light-receiving layer 104 from the support 101 side.
If a decreasing change towards the side is given, or vice versa, the required change rate curve of uni-distribution degree C can be designed arbitrarily as desired. The first layer region (G) 105 having such characteristics can be realized as desired.

For example, germanium D in the width of the first layer region (G) 105; By applying a change in the distribution concentration C to the distribution concentration curve of germanium atoms so as to reduce it as much as possible, it can be In addition to achieving high photosensitivity, it is also possible to effectively prevent interference with coherent light such as laser light.

In the present invention, the layer thickness T of the first layer region (G) 105,
is preferably 30λ to 50μ, more preferably 40
It is desirable that it be λ~40μ, optimally 50A~30μ.

Further, the layer thickness T of the second layer region (S) 106 is preferably 0.5 to 90. , more preferably 1-80 pL, optimally 2-50 pL. It is desirable that this is done.

The layer thickness TB of the first layer region (G) 105 and the second layer region (
S) The sum of the layer thicknesses T (TB+T) of 106 is based on the organic relationship between the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer (and the photoconductive member It is determined as desired when designing the layers.

In the photoconductive member of the present invention, the numerical range of (TB+T) is preferably 1 to 100 IL, more preferably 1 to 80 JL, and most preferably 2 to 50 #L.

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

In selecting the numerical values of the layer thickness TB and the layer thickness T in the case of 1., more preferably the relationship TB/T≦0.9, optimally TB/T≦0.8, is satisfied. It is desirable that the values of the layer thickness TB and the layer thickness T be determined so as to satisfy the following conditions.

In the present invention, when the content of germanium atoms contained in the first layer region (G) 105 is 1X10 atomic ppm or more, the layer thickness TB of the first layer region (G) 105 is
is desirably quite thin, preferably 30.
Hereinafter, it is more preferably 25 liters or less, most preferably 20 liters or less.

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 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 (I) 102, In the first layer (I) 102, there is a first region (1) 108. in which the distribution concentration C(N) within the nitrogen thickness has a value of C(1). It has 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, 1. Second. The third regions do not necessarily need to contain nitrogen atoms in any of these three regions, but the distribution concentration C (
3) is larger than both distribution concentrations C(1) and C(2), and at least one of distribution concentrations C(1) and C(2) is not O or distribution concentration C(1) , C
(2) must be unequal.

When either the distribution concentration C(1) or C(2) is O, the first layer (I) 102 is a region containing no nitrogen atoms. or second
region (2) 109, with 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) 1O2 as a region where no

In the present invention, the third region (3) l-10 having the largest distribution density C(3) among the three is the first region (I) while maintaining good photosensitivity characteristics. When J improves the dark resistance of 102, min! It is desirable that the value of Oa degree C(3) is set to a relatively low value, and that the layer thickness is sufficient 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 should be as thin as possible within the range where the effect of charge injection and ejection can be sufficiently obtained, and the thickness of the second fi (II) 10
In cases where it is desirable to provide the third region (3) 110 at a position as close as possible to the 1'l surface 107 side of 3 or the support body 101 side, the third region (3) 110 is the support 10
When the first region (1) 108 is provided closer to one side, the layer thickness of the first region (1) 108 is made sufficiently thin within the necessary range, and the layer thickness between the support 101 and the light-receiving layer 104 is reduced. It is provided mainly to measure the direction of adhesion.

When the third region (3) tio 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 41 concentrations C(1) and C(2), but is preferably 0.003 to 100 l, more preferably 0.003 to 100 l. 004
-80IL, optimally 0.005-50Ii.

Further, the layer thickness of the third region (3) 110 is 1 distribution concentration C(3
), but preferably 0.
003-80JL, more preferably 0.004-50μ
, most preferably from 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 scrap (I) 102, and The layer thickness is preferably 30 IL or less, more preferably 20 g or less, optimally 10 pL or less, when the third region (3) 110 is on the side of the support 101 provided close to it. First area (1) 108 or 1 [
The layer thickness of the region (2) 109 of the 1-yield surface 107 polarized nial ff12 is determined by the value of the distribution concentration C(3) of the g nitrogen atoms contained in the third region (3) 110 and from the point of view of productive efficiency. Although it may be determined as appropriate, it is preferably 5 pL or less, more preferably 3 pL or less, and most preferably lpL or less.

In the present invention, the maximum value of the nitrogen atom content distribution concentration C(3) is defined as #f is preferably 67 atomic %, more preferably 50 atomic %, most preferably 40 atomic %.

Further, the minimum value of the distribution concentration C(3) is preferably lO atoms ppm, more preferably 1
It is desirable to set the amount to 5 atomic ppm, optimally 20 atomic ppm. When the distribution concentrations C(1) and C(2) are not O, the minimum value is preferably 1 atom ppm, more preferably 3 atom ppm, and optimally 5 atom ppm relative to T (SiGeN). It is desirable that this is done.

In the present invention, the distribution state of nitrogen atoms is determined in the first layer CI
) 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. In 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, the distribution concentration of nitrogen atoms C, (N
) is C21 from position 1B to position t, and position t9
From position t, 1 is set as C2□, and from position tl+ to position t□ is set as C21.

In the example shown in FIG. 13, the distribution concentration C(N
) is C2 from position 1B to position t12, and position t
From 1□ to position t13, increase stepwise with C14,
From position t13 to position t1, C and y are decreased.

In the example shown in FIG. 14, the distribution concentration C(N) of nitrogen atoms is set to C2 from position tB to position t,4, increases stepwise to C27 from position t14 to position t15, and increases stepwise to position t+r.
The density C22 is lower than the initial density from position tT to position tT.

In the example shown in FIG. 15, the distribution concentration C(N
) is position t, and from position t14 is C2, and position t1
4 to position tI7, decrease to C1, and position 1.7
from position t1. It increases stepwise to C3I up to C3I, and decreases to C36 from position t+s to position t8.

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. (consisting of at least two regions of the third region), when the direction of photosensitivity and dark resistance is the main one.

It is provided so as to occupy the entire layer area of the first layer (I) 102, and in order to prevent charge injection from the free surface 11% 107 of the first layer (I) 102, it is provided near the free surface side. If the main purpose is to strengthen the adhesion between the support 101 and the photoreceptive layer 104, the photoreceptive layer 10
It is provided so as to occupy the support side end layer area of No. 4.

In the first case, the nitrogen atom content ri' contained in the layer region (N) is relatively small to maintain high photosensitivity, and in the second case the free content of the first layer (I) 102 surface 1
In order to prevent the injection of charge from 07, the content of nitrogen J9 is relatively high, and in the case of No. 3 11, support 1
In order to reliably strengthen the adhesion with 01, it is desirable that the content of nitrogen atoms be relatively large.

Also, for the purpose of achieving the former champion at the same time, support lo
Nitrogen atoms are distributed at a relatively high concentration on the t side and at a relatively low concentration at the center of the first layer (I) 102, and the free surface 107 of the first layer (I) 102 is In the surface layer region on the side, 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 lot, it may be selected as appropriate in terms of 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 ( (hereinafter referred to as rT (SiGeN)), preferably o, ooi to 50 atomic %, more preferably 0.002 to 40 atomic %, optimally 0.003 to 40 atomic %.
It is desirable that the content be 30%.

In the present invention, the layer region (N) is the first layer (I) 102
Or, even if it does not occupy the entire area of the first layer (I) 102, it occupies the layer thickness T of the first layer (I) 102 where the layer thickness of the layer region (N) is '■゛0. When the ratio is sufficiently large, it is desirable that the content of nitrogen atoms in the layer region (N) be sufficiently smaller than the above value.

In the present invention, if the layer thickness TO of the layer region (tS) occupies two-fifths or more of the layer thickness T of the first layer (I) 102, the layer region As a limit for the amount of nitrogen atoms contained in (N), T(SiGeN)
It is preferably 30 atom % or less, more preferably 20 atom % or less, and optimally 10 atom % or less.

In the present invention, the layer region (N) containing nitrogen atoms
As mentioned above, the support lot side or/and the second layer (
II) It is desirable to provide a localized region (B) containing nitrogen atoms at a relatively high concentration near the 103 side. In this case, the support lot and the first layer (I ) 102 and the acceptance potential can be further improved.

The localized region (B) is located 5 times from the surface of the first layer (I) 102 on the support 101 side and the second layer (II) 103 side.
It is desirable that it be established within

In the present invention, the localized region (B) is.

The layer region of the first layer (I) 102 from the support 101 or from the surface on the second layer (II) 103 side up to 5 layers thick (
In some cases, the entire layer region (LT) may be considered as the entire layer region (LT
).

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

In the localized region (B), the maximum value Cmax of the distribution concentration C(N) of nitrogen atoms is preferably 500 atomic ppm or more as the 4j state of the nitrogen atoms contained therein in the layer thickness direction,
More preferably 800 atomic ppm or less, optimally 10
It is desirable that the layer be formed in such a manner that a distribution state of 0.00 atomic ppm or more can be achieved.

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

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 (D) that controls conduction properties may be provided in part or all of the first layer (1) 102. Alternatively, the single layer region (PN) may be provided in part or all of the layer region (G) or (S).

As the substance (D) that controls such conduction characteristics, there are so-called impurities in the semiconductor field, which are considered uninvented and 1. For X and t, list the p-type impurity that gives p-type conductivity and the n-type impurity that gives n-type conductivity to silicon atoms or germanium atoms.
tjj is coming. Specifically, p-type impurities include atoms belonging to the periodic table (Group ■ atoms), such as boron (B), aluminum (All), and gallium (Ga).
, indium ('In), and IJum (1 sentence), and the most suitable one is 33.Ga.Also, n-type impurities include Atoms belonging to group V (group V atoms), such as phosphorus (P), arsenic (As)
, antimony (S b ), bismuth (Bi), etc., and particularly preferably used are P and As.

In the present invention, the needle containing the substance (D) that controls the conductive properties contained in the first layer (I) 102 has the conductive properties required for the second layer (I) 102 or The support 10 provided in contact with the second layer (I) 102 by 1μ
It can be selected as appropriate based on the organic relationship, such as the relationship with the properties at the contact interface with 1.

In addition, the substance CD that controls the conduction characteristics described above is added to the first layer (CD).
I) 10.2, said second layer (I) 1
When it is locally contained in a desired layer region of 02, especially when it is contained in the end layer region of the first layer (I) 102 on the side of the support, the side layer is in direct contact with the layer region. The content of the substance (D) that governs the conduction characteristics is appropriately selected by taking into consideration the characteristics of other layer regions provided in the conductive layer and the relationship with the characteristics at the contact interface with the other layer regions.

In the present invention, the content of the substance (D) that controls the conductive properties contained in the first layer (I) 102 is preferably 0. 1 to 5 x 104 atoms ppm of O, more preferably o, 5 to txto' atoms ppl! 1.
The optimum content is preferably 1 to 5 X I O3 atomic ppm.

In the present invention, the content of the substance (CD) in the layer region (PN) 4 containing the substance (D) that controls conduction properties is preferably 30 W, ppm or more, more preferably l. 50 atomic ppm or more, optimally lOO element f ppm or less, in the second case and l, the substance that governs the conduction properties (D) i±, the -i of the first layer (i) 102; It is desirable to contain it locally in the layer region of the first layer (
I) It is highly desirable that it be unevenly distributed in the support side end layer region (E) of 102.

Among the above, the substance controlling the conduction characteristics (D ), even if the substance (D) is the p-type impurity described above, when the free surface lO·γ of the photoreceptive layer 104 is subjected to polarization treatment, It is possible to effectively block the movement of the charge r- injected into the photoreceptive layer 104 from the support lO1 side force), and when the substance controlling the conduction characteristics is the n-type impurity, and t±, the free surface 107 of the photoreceptor layer lO4. C)! When subjected to 5-character di-Rf electrolysis Fl, it is possible to effectively prevent the movement of holes injected from the support 1O1 (III force) to the photoreceptive layer 104Φ.

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. , layer area (Z) excluding the support side end layer area (E, )
may contain a substance that controls the conduction properties of the other polarity, or a substance that controls the conduction properties of the same polarity may be added to the actual amount contained in the support side end layer region (E). It may be contained in a much smaller amount.

In such a case, the needle containing the substance (D) that controls the conductive properties contained in the layer region (Z) may be It is determined as desired depending on the needle contained, but
Preferably 0.001-1000 atomic ppm, more preferably 0.05-500 atomic ppm, optimally 0.1-1000 atomic ppm
It is desirable that the content be 200 atomic ppm.

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)! 1X is preferably 30 atomic ppm or less. In addition to the above-described case, in the present invention, the first layer (I) 102 includes a layer region containing a substance that controls conductivity having one polarity and a conductivity region having the other polarity. It is also possible to provide a so-called depletion layer in the contact layer region by providing it in direct contact with a layer region containing a substance controlling the properties. For example, in the first layer (I) 102, the layer region containing the p-type impurity and the nyJ,
A depletion layer can be provided by directly contacting a layer region containing impurities to form a so-called pn junction.

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 scum 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 (St, 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 pieces of Targera I, or using a mixed target of silicon atoms and germanium atoms, if necessary, He.

A raw material gas for supplying germanium atoms diluted with a diluting gas such as Ar, or a gas for introducing hydrogen atoms and/or halogen atoms as necessary, is introduced into the deposition chamber for snot tuttering to create a plasma of the desired gas. A first layer top m (G) IO'5 is formed by forming an atmosphere. In this sputtering method, if the distribution of germanium atoms is to be made non-uniform, the target may be snorted while controlling the gas flow rate of the raw material gas for supplying germanium atoms according to a desired rate of change curve. good.

In the case of the ion blating method, for example, polycrystalline silicon or crystalline 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 the raw material gas for supplying silicon atoms used in the present invention include Si H4°Si, H,
,S i,H,,S i4H,. Silicon hydride (silanes) in a gaseous state or that can be gasified, such as S i H4,
Preferred examples include S i2H.

Logs for supplying germanium atoms! 1 gases include G e H4, G e2H,, G e, H,
.

G e4H,,,G esH,2,G e,H,4,G
e7H,,,G e,H,,.

Germanium hydride in a gaseous state or that can be gasified as Ge9H26 is cited as one that can be effectively used, especially in terms of ease of handling during layer creation work, good efficiency of gel manila A supply, etc. I4, Ge, H4, Ge3
H, is preferred.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gases, halides, interhalogen compounds, and silane derivatives substituted with / Or a halogen compound that can be gasified is preferably mentioned. In addition, silicon 15 and halogen atoms are in a gaseous state or can be gasified as constituent elements. Silicon hydride compounds containing halogen atoms can also be mentioned as effective in the present invention.

Examples of halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, and CIF.

CIF,,B r F,,P r F3,IF,,I
Interhalogen compounds such as F7 and ICJJI-Br can be mentioned.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
i, F4, Si, F,, Si0 sentence. , S i B r,
Preferred examples include silicon halides such as the following.

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.
A car that forms 105 is created.

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 a gas such as Ar, H, He, etc. are introduced into a deposition chamber forming a first layer region (G) 105 at a predetermined mixing ratio and gas flow rate to generate a glow discharge. By forming a plasma atmosphere of these gases, the first layer region (G) 105 can be formed on the desired support 101J2, but it is possible to control the introduction ratio of atoms on water. In order to make the process even easier, a desired amount of hydrogen gas or silicon compound residue containing hydrogen atoms may be mixed with these gases to form a layer.

Moreover, each gas may be used not only in Chinese and German types but also in a mixture of multiple types 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.

In addition, when introducing hydrogen atoms into the first layer region (G) 105, a raw material gas for introducing hydrogen atoms, such as H2,
Alternatively, gases such as the silanes and/or germanium hydride described above may be introduced into the two deposition chambers 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 halogenated compounds such as HF, HCU, HBr, and HI are also used. hydrogen.

S i H, F2, S i H, I2, S i H2C
l,,5iHC1,,S i H,Br,,5iHB
r, isohalogen-substituted silicon hydride, and GeHF3, G
e H2Fm, G e H3P, G e HCl,
, G e H, Cl, , G e H3Cl, G e H
B r, , G e H, B r, 1. G e I (3
B r, G e HH3, G e H, I,, G e
Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides such as H and I, GeF4. G
eC1,, G e B r4, G e I+, G e
F, +, G e Cl,.

GeBr2. Gaseous or gasifiable substances such as kermanium halides such as GeI can also be mentioned as useful substances 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 introducing halogen in the present invention.

In order to structurally introduce hydrogen atoms into the first layer region (G) 105, in addition to the above, H7 or S i H4,S
i,H,,S i,H,,S i4H,. silicon hydride such as germanium or germanium compound for supplying germanium atoms, or GeH9, Ge, H
,,G e3Hf,G e,,H,. ,G e,H,2
,G e,H14,G e7H,,,G e,H,,,
G e91-1. , ; silicon or silicon compound for supplying the germanium hydride of the cap and silicon atoms;
This can also be done by coexisting in the deposition chamber and causing discharge.

In a preferred example of the present invention, the amount of hydrogen atoms, the amount of halogen atoms, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the ↓ -th layer region (G) 105 to be formed is: Preferably 0.01 to 40 atom%
, more preferably 0°05 to 30 at%, optimally 0.1
It is desirable that the content be 25 atomic %.

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 the hydrogen atoms or halogen atoms 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.
105 starting material (I) for forming the starting material excluding the starting material that becomes the raw material gas for supplying germanium atoms [starting material for forming the second layer region (s) IOE (TI)
) can be formed according to the same method and conditions as when forming the first layer region (G) 105.

That is, in the present invention, the second layer region (S) 106 composed of a-3t (H, Formed by law. For example, to form the second layer region (S) 106 composed of a-3i (H,X) by a glow discharge method,
Basically, the above-mentioned silicon atoms are supplied, and along with the raw material gas for supplying silicon atoms, if necessary, hydrogen nuclear power is required or/and / \ \\Product for introducing rogen atoms '1
A gas is introduced into a deposition chamber whose interior can be depressurized to generate a glow discharge within the deposition chamber, and a-3i (II,
A layer consisting of X) may be formed. In addition, when forming by a 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, hydrogen atoms or/and halogen;(
It is only necessary to introduce the necessary gas into the deposition chamber for sputtering.

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 a layer region (N) containing 10 mere atoms in the first layer (I), 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 (■) 102 described above, and the amount thereof can be controlled and contained in the formed layer. good.

When the glow discharge method is used to form the layer region (N), one selected from the starting materials for forming the first layer (I) 102 described above is used as a nitrogen atom introduction material. Starting materials are 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 desired mixture of a raw material gas containing silicon atoms as constituent atoms, a raw material gas containing nitrogen atoms as constituent atoms, and a raw material gas containing hydrogen atoms and/or halogen atoms as necessary 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 It is possible to mix and use a raw material gas containing silicon atoms as constituent atoms and a raw material gas containing three constituent atoms: silicon atoms, nitrogen atoms, and hydrogen atoms.

Alternatively, a raw material gas containing silicon raw material f and hydrogen atoms as constituent atoms may be mixed with a raw material gas containing nitrogen atoms as constituent atoms -r.

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 (N, ), ammonia (NHJ
), hydrazine (H,N N H,), hydrogen azide (
Nitrogen compounds such as scum-like nitrogen, nitride, and azide can be mentioned. Nitrogen halides such as nitrogen trifluoride (F, N) and nitrogen tetrafluoride (F, NJ) can be mentioned since they can also be introduced.

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.

Examples of raw material scraps for introducing oxygen atoms into the layer region (N) include oxygen (02) and ozone (0
3), -nitrogen oxide (NO), nitrogen dioxide (No2),
-Nitrogen dioxide (N, O), nitrogen sesquioxide (N, 0ρ, quadruple nitrogen oxide (N20.), nitrogen sesquioxide (N, Oρ, nitrogen trioxide (NO3)) composed of silicon atoms, oxygen atoms, and hydrogen atoms For example, disiloxane (H, SiO
5iH3).

Trisiloxane (II, S i OS i 11.OS
Examples include lower siloxanes such as 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/X- or 5i5N4 wafer,
Alternatively, sputtering may be performed in various gas atmospheres using a target wafer /\- containing a mixture of silicon atoms and S f3N4.

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 Si, N can be used as separate targets, or by using a single target in which silicon atoms and Si, N are mixed, a dilution gas can be used as a sputtering gas. Sputtering may be carried out in an atmosphere of 1 or in a gas atmosphere containing at least hydrogen atoms and/or halogen atoms as constituent atoms.

As the raw material gas for nitrogen atom introduction, the raw material gas for nitrogen atom introduction among the raw material gases shown in the glow discharge example described above can be used as an effective dregs 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
/ p t hprofile) to form a layer region (N) in the case of a glow discharge, a minute tri'm
A starting material gas for introducing nitrogen atoms whose degree C(N) is to be changed may be introduced into the deposition chamber while the gas flow rate is appropriately changed according to a desired rate of change 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 an externally driven motor. At this time, it is also possible to obtain a desired content rate curve by controlling the flow rate according to a rate of change curve that has been prepared in advance, using a microcomputer or the like.

When forming the layer region (N) by a sputtering method, the desired distribution state (d
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 Tokoro 9! This can be done by changing it appropriately according to the following.

Second, as a target for sputtering, for example, the mixing direction of silicon raw material f- and 313 N4 is changed 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 in a gaseous state during layer formation. Then, it may be introduced into the deposition chamber together with other starting materials for forming the second region (S) 106. It is preferable to use a starting material for the introduction of Group (I) atoms that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. . Specifically, B2)1. ,B4H,,BS horse,B,H,,,B
,H,. ,B ,H,2,B.

Examples include boron hydride of H, ;', boron halides such as BCl3, BBr, and the like. In addition, A u Cl
,,GeC sentence 1,Ge(CI(ρ,InCu,,T u
Cu, etc. can also be mentioned.

In the present invention, effective starting materials for introducing Group V atoms include PH?
, the hydrogen north end of P Yu II4, etc., PH, cI, P F,,
P Fi, P Cu3, P Clr, PBr3, PBr
r.

An example is the northern end of halogen such as PH Yo. In addition, A s
H? , A s Fa, A s Cfar, A s B
ry, A s Fr.

SbH3, Sb Fy, with SbF, 5bCJJp, 5
bCJJζ.

B i Hz, B i CQ3, B i B r3. etc. can also be mentioned as effective starting materials for the introduction of Group V atoms.

In the present invention, the layer thickness of the layer region (PN) that constitutes the first layer (I) 102, contains a substance that controls conduction properties, and is unevenly distributed on the support lot side is as follows: Appropriately determined according to 1/1 according to the characteristics required for the layer region (PN) and other layer regions forming the first layer (I) 102 formed in the layer region (PN) j- However, the limit is preferably 30 or more people, more preferably 40λ or more, and optimally 50 people or more. In addition, the content of the substance that controls the conduction characteristics contained in the Jiff recording layer (region) is 30 atoms
Preferably more than pm.

In the photoconductive member 100 shown in FIG. 1, the second layer (II) 103 formed on the first layer (I) 1021
has a free surface and is mainly characterized by temperature 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.

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

The second layer (II) 103 in the present invention is an amorphous material (hereinafter ra-(Six
Ct=x) y(H,X)+-y''i[''shi, O<x,
y<1. ).

The second layer 103 (II) composed of a - (SixC+ -X) y (H, This is accomplished by ion plantation method, ion brating method, electron beam 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. It is relatively easy to control the manufacturing conditions for manufacturing the photoconductive member, and it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the second layer (II) 103 to be manufactured. The glow discharge method or sputtering method, which has the following advantages, is preferably employed.

Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same system to form the second layer (II) 10.
3 may be formed.

In order to form the second layer (TI) 103 by the glow discharge method, a - (S'+xC+-x)y(H,X)+
-7 The raw material gas for forming 7 is mixed with a dilution gas at a predetermined mixing ratio as necessary, and introduced into the deposition chamber for vacuum deposition where the support 101 is installed, and the introduced gas is Converts into gas plasma by causing glow discharge,
The first layer (I) has already been formed on the support 101.
)102 JZ a −(S ixc+ −x) y(
H, X)+-y may be deposited.

In the present invention, a-(S lxC+-x)y (H,
X) As raw material scraps for r7 formation, silicon atoms,
At least one of carbon atoms, hydrogen atoms, and halogen atoms
Most gaseous substances or gasified substances having two constituent atoms can be used.

An original in which a silicon atom is one of the constituent atoms of a silicon atom, a carbon atom, a hydrogen atom, or a \\rogen atom; l
When gases are used, for example, a raw material gas whose constituent atoms are silicon atoms, a raw material gas whose constituent atoms are carbon atoms, and, if necessary, a raw material gas whose constituent atoms are hydrogen atoms or/and halogen. Atoms are the constituent atoms of the raw material gas and the desired 11! The combined ratio is 411! or a raw material gas containing silicon atoms as constituent atoms and a raw material gas containing carbon atoms and hydrogen atoms or/and raw material scum containing halogen)+:Cf- as constituent atoms, This can also be mixed at a desired mixing ratio or
A raw material gas consisting of - as an atom and a raw material gas consisting of silicon atoms, carbon atoms and hydrogen atoms, or a raw material gas consisting of three constituent atoms of silicon atoms f-1 carbon atoms and halogen atoms. It can be used in combination with 1 dregs.

Alternatively, a source gas containing carbon atoms as constituent atoms may be combined with an original gas composed of silicon atoms and hydrogen atoms, or a mixture of silicon atoms and halogen atoms may be used. A raw material gas containing carbon atoms as constituent atoms may be mixed with a raw material gas containing carbon atoms as constituent atoms.

In the present invention, halogen atoms contained in the second layer (II) 103 are preferably fluorine, chlorine, bromine,
Iodine, especially fluorine, 1! A element is preferable.

In the present invention, raw material scraps that can be effectively used to form the second layer (IT) 103 include:
Examples include substances in a scum state or substances that can be easily gasified at room temperature and pressure.

In the present invention, 5IH4゜Si>H6, S
1zHt, S i4H,. Siane
Silicon hydride scum such as the following, carbon atoms and hydrogen atoms as constituent atoms, such as Yuwa hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene having 2 to 3 carbon atoms Hydrocarbons, single halogens (4, hydrogen halides, )＼
Examples include interlockenic compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides.

Specifically, methane (CH, J) is a saturated hydrocarbon.
, ethane (C2H&), propane (CaHr), n-
Butane (n'j(lo), penta7 (CtH+x)
, ethylene hydrocarbons include ethylene (C-H4
), propylene (CyoH&), butene-1 (C4Ht
), butene-2 (CJ(g), isobutylene (C
and Hv), pentene (C==-H+o), acetylene hydrocarbons include acetylene (C,H,), methylacetylene (C3H4), butyne (Cd(b)), and interhalogen compounds include fluorine and chlorine. , bromine, iodine halogen gas, hydrogen halide, FHlHI
, He sentence, HIl r, as an interhalogen compound,
B r F , CI F , CI Fa , CI F
r, BrFC-.

B r Fr, I F,, I F,, I(4, IBr,
As silicon halide, SiF÷, Si2F, and Si
C sentence 4, S i CIgB r, S i C! 1C
LB ru, Si CI Br,, SiC Matata 3,
S f B r4, halogeno-substituted silicon hydride,
S i H3P,, S i H-C! It, 5iHC island S 1H3Cl, S i H3I3 r, 5iHJ
3r,, S i HB ra, water Δ-element is S
i H4, S i Yuuma, S i4H edition of Silan
ane) Class 1, etc.

In addition to these, CF4, CCl, CB r4, CHFa
, CH, F, , CHiF , CH2Ol, CHiB r
, CH, I, halogen-substituted paraffinic hydrocarbons such as C5HcC, fluorinated sulfur compounds such as SF<, SF4, 5t(OH-)+, S i (CjHθ4A4
Alkyl silicide or 340 sentences (c H,)? , SiC p(C1(□)2.5iC1yCHs) and other silane derivatives such as halogen-containing alkyl silicides can also be cited as effective.

These second layer (II) 103 forming substances contain silicon atoms, carbon atoms, halogen element f-, and optionally hydrogen in a predetermined composition ratio in the second layer (II) 103 to be formed. It is selected and used as desired when forming the second layer (II) 103 so that it contains atoms.

For example, S can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and can form a layer with desired characteristics.
i (CHJ (and S + HCl as a substance containing a halogen atom, Si H, C11, Si CfL
4, or S i IbC etc. at a predetermined mixing ratio and introduced in a gaseous state into the apparatus for forming the second layer (II) 103 to cause glow discharge.
A second layer (II) 103 consisting of ixC+-X)V CC1+H)+y can be formed.

In order to form the second H(II) 103 by the sputtering method, a medium-crystalline or polycrystalline silicon wafer, a one-dimensional crystalline wafer, or a wafer containing a mixture of silicon atoms and carbon atoms is used as a target. , these may be performed by sputtering in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements, if necessary. for example,
When used as a silicon wafer target, the raw material residue for introducing carbon atoms and hydrogen atoms or/and halogens is diluted once with diluted gas as necessary, and then washed.

The silicon wafer may be sputtered by introducing these gases into a deposition chamber to form a gas plasma of these gases. Alternatively, by using silicon atoms and carbon atoms as separate targets, or by using a single target in which silicon atoms and carbon atoms are mixed,
Sputtering may be performed in a gas atmosphere containing hydrogen atoms and/or halogen atoms, if necessary. As the material gas for introduction of carbon atoms, hydrogen atoms, and halogen atoms, the second! (II) 103-forming materials can also be used as effective materials in sputtering methods.

The diluting gas used when forming the second layer (H) 103 by the glow discharge method or sputtering method in Ki95 Ming includes a mixture of gases such as He, Ne, and A.
r, etc. can be mentioned as suitable ones.

The second layer (II) 103 in the present invention is carefully formed so that its required properties are imparted as desired. That is, substances whose constituent atoms are silicon atoms, carbon atoms, hydrogen atoms and/or halogen atoms as necessary,
Its structure varies from crystalline to amorphous depending on its production conditions, and its gas-physical properties range from conductive to semiconductive to insulating, and from photoconductive to non-photoconductive. In the present invention, a that has desired characteristics according to the purpose is used.
-(S ixc+ -x) y(H, For example, in order to provide the second layer (II) 103 with the main purpose of improving electrical voltage resistance, a-(
S1xc1-X)Y (H,'

In addition, when the second layer (II) 103 is provided, the degree of electrical insulation is relaxed to some extent,
As an amorphous material that has a certain degree of sensitivity to irradiated light, a − (S : x C + − x ) y (H,
)+-y is created.

On the surface of the first layer (I) 102, a−(Sixc+X
)y (H,X)+-y second layer (II)1
The temperature of the support 101 during layer formation is an important factor that influences the structure and properties of the formed layer. (SixC.

It is desirable that the temperature of the support during image formation be tightly controlled so that -x)y (H,X)+-y can be produced as desired. In the present invention, the formation of the second layer (II) 103 is carried out by selecting an appropriate optimum range in accordance with the method of forming the first layer (II) 103 in order to effectively achieve the desired purpose. However, the temperature of the support during image 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. However, when forming the second layer (II) 103 using these layer forming methods, the discharge temperature during layer formation as well as the above-mentioned support temperature This is one of the important factors that influences the characteristics of a-(S1xc1-x)yX+-y, which generates power.

a having the characteristics for achieving the object of the present invention;
-(Si*c+ -x)yx, -y can be effectively created with high productivity under the discharge power conditions of 5, preferably from 10 to 300 W, more preferably from 20 to 250 W, and most preferably from 50 to 300 W. It is desirable that the power be 200W.

The gas pressure in the deposition chamber is preferably between 0.01 and I Torr.
, more preferably, one boat with a pressure of 0, 1 to 0, 5 Torr.

In the present invention, the support temperature and hair emitting power for creating the first layer (II) 1O3 are preferably within the ranges described above, but these layer creation factors are independent. The desired characteristic a - (S 1xCI-x) y (H, x)
It is desirable that the optimum value of each layer formation factor be determined based on the organic relationship so that the second layer (II) 103 consisting of ly is formed.

Second layer (II) 103 in the photoconductive member of the present invention
The carbon atoms contained in the second layer (II) 103
This is an important factor for forming the second layer (II) 103 that provides the desired characteristics to achieve the object of the present invention. Second layer (■■) 1 in the present invention
The amount of carbon atoms contained in 03 is the same as that of the second layer (II).
It can be determined as desired depending on the type of amorphous material constituting 103 and its characteristics.

That is, the general formula a-(SixC1-x) V(H,
The amorphous material denoted by

However, O < a < 1), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as r a
It is written as -(Sibc+-b)cHl-cJ.

However, Orb, cal), and non-Shinaga material I (hereinafter ra-(SjdC+-d)), which is composed of silicon atoms, carbon atoms, halogen atoms I', and hydrogen atoms as necessary.
It is written as e(H,X)I-eJ. However, O<d, e<
It is classified as 1).

In the present invention, the second layer (II) 103 is a-S
iac+ -a, the second layer (II) 1
The carbon atom star contained in 03 is preferably 1XIO
It is desirable that the content be 90 atomic %, more preferably 1 to 80 atomic %, most preferably 10 to 75 atomic %. That is, if expressed in 'rL a-3iaC+-a(7)a(1), a is preferably O, l-0,99999, more preferably 0.2 to 0.99, optimally 0. .25-0.9
It is.

In the tree invention, the second layer (II) 103 is a −(S
1bC1-b)c H+-c, the amount of carbon atoms contained in the second layer (II) 103 is preferably lXl0 to 90 at%, more preferably 1
The content of hydrogen atoms is preferably 1 to 40 at%, more preferably 2 to 35 at%, most preferably 10 to 80 at%. A hydrogen content of 5 to 30 atom % is desirable, and light guide members formed when the hydrogen content is in this range are excellent in practice and can be sufficiently applied.

That is, in the above expression a-(S 1bCrb) Hl-c, b is preferably 0.1 to 0.99999, more preferably 0.1 to 0.99, and most preferably 0.15 to 0. .9
, C is preferably 0.6 to 0.99, more preferably 0.
It is desirable that the angle is 65 to 0.98°, most preferably 0.7 to 0.95.

The second layer (II) 103 is a - (S id Q-d
)e (H,X)1-,e, the content of carbon atoms in the second layer (11) 103 is preferably l %, more preferably 1 to 90 atomic %, optimally 10 to 80 atomic %, and the content bt of halogen atoms is preferably 1 to 20 atomic %, more preferably 1 -1
It is desirable to set the content to 8 at.%, most preferably from 2 to 15 at.%, and the photoconductive member produced when the rogen atom content is in this range will be sufficiently applied to practical situations44)
Furthermore, it is desirable that the WI is lower than the required WI.

That is, the previous a −(S idc+−d) e (H,
)+-e, d is preferably 0.
．． 1 to 0.99999, more preferably 0.1 to 0.99
, optimally 0.15-0.96f or 0.8-0
, 99. More suitable is 0.82 to 0.99. The optimum value is 0.85 to 0.98! Delicious.

The number range of the layer thickness of the first and second layer (II) 103 in the wood invention is one of the important factors for effectively achieving the object of the invention, It can be determined as desired depending on the intended purpose.

In addition, the layer thickness of the second layer (II) 103 is determined by the relationship between the layer i; the star of carbon atoms contained in (II) 103 and the layer thickness of the first layer (I>102). It needs to be determined appropriately based on the organic relationship according to the characteristics required for each layer area! It is also desirable to consider this.

The layer thickness of the second layer (II) 103 in the present invention is preferably 0.003 to 30 p, more suitable niha O, oo4 to 2oIL, maximum M i: Lto, 005
~Log is desirable.

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

Examples of the conductive support include NiCr, stainless steel, A1. Cr, Mo, Au, Nb.

Examples include metals such as Ta, V, Ti, 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 314ide, polystyrene, polyamide, glass, ceramics, paper, etc. are usually used. be done. These electric M! Preferably, at least one surface of the two-sided female support is electrically conductively treated, and is preferably provided with another layer on the electrically conductive surface.

For example, if it is a crow, NiCr1, A
n, Cr, Mo, Au, Ir, N b , T a , V
, T 1. P L , P d , I nzo2゜S n (b, I To (T II!lOJ+ S
Conductivity is imparted by providing a thin layer of +1q consisting of NiCr, Au, Ag, Pb, etc., or if it is a synthetic resin film such as a polyester film.
Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, ■
A thin film of metal such as , Ti, PL, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, so that conductivity is imparted to the surface. .

The support 101 may have any shape such as a cylinder, a belt, or a plate, and the shape may be determined as desired. For example, the photoconductive member 100 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 appropriately determined so as to form a desired photoconductive member, but if workability is required as a lead or h member, the thickness of the support 101 may be determined to have a sufficient function as a support. It is made as thin as possible within the range of performance. However, in such a case, the thickness of the support 101 is preferably set to 10 mm or more from the viewpoint of manufacturing and handling of the support, 2. mechanical strength, etc.

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

An example of a photoconductive member manufacturing apparatus is shown in No. 16 II.

In the figure, gas cylinders 1102 to 1106 are sealed with raw material gases for forming the photoconductive member of the present invention. As an example, 1102 is SiH4 gas diluted with He (purity 99. 999%, hereinafter S i
Abbreviated as H4/He. ) cylinder, 1103 is G e H4 residue diluted with He (purity 99.999%, hereinafter abbreviated as G e H4/He) cylinder, 1104 is 1
105 is He waste (1i99.999% pure) cylinder, 1
106 is an H gas (purity 99.999%) cylinder.

To allow these gases to flow into the opposite chamber 1101, valves 1122 to 112 of gas cylinders 1102 to 1106 are used.
6. Check that leak valve 1135 is closed, and inlet valves 1112-1116. Outflow valve 1
117 to 1121, confirm that the auxiliary valves 1132 and 1133 are open, and first open the main valve 1134.
is opened to exhaust the reaction chamber 1101 and each gas pipe. Next, when the vacuum gauge 1136 reads 6T or approximately 5 x 107 orr, the auxiliary valve 113
2,1133, close the outflow valves 1171-1121.

Next, to give an example of forming a photoreceptive layer on the cylindrical substrate 1137 as a support, S i H,/He gas from the gas cylinder 1102,
GeH4/He gas from gas cylinder 1103, NH sludge from gas cylinder 1104, /Help 1122,1
Open 123.1124 and exit [l positive gauge 1127.1
By adjusting the pressure at 128°1129 to 1 kg/cm'' and gradually opening the inlet valves 1112, 1113, 1114, the mass flow controller 11071108
．． 1110 respectively. Then the outflow valve 1117.111B.

1119, the auxiliary valve 1132 is gradually opened to allow each scum to flow into the reaction chamber 1101.

At this time, S i H4/ He gas flow rate and G e H
4/ Adjust the outflow valves 1117, 1118° and 1119 so that the ratio of He gas flow rate and N H gas flow rate 77' becomes the desired value, and also adjust the pressure inside the reaction chamber 1101 to the desired value. Adjust the main valve 1134 to 1 while checking the reading on the vacuum gauge 1136.
The temperature of 37 is set to 50 to 400 by heating heater 1138.
After making sure that the temperature is set in the range of °C,
A glow discharge is generated in the reaction chamber 1101 by setting the power source 1140 to a desired power, and at the same time applying methods such as G e ) (4/ He gas and drive or external drive motor) according to a pre-designed rate of change curve. The apertures of the help/helps 1118 to 1120 are appropriately changed to adjust the NH gas meteor, thereby controlling the distribution concentration C(N) of germanium atoms and nitrogen atoms contained in the formed layer.

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 1116 is completely closed, and the same conditions and procedures are followed except for changing the discharge conditions as necessary. By maintaining the desired JP-A glow discharge, a second layer region (S) 106 substantially free of germanium atoms can be formed in the first layer region (G) 105J-.

First layer region (G) 105 and second layer region (S) 1
06 In order to contain the substance (D) that controls conductivity, the first layer region (G) 105 and the second layer region (S
) 106, for example, a gas such as B2H6, PH, 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, C2H, . If necessary, dilute with diluent gas such as He and add to reaction chamber 1.
101 and generate glow discharge according to desired conditions.

In order to contain halogen atoms in the second layer (II) 103, for example, add S i F4 gas and 02 horse gas, or add S i H2 gas thereto and form the second layer (II) in the same manner as above. 103 may be formed.

Needless to say, all the gas outflow/outflow valves other than the gas valves necessary for forming each layer must be closed, and when forming each layer, the residue used to form the previous layer may leak into the reaction chamber. 1101 and the gas piping leading from the outflow valves 1117 to 1121 to the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary valves 1132 and 1133 are opened, and the main valve 113 is closed.
If necessary, fully open 4 and evacuate the system to high vacuum.

The amount of carbon atoms contained in the second layer (II) 103 can be determined by, for example, changing the flow rate ratio of SiH4 gas and C2H gas introduced into the reaction chamber 1101 in the case of glow discharge as desired. Alternatively, when forming a layer by sputtering, by changing the sputter area ratio of the silicon unihat graphite wafer when forming the target, or by changing the mixing ratio of silicon powder and graphite i powder and molding the target. It can be controlled as desired. The amount of the halogen source f− contained in the second) M(II) 103 is determined by the amount of the halogen source f- contained in the reaction chamber 110
This is accomplished by adjusting the flow rate when introduced into 1.

Further, while one layer is being formed, 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, a sample (sample No. 1-1-17-
6) respectively (Table 2).

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 Fig. 1 δ shows the nitrogen atom content distribution concentration.

This way! Each sample was placed in a charging exposure experimental device (15), corona charged with OKV for 0.3 seconds (see), and immediately irradiated with a light image.

The light image uses a tungsten lamp light source, and
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 charged developer (including toner and carrier). 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.

2, an 810 nm GaAs semiconductor laser (10 mW) was used as the light source instead of a tungsten lamp.
Image quality evaluations of toner transfer images were obtained for each sample under the same toner image forming conditions, except that an electrostatic image was formed using .

Example 2 A cylindrical AIJ was manufactured using the manufacturing apparatus shown in Fig. 16.
, Samples (Samples Nos. 211 to 27-El) as electrophotographic image forming members were prepared under the conditions shown in Table 3 (Table 4) 6 Content of germanium atoms in each sample The distribution concentration is the first
7 and FIG. 18 shows the nitrogen atom content distribution concentration C.

When each of these samples was subjected to the same image evaluation test as in Example 1, all samples t'+ gave high quality toner transfer images. Also, for each sample, 38°
When a repeated use test was conducted 200,000 times in an environment of 180% RH, no deterioration in image quality was observed even with the λ deviation test case 1.

Example 3 A china-shaped A was manufactured using the manufacturing apparatus shown in FIG.
Samples as electrophotographic ITJ (elephant) forming members (sample Nos. 31-1 to 37-8) were placed on the text base under the conditions shown in Table 5.
(Table 6).

In each sample], the content of germanium atoms')I
The β concentration is shown in FIG. 17, and the nitrogen atom content distribution concentration is shown in FIG.

When the same image evaluation test I as in Example 1 was conducted on each of these samples, high-quality toner transfer images were obtained even with I7X deviation. 3
When a repeated use test I was conducted for 200,000 times in an environment of 8° C. and 80% R11, no deterioration in image quality was observed even when wiping at an angle of 1 and X.

Example 4 A cylindrical AI was manufactured using the manufacturing apparatus shown in FIG.
Samples (sample Nos. at-t to 47-13) as electrophotographic image forming members were prepared on substrates 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 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.

Toga 1 (Zou 11 Hydra ← + Yo plan half-sieved handgo; Kipesha Rorei - in 51 volumes) - m -, ・Ten 4 image ・ Image 1 giant body i Go 5 Example closing layer (Example 1 except that the production line f1 of IIHO3 was set to each condition shown in Table 1), 11-1.12-1.13
Article I similar to -1: and each of the electrophotographic imaging members according to Chien (sample positive, +1-11 to 11-1 to 8
．． 12-1-1~12-18.13-11~13-1-
24 samples of 8) were created.

Each of the electrophotographic image forming members obtained in this way is individually installed in a copying machine, and the electrophotographic image forming members corresponding to each example are prepared using the same method 1 as described in each example. For each, the overall image quality of the transferred image was evaluated and the durability was rated 11 times after repeated and continuous use.

Comprehensive image quality evaluation of transferred images of each sample and repeated I! I!
Table 1 shows the results of durability evaluation after continuous use.

When forming W (II) 103, the target area ratio of the silicon wafer and graphite was changed to form the layer (II).
Each of the image forming members was created in exactly the same manner as Sample No. 11-1 of Example 1 except that the content ratio of silicon atoms and carbon atoms in +03 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.

Example! Sample 11b of Example 1 except that when forming layer (II)+03(7), the flow rate ratio of S i H4 gas c2H4 gas was changed to change the content ratio of silicon atoms and carbon atoms in layer (II) 103. , 12-1, each of the image-forming members was produced by a method completely similar to that of Example 1.

After repeating the process up to transfer approximately 50,000 times2 for each of the image forming members prepared in this way using the method described in Example 1, image evaluation was performed, and the results shown in Table 1 were obtained. Ta.

The image forming member was prepared in exactly the same manner as Sample No. +3-1 in Example 1, except that the content ratio of silicon atoms and carbon atoms in the first layer (II) +03 was changed by changing the flow rate ratio of CH gas. I created each one. After repeating the image forming, developing, and cleaning steps as described in Example 1 approximately 5 times for each image forming member thus obtained, image evaluation was performed, and the results shown in Table t0 were obtained. Obtained.

Each of the image forming members was created in exactly the same manner as in Sample No. +1-1 of Example 1, except that the thickness of the layer (II) 103 was changed. As described in Example 1, the steps of image formation, development, and cleaning were repeated.4 The results shown in Table μ were obtained.6 Table 6. is shown below.

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

[Brief explanation of drawings]

Fig. 1 is a schematic layer structure diagram for explaining the layer structure of the light guide member of the present invention, Fig. 2 to Fig. 10, and Fig. FIG. 16 is a schematic explanatory diagram of the apparatus used in the present invention, FIG. 17, and FIG.
Figure 7' is a distribution state diagram showing the content distribution concentration state of each atom in two embodiments of the present invention. 100... Light/n-type member 101... Support 102... First layer (I) 103... Second layer (II) 104... Light receiving layer Fig. 1 +07100 Second Figure 4 Figure 5 121-C C C Figure 13 C (N) Figure 14 Figure 15 C (N)

Claims (8)

[Claims] (1) A support for a photoconductive member and an amorphous material containing germanium atoms, comprising a first layer region (G) provided on the support and a non-crystalline material containing silicon atoms. a second layer region (S) made of a crystalline material and exhibiting photoconductivity and provided on the first layer region (CG); . a photoreceptive layer made of a second layer made of an amorphous material containing silicon atoms and RJ atoms; the first layer contains nitrogen atoms and nitrogen atoms in the layer thickness direction; The distribution density of //,C'(1),,C(3),C
(2) tt6 first area (1), third area (3), t
A photoconductive member characterized in that it has 52 regions (2) in this order from the support side (however, C(3) > C(2)
, C(1)-c, and at least one of C(1) and c(2) is not O, or C(1) and C(2) are not equal). (2) The photoconductive member according to claim 1 XJI, wherein at least one of the first layer region (G) and the second layer region (S) contains hydrogen atoms. (3) The photoconductive member according to Claims 1 and 2, wherein at least one of the first layer region CG) and the second layer region (S) contains a halogen atom. . (4) The photoconductive member according to claim 1, wherein the distribution shape fffi of the gel ==tl, original -r- in the first layer region (I) is non-uniform. (5) The photoconductive member according to claim 1, wherein the germanium atoms are uniformly distributed in the first layer region. (6) The photoconductive member according to claim 1, wherein the first layer contains a substance that controls conductivity. (7) The photoconductive member according to claim 6, wherein the substance that controls conductivity is an atom belonging to Group 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.