JPS6060778A - Photoconductive member - Google Patents

Abstract

PURPOSE:To contrive the high photosensitivity and dark resistance by providing the layer region in which nitrogen atoms are included in a light accepting layer. CONSTITUTION:A photoconductive member 100 is composed of a supporting body 101 and a light accepting layer 102 used for as photoconductive members. The layer 102 is composed of the first layer region 103 consisting of a-Ge (Si, H, X) and the second layer region 104 consisting of a-Si (H, X), which has a photoconductivity. Further in the layer 102, the layer region including nitrogen atoms is arranged. The nitrogen atoms in this region can be included uniformly over the whole layer region and also can be included only in a part of the layer region.

Description

Detailed Description of the Invention The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (herein, light in a broad sense refers to ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, etc.). As a photoconductive material forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it has a high sensitivity and a high signal-to-noise ratio [photocurrent (Ip)].
/dark current (Id)), has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has the desired dark resistance value, and is non-polluting to the human body during use. In addition, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point.

Based on these points, amorphous silicon (hereinafter referred to as a-8i) is a photoconductive material that has recently attracted attention.
For example, German Publication No. 2746967, German Publication No. 28
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

However, a photoconductive member having a photoconductive layer made of conventional A-8T has excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance, etc. The reality is that there are points that can be further improved in terms of usage environment characteristics and stability over time, which require a combined improvement in 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 was often observed that residual potential remained during use. When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speed, the response gradually decreases, etc. There were many cases where problems occurred.

Furthermore, a-8i has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there remains room for improvement in that the light on the longer wavelength side cannot be used effectively.

In addition, if the amount of irradiated light that reaches the support without being sufficiently absorbed in the photoconductive layer 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 image blurring.

The influence of ξ becomes larger as the irradiation spot is made smaller in order to improve the resolution, and is a major problem especially when a semiconductor laser is used as the optical source.

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 is characterized by its applicability and applicability to a-8T 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 point of view, we have developed an amorphous material based on silicon atoms, especially an amorphous material based on silicon atoms, containing at least either a hydrogen atom (H) or a halogen atom (X). Amorphous material, P
From Jr "f = fi hydrogenated hydrogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [a-8t (H,X) J will be used hereafter as a generic notation] A photoconductive member designed and produced by specifying the layer structure of a photoconductive member having a photoreceptive layer that is structured and exhibits photoconductivity as explained hereinafter exhibits extremely excellent properties in practical use. Not only that, it is superior in all respects to conventional photoconductive materials, especially as a photoconductive material for electrophotography, and it has outstanding properties on the long wavelength side. This is based on the discovery that it has excellent absorption spectrum characteristics.

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

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

Another object of the present invention is that when applied as an image forming member for electrophotography, the electrostatic charge is retained during the charging process for formation 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 performance.

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 no-fttones, and high resolution. O Yet another object of the present invention is to provide a photoconductive member having high photosensitivity and high signal-to-noise ratio characteristics.

The photoconductive member of the present invention includes a support for the photoconductive member, a germanium atom, and optionally an amorphous material containing at least one of a silicon atom, a hydrogen atom, and a rogen atom (X). The first layer region (G) is made of a transparent material (hereinafter referred to as "a-Ge (Si, H, The second layer region (S) has a light-receiving layer having a layered structure provided in order from the support side, and the light-receiving layer contains nitrogen atoms and has a concentration distribution in the layer thickness direction. C(11, C(
31, C (21), a first layer region (1), a third layer region (3), and a second layer region (2) in this order from the support side (However, Cf31 >C(2).

C(1) and either C(1) or C(2+ is 0
(not).

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

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

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

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

FIG. 1 is a schematic configuration diagram schematically shown to explain a 1 m configuration of a photoconductive member of the present invention. A photoconductive member 100 shown in FIG. 1 is a support for a photoconductive member. On top of 101 is a photoreceptive layer 102, which has a free surface 105 on one end.

The light-receiving layer 102 is made of a-Ge(S) from the support 101 side.
i, H, X) 103
It has a layer structure in which a second layer region (8) 104 consisting of a-s i (H, IX) and having photoconductivity are laminated in this order.

The germanium atoms contained in the first layer region (G) 103 are contained in the first layer region (G) 10 together with other atoms.
3, it may be contained in the first layer region (G) 103 so as to be completely and uniformly distributed, or it may be contained evenly in the layer thickness direction. The distributed concentration may be non-uniform. However, in any case, in the in-plane direction parallel to the surface of the support, it is ensured that it is contained in a uniform distribution in order to make the properties uniform in the in-plane direction. is also necessary. In particular, the support 101 is contained evenly in the layer thickness direction of the layer region (G).
The distribution should be made such that it is more distributed on the support 101 side than on the side opposite to the side where it is provided (the surface 105 side of the photoreceptive layer 102), or the opposite distribution is made. Status! It is preferable that the first layer region (Gl 103) be filled in such a manner as to be thick.

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

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

In addition, the distribution state of germanium atoms in the first layer region (G) is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration C of germanium atoms in the layer thickness direction is from the support side to the second layer region. When a change is given that decreases toward the layer region (S), there is excellent affinity between the first layer region (G) and the M2 layer region (S), and as will be described later. Similarly, by making the distribution concentration C of germanium atoms extremely large at the edge of the support, when a semiconductor laser or the like is used, the second layer region (S) can hardly absorb it. Light on the wavelength side can be substantially completely absorbed in the first layer region (G), and interference due to reflection from the support surface can be prevented.

Further, when silicon atoms are contained in the first layer region (G), which is one of the preferred embodiments of the photoconductive member of the present invention, the first layer region (G) and the second layer region (G) Layer area (S)
Since each of the amorphous materials constituting the two has a common constituent element of silicon atoms, chemical stability is sufficiently ensured at the laminated interface.

2 to 10 show the thickness direction of germanium atoms contained in the first I-region (G) of the photoconductive member when the germanium atoms are contained in a non-uniformly distributed manner. A typical example of the distribution state is shown.

2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer region (G), and tB represents the first layer region (G) on the support side. ), and tT is the position of the end surface of the first layer region (G) on the opposite side to the support side.
Indicates the position of the end face.

That is, the first layer region containing germanium atoms (G
), layers are formed from the tB side toward the ptT side.

FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the first layer region (G) 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 CI and is contained in the first layer region (G) where germanium atoms are formed. has been gradually and continuously reduced.

At the interface position tT, the degree of distribution C of germanium atoms is C8.

In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C6 from the position tB to the position tA, and reaches the concentration C1 at the position tT. forming a state.

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

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

In the example shown in Figure @6, the distribution density C of germanium atoms is a constant value of concentration C9 between position tB and position t3, and is set to concentration CIO at positions t and r. Between the position t3 and the position tT, the distribution concentration C decreases in a linear function until it reaches the position t, and further reaches the position 1T.

In the example shown in FIG. 7, the distribution concentration C is at the position tB.
The concentration C11 takes a constant value up to position t4, and
, the distribution state decreases linearly from the concentration CI2 to the concentration C13 up to the position tT.

In the example shown in FIG. 8, position t. Further up to position tT, the distribution concentration C of germanium atoms decreases in a linear function so as to reach substantially zero from the degree C14.

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

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration CI7 at the position tB, and is initially slowly decreased from this concentration cn until reaching the position t6, and then rapidly decreases near the position ill. The concentration is reduced to Cll1 at position t6.

Between positions t and t, the concentration decreases rapidly at first, and then slowly decreases to reach CI9 at position t7, and between positions t and t, the concentration CI It is slowly and gradually decreased to reach the concentration C20 at position t8. Between position t8 and position t, the concentration C2° is reduced to substantially zero according to a curve shaped as shown in the figure.

As described above, according to FIGS. 2M to 10, the first layer region (G)
As described above, some typical examples of the distribution state of germanium atoms contained in the layer thickness direction, in the present invention,
On the support side, there is a part with a high distribution concentration C of germanium atoms, and on the interface 1T side, the distribution concentration C is high.
A preferable example is a case where the first layer region (Gl) has a distribution state of germanium atoms having a portion that is considerably lower than that on the support side.

The first layer region (G) constituting the photoreceptive layer constituting the photoconductive member of the present invention is preferably a layer region (G) containing germanium atoms at a relatively high concentration on the support side, as described above. It is desirable to have a location area (A).

For example, if the localized region (A) H1 is explained using the symbol h shown in FIGS. 2 to 10, it is desirable that it be provided within 5 μm from the interface position tB.

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

Whether the localized region (A) is a part or all of the layer region (LT) is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed. As for the distribution state of germanium atoms contained in the layer thickness direction, the maximum value Cmax of the distribution concentration of germanium atoms is preferably 1000 atomic ppm or more, preferably 5000 atomic ppm or more - optimally, with respect to the sum of the germanium atoms and the silicon atoms. IX
It is desirable that the layer be formed in such a manner that a distribution state of 10' atomic ppm or more can be obtained.

That is, in the present invention, the layer region (G) containing germanium atoms has a layer thickness of 5 μm or less (1 μm or less) from the support side.
It is formed so that the maximum value Cmax of the distribution concentration exists in a layer region with a thickness of 5 μm from B.

is preferable.

In the present invention, the germanium atom-containing needle contained in the first layer region (G) may be appropriately determined as desired so as to effectively achieve the object of the present invention, but , preferably 1 to 10
10' atomic ppm.

More preferably 10 (1-9,5X 10' ato
mic ppm.

Optimally 500-8 X 105 atomic ppm
It is desirable that this is done.

In the present invention, the first layer region (G) and the second layer region (S
) is one of the important factors for effectively achieving the object of the present invention, so the photoconductive member should be designed so that the formed photoconductive member has sufficient desired properties. Sufficient care needs to be taken when

In the present invention, the layer thickness TB of the first layer region (G) is preferably 30A to 50μ, more preferably 40λ to 4
It is desirable that the thickness be 0μ, and optimally 50λ to 30μ.

Further, the layer thickness T of the second layer region (S) is usually 0.
5-90μ, preferably 1-80μ, optimally 2-50
It is preferable that it be μ.

The sum (TB + T) of the layer thickness TB of the first layer region (G) and the layer thickness T of the second layer region (81) is determined by the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. In the photoconductive member of the present invention, the above numerical range of (Tn+T) is determined as desired when designing the layers of the photoconductive member based on the organic relationship between the characteristics and the characteristics of the photoconductive member. is preferably 1 to
100μ, more preferably 1-80μ, optimally 2-50
It is preferable that it be μ.

In a more preferred embodiment of the present invention, the above layer thickness TB and layer thickness T are preferably TB/T≦1.
When satisfying the following relationship, it is desirable to select appropriate numerical values for each of them.

In selecting the numerical values of layer thickness TB and layer thickness T in the above case, it is more preferable that TB/T≦0.9, optimally T
It is desirable that the values of layer thickness TB and layer thickness T be determined so that the relationship B/T≦0.8 is satisfied.

In the present invention, the content of germanium atoms contained in the first layer region (G) is I x 105 atomic
ppm or more, the layer thickness T of the first layer region fG)
It is desirable that B be fairly thin, preferably 30 μm or less, more preferably 25 μm or less, and optimally 25 μm or less.
It is desirable that the thickness be 0μ or less.

In the present invention, the tray of hydrogen atoms (H) contained in the second layer region (S) constituting the photoreceptive layer to be formed is determined by the amount of halogen atoms (X) or the amount of hydrogen atoms and halogen atoms. The sum of the amounts (H x) is preferably 1 to 40 atomic%, more preferably 5 to 30 atomic%, most preferably 5 to
It is desirable that the value be set to 25 atomic $.

In the present invention, if necessary, the first
The logon atom (X) contained in the layer region (G) and/or the layer region (S) of g2 includes fluorine, chlorine, bromine, and iodine, especially fluorine. , chlorine is preferred.

In the photoconductive member of the present invention, the photoreceptive layer contains a , a layer region (N) containing nitrogen atoms is provided. The phoneme atoms contained in the photoreceptive layer may be contained in the entire layer area of the photoreceptive layer, or may be contained in only a part of the layer area of the photoreceptive layer and remain there. It's okay.

In the present invention, the distribution state of nitrogen atoms is non-uniform in the layer thickness direction in the entire photoreceptive layer, as described above. Second. Each third layer region is uniform in the layer thickness direction. FIGS. 11 to 20 show typical examples of the distribution of nitrogen atoms in the entire photoreceptive layer. In each of these figures, the horizontal axis shows the distribution concentration cH of nitrogen atoms, and the vertical axis shows the layer thickness of the photoreceptive layer. tB shown on the vertical axis indicates the position of the end surface of the photoreceptive layer on the support side, and t and r indicate the positions of the end surface of the photoreceptive layer on the opposite side from the support. That is, the photoreceptive layer is formed from the tB side toward the t and r sides.

In the example shown in FIG. 11, the distribution concentration C (to) of oxygen atoms from position tB to position t is the concentration C2□, and the distribution concentration C (to) of nitrogen atoms from position t to position t11. is density 02□', and from position tll to position t? Up to this point, the concentration is CZt.

In the example shown in FIG. 12, the distribution concentration C(N
) is the concentration Cps from position tB to position t12, and position 1i
sj t+□ to position t1. The concentration is increased stepwise to ct, and is decreased to ct from position t13 to tT.

In the example of FIG. 13, the distribution concentration C of nitrogen atoms (Nl is the concentration C26 from the position tB to the position 1, and the position 1iffi
From t14 to position t, the concentration increases stepwise to q, and from position t's to position t, the initial concentration C7,
The concentration Cta is set to be lower than that.

In the example shown in FIG. 14, the distribution density C axis has a density of 9 from position tB to position tl11, and from position t16 to position tl? From the position toy to the position t18, the concentration is decreased to C30, and from the position toy to the position t18, the concentration is increased stepwise to C1l+, and from the position IIi+a to the position tB, the concentration is decreased to C8°.

In the example shown in FIG. 15, a layer region with a high distribution concentration C of nitrogen atoms is provided on the support side of the photoreceptive layer. By setting the distribution concentration C(to) of nitrogen atoms like this,
When subjected to charging treatment, it is possible to effectively prevent the injection of charges from the support side, and at the same time, it is possible to strengthen the adhesion between the support and the photoreceptive layer.

Further, by containing nitrogen atoms at a very low concentration in the layer region between t20 and tT, the dark resistance is further improved without reducing the photosensitivity.

In the examples shown in FIGS. 16 to 20, a layer region containing no nitrogen atoms is provided in the photoreceptive layer on the support side of the photoreceptor layer or on the opposite side from the support. When the main purpose is to improve photosensitivity and dark resistance, the nitrogen atom-containing layer region (N) provided in the receptor layer is provided so as to occupy the entire layer region of the photoreceptor layer, Charge injection from the free surface of the photoreceptor layer (
In order to prevent this, if the main purpose is to strengthen the adhesion between the support and the photoreceptive layer, it is provided near the free surface, and if the main purpose is to strengthen the adhesion between the support and the photoreceptive layer, the layer region ( B).

In the first case mentioned above, the content of nitrogen atoms contained in the layer region (N) is made relatively low in order to maintain high photosensitivity, and in the second case the content of nitrogen atoms contained in the layer region (N) is kept relatively low in order to maintain a high photosensitivity, and in the second case the content of nitrogen atoms contained in the layer region (N) is kept relatively low in order to maintain a high photosensitivity; It is desirable to use a relatively large amount to prevent injection, and in the case of 8K3, to ensure strong adhesion to the support.

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

In order to prevent charge injection from the free surface, a shingle layer region with a high distribution concentration C of N atoms is formed on the free surface side.

In the present invention, the content of nitrogen atoms contained in the layer region (N) provided in the photoreceptive layer depends on the characteristics required for the layer region (N) itself, or when the layer region (N) is attached to the support. When provided in direct contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the percent property at the contact interface with the support.

In addition, when another layer region is provided in direct contact with the layer region (0), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of nitrogen atoms is appropriately selected by considering the following.

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 the amount of nitrogen atoms contained in the layer region (N) may be determined as desired depending on the characteristics required of the photoconductive member to be formed. Preferably 0,001 to 50 atomic% with respect to "T(SiGeN) J"
, more preferably 0,002-40 atomic%
The optimum range is preferably 0.003 to 30 atomic%.

In the present invention, whether the layer region (N) occupies the entire area of the photoreceptive layer, or even if it does not occupy the entire area of the photoreceptor layer, the layer thickness T0 of the photoreceptor layer is When the proportion of nitrogen atoms in the layer region (0) is sufficiently large, the upper limit of the content of nitrogen atoms contained in the layer region (0) is desirably set to be sufficiently larger than the above value.

In the case of the present invention, if the ratio of the layer thickness T0 of the layer region (N) to the layer thickness T of the photoreceptive layer is two-fifths or more, The upper limit of the amount of air atoms contained is preferably 30 atomic% or less, more preferably 20 atomic% or less, and optimally 10 atomic% or less.

In the present invention, the layer region (N) containing nitrogen atoms constituting the photoreceptive layer is a localized region where oxygen atoms are contained at a relatively high concentration on the support side and near the free surface, as described above. It is desirable that the photoreceptive layer is provided as having the region (B), and in this case, it is possible to further improve the adhesion between the support and the photoreceptive layer and to improve the receptive potential.

The localized region (B) can be explained using the symbols shown in FIGS. 11 to 20, such as the interface position tB or the free surface t
It is desirable that it be provided within 5μ from T.

In the present invention, the localized region (B) is located at the interface position t
B or the entire layer area up to 5μ thick from the free surface tT (LT
) or as a part of the layer region (LT).Whether the 0 localized region (B) is part of the layer region (LT) or the whole layer region (LT) is determined. is determined as appropriate according to the characteristics required of the photoreceptive layer to be formed.

In the localized region (B), the maximum value Cmax of the distribution concentration C(0) of nitrogen atoms is preferably 500 atomic ppr as the distribution state of the nitrogen atoms contained therein in the layer thickness direction.
It is desirable that the layer be formed in such a manner that a distribution state of n or more, more preferably 800 atomic ppm or more, optimally 1000 atomic ppm or more can be obtained.

That is, in the present invention, the layer region (N) in which nitrogen atoms are included is within 5 μm in layer thickness from the support side or free surface (layer region 5 μ thick from tn or tT) with a distribution sophistication C
It is desirable that the maximum value Cmax of (N) exists.

In the present invention, in order to form the first layer region (G) composed of a-Ge (St, H, This is accomplished by utilizing a vacuum deposition method. For example, to form the layer region (G) by the glow discharge method, basically a raw material gas for supplying Ge that can supply germanium atoms (Ge) and, if necessary, silicon atoms (St) are used. The raw material gas for supplying St, the raw material gas for introducing hydrogen atoms (H), and/or the raw material gas for introducing halogen atoms (X) that can be supplied are kept at a desired gas pressure in a deposition chamber whose interior can be reduced in pressure. A glow discharge is caused in the deposition chamber, and a-Ge (St , H,
What is necessary is to form a layer consisting of. In addition, in order to contain germanium atoms in a non-uniform distribution state, the distribution concentration of germanium atoms is controlled according to a desired rate of change curve, and a-
A layer consisting of Ge (8i, H, X) may be formed.

Substances that can be used as raw material gas for Si supply used in the present invention include 5IH4t SItru, St, H
,.

5t4n,. Gaseous or gasifiable silicon hydride (silanes) such as 8iL, si and aa are preferred.

Substances that can become raw material waste for supplying Ge include Ge)
I, , Ge, H6, Ge, H4, Ge, H, o ,
Ge@H,2,Ge,H,,.

Ge7H,6,Ge,H,,G+4H,o, etc.Ge7H,6,Ge,H,,G+4H,o, etc.Germanium hydride in a gaseous state or which can be gasified is mentioned as one that can be effectively used, especially for ease of handling during layer creation work and Ge supply. In terms of efficiency etc., Gem, ,
Preferable examples include Ge, Ha, Ge, and L.

Many halogen compounds are effective as the raw material residue for introducing nitrogen atoms used in the present invention, such as nitrogen gas, nitrogen compounds, inter-halogen compounds, Preferred examples include gaseous or gasifiable -.logen compounds such as silane derivatives.

Further, silicon hydride compounds containing halogen atoms, which are in a gaseous state or can be gasified and have silicon atoms and 7-halogen atoms as a constituent aqueous solution, can also be mentioned as effective compounds in the present invention. Examples of halogen compounds that can be suitably used in the invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CIF, and CeF3'.

BrF, , BrF3, IF3, IF7,
Examples include halogen compounds such as Ice and IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF4.5i2F, , 5tcl! , , 5iBr
.

Preferred examples include silicon halides such as the following.

When forming the characteristic optical conductor part of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, a raw material gas capable of supplying Si together with a raw material gas for supplying Ge is used. The tenth layer region (G) made of a-8iGe containing halogen atoms can be formed on a desired support without using silicon hydride scum.

In the case of creating the first layer region (G) containing nitrogen atoms according to the glow discharge method, for example, silicon chloride, which also serves as a source gas for supplying St, and hydrogen, which serves as a raw material gas for supplying Ge, are used. germanium chloride and Ar, F2, He
and the like are introduced into the deposition chamber for forming the first layer region (G) at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. By this, the first layer region (G) can be formed on the desired support, but in order to more easily control the ratio of hydrogen atoms introduced, hydrogen may be added to these gases. A desired amount of gas or a silicon compound gas containing hydrogen atoms may be mixed to form a layer.

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

In order to form the first layer region (G) made of a-Ge (St, H, In the case of the ion blating method, sputtering is performed in a desired gas plasma atmosphere using a target consisting of Ge and Ge, or a target consisting of the target and Si, or a target consisting of Si and Ge. For example, polycrystalline germanium or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated by a resistance heating method, an electron beam method (EB method), or the like. This can be done by passing the flying evaporates through a desired gas plasma atmosphere.In addition, when sputtering a target made of St, a raw material gas for supplying Ge is introduced to form a layer region (G). When the distribution of germanium atoms is made non-uniform, for example, the above G
The target may be sputtered while controlling the gas flow rate of the raw material gas for e supply according to a desired rate of change curve.

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

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

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCe.

Hydrogen halides such as HBr and HI, Si'HtF2
．． SiH2■2゜5if (2C1!2H5IHC1!s
+5tH2Br218tHBrs etc./'tlff
Gen [silicon hydride, and GeHF3, GeH, F2
゜GeHsF, GeHCIB', GeH2C/! ,
GeH3C1! , GeHBr, .

GeH2Br, , GeH3Br, GeHI3
, GeH2I2, hydrogenated germanium halides such as GeHsI, halides containing hydrogen atoms as one of their constituent elements, GeF4゜GeCe, , GeBr4
, GeI, , GeFt, GeC1,, GeB
r, l.

A first layer region (G) in which gaseous or gasifiable substances such as germanium halides such as GeI, etc. are also effective.
It can be mentioned as a starting material for the formation.

Halogen atoms containing hydrogen atoms in these substances are hydrogen atoms that are extremely effective for controlling electrical or photoelectric properties at the same time as halogen atoms are introduced into the layer during the formation of the first layer region (G). Since atoms are also introduced, -
・Used as a raw material for introducing rogens.

In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, Ht1 or SiH4°Si, H, S
i, H,, 5t4H, etc. with germanium or germanium compound for supplying Ge, or GeH,, Ge, H,, GeBH@, Ge4H,
6゜Ge,H,2,GeaH14,Ge7H,,Ge
, H, ,GegH2o and other germanium hydrides and St
This can also be carried out by coexisting silicon or a silicon compound in the deposition chamber to generate a discharge.

In a preferred example of the present invention, hydrogen atoms (H
), or the amount of halogen atoms (X), or the sum of hydrogen atoms and halogen atoms (H + X) is preferably 0.01
~40 atomic%, more preferably 0.05-30
atomic%, optimally 0.1-25 atomic
It is desirable to set it to c%.

To control the amount of hydrogen atoms/and halogen atoms (3) contained in the first layer region, for example, the temperature of the support or/and hydrogen atoms, or the amount of halogen atoms (3)
What is necessary is to control the amount, discharge force, etc. of the starting material used to contain the material into the private equipment system.

In the present invention, in order to form the layer region (S) of MS 2 composed of a-Si (H,X), in the starting material (I) for forming the first layer region 0 described above, Okay, the starting material excluding the starting material that becomes the raw material gas for Ge supply [Second
This can be carried out using the same method and conditions as in the case of forming the first layer region 0 using the starting material (II) for forming the layer region (S).

That is, in the present invention, the second layer region (S) composed of a-8i (H, This is accomplished by the vacuum N:1j'J method that utilizes a discharge phenomenon. For example, a-
To form the 20th ground region (S) composed of 8i (H,
) and/or halogen atoms (a) for introducing hydrogen atoms as needed
A raw material gas for introduction is introduced into a deposition chamber whose interior can be reduced in pressure, a glow discharge is generated in the deposition chamber, and a-8i (
It is sufficient to form a layer consisting of H,,X).

In addition, when forming by sputtering method, for example, Ar
When sputtering a reta target composed of Si in an atmosphere of an inert gas such as He or a mixed gas based on these gases, sputtering a gas for introducing hydrogen atoms and/or halogen atoms (3) It is sufficient to introduce it into the deposition chamber for use.

In the present invention, in order to provide a layer region containing nitrogen atoms in the photoreceptor H, the starting material for introducing VC nitrogen atoms during the formation of the photoreceptor layer is prepared from the starting material for photoreceptor layer formation 1 described above. It may be used in conjunction with a substance to control the amount and contain it in the formed layer.

When the glow discharge method t-m is used to form the layer region, a starting material for introducing nitrogen atoms is added to the starting material selected as desired from among the starting materials for forming the photoreceptive layer described above. It will be done. As the starting material for introducing nitrogen atoms, at least a gaseous substance containing nitrogen atoms as an atom or a gasified substance that can be gasified can be used.

For example, a raw material gas whose constituent atoms are silicon atoms (Si), a raw material gas whose constituent atoms are nitrogen atoms (he), and a raw material gas whose constituent atoms are hydrogen atoms or halogen atoms as necessary. Alternatively, a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing nitrogen atoms and hydrogen atoms (also Also, mix at the desired mixing ratio, or
Alternatively, a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing three constituent atoms: silicon atoms (Si), nitrogen atoms N, and hydrogen atoms σ can be used in combination. .

Alternatively, a raw material gas having nitrogen atoms as its constituent atoms may be mixed with a raw material gas having silicon atoms (Si) and hydrogen atoms σ as its constituent atoms.

The starting material that can be effectively used as a raw material gas for introducing nitrogen atoms to form the layer region (into) is one in which N is the constituent atom or N and H are the constituent atoms. For example, nitrogen (Nt).

Ammonia (NH3), hydrazine (H2NNH,)
, hydrogen azide (HNs), gamma azide, mu(
gaseous or gasifiable nitrogen, such as NH<Ns);
Mention may be made of nitrogen compounds such as nitrides and azides.

In addition to this, in addition to the introduction of nitrogen atom ■, halogen atom (
3), it is possible to introduce nitrogen trifluoride (FsN).
) and nitrogen tetrafluoride compounds such as nitrogen tetrafluoride (F4 N2 ).

In the present invention, in order to further enhance the effect obtained by nitrogen atoms, oxygen atoms can be contained in addition to nitrogen atoms in the layer region.

As the raw material gas for introducing oxygen atoms into the layer region (N), for example, oxygen (02) is used.

Ozone (0,), -nitrogen oxide (No), nitrogen dioxide (
NO2).

-Nitrogen dioxide (N20), nitrogen sesquioxide (N203)
, trinitrogen tetraoxide (N204), nitrogen sesquioxide (N20
! 1) , nitrogen trioxide (NOs), silicon atom (S
i), an oxygen atom (0), and a hydrogen atom ■ as constituent atoms, for example, disiloxane (1,■3siO8iH3),
Trisiloxane (1-Is8 + OS r H2OS
Examples include lower silxanes such as IHA).

By a sputtering method, a layer region containing nitrogen atoms (to form N, a carved or polycrystalline Si wafer or a wafer containing a mixture of Si, N, wafers, and 5t3N) is formed. This can be done by taking a target and sputtering it in a gentle gas atmosphere.

For example, if an 81 wafer is used as a target, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms can be diluted with a diluent gas as necessary for spunter deposition. The Si wafer may be sputtered by introducing the gas into a chamber and forming a gas plasma of these gases.

In addition, by using a mixed target of Si and Si3N as separate targets for i, S+ and Si3N, it is possible to use a mixed target of Si and Si3N in an atmosphere of dilution gas as a sputtering gas or at least hydrogen. This is accomplished by sputtering in a gas atmosphere containing atoms (3) and/or halogen atoms (3) 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 example of Ge4-discharge mentioned above can be used as an effective gas also in the case of sputtering.

In the present invention, when forming the photoreceptive layer, the layer region containing nitrogen V atoms (if N is provided, the distribution concentration C (N) of nitrogen atoms contained in the layer region (N)) By changing stepwise in the layer thickness direction, the desired distribution state in the layer thickness direction (dept
h profile), in the case of gelow discharge, the gas of the starting material for introducing nitrogen atoms whose distribution concentration C(N) is to be changed is adjusted to the desired gas flow rate. This is accomplished by introducing it into the deposition chamber while changing the rate of change appropriately according to the rate of change line.

For example, the opening of a predetermined needle pulp serving in the middle of the gas passage system may be appropriately changed by any commonly used method such as manual operation or an external drive motor. At this time, in addition to changing the flow rate manually, it is also possible to control the flow rate according to a pre-designed rate of change line using, for example, a microcomputer to obtain a desired content distribution concentration curve. (N) by the Svatutaringe method VC, the distribution concentration C(N) of pixel atoms in the layer/thickness direction is changed in the layer thickness direction to obtain a desired distribution state (depth profile) of nitrogen atoms in the layer thickness direction. To form f, 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 adjusted as desired. This is accomplished by making appropriate changes.

Second, the target for spa sota ringae, for example, S
If a target containing a mixture of i and Si3N is used, this can be done by changing the mixing ratio of Sl and Si3N in advance in the thickness direction of one target.

In the photoconductive part of the present invention, the conduction properties are controlled in the first layer region (G) containing germanium atoms and/or the second layer region (S) not containing germanium atoms. By containing a substance (Q) in the photoreceptive layer, the conduction properties of each layer region can be controlled as desired. That is, a layer region (PN) containing a substance (Q) that controls conduction properties in the photoreceptive layer. At 5tv, the layer area (
The conduction properties of the PN) can be arbitrarily controlled as desired.

Examples of such substances include impurities that are commonly referred to in the semiconductor field, and in the present invention, n-type impurities that give p-type conductivity to 84 or Ge, and n-type Examples include n-type conductive properties.

Specifically, n-type impurities include atoms belonging to group ■ of the periodic table (group ■ atoms), such as B (硼!), A
, fl' (aluminum), Ga (gallium), In
(indium), Tl (thallium), etc., and B and Ga are particularly preferably used.

Examples of n-type impurities include atoms belonging to Group V of the periodic table (Group V atoms), such as P (phosphorus) and As (alcohol).

3b (antimony), Bi (bismuth), etc., and P and As are particularly preferably used.

In the present invention, the layer region (PN) VC contains a layer containing a substance that controls the conduction properties, the conduction properties required for the layer region (PN), or the layer region (])N). It can be selected as appropriate based on the organic relationship, such as the characteristics of other layer regions provided in contact with the ρ layer region and the relationship with the characteristics at the contact interface with the other ρ layer region.

In addition, when the substance (Q) that controls the conduction properties of the front P is locally contained in a desired layer region of the photoreceptive layer, it is particularly necessary to contain the substance (Q) in the end layer region (G) of the photoreceptive layer on the side of the support. When containing, the layer region (other Ii4 provided in direct contact with the odor)
The content of the substance that controls conduction characteristics is appropriately selected without considering the characteristics of the region or the relationship with the characteristics at the contact interface with other layer regions.

In the present invention, a substance controlling conduction properties contained in the layer region (PN) (the content of q is preferably h
: 0.01~5X 10'atomic pprs,
More suitable 11m1d0.5~I x 10'atomi
c ppm, optimally 1-5 x 10"atomi
It is preferable that it be c q.

In the present invention, the substance that governs the conduction characteristics (the content of q in the layer region (PN) is preferably 30 atomic or more, more preferably 50 atomic
atomic 1 lplN or more, optimally 100 a
tomic pP or higher, it is desirable to locally contain the substance (q) in a part of the layer region of the photoreceptive layer, especially in the layer region (PN) of the support side end Vc of the photoreceptor layer. It is desirable to have them unevenly distributed.

In the present invention, the layer region (PN) can be provided in a part or all of the layer region ((S) constituting the photoreceptive layer. ') may be provided in a part or all of the layer region (a), or may be provided so as to be included as a part of the entire layer region (a).

By incorporating the substance (Q) that controls the conduction characteristics so that the layer region at the end of the support side of the photoreceptive layer (contains more than the above value in the odor), for example, the substance (Q) to be included can be
In case 1c is the above-mentioned p-type impurity, it is possible to effectively block the movement of electrons injected from the support side into the photoreceptive layer when the free surface of the photoreceptive layer is subjected to polar charging treatment. In addition, when the substance to be contained is the n-type impurity, holes injected from the support side into the photoreceptive layer when the free surface of the photoreceptive layer is charged to e polarity. can effectively prevent the movement of

In this way, when the end layer region (8) contains a substance that controls conduction characteristics of one polarity, the remaining layer region of the photoreceptive layer, i.e., the end layer region (excluding the The layer region ttC of the part may contain a substance that controls the conduction characteristics of the other polarity, or the material that controls all the conduction characteristics of the same polarity may be added to the end JVIJfi′i region (noodles). It is also possible to contain a much smaller amount of sake than the actual amount of sake contained.

In such a case, the content of the substance controlling the conductive properties contained in the layer region (Z) is as follows:
It is determined as desired depending on the polarity of the substance contained in the substance and the content 1δ, but it is preferably 0.001 to 1000 ato+nic pIB.

More preferably, it is 0.05 to 500 atomic P, and most preferably 0.1 to 200 ato+nic4.

In the present invention, when the end layer region (4) contains the same type of substance that controls conductivity, the content in the layer region is preferably 30 ato
It is desirable to set it to Lord Mic or lower.

In addition to the above-mentioned cases, in the present invention, the photoreceptive layer contains a layer region containing a substance controlling conductivity having one polarity, and a substance controlling conductivity having the other polarity. It is also possible to provide a so-called depletion layer in the contact region by directly contacting a layer region containing . For example, in the photoreceptor layer, the layer region containing the p-type impurity described above and the layer region containing the n-type impurity described in IJ are separated by 1 JLv.
It is possible to provide a depletion layer by providing a so-called pn junction by providing it so that it touches cL.

Substances that control conduction compatibility in the photoreceptive layer, such as No. 1 II
In order to structurally introduce group V atoms or group V atoms, the starting material for introducing group V atoms or group V atoms must be prepared in a gaseous state during layer formation. In the chamber, the second
It is good to do this together with other starting materials to form the area of ~.

In this way, substances that can be used as starting materials for the incorporation of group 7I atoms are those that can be easily formed into scum under conditions of fiXJ. It is desirable that j'L be. Specifically, as a starting material for such a boron atom, B
tHa, H4) 110. B! IH9, BIIHll.

Examples include hydrated boron of BekiIo-k3oHrt-B6Hu'4, k3F, PCl3°HBr, and halogenated boron of A4. In addition, AJICIIB
, (laclB, Ga(CH,)s, '1n
C/1, 'l'1lc4, etc. can also be mentioned.

In the present invention, phosphorus atoms are effectively used as starting materials for the introduction of Group Ⅰ atoms, including PR,
P, )(hydrogenated phosphorus, P)l, I, ))F3
゜PFs * PCl31 PClm * P , Br
Examples include phosphorus halides such as l I PHr and l "Is. In addition, AsH3, Asl!', and the like.

AsC4, AsBr1, AsF, , SbH,,
SbF3. SbF, , 5bC1!3.

5b (J, , BiH, , B1C4, HiBr3, etc. can also be mentioned as effective starting materials for the introduction of the VI atom.) The support used in the present invention may be either electrically conductive or electrically insulating. There may be.° As a specialized support,
For example, NiCr, stainless steel.

kl, Cr, Mo, Au, Nb, Ta, V
, 'l'i, i't, Pd, or 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, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these insulating supports is subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface 01 side.

In other words, glass has Ni and Cr on its surface.
.

A, ll, Cr, Mo, Au, Ir, Nb,
'l'a, V, Ti, Pt, Pd.

In, 0. , SnO,, l TO(In, 0. +
Conductivity is imparted by laying down a thin film made of SnO, ), etc., or a synthetic resin film such as polyester film, NiCr, IJ, Ag, P.
b, Zn, Ni, Au.

A thin film of metal such as Cr, No, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with ifl'ffi metal, Conductivity is imparted to the surface. The shape of the support body is cylindrical, belt-shaped,
The photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member, for example, if the photoconductive member 100 of FIG.
In the case of I# copy, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is determined as appropriate so that a photoconductive member can be formed exactly as required, but if flexibility is required as a photoconductive member, the thickness of the support may be determined to ensure that it does not fully perform its function as a support. It will be covered as much as possible within the range. However, in such a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the number is preferably 103 or more.

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

FIG. 21 shows an example of a photoconductive member manufacturing apparatus. In the gas cylinders 1102 to 1106 in the figure, five raw material gases for forming the photoconductive member of the present invention are sealed. 1102 is SiH gas diluted with He (purity 99.999N, hereinafter 5il (
It is abbreviated as 4/He. ) cylinder, 1103 is Ge diluted with He) T4 gas (purity 99.999%, hereinafter GeH
4/He (abbreviated as 0゛) cylinder, 1104 is NH, gas (
Purity 99.99%) Bombe 5.11”O; 51 is
He gas (purity 99.999N) cylinder 1106 is H gas (purity 99.999%) cylinder.

In order to flow these gases into the reaction chamber 1101, pulps 1122 to 1126 of gas cylinders 1102 to 1106,
Confirm that the IJ valve 1135 is closed, and also close the inflow valves 1112 to 1116 and the outflow pulp 11.
After confirming that the auxiliary pulps 1132 and 1133 of 17 to 11211 are open, the main valve 1134 is first opened to exhaust the reaction chamber 1101 and each gas pipe. Next, the reading on the vacuum gauge 1136 is approximately 5 x 10'tor.
When reaching r, the auxiliary pulps 1132 and 1133 and the outflow pulps 1117 to 1121 are closed.

Next, to give an example of forming a photoreceptive layer on the cylindrical substrate 1137, SiH
,/He gas, gas cylinder 1103 J) GeH.

/He gas, NH gas from the gas cylinder 1104, open the pulps 1122, 1123, 1124, adjust the pressure of the outlet pressure gauges 1127, 1128, 1129 to 1 odor/d, and gradually open the inflow pulps 1112, 1113, 1114. Mass flow controller 1107.1108.11
09 respectively. Subsequently, the outflow pulp 111
7, 1118, 1119, the auxiliary valves 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, the outflow pulp 1117° 1118, 1119 is adjusted so that the ratio of the SiH,/He gas flow rate, the GeH4/He gas flow rate, and the NH, gas flow rate becomes the desired value, and the pressure inside the reaction chamber 1101 is vacuum gauge 1 so that it reaches the desired value.
Adjust the opening height of the main valve 1134 while checking the reading of 136. Then, the temperature of the base 1137 becomes higher than that of the heating heater 1.
After confirming that the temperature is set in the range of about 50 to 400 °C by 138, the power supply 1140 is set to the desired power to generate a glow discharge in the reaction chamber 1101,
At the same time, according to the pre-designed change output line, GeH,
The germanium atoms and nitrogen atoms contained in the layer formed by appropriately changing the openings of the valves 1118 and 1120 by adjusting the flow rates of /He gas and NH gas manually or using an external drive motor, etc. Control distribution concentration.

In the manner described above, glow discharge is maintained for a desired period of time to form a first layer region (G) on the substrate 1137 to a desired layer thickness. At the stage where the first layer region (G) has been formed to the desired layer thickness, the desired thickness is obtained by following the same conditions and procedures, except for completely closing the outflow valve 111B and changing the discharge conditions as necessary. The first by maintaining the glow discharge for an hour
A second layer region (S) containing substantially no germanium atoms can be formed on the layer region (G) of the first layer region (G) and the second layer region (S). , in order to contain a substance that controls conductivity, the first layer region (
G) and the second layer region (S), for example B2
Gases such as H, PH3, etc. may be added to the gas introduced into the deposition chamber 1101.

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 Samples (Samples 1611-1 to 17-6) as electrophotographic image forming members were prepared on a cylindrical M substrate under the conditions shown in Table 1 using the manufacturing apparatus shown in FIG.
Table 2).

The content distribution concentration of germanium atoms in each sample is the second
FIG. 2 shows the distribution concentration of nitrogen atoms, and FIG. 23 shows the nitrogen atom content distribution concentration.

Place each sample obtained in this way in a charging exposure experiment device.■5. Corona charging was performed for 0.3 (8) minutes using OKV, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light intensity of 21 ux-soc was irradiated through a transmission type test chart.

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

In the above, the light source is 81 instead of a tungsten lamp.
The image quality of the toner transfer image was evaluated for each sample under the same toner image forming conditions as above, except that the electrostatic image was formed using a Qnm GaAs semiconductor laser (10 mW). , all samples have excellent resolution,
A clear, high-quality image with good gradation reproducibility was obtained.

Example 2 Samples (Samples Ah 21-1 to 27-6) as electrophotographic image forming members were prepared on a cylindrical M substrate under the conditions shown in Table 3 using the manufacturing apparatus shown in FIG. (Table 4).

The content distribution concentration of germanium atoms in each sample is the second
FIG. 2 shows the content distribution concentration of nine elementary atoms, and FIG. 23 shows the concentration distribution of nine elementary atoms.

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. Father, 38℃, 80%R for each sample.
, H environment, 200,000 times repeated use test, no deterioration in image quality was observed in any of the samples.

Example 3 Samples (Samples A31-1 to A37-6) as electrophotographic image forming members were prepared on a cylindrical AA substrate under the conditions shown in Table 5 using the manufacturing apparatus shown in FIG.
Table 6).

The content distribution concentration of germanium atoms in each sample is the second
FIG. 2 shows the distribution concentration of nitrogen atoms, and FIG. 23 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. Also, each sample was heated to 38°C and 80% I
When repeated use tests were conducted 200,000 times in environments of Samples (Samples/1641-1 to 47-6) as electrophotographic image forming members were prepared on a substrate under the conditions shown in Table 7 (Table 8).

The content distribution concentration of germanium atoms in each sample is the second
FIG. 2 shows the content distribution concentration of the elemental atoms, and FIG. 23 shows the concentration distribution of the element atoms.

When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. In addition, each sample was heated at 38°C and 80% R.
When a repeated usage test was carried out 200,000 times in an environment of H, no deterioration in image quality was observed in any of the samples.The common layer forming conditions in the above examples of the present invention are shown below.

Substrate temperature: germanium atom (Ge) containing layer...
・About 200℃, germanium atom (Ge)-free layer...
・About 250℃ Discharge frequency: 13.56 M, I (Reaction chamber pressure during z reaction: Q, 3 Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are illustrations for explaining the distribution state of germanium atoms in the photoreceptive layer, respectively. figure,
FIGS. 11 to 20 are explanatory views for explaining the distribution state of nitrogen atoms in the photoreceptive layer, respectively. FIG. 21 is a schematic explanatory view of the apparatus used in the present invention, and FIGS. FIG. 23 is a distribution state diagram showing the content distribution state of each atom in each example of the present invention. 100... Photoconductive member 101... Support body 102.
...Photoreceptive layer applicant Canon Co., Ltd. 0 C 0 1----→-C 1---→-C □C C(N) 111111-----→-C(N) C(N) C(N) 11------------→-C(N) Procedural amendment (voluntary) November 1, 1988 1, Indication of case 1988 Patent Application No. 170380 No. 2, Name of the invention Photoconductive member 3, Relationship to the amended case Patent applicant address 3-30-2 Shimomaruko, Ota-ku, Tokyo Address 146
3-30-25 Shimomaruko, Ota-ku, Tokyo, Subject of amendment (1) Specification 6, Contents of amendment (1) As shown in the attached document, between pages 64 and 65, Table 5, Table 6, Table 7, Add Table 8.

Claims (1)

[Scope of Claims] (1) A support for a photoconductive member, and a layer region (G
) and an amorphous material containing silicon atoms, and a layer region (S) exhibiting photoconductivity is provided in order from the support side, and the photoreceptor layer has , containing nitrogen atoms, whose distribution concentration in the layer thickness direction is CI
+), C(al, C(21), first layer region (1),
A photoconductive member characterized by having a third layer region (3) and a second layer region (2) in this order from the support side (however,
C(31>C(2+, C(1) and Cf1l,
C (one of 21 is not O). (2) The photoconductive member according to claim 1, wherein at least one of the layer region (S) and the layer region (G) contains hydrogen atoms. (3) The photoconductive member according to claim 2, wherein at least one of the j-region (S) and the layer region (G) contains a norogezo atom. (4) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the layer region (G) is non-uniform. (5) The photoconductive member according to claim 1, wherein the germanium atoms are uniformly distributed in the layer region (G). (6) The photoconductive member according to claim 1, wherein the photoreceptive layer contains a substance that controls conductivity. (The photoconductive member according to claim 6, wherein the substance governing conductivity is an atom belonging to Group I of the Periodic Table. (8) The substance governing conductivity is an atom belonging to Group V of the Periodic Table. The photoconductive member according to claim 6, which is an atom belonging to .