JPS60140258A - Photoconductive member - Google Patents

Abstract

PURPOSE:To improve and stabilize electrical, optical, and photoconductive characteristics, improve photosensitivity characteristics especially in the long wavelength region, and enhance mechanical strength and durability, by forming a photoreceptor having a specified layer structure made of a-SiGe(H, X) on a substrate. CONSTITUTION:The photoconductive member 100 consists of a substrate 101 and a photoreceptor 104 formed on it composed of the first layer 102 consisting of a layer region G105 made of amorphous Ge(a-Ge), and the second photoconductive layer region S106 formed on the region G; and the second layer 103 formed on the layer 102 and made of a-SiO. The first layer 102 has a region Y contg. N in a concn. distribution in the layer thickness direction continuously increasing from the substrate 101 side to the photoreceptor 104 side. At least one of the regions G, S contains H and halogen, and the concn. distribution of Ge in the region G may be uniform or nonuniform. This region G also contains a conductivity governor, such as an element of group III or V.

Description

Detailed Description of the Invention The great invention is a photoconductive member that is sensitive to electromagnetic waves such as light (here, light in a broad sense refers to ultraviolet light, visible light, infrared light, X-rays, gamma rays, etc.). Regarding.

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 has 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. In particular, in the case of an electrophotographic image forming member incorporated in an electrophotographic apparatus used in an office as a business machine, the above-mentioned
Pollution-free nature during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as a-9i) is a photoconductive member that has recently attracted attention.
Publication No. 855718 describes an electrophotographic image forming member,
Sec. Publication No. 2933411 describes an application to a photoelectric conversion/reading device.

According to Heigo et al., a conventional photoconductive member having a photoconductive layer composed of a-Si has a low dark resistance value and a low photosensitivity.

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 moisture resistance and stability over time, and it is necessary to improve overall characteristics.

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

Furthermore, a-3[ has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, making it difficult to match with semiconductor lasers currently in practical use. However, when using commonly used halogen lamps and light lamps as light sources, there is still room for improvement in that they cannot effectively use light on the longer wavelength side.

In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases,
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 Elementary atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, However, problems may arise in the electrical or photoconductive properties of the formed layer.

That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in the dark area. This occurs in many cases.

Furthermore, if the thickness of one layer exceeds 100 g, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes after it is left in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are some shortcomings to be solved in terms of stability over time. be.

Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the above-mentioned points, and has the object of applicability and applicability to A-3J as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive research and consideration from this perspective, we have discovered an amorphous material that has silicon atoms and germanium atoms as its base and contains at least either hydrogen atoms or halogen atoms, so-called hydrogenated amorphous silicon germanium, and halogenated amorphous silicon. Germanium or halogen-containing hydrogenated amorphous silicon germanium (hereinafter referred to as RA-3i)
G + (H, The conductive material not only exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in all respects, especially as a photoconductive material for electrophotography. The present invention is based on the discovery 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, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member that is durable, does not cause deterioration even after repeated use, and has no or almost no residual potential observed.

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

Still another object of the present invention is to provide excellent adhesion between a layer provided on a support and the support and between each of the laminated layers, and to have a delicate and stable structural arrangement; An object of the present invention is to provide a photoconductive member with high layer quality.

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

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

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

The photoconductive member of the present invention is composed of a support for the photoconductive member, an amorphous material containing germanium atoms, and a first layer region CG) provided on the support, and a first layer region CG) containing silicon atoms. The first layer region (
G) a photoconductive second layer region (S) provided thereon;
and a second layer provided on the second layer and made of an amorphous material containing silicon atoms and oxygen atoms; The layer has a layer region (N) containing nitrogen atoms, and the layer region (N) has a distribution concentration C(N') of nitrogen atoms in the layer thickness direction.
) has a region (Y) that continuously increases from the support side toward the photoreceptive layer side.

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

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

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

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

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

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

FIG. 1 is a schematic configuration diagram 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 (1)) 103 provided in the second layer (1). First layer (1
) 102 and the second layer (IL) 103 form the photoreceptive layer 1
Configure 04.

The first layer (I) 102 is made of an amorphous material (hereinafter ra-Ge) containing germanium atoms and, if necessary, at least one of silicon atoms, hydrogen atoms, and halogen atoms.
(Si, H, (hereinafter ra-'5t(H,X
) J), and is provided on the first layer region (G) 105 and exhibits photoconductivity (S) 10
6.

The germanium atoms may be contained in the first layer region (G) 105 so as to be uniformly distributed throughout the first layer region (G) 105, or evenly distributed in the layer thickness direction. However, the distribution concentration may be non-uniform. In either case, germanium atoms are uniformly distributed in the first layer region (G) 105 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 evenly in the layer thickness direction of the first layer (1) 102, and on the side opposite to the side where the support 101 is provided (the free surface 107 of the photoreceptive layer 104). side)
The support 101 side (the photoreceptive layer and the support 1
The germanium atoms are contained in the first layer region (G) 105 so that they are distributed more toward the interface side with the first layer region (G) 105 or vice versa.

In the photoconductive member of the present invention, as described above, the distribution state of germanium atoms contained in the first layer region (G) 105 is as described above in the layer thickness direction, and the distribution state of the germanium atoms is as described above. It is desirable to have a uniform distribution in the in-plane direction parallel to the 1010 surface.

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

Further, in one of the preferred embodiments, the distribution state of germanium atoms in the first layer region (G) 105 is such that germanium atoms are continuously and evenly distributed throughout the entire layer region, and germanium atoms are evenly distributed throughout the layer region. Since the distribution concentration C of atoms in the layer thickness direction decreases from the support 101 side toward the second layer region (S) 106, the first layer region (G) 1
05 and the second layer region (S) 106. ! l: (7) has excellent affinity between the two, and as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the end of the support 101, it is possible to use a semiconductor laser etc. , the first layer region (G) 105 can substantially completely absorb light on the long wavelength side, which is almost completely absorbed by the second layer region (S) 106, and the support Interference due to reflection from the 101 plane 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 OrgJ 1, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer region (G) 105 exhibiting photoconductivity, and tB represents the layer thickness on the support 101 side. 1T indicates the position of the surface of the first layer region (G) 105 on the side opposite to the support side. That is, in the first layer region (G) 105 containing germanium atoms, layers are formed from the tB side toward the tl- side.

FIG. 2 shows a first typical state of the distribution of germanium atoms contained in the first layer region (G) 105 in the layer thickness direction.

In the example shown in FIG. 2, 1. Up to the position, the distribution concentration C of germanium atoms takes a constant value of 01, while the distribution concentration of germanium atoms contained in the first layer (I) gradually increases from C to the interface position t1. has been continuously decreased. At the interface position it7, the distribution concentration C of germanium atoms is C8.

In the example shown in FIG. 3, the first layer region fm(G)
The distribution concentration C of germanium atoms contained in 1o5+ gradually and continuously decreases from the concentration C4 from the position tB to the position tT, forming a distribution state in which the concentration C5 is reached at 111tT.

In the case of FIG. 4, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 is constant at a concentration C6 from the position te to the position t2, and the concentration C6 is a constant value from the position te to the position it.
γ is gradually and continuously decreased until the position 1T
In this case, the distribution concentration C is substantially zero (substantially zero here means that it is less than the detection limit amount).

In the case of FIG. 5, the I6 concentration C of germanium atoms contained in the first layer region (G) 105 is at position 1. From position 1. The concentration Cs gradually decreases continuously until reaching the concentration Cs, and becomes substantially zero at the first position ta.

In the example shown in FIG. 6, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in the position t
Between B and position t5, the concentration C9 is a constant value and is 1
At position tT, the concentration is q. Between position 1J and the position meter, the distribution W;C is reduced numerically over time from position t4 to position 1T.

In the example shown in FIG. 7, the first layer region (G) 1
The distribution concentration C of germanium atoms contained in 05 is from the position t& to the concentration C until now.

takes a constant value, and from position Ht+ to position f/'l ty, the distribution is such that the concentration decreases linearly from CJ2 to C,j! It is said to be a claw.

In the example shown in FIG. 8, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in is fFt
tI! The concentration decreases in a linear manner from Cl41 to substantially zero as the concentration approaches the position.

In FIG. 9, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 is the concentration CI from the position tβ to the position tT.

An example is shown in which the density C/j is linearly decreased to CI6, and the density C/j is kept at a constant value between positions tr and tr.

In the example shown in FIG. 10, the first layer region (G)
The distribution concentration C of germanium atoms contained in 105 is at position 1. The concentration is c17 at 71b, and this concentration CI7 is slowly decreased from t±6 to 71b.
Near the position t6, 1 and 1 are rapidly decreased to position 1. In this case, the concentration is set to CI8.

Position 1. Between position fit Rt7, the concentration is first rapidly decreased, and then slowly and gradually decreased to reach CI9 at position tγ, and between position fit t7 and position t8, it is extremely slowly and gradually decreased. Between the 0th position flt, La and the position 1, where the density is reduced to a density at position t8, the density is reduced from C2ρ to substantially zero according to a curve shaped as shown in the figure.

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

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

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

The above localized region (A) may be the entire layer region (LA) up to 5 diameters thick from the interface position t, or may be a part of the layer region (Lr). .

Whether the localized MJ* (A) is a part or all of the layer region (I7) depends on the first layer region (G) 1 to be formed.
05 as appropriate according to the characteristics required.

In the localized region (A), the distribution state of the germanium atoms contained therein in the layer thickness direction is such that the maximum value Cmax of the distribution concentration of germanium atoms is the sum of the distribution concentration of germanium atoms and silicon atoms.
Preferably 1000 atomic ppm or more, more preferably 50
It is desirable that the layer be formed in such a manner that a distribution state of 00 atomic ppm or more, optimally 1×10 atomic ppm or more, can be obtained.

That is, in the present invention, the first layer region (G) 105 containing germanium atoms has a maximum distribution concentration within 5 JL in layer thickness from the support 101 side (layer region 5 thick from ti). Preferably, it is formed such that there is a value Cl1ax.

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

The distribution state of germanium atoms in the first layer region (G) 105 is such that germanium atoms are continuous in the entire layer region.
The distribution concentration C of germanium atoms in the layer thickness direction is changed to decrease from the support 101 side to the free surface 107 side of the photoreceptive layer 104, or the reverse change is applied. In this case, by arbitrarily designing the rate of change curve of the distribution concentration C as desired, the first layer region (G) 105 having the required characteristics can be realized as desired.

For example, the distribution concentration C of germanium atoms in the first layer region (G) 1O5 is sufficiently increased on the support lot side, and as low as possible on the free surface 107 side of the photoreceptive layer 104. By applying a change in the distribution concentration C to the distribution concentration curve of germanium atoms, high photosensitivity can be achieved for light in the entire range of wavelengths from relatively short wavelengths to relatively long wavelengths, including the visible light region. In addition to being able to achieve
It is possible to effectively prevent interference with coherent light such as laser light.

In the present invention, the layer thickness T of the first layer region (G) 105,
is preferably 30A to 50. , it is desirable to set it to 30 ru.

Further, the layer thickness T of the second layer region (S) 106 is preferably 0.5 to 90 #L, more preferably 1 to 80 #L, and optimally 2 to 50 #L.

The layer thickness TB of the first layer region (G) 105 and the second layer region (
S) 1060 layer thickness T The layer thickness (TB+T) is determined based on the organic relationship between the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. The needle size is appropriately determined according to the desired conditions.

In the photoconductive member of the present invention, the above numerical range of (Tn+T) is preferably 1 to 100-1, more preferably 1.
~801t, optimally 2~50p.

In a more preferred embodiment of the present invention, the above layer thickness T
B and layer thickness T are desirably selected to have appropriate numerical values, respectively, so as to preferably satisfy the relationship Ts/T≦1.

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

In the present invention, when the content of germanium atoms contained in the first layer region (G) 105 is 1X10 atoms ppm or more, the layer thickness TB of the first layer region (G) 105 is It is best to make it quite thin, preferably 30#L.
The following, more preferably 25. Hereinafter, it is desirable to set it to 20 or less optimally.

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

In the present invention, the layer thickness TJ of the first layer region (G) 105
l is preferably 30s to 50IL, more preferably 40A to 40h, optimally 50'A to 30#L.

Further, the layer thickness T of the second layer region (S) 106 is preferably 0.5 to 90 IL, more preferably 1 to 80 IL,
The optimum number is preferably 2 to 50 #i.

The sum (Tβ + T) of the layer thickness TB of the first layer region (G) 105 and the layer thickness T of the second layer region (S) 106 is determined by the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. Based on the organic relationship between the characteristics and the characteristics to be determined, the thickness is appropriately determined as desired when forming the layer of the photoconductive member.

In the photoconductive member of the present invention, the above numerical range of (Tβ+T) is preferably 1 to 100 l, more preferably 1
~80 IL, optimally 2 to 50 pots.

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 P and layer thickness T so as to preferably satisfy the relationship Tβ/T≦1.

In selecting the numerical values of the layer thickness Tβ and the layer thickness T in the above case, it is preferable that the layer thickness TB be selected so that the relationship Ts/T≦0.9, optimally TB/T≦0.8, is satisfied. Preferably, the values of and the layer thickness T are determined.

In the present invention, when the content of germanium atoms contained in the first layer region (G) 105 is above I x 10'' atoms ppm, the layer thickness of the first layer region (G) 105 is It is desirable that the TB be fairly thin, preferably 30 IL or less, more preferably 25 IL or less, optimally 2
It is desirable that it be 0g or less.

In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the first layer (1) Layer (I) 102
Nitrogen atoms are contained therein. First layer (I) 102
A particularly large amount of nitrogen atoms are contained in the vicinity of the second layer (4) 103 and, if necessary, in the vicinity of the support 101.

11 to 13 show typical examples of the distribution of nitrogen atoms in the first layer (I) 102 as a whole. It should be noted that in these descriptions, signals used without exception have the same meanings as used in FIGS. 2 to 10. In the example shown in FIG.
The rJ concentration C(N) continuously increases by mts from 0 to 02 from position t11 to position t7.

In the example shown in FIG. 12, the distribution concentration C(N
) is at position 1. In, the distribution concentration Cyu.

Then, from the distribution density C21, the position t? It decreases monotonically and continuously until reaching position 1. The distribution concentration is CJ. Between position t9 and position t7, the distribution concentration C(N) of nitrogen atoms monotonically increases continuously from position t9, and reaches a distribution concentration of 9 at one position 1T.

The example in FIG. 13 is relatively similar to the example in FIG. 12, but the difference is that no nitrogen atoms are contained at position t10 and position 1//.

Between position t, and position tLD, the distribution density decreases continuously and monotonically from 0 at position tB to 0 at position tra, and between position t, / and itγ, position 1
The distribution concentration increases continuously and monotonically from the distribution concentration O at ++ to the distribution concentration Q4 at position tT.

In the photoconductive member of the present invention, as typical examples thereof are shown in FIGS. 11 to 13, the first layer (I) 102
Contain more nitrogen atoms on the lower surface and/or the surface of part E and less nitrogen atoms toward the inside of the second layer (I) 102, and distribute the nitrogen atoms in the layer thickness direction. By continuously changing the concentration 9 (N), for example, high photosensitivity and high dark resistance of the photoreceptive layer are achieved.

In addition, by continuously changing the distribution concentration C(N) of nitrogen atoms, the change in refractive index in the layer N direction due to the inclusion of nitrogen atoms is made gradual, and interference caused by coherent light such as laser light is effectively suppressed. It is prevented.

In the present invention, the nitrogen atom content in the nitrogen atom-containing layer region (N) provided in the first layer (r)to2 depends on the characteristics required for the layer region (N) itself or the layer region (N). When the region (N) is provided in direct contact with the support 101, the region (N) may be appropriately selected depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support 101. I can do it.

In addition, when another layer region is provided in direct contact with the layer region (N), the relationship between the characteristics of the nucleation layer region and the characteristics at the contact interface with the nucleation layer region may also be determined. Taking this into consideration, the content of nitrogen atoms is selected accordingly.

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

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, the ratio of the layer thickness TO of the layer region (N') to the layer thickness T of the first layer (I) 102 When the amount is sufficiently large, it is desirable that the upper limit of the content of nitrogen atoms contained in the layer region (N) is sufficiently smaller than the above value.

In the present invention, the layer thickness T of the layer region (N,).

When the ratio of nitrogen atoms to the layer thickness T of the first layer (I) 102 is 2/5 or more, the upper limit of the amount of nitrogen atoms contained in the layer region (N) is is T (S 1G
eN), 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 is located on the support 101 side or/and the second layer (J
I) It is preferable to provide a localized region (B) in which nitrogen atoms are contained at a relatively high concentration near the 103 side, and in this case, the support 101 and the first layer (I ) 102 and the acceptance potential can be further improved.

The localized region (B) is located 5 times from the surface of the first layer (I) 102 on the support 101 side and the second layer (In) 103 side.
It is desirable that the facility be installed within the required time.

In the present invention, the localized region (B) is formed in the first layer (
I) 102 from the support 101 or the second layer (2)
It may be the entire layer region (L) from the surface on the 103 side to the five color primaries, or it may be a part of the 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 as the distribution state of the nitrogen atoms contained therein in the layer thickness direction is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more. Atomic ppm or more, optimally 100
It is preferable that the layer be formed in such a manner that a distribution state of 0 atomic ppm or more can be obtained.

That is, in the present invention, in the first layer (I) 102,
The layer region (N) containing nitrogen atoms is such that the distribution concentration Cmax exists within 5 degrees in layer thickness from the support 101 side or the surface of the second layer (■) 103. preferably formed.

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 containing germanium atoms and/or the second layer region (S) 106 not containing germanium atoms have conductive properties. By containing the controlling 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 (D) 102. Alternatively, the layer region (1)N) may be provided in part or all of the layer region (G) or (S).

Substances (D) that control such conductive characteristics include so-called impurities in the semiconductor field. Examples include a p-type impurity that provides a conductive property, and an n-type impurity that provides an n-type conductivity. Specifically, p-type impurities include atoms belonging to Group 1 of the periodic table (atomic group 1), such as ceramic (B), aluminum (All), gallium (Ga), and indium (In).
, thallium (T u, ), etc., and B and Ga are particularly preferably used. In addition, as an n-type impurity, 1
Atoms belonging to group V of the periodic table (group V atoms), for example,
Phosphorus (P), A's, Antimony (Sb),
Bismuth (Bi), etc., and particularly preferably used are P and As.

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

In addition, the substance CD controlling the conduction characteristics described above is used as the first MI
(I) 102, the second layer (I) 1
When it is contained locally in a desired layer region of 02, especially when it is contained in the support side end layer region of the first layer (I) 102, it is in direct contact with the layer region. The properties of other layer regions provided and the relationship with the properties at the contact interface with the nucleation layer region are also taken into consideration, and the material controlling the conduction properties (
The content of D) is selected as appropriate.

In the present invention, the content of the substance (D) controlling the conductive properties contained in the first layer (I) 102 is preferably 0.01 to 5 x 10 atomic ppm, more preferably is 0.5-1X10 atomic ppm, optimally 1-5X1
It is desirable that the content be 0 atomic ppm.

In the present invention, the content of the substance (D) that controls conduction characteristics in the layer region (PN) containing the substance (D) is preferably 30 atomic ppm or more, more preferably 50 atomic ppm or more. ppm or less]-1 Optimally, in the case of 100 atomic ppm or more, the substance (D) governing the conduction characteristics is locally contained in a part of the layer region of the first layer (I) 102. In particular, it is desirable that the first layer (I) 102 be unevenly distributed in the end layer region (E) on the side of the support.

Among the above, by containing the substance (D) that controls the conductive characteristics in the support side end layer region (E) of the first layer (I) 102 in a content equal to or higher than the above value, For example, if the substance (D) is the p-type impurity described above, it is injected into the photoreceptive layer 104 from the support 101 side when the free surface 107 of the photoreceptive layer 104 is subjected to polar charging treatment. When the substance that can effectively block the movement of electrons and controls the conduction properties is the n11 impurity, the free surface 107 of the photoreceptive layer 104 is subjected to e8j charging treatment. When the photoreceptive layer 1 is removed from the support 101 side,
It is possible to effectively block the movement of holes into the 04.

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

In such a case, the content of the substance (D) that controls the conductive properties contained in the layer region (Z) depends on the polarity and the content of the substance contained in the support side end layer region (E). It is determined as desired depending on the content, but
Preferably 0.001 to 1000 atomic ppm, more preferably 0.05 to 500 atomic ppm, optimally O01 to 500 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) The content is preferably 30 atomic ppm or less. In addition to the above-mentioned cases, in the present invention, the first layer (
I) In 102, a layer region containing a substance controlling conductivity having one polarity and a layer region containing a substance controlling conductivity having the other polarity are brought into direct contact. It is also possible to provide a so-called depletion layer in the contact layer region. Clogging, for example in the first layer (I) 102, the aforementioned p K'! The layer region containing the impurity and the layer region containing the n-type impurity are provided so as to be in direct contact with each other.
A depletion layer can be provided by forming a -n junction.

The first layer region (G) 105 composed of the niobium of the present invention, a-Ge (S i , H, It is formed by a vacuum deposition method. For example, by glow discharge method, a-Ge(S
i, H, X) first layer region (G) 10
5, basically a raw material gas for supplying germanium atoms that can supply germanium atoms, a raw material gas for supplying silicon atoms that can supply silicon atoms, and a raw material for introducing hydrogen atoms as necessary. A gas and/or a raw material gas for introducing halogen atoms is introduced at a desired gas pressure into a deposition chamber whose interior can be depressurized to generate a glow discharge within the deposition chamber, which is installed in a predetermined position in advance. , a-Ge(S i , H.

It is sufficient to form a layer consisting of X). 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 while a-Ge (S i ,
What is necessary is to form a layer consisting of H, X). In addition, in the sputtering method, a target composed of silicon atoms, or a target composed of the target and germanium atoms in an atmosphere of an inert gas such as Ar, )(e) or a mixed gas based on these gases is used. For supplying germanium atoms diluted with a diluent gas such as He or Ar, if necessary, use two of the prepared targets, or use a mixed target of silicon atoms and germanium atoms. The raw material gas and, if necessary, a gas for introducing hydrogen atoms and/or halogen atoms are introduced into the deposition chamber for sputtering to form a plasma atmosphere of the desired gas, thereby forming the first layer region (G) 105. In this sputtering method, when the distribution of germanium atoms is to be made non-uniform, the target is sputtered while controlling the gas flow rate of the raw material gas for supplying germanium atoms according to a desired rate of change curve. Just do it.

In the case of the ion blating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in the evaporation port as M sources, respectively, and these evaporation sources are heated using the resistance heating method or the electron beam heating method. Except for heating and evaporating by beam method (EB method) etc. and passing the flying evaporated material through the desired gas plasma atmosphere,
The first layer region (G) 105 can be formed in the same manner as in the sputtering method.

Substances that can be used as raw material gas for supplying silicon atoms used in the present invention include SiHa, Si, H4
,S i)H,,S i4H,. Silicon hydride (silanes) in a gaseous state or that can be gasified are mentioned as those that can be effectively used.In particular, S i H41
, S 1JLH4 are listed as preferred.

.

Substances that can be used as raw material gas for supplying germanium atoms include G e H,, G e, H7, G elHB, and G
e,H,,,G etH7ko,G eAH141,G
Germanium hydride in a gaseous state or that can be gasified, such as e7H74, GegH7y, and Geq, can be effectively used, and in particular, it is easy to handle during layer creation work, and has good germanium atom supply efficiency. At the point, Ge
Preferred examples include H,,Ge2H6,Ge)HII.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gases, halogen compounds, interhalogen compounds, and halogen-substituted silane derivatives. Preferred examples include halogen compounds that can be converted into Furthermore, hydrogenated silicon compounds containing halogen atoms, which are in a gaseous state or can be gasified and which have silicon atoms and halogen atoms as constituent elements, can also be mentioned as effective in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, C, CIF, BrF3. B
Examples include interhalogen compounds such as rFa, IF1#, IH7, IC compound, and IBr.

Specific examples of the compound containing a halogen atom, the so-called silane derivative substituted with a halogen atom, include S 1xF4. S 1zF7. S f C%, S
Preferred examples include halogenated elements such as iBr4.

When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a tetragonal compound containing halogen atoms, silicon atoms are supplied together with a raw material gas for supplying germanium atoms. A first layer region consisting of a-3iGe containing halogen atoms (
G) 105 can be formed.

When manufacturing the first layer region (G) 105 containing halogen atoms according to the glow discharge method: 1. Basically, for example, a halogenated element serving as a raw material gas for supplying silicon atoms, a germanium hydride serving as a raw material gas for supplying germanium atoms, and a gas such as Ar, H, He, etc. are mixed at a predetermined mixing ratio. First layer area (G) 10 so that the gas flow rate is
5 into a deposition chamber to form a plasma atmosphere of these gases by generating a glow discharge and forming a plasma atmosphere of these gases.
Although it is possible to form the first N-Kicheng (G) 105 on the desired support 101, hydrogen may be added to these gases in order to more easily control the introduction ratio of hydrogen atoms. A desired amount of a gas or a gas of a 76 biochemical compound containing a hydrogen atom may be mixed to form a layer.

Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio.

In order to introduce halogen atoms into the first layer region (G) 105 formed in either the sputtering method or the ion blating method, the above-mentioned halogen compound or the above-mentioned halogen atom-containing stone is mixed with an elementary compound. It is sufficient to introduce a gas into the deposition chamber to form a plasma atmosphere of the gas.

When hydrogen atoms are introduced into the first layer region (G) 105, the raw material gas for introducing hydrogen atoms, H2,
Alternatively, gases such as the above-mentioned silanes and/or germanium hydride may be introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gases.

In the present invention, the halogen compounds listed in 1 or group element compounds containing halogen are effectively used as the raw material gas for introducing halogen atoms, but in addition, HF, H(11, HBr, H
Hydrogen halides such as I, 3 i HxFz, S i F
2I2, S i H2CJL2, S i HCII-a
, S i H2B r2.5iHBr3, etc., and G e HF, G e H
, F2, GeH3F, Ge HCiJ, Ge HIC
9, x, G e HiCIL, G e HB r,,G
e HUB r,, GeH3Br, GeHI3, Ge
Hydrogenation of H2■2, G e H, I, etc./Halides containing a hydrogen atom as one of the constituent elements such as germanium chloride, G e F,, G e C9,t,, G e
B F41, cety, G e Fl, G e Cl
,, G e B r2, G e I.

Gaseous or gasifiable substances such as germanium halides, etc., can also be mentioned as useful starting materials for forming the first layer region (G) 105.

Among these substances, /\logenides containing hydrogen atoms are
When forming the first layer region (G) 105, hydrogen atoms, which are extremely effective in controlling electrical or photoelectric characteristics, are also introduced at the same time as halogen atoms are introduced into the layer, so halogen introduction is preferred in the present invention. It is used as a raw material for

In order to structurally introduce hydrogen atoms into the first layer region (G)' 105, - in addition to the above, F2 or SiH4,
A hydrogenated IL element such as S t, H, 1, S sl Hl, 314H/# with germanium or a germanium compound for supplying germanium atoms, or G e H
4,G e2H7,G e)F3,G e4H,,,G
e, (H,,,G e6H(q,G et7H,z,
This can also be achieved by causing discharge to occur by coexisting germanium hydride of G8i1H#, Ge5H, μ with silicon or a silicon compound for supplying silicon atoms in a deposition chamber.

In a preferred example of the present invention, the amount of hydrogen atoms contained in the first layer region (G) 105 to be formed, the amount of halogen atoms, or the sum of the amounts of hydrogen atoms and halogen atoms (
Hx
It is preferable to express it in atomic percent.

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 hydrogen atoms or halogen atoms can be contained. The amount of starting material introduced into the deposition system, the discharge force, etc. may be controlled.

In the present invention, the second
The layer region (S) 106 is the first layer region (G) described above.
Starting materials (starting materials for forming the second layer region (S) (L) for forming the second layer region (S)) from the starting materials for forming 105 (CI) excluding the starting materials that serve as raw material gas for supplying germanium atoms
It can be formed using the same method and conditions as in the case of forming the first layer region (me) 106.

That is, in the present invention, the second layer region (d) 105 composed of a-St (H, Formed by deposition method. For example, a-3t(H,
In order to form the second layer region (S) 106 composed of A raw material gas for introducing halogen atoms and/or halogen atoms is introduced into a deposition chamber whose interior can be depressurized to generate a glow discharge in the deposition chamber, and a predetermined support surface toner, which has been previously installed at a predetermined position, is What is necessary is to form a layer consisting of a-3t(H,X). When forming by sputtering method, 1. 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 a gas for introducing halogen atoms may be introduced 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 halokene atoms (H+X) is preferably 1 to 40 at%, more preferably 5 to 30 at%
The optimum content is preferably 5 to 25 atomic %.

In the present invention, in order to provide the layer region (N) containing nitrogen atoms in the first layer (I) 102, the first layer (I) 10
2, using the starting material for introducing nitrogen atoms together with the starting material for forming the first layer (I) 102,
It may be contained in the formed layer while controlling its amount.

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

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

The starting materials that can be effectively used as raw material gases for introducing nitrogen atoms used when forming the layer region (N) are those whose constituent atoms are nitrogen or whose constituent atoms are % V element and hydrogen. For example, nitrogen (N2), ammonia (NH
,), hydrazine (IffNNH,), hydrogen azide (
Gaseous or gasifiable nitrogen such as HN, ), ammonium azide (and N3), and nitrogen compounds such as nitrides and azides can be mentioned. In addition to this, in addition to introducing nitrogen atoms, halogen atoms can also be introduced, so nitrogen trifluoride (F, N), nitrogen tetrafluoride (F, N2)
Examples include halogenated nitrogen compounds such as.

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 gases for introducing oxygen atoms into the layer region (N) include oxygen (02) and ozone (02).
3), -nitrogen oxide (NO), nitrogen dioxide (N20), -
Nitrogen dioxide (NO), nitrogen sesquioxide (Nap3), trinitrogen tetraoxide (N, Oda), nitrogen dioxide (N, O,),
Nitrogen trioxide (N Oi) Constituent atoms are silicon atoms, oxygen atoms, and hydrogen atoms, for example, disiloxane (H)
SiOSiHi), l・! J Shiro* San (HtS
Examples include lower siloxanes such as iO9iH20SiHi).

In order to form the layer region (N) by a sputtering method, a monocrystalline or polycrystalline silicon wafer or a silicon atomic wafer or a silicon atomic wafer is used during the formation of the first layer (I) 102. Sputtering may be carried out by using a wafer containing a mixture of as a target and sputtering them in various gas atmospheres.

For example, if a silicon wafer is used as a target, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary, and then the material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary, and a deposition chamber for sputtering is prepared. A gas plasma of these gases may be formed to sputter the silicon wafer onto the silicon wafer.

Alternatively, silicon atoms and St, N, may be used as separate targets, or by using a single target containing silicon atoms and Si;N4, in a dilution gas atmosphere as a sputtering gas. Sputtering may be performed in a gas atmosphere containing at least hydrogen atoms and/or halogen atoms as constituent atoms.

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

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

When the layer region (N) is formed by the sputtering method 7, the distribution concentration C(N) of nitrogen atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution of nitrogen atoms in the layer thickness direction. In order to form the shape M (depth 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 when the gas is introduced into the deposition chamber, This is accomplished by appropriately changing the gas saturation as desired.

Second, if a target containing a mixture of silicon atoms and SiJN4 is used as a sputtering target, for example, the mixing ratio of silicon atoms and SiJN4 should be adjusted in the layer thickness direction of the target. This is done by changing it in advance.

In the first layer (I) 102, a substance that controls the conduction properties;
For example, to structurally introduce a group V atom or a group V atom, a starting material for introducing a group I atom or a starting material for introducing a group V atom is deposited in a gaseous state during layer formation. It may be introduced into the chamber together with other starting materials for forming the second region (S) 106. As the starting material for such introduction of Group (I) atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing atoms of the plate group group include B, H,, B*) (Io, B'; Hm, B, H
27, B4H#, B6H,, B6H,q, etc.; halogenated hardenes such as BF, Blj, B B rj, and the like. In addition, A text commercial,...
G e Clx, G e (CHJ).

I n Cl), T C C sentence 1, etc. can also be mentioned.

In the present invention, effective starting materials for introducing Group V atoms include P H,
, P2H, , hydrogen north neighbor, PH,1, PF, , P F
,,P Cl,,P CfLf,PBrO PBr,H
Examples include halogen north neighbors such as lP Ij. In addition, A
sHj, AsF,? , As Cft), AsB rJ
, ASF, r, sbH,, S bFj, S bFr
, Sb0 sentence 8, sbc sentence! , B i H3, BiC sentence j
, B iB r, ), etc. can also be mentioned as effective starting materials for introducing Group V atoms.

In the present invention, the support 101 is made of steel that constitutes the first layer (I) 102 and contains a substance that controls conductive properties. The layer thickness of the layer region (P The lower limit is preferably 50A or more, and the lower limit is preferably 50A or more. When the content of the substance controlling the conductive properties is 30 atomic ppm or more, the upper limit of the layer thickness of the layer region (P N) is preferably 10 colors or less, preferably 8p or less. ,
Optimally, it is desirable to set it to 5p or less.

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

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

The second layer (IL) 103 composed of a-(5ixo1-x)y(H,X)+-y can be formed by glow discharge method, sputtering method, electron beam method, ion plantation method, ion blating method , etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be produced. It is relatively easy to control the manufacturing conditions for manufacturing the conductive member, and the second layer (1) contains oxygen atoms and halogen atoms together with silicon atoms.
) A glow discharge method or a sputtering method, which has the advantage of being easy to introduce into the material 103, 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 (n) 10.
3 may be formed.

To form the second layer (n) 103 by the glow discharge method, a −(S ixo+−x) y(H,X)+−
The raw material gas for forming y is mixed with a dilution gas at a predetermined mixing ratio if necessary, and introduced into the deposition chamber where the support 101 is installed, and the introduced gas is used to cause glow discharge. The support 10 may be converted into gas plasma by
The first layer (I) 102 which is already formed on 1 is a
-(Sixo+-x)y(H,X)+-y may be deposited.

The present invention, a-(S ixo+-x)y (H,
X) The raw material gas for ly formation is a gaseous substance or a gasified substance whose constituent atoms are at least one of silicon atoms, oxygen atoms, hydrogen atoms, and halogen atoms. Most of them can be used.

When using a raw material gas that has a silicon atom as one of silicon atoms, oxygen atoms, hydrogen atoms, and halogen atoms, for example, a raw material gas that has silicon atoms as a constituent atom and an oxygen atom as a constituent atom. If necessary, a raw material gas containing hydrogen atoms and/or a raw material gas containing halogen atoms may be mixed at a desired mixing ratio, or silicon atoms may be used as constituent atoms. The raw material gas and the raw material gas whose constituent atoms are oxygen atoms and hydrogen atoms and/or the raw material gas whose constituent atoms are oxygen atoms and halogen atoms are also mixed at a desired mixing ratio, or A raw material gas whose constituent atoms are silicon atoms, and a raw material gas whose constituent atoms are silicon atoms, oxygen atoms, and hydrogen atoms, or raw material gases whose constituent atoms are silicon atoms, oxygen atoms, and halogen atoms. Can be used in combination.

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

In the present invention, halogen atoms contained in the second layer 103 are preferably fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly desirable.

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

When forming the second layer ([) 103 by a sputtering method, for example, it is performed as follows.

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

Secondly, S i as a target for sputtering
It is formed by using a target composed of 62, a target composed of silicon atoms and a target composed of SiO, or a target composed of silicon atoms and SiO. Oxygen atoms can be introduced into the second layer (n) 103.

At this time, if the aforementioned raw material gas for introducing oxygen atoms is also used, the flow rate can be controlled to form the second layer (li) 10.
It is easy to arbitrarily control the amount of oxygen atoms introduced into 3.

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

The starting materials used in the present invention as raw material gas for supplying silicon atoms include SiH, Si, H4, S
Gaseous or gasifiable hydrides (silanes) such as i, H, and S 14Htθ are cited as effective uses, especially for ease of handling in layer creation work and silicon atom supply. S i H4,S in terms of efficiency etc.
izHΔ is preferred.

If these starting materials are used, hydrogen atoms can be introduced together with silicon atoms into the second layer (1) 103 formed by appropriately selecting the layer forming conditions.

In addition to the above-mentioned silicon hydride, effective starting materials that serve as raw material gases for supplying silicon atoms include halogen-containing compounds, so-called silane derivatives substituted with halogen atoms, specifically, for example, SiF. ,,Si,Fl,5iC
1, SiBrg.

The halogenated it element of Gou can be mentioned as a preferable example. Furthermore, S i H, F, S i
H27, S i H2CA, 2. S i HCl2
．． For the formation of the second layer (II) 103, halogen-substituted hydrogen fossils such as S i H2B r2゜5iHBr2 and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituent elements are also effective. It can be mentioned as a starting material for supplying silicon atoms.

When using these layered elementary compounds containing halogen atoms, as mentioned above, by appropriately selecting the layer forming conditions,
Halogen atoms can be introduced together with silicon atoms into the second layer (m) 103 to be formed.

Among the above-mentioned starting materials, a halogenated shoulder compound containing a hydrogen atom is used to control electrical or photoelectric properties at the same time as introducing a halogen atom into the layer during the formation of the second R (and) 103. Since hydrogen atoms, which are extremely effective for hydrogen atoms, are also introduced, they are used as suitable starting materials for introducing halogen atoms in the present invention.

In addition to the above-mentioned materials, examples of effective starting materials used as raw material gas for introducing halogen atoms when forming the second layer (II) 103 in the present invention include fluorine, chlorine, bromine, iodine ( 7) Hatff Gengas, Br
F,(,9,F,CJIF,.

BrF,), BrF,, IF7. IF7. ICU, IB
Interhalogen compounds such as r, HF, N0, HB r
.

Examples include hydrogen halides such as HI.

Starting materials that can be effectively used as raw material gas for introducing oxygen atoms used when forming the second layer (II) 103 include oxygen atoms as constituent atoms or nitrogen atoms and oxygen atoms. For example, oxygen (02
), ozone (07), -nitrogen oxide (No), nitrogen dioxide (NOJ), -nitrogen dioxide (N20), nitrogen sesquioxide (
Nyu0. ), nitrogen tetroxide (NJO,), nitrogen sesquioxide (N-0r), and nitrogen trioxide (No, ), and nitrogen atoms composed of silicon atoms, oxygen atoms, and hydrogen atoms, such as , disiloxane (H,5iOS
iHa), trisiloxane (H, Si OS N20
Examples include lower siloxanes such as S i N7).

In the present invention, a so-called rare gas such as He, Ne, Ar,
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.

In other words, substances whose constituent atoms are silicon atoms, oxygen atoms, and optionally hydrogen atoms and/or halogen atoms have structural forms ranging from crystalline to amorphous depending on the conditions for their creation, and in terms of electrical properties, From conductive to semiconducting,
Furthermore, it exhibits properties ranging from insulating to photoconductive to non-photoconductive. Therefore, in the present invention, a −(S ix
o + -x) V (H, To provide the main purpose of improvement is a-(S 1x01-
x)y (H,

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

6-(SixO+-x
)y (H,X)+-y second layer (Jlr)1
The temperature of the support 101 during layer formation is an important factor that influences the structure and properties of the formed layer. In the present invention, the temperature of the support during layer formation is strictly controlled so that a-(SixO+-X)V (H,'X)+-y having the desired properties can be created as desired. It is desirable to In the present invention, the second layer (]II) 10 for effectively achieving the desired purpose
Formation of the second layer (n) 103 is carried out by appropriately selecting the support temperature in the optimum range in accordance with the formation method of 3. The support temperature during layer formation is preferably 20 to 400℃. °C,
More preferably 50-350°C, optimally 100-300°C
It is preferable to set the temperature to ℃.

To form the second layer (JI) 103, glow discharge is used to form the second layer (JI) 103, as it is relatively easy to finely control the composition ratio of atoms constituting the layer and control the layer thickness compared to other methods. Adoption of sputtering method or sputtering method is advantageous. When forming the second layer (][) 103 using these layer forming methods, the discharge power during layer formation is created in the same manner as the support temperature described above.
-(S 1xol -x )yX+ - It is one of the important factors that influences the characteristics of -y.

a having the characteristics for achieving the object of the present invention;
-(S ixo+ -x )y It is desirable that the

The gas pressure in the deposition chamber is preferably 0. O1~I Torr
, more preferably about +, O, 1 to 0, 5 Torr.

In the present invention, the support temperature and discharge power for forming the second layer (II) 103 may be within the above-mentioned ranges, but these layer formation factors may be determined independently and separately. It is not determined by the desired characteristic a − (SixO+−x)”! (H,X)I−
It is desirable that the optimum value of each layer creation factor be determined based on the mutual organic relationship so that the second layer (1) lo3 consisting of y is formed.

The amount of oxygen atoms contained in the second layer (JL) 103 in the photoconductive member of the present invention is the same as the production conditions of the second layer (1) 103. This is an important factor for forming the resulting second layer (n) 103.

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

That is, the general formula a-(S1xoI-X)V
The amorphous material represented by (H,
Hereinafter, it will be written as r a -S 1aol-aJ.

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

In the present invention, the second layer (5) 103 is a-3iaO
1-&, the amount of oxygen atoms contained in the second layer (I[) 103 is represented by a of a-3ia(]-a, where a is preferably 0.33 ~0.99999
, more preferably 0.5-0.99, optimally 0.6-0
．． It is 9.

In the present invention, the second layer (]l[) 103 is a-(S
ibo 1-b) c Hl-c te, the amount of oxygen atoms contained in the second layer (II) 163 is a
-(S 1boI -b)c Hl-C(7) When expressed as b and C(7), b is preferably 0.33 to 0
．． 99999, more preferably 0.5 to 0.99, optimally 0.6 to 0.9, C preferably 0.6 to 0°99,
More preferably 0.65-0.98, optimally 0.7-0
．． 95 is desirable.

m2 layer (If-) 103 is a-(S 1dO1-
d ) e (H+ (H
, X)+-e, d is preferably 0.33 to 0.99999, more preferably 0.5 to
0.99, optimally from 0.6 to 0.9, and e is preferably from 0.8 to 0.99, more preferably in the second layer (
The range of the layer thickness of X) 103 is one of the important factors for effectively achieving the object of the present invention. The layer thickness is appropriately determined as desired depending on the intended purpose so as to effectively achieve the purpose of the present invention. Furthermore, this layer thickness is determined by the amount of oxygen atoms contained in the layer (n) 103 and the amount of oxygen atoms contained in the first layer (n) 103.
1) The relationship with the layer thickness of 102 also needs to be appropriately determined as desired based on the organic relationship depending on the characteristics required for each layer region.

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

The layer thickness of the second layer (JI) 103 in the present invention is preferably 0.003 to 30. , more preferably 0.0
It is desirable to set it to 0.04-20IL, optimally 0.005-1Op.

Further, in the present invention, in order to further enhance the effect obtained by oxygen atoms, carbon atoms may be included in the second layer (rL) 103 together with oxygen atoms. As a raw material gas for introducing carbon atoms to introduce 1034 carbon atoms into the second layer (and) <1, carbon atoms and hydrogen atoms are used as constituent atoms, for example, saturated hydrocarbons having 1 to 5 carbon atoms, carbon Number 2
-5 ethylene hydrocarbons, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like. Specifically, saturated hydrocarbons include methane (CH4), ethane (C, HΔ),
Propane (C)H@) *n-buta7 (n C4H
I, ) + pentane (C5H+2), ethylene hydrocarbons include ethylene (C2U4), propylene (
CiHa) + Butene-1 (C4H1l) + Butene-2 (C,H,)l Isobutylene (C4H1?),
Pentene (CtH7o), acetylene hydrocarbons include acetylene (C2H4), methylacetylene (
Examples include CaI (Hiro), butyne (C4H7), etc.
In addition to these, raw material gases containing silicon atoms, carbon atoms, and hydrogen atoms as constituent atoms include 5t(CHa)4c,
Mention may be made of alkyl silicides such as S 1 (CaHr)4'.

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

Examples of the conductive support include NiCr, stainless steel, A4Q, Cr, Mo, Au, and 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 chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are usually used. Ru.

Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, NiCr1, A
Moon, Cr, Mo, Au, Ir.

Nb, Ta, V, Ti, Pt, Pd, I n20B, S
nO2, I To (I n103+ S n 02)
Conductivity is imparted by providing a thin film consisting of NiCr', Ajlj, Ag, Pb, etc., or if it is a synthetic resin film such as a polyester film.

Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, v
, Ti, Pt, or the like is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, or the like, or the surface is laminated with the metal to impart conductivity to the surface.

The support 1O1 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 in FIG. If used as a member for continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support 101 is determined as appropriate so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the thickness of the support 101 may be determined so that it can sufficiently function as a support. It is made as thin as possible within the range. In such a case, the thickness of the support 101 is preferably 1.5 mm from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.
It is considered to be more than 0 ru.

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

FIG. 14 shows an example of a photoconductive member manufacturing apparatus.

In the figure, raw material gases for forming the photoconductive member of the present invention are sealed in gas cylinders 1102 to 1106. As an example, 1102 is a Si Hy gas (purity 99.999%, hereinafter S
It is abbreviated as tHg/)l6. ) cylinder, 1103 is G e H, + gas diluted with He (purity 99.99
9%, hereinafter abbreviated as G e 1%/He. ) cylinder, 1
104 is NH gas (purity 99.99%) cylinder, 1
105 is a He gas (99.999% purity) cylinder, 11
06 is a H2 gas (purity 99.999%) cylinder.

In order to flow these gases into the reaction chamber 1iot, valves 1122 to 1126 of gas pumps 1102 to 1106,
Make sure the leak valve 1135 is closed,
In addition, inflow valves 1112 to 1116 and outflow valve 111
After confirming that 7 to 1121 and auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, the reading on the vacuum gauge 1136 is approximately 5X I OTo r r
When the auxiliary valves 1132, 1133. Close the outflow valves 1171-1121.

Next, to give an example of forming a photoreceptive layer on a cylindrical substrate 1137.1- as a support, Si H4/He gas from gas pump 1102, GeH/He gas from gas pump 1103, gas pump NHA gas from 1104 is transferred to valve 1122.
, 1123, 1124 is opened and the outlet pressure gauge 1127,
1128°1129 (7) By adjusting the pressure to 1 kg/crn' and gradually opening the inlet valves 1112, 1113, and 1114, the mass flow controller 1107
．． 1108 and 1110 respectively. Subsequently, the outflow valves 1117, 1118, 1119, and auxiliary valve 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101.

At this time, S i 84/H'e gas flow rate and G e
The outflow valves 1117.1118°1119 are adjusted so that the ratio of the Hp/He gas flow rate to the NH gas flow rate becomes the desired value.
Also, adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value. After confirming that the temperature of the base 1137 is set to a temperature in the range of 50 to 4'OO'O by the heater 1138, the power source 1137
140 to a desired power to generate a glow discharge in the reaction chamber 1101, and at the same time apply methods such as GeH÷/He gas and manual or externally driven motors according to a pre-designed rate of change curve to power the valves 1118 to 140 to a desired power. 1
The flow rate of NH3 gas is adjusted by appropriately changing the opening of 120, thereby controlling the distribution concentration C(N) of germanium atoms and nitrogen atoms contained in the formed layer.

In the manner described above, glow discharge is maintained for a desired period of time to form a layer region (G) 105 of $1 on the substrate 1137 to a desired layer thickness. 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 glow discharge for a desired period of time, a second layer region (S) 106 substantially free of germanium atoms can be formed on the first layer region (G) 105.

First layer region (G) 105 and second layer region (S) 1
In order to contain the substance (D) that controls conductivity in 06, the first layer region (G) 105 and the second layer region (S
) 106, a gas such as BzHt*PH3 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.

The first N(I)1 formed to a desired layer thickness as described above
02jj: To form the second layer (and) 103, for example, S i H4 gas and No gas are added as necessary by the same valve operation as in the formation of the first layer 102 (I). It is sufficient to dilute it with a diluent gas such as He and supply it into the reaction chamber 1101 to cause glow discharge according to desired conditions.

In order to contain halogen atoms in the second layer (JI) 103, for example, add SiF4 gas and No gas, or add SiH2 gas thereto and form the second layer (In) 103 in the same manner as above. All you have to do is form.

Needless to say, all outflow valves other than those required for forming each layer must be closed, and when forming each layer, the gas used to form the previous layer may be in the reaction chamber 1101. In order to avoid gas remaining in the gas piping leading from the outflow valves 1117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary valves 1132 and 1133 are opened, and the main valve 1134 is closed.
If necessary, fully open the system and evacuate the system to high vacuum.

The amount of oxygen atoms contained in the second layer (1) 103 is determined by, for example, SiHq gas and N
The flow rate ratio of O gas introduced into the reaction chamber 1101 can be changed as desired, or when forming a layer by sputtering, the silicon wafer and the
It can be controlled as desired by changing the sputtering area ratio of the i02 wafer or by changing the mixing ratio of silicon powder and Si02 powder and molding the target. The amount of halogen atoms contained in the second layer (It)' 103 can be determined by adjusting the flow rate when a raw material gas for introducing halogen atoms, for example, SiF4 gas, is introduced into the reaction chamber 1101. will be accomplished.

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

Examples will be described below.

Example 1 Using the manufacturing apparatus shown in FIG. 14, a sample (sample Mail-1-17-
(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. 5, and in FIG. 16.

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

The light image uses a tungsten lamp light source, 2JLux*
The light amount of .see was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the sample (imaging member 9) by cascading the surface of the sample (imaging member) with an e-chargeable developer (including toner and carrier). The above toner image, ■5
When transferred onto transfer paper using OKV's corona charging, clear, high-density images with excellent resolution and good gradation reproducibility were obtained in all samples.

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

Example 2 Cylindrical All
Samples (sample Nos. 21-1 to 27-5) as electrophotographic image forming members were prepared on a substrate under the conditions shown in Table 3 (Table 4).

The content distribution concentration of germanium atoms in each sample is the first
FIG. 5 shows the distribution concentration of nitrogen atoms, and FIG. 16 shows the nitrogen atom content distribution concentration.

When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. In addition, for each sample, 38℃, 8
When a repeated use test was conducted 200,000 times in an environment of 0% RH, no deterioration in image quality was observed in any of the samples.

Example 3 Sample tooth 11-1.12-1.13 of Example 1 except that the conditions for creating layer (II) 103 were as shown in Table 5.
Each of the electrophotographic imaging members (sample teeth, 11-1-1-11-1-8.
12-1-1 to 12-1-8 13-1-1 to 13-1
-8 samples) were created.

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

Table 6 shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability after repeated and continuous use.

Example 4 When forming layer (II) xo3, silicon wafer and S
By changing the iOS target area ratio, layer (X) 103
Each of the image forming members was created in exactly the same manner as in Sample No. 11-1 of Example 1, except that the content ratio of silicon atoms to oxygen atoms was changed. After repeating the image forming, developing, and cleaning steps approximately 50,000 times as described in Example 1 for each of the image forming members thus obtained, image evaluation was performed, and the results shown in Table 7 were obtained. Obtained.

Example 5 J! Sample No. 12- of Example 1 except that when forming (Jl) 103, the flow rate ratio of SiH gas and NO gas was changed to change the content ratio of silicon atoms and oxygen atoms in layer (It) 103. Each of the imaging members was made in exactly the same manner as in Example 1.

After repeating the steps up to transfer approximately 50,000 times using the method described in Example 1 for each image forming member thus obtained,
When the image was evaluated, the results shown in Table 8 were obtained.

Example 6 When forming the layer (n) 103, the flow rate ratio of SiH gas, SiF gas, and NO gas was changed to change the content ratio of silicon atoms and oxygen atoms in the layer (and) 103. Each of the image forming members was prepared in exactly the same manner as Sample No. 13-1 of Example 1. For each imaging member thus obtained, imaging as described in Example 1,
After repeating the development and cleaning steps about 50,000 times, one image was evaluated and the results shown in Table 9 were obtained.

Example 7 Each of the image forming members was created in exactly the same manner as in Sample No. 11-1 of Example 1, except that the layer thickness of the layer (IL) 103 was changed. The image forming, developing and cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 1θ.

The layer forming conditions in the Examples of the present invention shown in Table 2, Table 4, Table 10 and above are shown below.

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

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the light guide member of the present invention, and FIGS. 2 to 10 respectively show the distribution state of germanium atoms in the first layer (I). The explanatory diagrams for explanation, FIGS. 11 to 13, respectively show the first layer CI
), FIG. 14 is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS. 15 and 16 are diagrams for explaining the distribution state of nitrogen atoms in the present invention. FIG. 2 is a distribution state diagram showing the content distribution concentration state of atoms. 100... Photoconductive member, 101... Support, 102... First layer (I), 103... Second layer (IL), 104... Photoreceptive layer. Figure 1 C C Figure 11 Figure 12 Figure 13 C (N) C (N) C (N) Figure 15 (+ri01) (+502) (15031 (+504)
1 germanium containing π power No. 1 reversal (original + %)

Claims (1)

[Scope of Claims] (1) A support for a photoconductive member, a first layer region (G) made of an amorphous material containing germanium atoms, and provided on the support, and a silicon atom. a first layer comprising an amorphous material comprising a photoconductive second layer region (S) provided on the first layer region (G), and the second layer; A photoreceptive layer is provided thereon and is composed of a second layer made of an amorphous material containing silicon atoms and oxygen atoms, and the first layer has a layer region containing nitrogen atoms. (N), and the layer region (N) is a region (Y) in which the distribution concentration C(N) of nitrogen atoms in the layer thickness direction continuously increases from the support side toward the light-receiving layer side.
A photoconductive member comprising: The photoconductive member according to claim 1, wherein at least one of (S) contains a hydrogen atom. (3) The photoconductor according to claims 1 and 2, wherein at least one of the first layer region (G) and the second layer region (S) contains a halogen atom. Element. (4) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the 10th layer region (G) is non-uniform. (5) The photoconductive member according to claim 1, wherein the germanium atoms are uniformly distributed in the first layer region (G). (6) The light distribution conductive member according to claim 1, wherein the first Wll region (G) contains a substance that controls conductivity. (7) The photoconductive member according to claim 6, wherein the substance governing conductivity is an atom belonging to Group 5 of the periodic table. 7. The photoconductive member according to claim 6, which is an atom of the present invention.