JPS60143357A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member excellent and stable in electrical, optical, and photoconductive characteristics, improved in photosensitivity in a longer wavelength region, and superior in both mechanical strength and durability, by forming a photoreceptor specified in layer structure made of a-SiGe(H,X) on a substrate. CONSTITUTION:A photoconductive photoreceptor layer 102 is formed on a substrate 101, and it is composed of the first layer 103 made of amorphous Si, the second layer 104 made of amorphous Si and Ge, and the third layer 105 made of amorphous Si contg. N from the substrate side. The layer 104 contains Ge in a concn. distribution nonuniform in the layer 104 thickness direction, and at least one of the layers 103 and 104 contains H and/or halogen, and further, preferably, a conductivity governor, such as group III or V. The formation of the photoreceptor layer 102 having such a layer structure can improve electrical, optical, photoconductive, voltage withstanding, and use environment withstanding characteristics.

Description

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

[Prior Art] Photoconductive materials that form photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, and document reading devices have 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, and has a desired dark resistance value.
Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use and being able to easily dispose of afterimages within a predetermined time.

Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point.

Based on this viewpoint, amorphous silicon (hereinafter referred to as a-3i) is a photoconductive material that has recently attracted attention. The application to an image forming member for use in photoelectric conversion is described, and the application to a photoelectric conversion/reading device is described in German Published Publication No. 2,933,411.

However, photoconductive members having a photoconductive layer composed of conventional a-5i have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and temperature resistance. The reality is that there is a problem that needs to be further improved in terms of the use environment characteristics and also the stability over time, and it is necessary to improve the 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, and a so-called ghost phenomenon, which causes an afterimage, may occur.
In addition, there are many disadvantages such as a gradual decrease in responsiveness when used repeatedly at high speeds.

Furthermore, a-Si 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. Furthermore, there remains room for improvement in that when a halogen lamp or fluorescent lamp, which is used as a waste, is used as a light source, it is not possible to effectively use light on the long wavelength side. Alternatively, if the amount of irradiated light that reaches the support without being absorbed in the photoconductive layer increases, the support itself will have a high reflectance to the light that passes through the photoconductive layer. In some cases, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes more pronounced as the irradiation band becomes smaller in order to increase the resolution, and becomes a serious problem especially when a semiconductor laser is used as the light source.

Furthermore, when the photoconductive layer is composed of a-3i material,
In order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and boron atoms and phosphorus atoms to control electrical conductivity, or other properties. Other atoms for improvement
Each of these constituent atoms is contained in the photoconductive layer, but depending on the manner in which these constituent atoms are contained, problems may arise in the electrical or photoconductive properties of the formed layer.

That is, for example, sufficient image density may not be obtained because the life of photocarriers generated in the formed photoconductive layer by light irradiation is not sufficient, or in dark areas, photocarriers generated by light irradiation may not have sufficient image density. Problems often arise due to insufficient prevention of charge injection.

Therefore, while efforts are being made to improve the properties of the a-3i material itself, it is necessary to take measures to obtain the desired electrical and optical properties as described above when designing the optical core member.

The present invention has been made in view of the above points, and from the viewpoint of the applicability of a-5i as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive and intensive research, we have found that an amorphous material with silicon (Si) as its matrix, especially silicon atoms (Si) as its matrix, with either a hydrogen atom ()l) or a halogen atom (X). An amorphous material containing at least one of the above, i.e., so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter collectively referred to as a-5i(H,X)], and silicon atoms. (
Si) and germanium atoms (Ge) as a matrix, especially amorphous materials with these atoms as a matrix and hydrogen atoms (H)
or an amorphous material containing at least one of the halogen atoms (X), so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter these will be collectively referred to as a -9iGe (H,
The photoconductive member prepared using the 1 yen standard not only shows extremely superior properties in practical use, but also surpasses conventional photoconductive members in all respects, especially for electrophotography. This is based on the discovery that it has extremely excellent properties as a photoconductive member and that it has excellent absorption spectrum properties on the long wavelength side.

[Objective of the Invention] The present invention is an all-environment type in which the electrical, optical, and photoconductive properties are always stable and are almost unaffected by the usage environment, and it has excellent light sensitivity characteristics on the long wavelength side and is light resistant. It has excellent fatigue properties and does not deteriorate even after repeated use.
The main objective is to provide a photoconductive member in which no or almost no residual potential is observed.

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

Another object of the present invention is to provide a charge retention capacity during charging processing for electrostatic image formation to such an extent that associative 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 having sufficient electrophotographic properties and excellent electrophotographic properties.

Still another object of the present invention is to provide an electrophotographic light source capable of easily obtaining high-quality images with high density, clear /\-tones, and high resolution, without image defects or image deletion. An object of the present invention is to provide a conductive member.

Yet another object of the present invention is to provide a photoconductive member with sufficiently high dark resistance and sufficient acceptance potential, and to improve productivity by improving adhesion between each layer. It is in.

Yet another object of the present invention is to provide a photoconductive member having high photosensitivity and high signal-to-noise ratio characteristics.

[Structure of the Invention] That is, the photoconductive member of the present invention includes a support for the photoconductive member and a photoreceptive layer provided on the support and having photoconductivity. The photoreceptive layer includes, from the support side, a first layer (I) made of an amorphous material containing silicon atoms, and a second layer (I) made of an amorphous material containing silicon atoms and germanium atoms. Layer (II
) and a third layer (m) made of an amorphous material containing silicon atoms and nitrogen atoms, and
The layer (II) is characterized in that the germanium atoms contained in the layer (II) are non-uniformly distributed in the thickness direction of the layer. in the first layer (I) and in the second layer (I
It is desirable that at least one of the first layer (1) and the second layer (n) contains a hydrogen atom and/or a halogen atom, and at least one of the first layer (1) and the second layer (n) Preferably, the material contains a substance that controls conductivity.

The photoconductive member of the present invention, in which the photoreceptive layer has the layer structure described above, can solve all of the problems described above, and has extremely excellent electrical, optical, and optical properties. Indicates conductive properties, electrical voltage resistance, and usage environment characteristics.

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

Furthermore, the photoconductive member of the present invention can be used in the entire visible light range.

It has high photosensitivity, particularly good matching with semiconductor lasers, and fast photoresponse.

[BEST MODE FOR CARRYING OUT THE INVENTION] The photoconductive member of the present invention will be described in detail below with reference to the drawings.

FIG. 1 is a diagram schematically showing a layer structure for explaining the layer structure of a photoconductive member of the present invention.

The photoconductive member 100 of the present invention includes a photoreceptor 5102 having sufficient volume resistivity and photoconductivity on a support 101 for the photoconductive member, as shown in FIG. Photoreceptive layer 10
2 is a -5i (H,X) caranal first layer (I) 103, a -3iGe (H, X) Constructed with a third layer (m) 105 that is empty. Photoconductivity may be applied to either the first layer (CI) or the second layer (U), but in any case, the layer to which incident light reaches has photoconductivity. needs to be designed.

Moreover, in this case, the first scrap (I) and the second layer (II
) are preferably designed as layers that have photoconductivity for light in a desired wavelength spectrum and can generate a sufficient amount of photocarriers.

In the photoconductive member of the present invention, by containing a substance (C) that controls conductivity in at least one of the first layer CI) or the second layer (IT), the conductivity of the contained layer can be improved. sex can be controlled as desired. The substance (C) may be distributed uniformly or non-uniformly in the layer thickness direction in both or each of the first layer (I) and the second layer (II). Contained in In addition, the layer region (PN) containing the substance (C)
In this case, the substance (C) is continuous in the layer thickness direction.

It is contained in a uniform or non-uniform distribution state.

For example, the thickness of the second layer (II) is made thicker than that of the first layer (I), so that the second layer (II) mainly functions as a charge generation layer and a charge transport layer. When used in the first layer (I), the substance (C) controlling the conductivity is
), it is desirable to have a distribution state in which it is concentrated on the support side, and the substance (C) that controls conductivity is
is the second layer (II), the first layer (1) and WrJ2
It is desirable to have a distribution state in which the amount of silica is concentrated at or near the interface of layer (II).

On the other hand, the layer thickness of the first layer (r) is made thicker than the layer thickness of the second layer ([), and mainly the second layer ([)] is made thicker than the second layer ([). When (II) is used as a charge generation layer and the first layer (I) is used as a charge transport layer, the substance (G) that controls conductivity is used in the first layer ( It is desirable to contain it so that it is distributed more on the support side of I).

As described above, in the present invention, at least one of the first layer (1) and the second layer (II) is a layer containing the substance (C) that controls conductivity continuously in the layer thickness direction. Area (P
By providing N), it is possible to increase sensitivity, improve electrical withstand voltage, etc.

Examples of the substance (C) that controls such conductivity include so-called impurities in the semiconductor field. Mention may be made of n-type impurities and n-type impurities that provide n-type conductivity properties. Specifically, as p-type impurities, atoms belonging to Group ■ of the periodic table (Group ■ atoms)
For example, B, A1, Ga, In, TI, etc. are used, and B and Ga are particularly preferably used. Examples of n-type impurities include atoms belonging to the V group of the periodic table (V group atoms), such as P, As, Sb, B1. Among them, P and As are particularly preferably used.

In the present invention, the content of the substance controlling conductivity (C) contained in the layer region (PN) containing the substance controlling conductivity (C) provided in the photoreceptive layer is , the conductivity properties required for the layer region (PM), or when the layer region (PN) is provided in direct contact with the support, the relationship with the properties at the contact interface with the support, etc. , can be selected as appropriate depending on the organic relationship. In addition, we also consider the characteristics of other layer regions provided in direct contact with the layer region (PN) and the relationship with the characteristics of the contact interface with the layer region of the layer, and consider the substances that govern conductivity. The content of (C) is appropriately selected.

In the present invention, the content of the substance (C) that controls conductivity contained in the layer region (PN) is preferably 0.
．． 001~5X10'' atomic ppm, more preferably 0.5~LX 104104ato ppm,
The optimum value is i -5X 103103ato ppm.

In the present invention, the content of the substance (C) that controls conductivity in the layer region (PM) is preferably 30 atoms.
ic ppm or more, more preferably 50 atoms
PpI! l - J2, optimally 100100ato
ppm or more, for example, when the substance (C) is the p-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, it is possible to prevent the material from entering the photoreceptor layer from the support side. can effectively prevent the electron injection of
When the substance (C) is the n-type impurity, when the free surface of the photoreceptive layer is charged to e-polarity, holes can be effectively injected from the support side into the photoreceptor layer. can be prevented.

In the above case, the layer region (Z) excluding the layer region (PN) has a polarity different from the polarity of the substance (C) that controls conductivity contained in the layer region (PN). A substance (C) controlling the conductivity of the same polarity may be contained in the layer region (PN
) may be contained in a much smaller amount than that contained in ().

In such a case, the content of the substance (G) that controls the conductivity contained in the layer region (Z) is as follows:
It is determined appropriately depending on the polarity and content of the substance (C) contained in PN), but preferably 0.00
1”-1000 atomic ppm, more preferably 0.05-500 atomic jc ppm, optimally 0
．． It is desirable that the content be 1 to 200 atomic ppm.

In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance (C) that controls conductivity, the content in the layer region (Z) is preferably is preferably 3 (atomic ppm or less).

In addition to the above-described case, in the present invention, a layer region containing a substance (C) having one polarity and controlling conductivity in the photoreceptive layer, and a layer region having the other polarity and controlling conductivity. It is also possible to provide a so-called depletion layer in the contact region by providing a layer region containing a substance (G) in direct contact with the contact region.

That is, for example, a layer region containing the above-mentioned P-type impurity and a layer region containing the above-mentioned n-type impurity are provided in the photoreceptive layer so as to be in direct contact with each other to form an mPn junction, thereby forming a depletion layer. can be provided.

In the present invention, specific examples of the halogen atom (X) contained in the first layer (I) if necessary include fluorine, chlorine, bromine, and iodine, but in particular fluorine, chlorine, can be mentioned as suitable.

In the present invention, the first
To form the layer CI), for example, a glow discharge method, a sputtering method, or a vacuum deposition method using a discharge phenomenon such as an ion blating method or an f-ing method is applied.

For example, in order to form the first layer (I) composed of a-5i (H, At the same time, a raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) is introduced into a deposition chamber in which the internal pressure can be reduced at a predetermined ratio and gas flow rate. By generating a glow discharge in the deposition chamber and forming a plasma atmosphere of these gases,
a-5i on the surface of the support which has been installed in a predetermined position in advance.
A first layer (I) composed of (H,X) is formed.

In addition, when forming by sputtering method, for example, A
When sputtering a target composed of Si in an atmosphere of an inert gas such as r, He, or a mixed gas based on these gases, it is necessary to introduce hydrogen atoms (H) and/or halogen atoms (X). The gas may be introduced into a deposition chamber for sputtering.

In the present invention, the following are effective starting materials for the raw material gas used to form the first layer (D).

First, the starting materials that will become the raw material gas for supplying Si are as follows:
SiH,, Si2H61, 5i3HB, Si4H1
Silicon hydride (
Silanes) can be effectively used, and SiH4 and Si2H6 are particularly preferred in terms of ease of layer-forming work and good Si supply efficiency.

Effective starting materials that serve as raw material gas for S1 supply include:
In addition to the silicon hydride mentioned above, silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, specifically, for example, 5iFa.

5i2F 6 , 5iCIa, SiBr4, etc. (7)
Silicon halides can be mentioned as preferred, furthermore SiH2F2.5iH2I2.5iH
2C]2, 5iHC13, 5iH2Br2.5iHB
Gaseous or cassizable halides having hydrogen atoms as one of their constituents, such as halogen-substituted silicon hydride 1 such as r3, can also be mentioned as effective starting materials for forming the first ffi (I).

Even when using silicon compounds containing these halogen atoms (X), the halogen atoms (X) can be added to the first layer (I) together with Si by appropriately selecting the layer forming conditions as described above. can be introduced.

In the present invention, effective starting materials that serve as raw material gas for introducing halogen atoms (X) used to form the first layer (I) include - in addition to the above, for example, fluorine, Halogen gas such as chlorine, bromine, iodine, CIF,
ClF3, BrF, BrF3, BrF5, HF3
, IF7. Interhalogen compounds such as ICI and IBr,
Examples include hydrogen halides such as HF, HCI, HBr, and Hl.

In order to structurally introduce a substance (C) that controls conductivity into the layer region constituting the layer (I) of the WJl, for example, a group Ⅰ atom or a group V atom, the The starting material for introducing the group atom or the starting material for introducing the group V atom may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the first layer (I). As a starting material for the introduction of Group (1) atoms, it is desirable to use a material that is gaseous at room temperature and pressure, or that can be easily turned into a scum under at least the layer-forming conditions.

Specifically, as a starting material for introducing a group Ⅰ atom, for introducing a boron atom, B2H6-B4H
IO, BSH9, BSHll, B6H10, B6H12
, borohydride such as B6H14, BF3, BCl3,
Examples include boron halides such as BBr3. Also,
In addition, for introducing other group Ⅰ atoms, AlCl3,
GaCl3, Ga (C:H3)3, InCl3 T
Examples include lG13 and the like.

As a starting material for introducing a group V atom, PH3 is effectively used in the present invention for introducing a phosphorus atom.
, P2H4, etc., P)I4I.

PF3, PFs, PCl3, pct3, PBr
3, PBr3, PI3, and other phosphorus halides. In addition, AsH3, AsF3, AsCl3, A
sBr3, AsF5, SbH3, SbF3, SbF
5.5bCI3.5bC15, BiI3, BiCl3
, B1Br3, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

In the present invention, the content of the substance (C) that controls conductivity contained in the first layer (I) depends on the conductivity properties required for the first layer (1) or the layer ( It is appropriately selected based on the organic relationship, such as the characteristics of other layers provided directly in contact with 1) and the relationship with the characteristics of the contact interface between the layer and the other layer.

In the present invention, the first! The content of the substance controlling conductivity contained in (I) is preferably 0.0
01-5X104 atomic ppm, more preferably 0.5-IX 104104ato ppm, optimally 1-5X 103103ato ppm.

In the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) that may be contained in the first layer (I) is preferably 1 to 40 atomic%, more preferably 5 to 30 atomic%
It is desirable to be able to read atomic%.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) that may be contained in the first layer (I), for example, the support temperature, hydrogen atoms (H) and halogen atoms (X ), the amount of the starting material introduced into the deposition system, the discharge power, etc. may be controlled.

The layer thickness of the first layer (1) of the present invention is determined by whether the first layer (1) mainly functions as an adhesive layer between the support and the second layer (II), or whether the first layer (1) mainly functions as an adhesive layer and a charge transport layer. It is appropriately determined depending on whether it functions as a layer or not.

In the former case, preferably 10008~50μ, more preferably 20008~30μ, optimally 2000A~
It is desirable that it be 10IiII+. In the latter case, preferably 1 to 100 pieces, more preferably 1 to 80 pieces
, the optimum value is preferably 2 to 50-.

In the photoconductive member of the present invention, the first layer (I) 103
A second layer (ff) 104 is formed on top. first layer C
I) and the second layer (II) are each mainly composed of an amorphous material having a common constituent atom, silicon atoms, so there is no chemical stability at the interface between the VI layers. is sufficiently secured.

In the photoconductive member of the present invention, the distribution state of germanium atoms contained in the second layer (II) is non-uniform in the layer thickness direction, but the distribution state is non-uniform in the layer thickness direction. It is desirable that the distribution be uniform in parallel in-plane directions.

By forming the second layer (II) in such a layered structure, it has excellent photosensitivity to light in the entire wavelength range from relatively short wavelengths to relatively long wavelengths, including the visible light region. A photoconductive member is formed.

In addition, the distribution state of germanium atoms in the second layer (II) is such that germanium atoms are continuously distributed in the entire region, and the distribution concentration C of germanium atoms in the layer thickness direction is the first
The distribution decreases from the boundary with layer (1) to the boundary with third layer (m), and from the boundary with first layer (I) to third layer (III). A layer structure in which the distribution increases toward the boundary of the two, or a layer structure that has the characteristics of both are allowed.

2 to 13 show typical examples of the distribution state of germanium atoms contained in the second layer (II) of the photoconductive member according to the present invention in the layer thickness direction.

In Figures 2 to 13, the horizontal axis shows the distribution concentration C of germanium atoms, the vertical axis shows the layer thickness of the second layer (II), and the number indicates the first layer (I). The position of the interface with the second layer (H), tT is the position of the interface between the second layer (II) and the third layer (I
The position of the interface with II) is shown. That is, the second layer (II) containing germanium atoms is formed from the te side to the t side.
Layer formation is performed toward the child side.

FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the second layer (II) in the layer thickness direction.

In the example shown in FIG. 2, the interface position tB with the first layer (I) where the second layer (rr) containing germanium atoms is formed is 1. Up to the position t1, germanium atoms are contained in the second layer (II) with the distribution concentration C taking a constant value CI, and from the position t1, the concentration C2 increases to the interface with the third layer (IU). It is gradually and continuously decreased until it reaches 1T.

At one boundary surface, the distribution concentration C of germanium atoms is assumed to be C3.

In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C4 until it reaches 1 at position tB, and then reaches the concentration C5 at position 1. The distribution state is formed as follows.

: In the case of Figure 34, the distribution concentration C of germanium atoms is assumed to be a constant value from the position 1 to position t2,
Between position t2 and position 1, the concentration C is gradually and continuously reduced, and at position 1, the 1 distribution concentration C is substantially zero (substantially zero is defined as detection). (if the amount is less than the limit amount).

In the case of FIG. 5, the distribution concentration of germanium atoms Ct is gradually decreased continuously from the concentration c8 from the position tB to the position 1T, and becomes substantially zero at the position Ct.

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is a constant value of concentration C9 between the position tB and the position E3, and is the concentration CIQ at one position. Between position 3 and position tT, the distribution density C is linearly decreased from position t3 to position 1.

In the example shown in FIG. 7, the distribution concentration C is at position tB.
The concentration C11 takes a constant value up to position t4, and
Position 1 from 4. The distribution state is such that the concentration decreases linearly from the concentration CI2 to the concentration C13.

In the example shown in FIG. 8, the distribution concentration C of germanium atoms is C1,1 from position tB to position 1A.
It decreases in a linear manner so as to substantially reach zero.

In FIG. 9, from position 1 to position 1s, the distribution concentration C of germanium atoms decreases linearly from concentration CIs to concentration CI6, and between position t5 and position 1, In this example, the concentration CI6 is set to a constant value.

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is at the concentration CI7 at the position tB, and it decreases slowly from this concentration CI7 until reaching the position t6, and then near the position t6. At position 1, it is rapidly decreased. In this case, the concentration is set to CI8.

Between position wt6 and position t7, the concentration decreases rapidly at first, and then slowly decreases to C19 at position t7, and between position t7 and position t8, the concentration decreases extremely slowly. The concentration is gradually decreased to reach a concentration of C2° at a position of 0. Between position 8 and position tτ,
The concentration is reduced from C7° to substantially zero according to a curve shaped as shown in the figure.

In the example shown in FIG. 11, the germanium concentration C22 is constant from position tB to position t9, and from position t9 to position t.
The germanium concentration C is kept constant at C21 up to B.

In the example shown in FIG. 12, the germanium concentration is substantially zero at position tB and at position 1. and the germanium concentration is C
In Fig. 13, the germanium concentration increases with the curve shown in the figure to reach 23, the germanium concentration is substantially zero at the position tB, and the germanium concentration increases from the position tB to the concentration C24 at the position tlo with the curve shown in the figure. increase, position t
The germanium concentration is constant at C24 from Io to position.

In addition, the germanium concentration distributions shown in FIGS. 2 to 13 are the same as the first ffi (I
) shows a distribution with a high germanium concentration near the interface with the third layer (III), and in Figures 11 to 13 shows a distribution with a high germanium concentration near the interface with the third layer (III). Alternatively, the germanium concentration distribution may be changed.

As described above, according to FIGS. 2 to 13, the second layer (II)
As described above, some of the typical examples of the distribution state of germanium atoms contained in the layer thickness direction, 1. In the present invention, in the vicinity of the interface with the first layer (I) and/or in the third layer (I), layer (
In the vicinity of the interface with I[[), there is a part where the distribution concentration C of germanium atoms is high, and in the center of the second layer (II), the distribution concentration C is higher than that of the first layer (II). The second layer (II) is provided with a germanium atom distribution state that has a considerably lower portion than near the interface with I) and near the interface with the third layer (m).

The second layer that constitutes the photoreceptive layer that constitutes the photoconductive member in the present invention! (II) is preferably the first O as described above.
Near the interface with N(I) and/or third layer (III)
It is desirable to have a localized region (A) in which germanium atoms are contained at a relatively high concentration near the interface with the material.

In the present invention, the localized region (A) is
Explaining using the symbols shown in the figure, it is desirable to provide in an area within 5 points from the boundary surface position tB or 1.

In the present invention, the localized region (A) is located at the interface position t.
Full thickness area from B or 1 piece to 511Jfi thickness (LT
), or as part of the layer region (LT).

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

The localized region (A) has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum distribution concentration Ctnax of germanium atoms is preferably 1000 atomic ppm or more, more preferably 1000 atomic ppm or more relative to silicon atoms. 5000 atomic ppm or more, optimally LX
It is desirable to form a layer so that a distribution state of 104104 at ppm or more can be obtained.

That is, in the present invention, the second layer (n) containing germanium atoms has a layer thickness from the first layer (I) side or from the free surface of the second amorphous layer (ff). Maximum value Cma of distribution concentration within 5 tiles (layer region 5μ thick from tB)
Preferably, it is formed such that x is present.

In the present invention, the content of germanium atoms contained in the second layer (IT) is determined as desired so as to effectively achieve the object of the present invention, but is preferably 1. ~9.5X 105105ato ppm,
More preferably 100-8×lO5105ato p
pm, optimally 500-7X105 atomic pp
It is desirable to set it to m.

In the photoconductive member of the present invention, when the first layer (I) is thin, the second layer (II) containing germanium atoms contains a substance (C) that controls conductivity. ) is locally provided on the first layer (I) side, so that the layer region (PN) can function as a so-called charge injection blocking layer.

That is, the content of the substance (C) that controls conductivity in the layer region (PN) containing the substance (C) is preferably 3.
0 atomic ppm or more, more preferably 50 at
omic PPm or more, optimally 100100ato
ppm or more, for example, when the contained substance (C) is the above-mentioned P-type impurity, the free surface of the photoreceptive layer (when subjected to charging treatment to D polarity, the photoreceptor from the support side Injection of electrons into the layer can be effectively blocked, and when the contained substance (C) is the n-type impurity, the free surface of the photoreceptive layer is charged to e-polarity. It is possible to effectively prevent the injection of holes from the support side into the photoreceptive layer when receiving the photoreceptor.

In the above case, in the layer region (zn) of the second layer (II) excluding the layer region (PN), 1
A substance controlling conductivity (C) contained in the layer region (PN)
) may be contained in a substance (C) that governs conductivity that is different from the polarity of It may be contained in a small amount.

In such a case, the content of the substance (C) controlling the conductivity contained in the layer region (zn>) is Fi!
It is determined as appropriate depending on the polarity and content of the substance (C) contained in the region (PN), but preferably 0.
．． 001-1001000 atomic p'pm, more preferably 0.05-500 atomic p'pm, most preferably 0.1-21-200 atomic p'pm.

In the present invention, when the layer region (PN) and the layer region (zn) provided in the second layer (LT) contain the same type of substance (C) that controls conductivity, the layer region (LT) ZI
The content of the substance (C) that controls conductivity contained in I) is preferably 30 atomic ppm or less. In addition to the above-mentioned case, in the present invention, a layer region (1) containing a substance (C) having one polarity and controlling conductivity in the layer (II) of @2, and It is also possible to provide a so-called depletion layer in the contact region by providing a layer region containing a polar conductivity-controlling substance (C) in direct contact with the contact region. That is, for example, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in the second layer (II) so as to be in contact with I to form a so-called p-n junction. can be formed to provide a depletion layer.

In the present invention, specific examples of the halogen atom (X) contained in the second i (ET) as needed include fluorine, chlorine, bromine, and iodine, but especially fluorine , chlorine may be mentioned as suitable.

In the present invention, in order to form the second layer (II) composed of a-SiGe (H, Deposition method is applied.

For example, by glow discharge method, a-5iGe(H,X)
In order to form the second layer (II), basically, a raw material gas for supplying Si that can supply silicon atoms (Si) and a gas for supplying G that can supply germanium atoms (Ge) are used.
e The raw material gas for supply and, if necessary, the raw material gas for introducing hydrogen atoms (H) and/or the raw material gas for introducing halogen atoms (X) are kept at a desired gas pressure in a deposition chamber whose interior can be reduced in pressure. distribution of germanium atoms contained on the support on whose surface the first layer (I) has been formed in advance and has been installed in a predetermined position. While controlling the curve so that it becomes a desired rate of change curve, the second
A layer (II) is formed.

In addition, when forming by sputtering method, for example, A
In an atmosphere of an inert gas such as r, He or a mixed gas based on these gases, a target composed of Si, two targets composed of the target and a target composed of Ge, or Sl and Gs Using a target ft mixed with
) A raw material gas for introduction and/or a raw material gas for introducing halogen atoms (X) is introduced into a deposition chamber for sputtering to form a desired gas plasma atmosphere, and the Ge
The target may be sputtered while controlling the gas flow rate of the raw material gas for supply according to a desired rate of change curve.

In the case of the ion blating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated using the resistance heating method or the electron beam method. Sputtering can be carried out in the same manner as sputtering, except that the evaporated material is heated and evaporated by (EB method) or the like and the flying evaporated material is passed through a predetermined gas plasma atmosphere.

In the present invention, the following are effective starting materials for the raw material gas used to form the second layer (ff).

First, the starting materials that will become the raw material gas for supplying Si are as follows:
SiH4, Si2H6, 5i3HB, 5i4HIo
Silicon hydride (silanes) in a scum state or which can be gasified are mentioned as those which can be effectively used, especially,
S in terms of ease of handling layer creation work, good Si mooring efficiency, etc.
Preferred examples include iH4 and Si2H6.

The starting material that becomes the raw material gas for supplying Ge is GeH.
4, Ge2H6, Ge3HB, Ge4H1o, Ge
5J2, Ge(, Hla, GetHIG, Ge(3
Gaseous germanium hydride such as H18, GegH26, etc., or germanium hydride that can be gasified can be effectively used. In particular, GeH, , Ge2H6, and Ge3He are preferred.

In the present invention, many halogen compounds can be cited as effective starting materials that serve as raw material gases for introducing halogen atoms (X) used to form the second layer (II). Gases, halides, interhalogen compounds, gaseous or gasifiable halogen compounds such as halogen-substituted silane derivatives are preferably mentioned. Furthermore, silicon hydride which is in a gaseous state or contains a halogen atom that can be gasified, which is composed of a silicon atom and a halogen atom, can also be effectively used.

In the present invention, halogen compounds preferably used to form the second layer (TI) include halogen gases such as fluorine, chlorine, bromine, and iodine, CIF
, ClF3, BrF, BrF3, BrF5
.

Examples include interhalogen compounds such as II3, IF7, ICI, and IBr.

Specifically, silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, include:
SiF4, Si2F6.5iCI4. Preferred examples include silicon halides such as SiBr4.

When forming the second layer ([) of the photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom (X), Si is used together with the raw material gas for supplying Ge. Even without using silicon hydride gas as a raw material gas capable of supplying A layer (11) can be formed.

According to the glow discharge method, the second one containing a halogen atom (X)
When forming N(Il[), basically, for example, S
Silicon halide, which will be the raw material gas for i supply, germanium hydride, which will be the raw material gas for Ge supply, Ar, H
Gases such as e and the like are introduced at a predetermined mixing ratio and gas flow rate into a deposition chamber where the second layer (TI) is formed, and a glow discharge is generated to generate plasma of these gases. By forming an atmosphere, the second layer (II) can be formed on the support on which the first layer (I) is formed. In addition, in order to more easily control the introduction ratio of hydrogen atoms, a desired amount of hydrogen residue or silicon compound gas containing hydrogen atoms is further mixed with these gases to form a second layer (LT). Good too. Moreover, each gas may be used not only as a single species but also as a plurality of them in a predetermined ratio.

In either the sputtering method or the ion blasting method, in order to introduce halogen atoms (X) into the formed layer, a gas of the above-mentioned halide or a silicon compound containing halogen atoms is introduced into the deposition chamber. However, a plasma atmosphere of the gas may be formed.

Further, when introducing hydrogen atoms, a gas for introducing hydrogen atoms, such as F2. Alternatively, a gas such as the aforementioned silanes and/or germanium hydride may be introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gas.

In the present invention, the above-mentioned halide or silicon compound containing a halogen atom is effectively used as the raw material residue for introducing a halogen atom when forming the layer (II) of @2. , HF, HCl, HB
r, l (I etc. (7) Hydrogen halide, S i F
2 F7.5iH2r2.5iH7C:17.5iHC
13,5iH2Br2.5iHBr3, etc., and halogen-substituted silicon hydrides such as GeHF3, GeF2F2.
GeH3F, GeHCl3, Ge6H14, GeH
Br3. GeHBr3, GeF2 Br2, GeH
Br3G[! Hydrogenated germanium halides such as H2I2 and GeH31, halides containing hydrogen atoms as one of their constituent elements, GeF4, GeCl4. Gebra
, Ge14, GeF2, GeC12, GeBr2,
Germanium halides such as Ge2, gaseous or gasifiable halides containing hydrogen atoms as one of their constituent elements can also be cited as effective starting materials for forming the second layer (U). .

Among these substances, halides containing hydrogen atoms are
When forming the second layer (II), hydrogen atoms, which are extremely effective in controlling electrical or photoconductive properties, are also introduced at the same time as halogen atoms are introduced into the layer. Used as a suitable raw material for introducing halogen atoms.

In order to structurally introduce hydrogen atoms into the second layer (II), in addition to the above, H2 is SiH4, Si2H6,5
Silicon hydride such as i3HB, 5i4H1°, etc. with germanium or germanium compound for supplying Ge, or GeH4, Ge2H6, Ge3HB,
Ge4HIo, Ge5H17, Ge6H14, Ge7
This can also be carried out by causing germanium hydride such as H16, GeBl (IB, ce9H20, etc.) and silicon or a silicon compound for supplying Si to coexist in the deposition chamber to generate a discharge.

In a preferred example of the present invention, hydrogen atoms (H) that may be contained in the second layer (II) of the photoconductive member to be formed
, the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 0.01-
40 atomic%, more preferably o, o5-30at
It is desirable that the content be omic%, most preferably 0.1 to 25 atomic%.

Hydrogen atoms (H) that may be contained in the second layer (IT)
And/or to control the amount of halogen atoms (X), for example, the support temperature, hydrogen atoms (H) and halogen atoms (X)
What is necessary is to control the amount of the starting material used to contain the material introduced into the deposition system, the discharge power, etc.

In the second layer (IT), a substance (C) that controls conductivity
For example, in order to structurally introduce a group Ⅰ atom or a group V atom, in the same manner as in the case of explaining the method for forming the first layer (r), the above-mentioned introduction of a group ① atom is performed during layer formation. The starting material for the first or the starting material for introducing the V-thon atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the second layer (II).

The layer thickness of the second layer (n) in the photoconductive member of the present invention is:
When the second layer (IT) is mainly used as a photocarrier generation layer, the absorption coefficient of the second layer (II) with respect to the excitation light source of the photocarriers is taken into consideration, and is preferably determined as appropriate. 100OA to 50OA, more preferably 1
It is desirable that the number is between 00OA and 30K, most preferably between 1000A and 30.

In addition, when the second layer (II) is used mainly as a layer for generating and transporting photocarriers, the second layer (II) is appropriately determined as desired so that photocarriers can be transported efficiently, and preferably 1 to 100. rams, more preferably 1 to 8
It is desirable that the number of houses be 0, and optimally 2 to 50 ILa+.

The third layer (m) 105 formed on the second layer (TI) 104 of the photoconductive member of the present invention has a free surface and mainly has moisture resistance, continuous repeated use characteristics, and electrical pressure resistance. , use environment characteristics, and durability to achieve the objects of the present invention. Second layer (II) and third layer (III)
Since each of them is mainly composed of an amorphous material having a common constituent atom, silicon atoms, sufficient chemical stability is ensured at the laminated interface.

The third layer (m) in Mokumei is composed of silicon atoms (Si
), nitrogen atom (N), and optionally hydrogen atom ()I)
and/or a material whose main component is amorphous containing a halogen atom (X) (hereinafter a= (Six lJ+ -x
)y (Hlx)+-y, where 0 < x, y
<1).

a-(St, Nl-x)y ()1. x) +
The third layer (m) composed of -y is formed by a glow discharge method, a sputtering method, an ion implantation method, an ion plate ink method, an electron beam method, or the like. 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 manufactured. Glowing has the advantages of being relatively easy to control the conditions for manufacturing the component, and of being able to easily introduce nitrogen atoms and halogen atoms together with silicon atoms into the third layer (III) to be fabricated. A discharge method or a sputtering method is preferably employed. Further, the third layer (m) may be formed by using a glow discharge method and a sputtering method in the same apparatus system.

To form the third layer (m) by the glow discharge method,
a-(Slx Nl-x)y (H,X)ry
The raw material gas for formation is mixed with a diluent gas at a predetermined mixing ratio if necessary, and introduced into the deposition chamber for vacuum deposition where the support on which the layer (II) of fjr, 2 is formed is installed. Then, the introduced dregs is turned into dregs plasma by causing a glow discharge, and the second ff(II) on the support is a-(St, N, -X)y (H,X)+ -y
All you have to do is deposit it.

In the present invention, a-(SlxN+-x)y(H,X)
The raw material residue for +-v formation is silicon atoms (Sl
), nitrogen atom (N), hydrogen atom () I), and halogen atom (X) as constituent atoms, or most of the dregs formed from gasifiable substances. can be used.

When using a raw material gas having Sl as a constituent atom among Sl, N, H, and X, for example, a raw material gas having Si as a constituent atom, a raw material gas having N as a constituent atom,
Source gas containing H as a constituent atom and/or X as necessary
The raw material scraps having constituent atoms are mixed at a desired mixing ratio, or the raw material scraps having Sl as constituent atoms and the raw material scraps having N and H as constituent atoms and/or N
and raw material scraps having constituent atoms of For example, raw material scum or raw material scum containing Si, N, and X as constituent atoms may be mixed at a desired mixing ratio.

Alternatively, as a side method, a raw material gas containing Sl and H as constituent atoms and a raw material gas containing N as constituent atoms may be mixed and used, or a raw material gas containing Si and X as constituent atoms may be used. and a raw material residue containing N as a constituent atom may be used in combination.

In the present invention, suitable halogen atoms (X) that may be contained in the third layer (m) are F, C1
, By, I, and F, CI are particularly desirable.

In the present invention, the starting material serving as the raw material residue for forming the third layer (m) is S containing Si and H as constituent elements.
i H4, Si2H6, S+3Hs, 5I4HIO
Silicon hydrides (silanes) in the form of scum or that can form scum can be effectively used.In particular, S
Preferred examples include iH4 and Si2H6.

By using these starting materials, it is possible to introduce H as well as Si into the third layer (III) to be formed by appropriately selecting the layer forming conditions.

Effective starting materials that serve as raw material gas for supplying Si include:
In addition to the above-mentioned silicon hydride, silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, specifically, for example, SiF4.5i2F 6 , 5
Silicon halides such as iCI4 and SiBr4 can be mentioned as feminine, and furthermore, S
i H2F2.5iH2I2.5iH2111:12
, halogen-substituted silicon hydrides such as 5iHCI3.5iH7Br2.5iHBr3, and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituents are also effective starting materials for forming the third layer (m). It can be mentioned as follows.

Even when using silicon compounds containing these halogen atoms (X), the halogen atoms (X) as well as 51 can be added to the third layer (m) to be formed by appropriately selecting the layer forming conditions as described above. can be introduced.

In the present invention, effective starting materials that serve as raw material residue for introducing halogen atoms (x) used to form the third layer (m) include, in addition to the above, for example, fluorine,
Halogen gas such as chlorine, bromine, iodine, CIF, CI
F,, BrF, BrF3, BrFl, IF3, I
Interhalogen compounds such as F7, 1CI, IBr, )I
Examples include hydrogen halides such as F, )ICI, )fBr, and old.

In the present invention, starting materials that are effectively used as raw material scraps for supplying nitrogen atoms (N) used to form the third layer (m) include those containing N as a constituent atom, or N and H are constituent atoms, such as nitrogen (N2), ammonia (NH3), hydrazine (82N NH2)
, hydrogen azide (HN3), anquinium azide (NH
Nitrogen compounds such as scum-like or gasified nitrogen such as 2N3), nitrides, and azides can be mentioned. In addition to the introduction of nitrogen atoms (N), halogen atoms (X
), nitrogen trifluoride (F3N) can also be introduced.
) Nitrogen halide compounds such as nitrogen tetrafluoride (F4N2) can be mentioned.

These third layer (Ill) forming substances include silicon atoms and
Nitrogen atoms and optionally halogen atoms and/or hydrogen atoms are selected and used as desired when forming the third layer (m).

To form the third layer (Illj) by sputtering, the following method can be adopted, for example.

The first method is to use a raw material gas for introducing nitrogen atoms (N) when sputtering a target composed of 81 in an atmosphere of an inert gas such as AT or He or a mixed gas containing these gases. , hydrogen atoms (
)I) They may be introduced into the deposition chamber in which sputtering is performed together with the raw material gas for introduction and/or/\rogen atom (X) introduction.

In the second method, the sputtering target is a target made of Si, a target made of Sl and a target made of Si3N4, or a target made of Si and SI3N4. By using , nitrogen atoms (N) can be introduced into the third layer (m). At this time, if the raw material scraps for introducing nitrogen atoms (N) mentioned above are also used,
By controlling the flow rate, it is easy to arbitrarily control the amount of nitrogen atoms (N) introduced into the third layer (III).

As the material gas for introducing N, H and X, the material for forming the third layer (m) shown in the glow discharge example described above is also used as an effective material in the sputtering method. obtain.

In the present invention, as the diluent gas used when forming the third layer (m) by the glow discharge method or the sputtering method, so-called rare gases such as He, Ne, Ar, etc. are mentioned as suitable ones. be able to.

The third layer (III) in the present invention is carefully formed to provide the desired properties.

In other words, substances whose constituent atoms are Si, N, and optionally H and/or sex.

In the present invention, a-(SiXN
, -X)y (H,X)+-y is formed, the conditions for its formation are carefully selected as desired.

For example, when providing the third layer (m) with the main purpose of improving electrical voltage resistance, a-(SiXN, -X)
y (H,

In addition, when a third layer (m) is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to a certain extent, and it has a certain degree of resistance to the irradiated light. Al as a sensitive amorphous material
sixN+-x)y(H,X)+-y is created.

a-(S1xNl-x)y on the surface of the second layer (II)
(H.

When forming the third layer (m) consisting of In invention,
a-(Si) having the desired properties.

It is desirable that the temperature of the support during layer formation be strictly controlled so that Nl-x)y(l(,X)ly can be formed as desired.

In the present invention, the formation of the third layer (m) is carried out by selecting an optimal range as appropriate according to the method of forming the third layer (m) in order to effectively achieve the desired purpose. but preferably 20 to 400°C, more preferably 50 to 350°C
The temperature is preferably 100 to 300°C. Glow discharge method and sputtering method are used to form the third layer (Ill) because delicate control of the composition ratio of atoms constituting the layer is relatively easy compared to other methods. is advantageous, but when forming the second layer by these layer forming methods, the discharge power during layer formation is created in the same manner as the support temperature described above, a-(SjxN+-x) y(H,
It can be cited as one of the important factors that influence the characteristics of X) + - y.

a-(StXN, -X)y (H,X)I having the characteristics to effectively achieve the purpose of the present invention
The discharge power conditions for effectively creating -y with high productivity are preferably 10 to 300 W, more preferably 20 to 250 W, and optimally 50 to 200 W.

The gas pressure in the deposition chamber is preferably 0. O1~l
Torr, preferably about 0.1 to (1.5 Torr).

In the present invention, the desirable numerical ranges of the support temperature and discharge power for creating the third layer (m) include the values in the above ranges, or these layer creation factors are determined independently. a of the desired characteristic, rather than one that can be determined separately.
-(Six Nl -X)y (It is desirable that the optimal value of each layer creation factor be determined based on the mutual organic relationship so that the third layer (m) consisting of H4xL-y is formed. .

The amount of nitrogen atoms contained in the third layer (m) in the photoconductive member of the present invention is the same as the production conditions of the third layer (m).
This is one of the important factors for forming the third layer (m) that provides the desired properties that achieve the object of the present invention.

The amount of nitrogen atoms contained in the third layer (m) in the present invention is determined as desired depending on the characteristics of the amorphous material constituting the third layer (m). .

That is, the general formula a-(SlxN+-x)y(H,x)
Amorphous materials composed of +-y can be roughly divided into amorphous materials composed of silicon atoms and nitrogen atoms (hereinafter referred to as a-
It is written as 3iaN1-a. However, O < a < 1), an amorphous material composed of silicon atoms, nitrogen atoms, and hydrogen atoms (hereinafter a-(Sib N, -b)c H+-
It is written as c. However, 0<b, c<1), an amorphous material composed of silicon atoms, nitrogen atoms, halogen atoms, and optionally hydrogen atoms (hereinafter a-(St, lN1-d)1)
1 (H,X)+-e. However, O< d, e
<1).

In the present invention, the third layer (m) is a-3iaN l-
;.

When the third layer (m) is composed of
%, more preferably 1-50 atomic%, optimally 1
O is preferably 0 to 45 atomic%, that is, a-3iaN I-a (7) If expressed as a, a is preferably 0.4 to Q, 99999,
More preferably 0.5 to 0.98, optimally 0.55 to 0
．． It is 9.

On the other hand, in the present invention, the third layer (III) is a-
(Si, N, -b)e H+-c, the amount of nitrogen atoms contained in the third layer (m) is preferably IX 10' to 130 atomic%, more preferably 1 to 50 atomic% %, optimally 10-10
It is desirable that it be -50 ato%. The content of hydrogen atoms is preferably 1 to 40 atoms.
c%, more preferably 2 to 35 atomic%, optimally 5 to 30 atomic%, and the photoconductive member formed when the hydrogen content is in these ranges has excellent practical properties. It can be fully applied as such.

That is, the previous a-(Sib N+ -b)e H+-c
b is preferably 0.45 to 0.999
99, more preferably 045 to 0.99, optimally 045
~09. It is desirable that C is preferably 0.6 to 0.98, more preferably 0.65 to 0.98, most preferably 0.7 to 0.95.

The third layer (m) is a−(S+=N1−+)e (H,
'X) 1-e, the third layer (m
) The content of nitrogen atoms contained in
It is desirable to set it to omic%. The content of halogen atoms is preferably 1 to 20ato
mic%, more preferably 1-11-18ato%, optimally 2-12-15ato%, and photoconductive members produced when the halogen atom content is in these ranges. It can be fully applied in practice.

The content of hydrogen atoms contained as necessary is preferably 19 atomic% or less, more preferably +3a
It is desirable that it be tomic% or less.

That is, the first (7)a-(Sl, +N+-1)e(H,X)
+-e d, if expressed as e, d is preferably 0
．． 4 to o, H2O2 more preferably 0.4 to 0.89, optimally 0.45 to 0.9, e preferably 0.8 to 0.
89, more preferably 0.82 to 0.99, optimally 0.89, more preferably 0.82 to 0.99, optimally 0.
It is desirable that it is 85 to 0.88.

The numerical range of the layer thickness of the third layer (m) in the present invention is one of the important factors for effectively achieving the object of the present invention. In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose.

In addition, the layer thickness of the third layer (m) is determined by the amount of nitrogen atoms contained in the third layer (m) and the layer thickness of the first layer (1) and the second layer (II). The relationship between the two layers also needs to be determined as desired based on the organic relationship depending on the characteristics required for each layer. In addition, it is desirable to take into account economic efficiency, taking into account productivity and souvenirs.

The thickness of the third layer (m) in the present invention is preferably 0.003 to 30μ, more preferably 0.003 to 3
0)un, which is preferably set to 0.003 to 30 μs.

The support 101 used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, A1, Cr, N
o, Au, Nb, Ta, V, Ti, Pt, Pd
Metals such as these or alloys thereof can be mentioned.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate-1, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. used. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

That is, for example, if it is glass, NiC is applied to the surface of the glass.
r, A1. Cr, Mo, Au, Ir, Nd
, Ta, V, Ti, Pt, In2O3,5n02
, ITO (In2O3+ 5n02) or the like, or if a synthetic resin film such as polyester film is used, NiC
r, A1. Ag, Pb, Zn, Ni, Au, Cr, N
A thin layer of metal such as O, 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 the above metal. conductivity is imparted to the

The shape of the support is determined as desired, but for example, if the photoconductive member 100 of FIG. It is desirable to have a belt shape or a cylindrical shape. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such a case, from the viewpoint of manufacturing and handling of the support, as well as mechanical strength, the number of threads is usually 10 or more.

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

FIG. 18 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method.

Gas cylinders 1102 to 1106 in the figure are filled with raw material waste for forming the photoconductive layer of the photoconductive member of the present invention.
1103 is a cylinder of SiH4 scum diluted with He
GeH4 gas (purity 99.999%, hereinafter abbreviated as GeH4/He gas) cylinder diluted with He
1105 is a He
B2H6 gas (purity 99.99S%, hereinafter abbreviated as B2H6/He scum) diluted with B2H6 gas.

1106 is 02H gas diluted with He (purity 99.
H% (hereinafter abbreviated as NH3/H, e-cass).

Although not shown in the drawings, it is possible to add cylinders of desired waste species in addition to these as needed.

In order to flow these gases into the reaction chamber 1101, gas hoses 1102-1108 (7) and each valve 1122-
1128 and leak valve 1135 are closed, and also check that inflow valves 1112-+116, outflow valves 1117-1121, and auxiliary valve 1132.
After confirming that valve 1133 is open, first open main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, the reading on the vacuum gauge 1136 is approximately 5X 10
``When the pressure reaches 6 torr, the auxiliary valve 1132.11
33 and outflow valves 1117-1121.

First, an example of forming the first layer (I) on the cylindrical substrate 1137 is shown.
6/ Open the valves 1122 and 1125 respectively to release the He gas and set the pressure in the pressure cage 1127 and 1130 to IKg.
/ cm2, gradually open the inlet valve 1112.1115 and mass flow controller 1107.111.
0 respectively. Subsequently, the outflow valve 11
17. Gradually open the 1120 and auxiliary valves 1132 to allow each gas to flow into the reaction chamber 1101. At this time, the outflow valve 1117 is adjusted so that the ratio between the SiH,,/He gas flow rate and the B2 H6/He gas flow rate becomes a desired value.
．． 1120 and the opening of the main valve 1134 while checking the reading on the vacuum gauge 1138 so that the pressure in the reaction chamber is at the desired value. Then, the temperature of the base cylinder 1137 is raised to 50 to 4 by the heating heater 1138.
After confirming that the predetermined temperature of 00°C is set, the power supply 1140 is set to the desired power and the reaction chamber 110 is heated.
1 by causing a glow discharge in the base cylinder 113.
A first layer (I) is formed on 7. During layer formation, the base cylinder 1137 is rotated once at a constant speed by a motor 1139 in order to ensure uniform layer formation. All the gas operating system valves used last are closed, and the reaction chamber 1101 is once evacuated to high vacuum.

Next, in an example where the second layer (Ir) is formed on the first layer (I) formed in this way, the reading of the vacuum gauge 1136 becomes approximately 5X 10' tart. If so, repeat the same operations as above.

That is, the SiH4/He force' from Casponbe 1102
GeH4/He gas from Kasupo 1103, B2H6/He gas from Kasupo 1105 to Kasupo 7, valve 1
122.1+23.1125 respectively and the pressure of outlet pressure gauge 1127.1128.1130 is IKg/cI.
Adjust to 112, inlet valve 1112, +113.11
15. Gradually open the mass flow controller 1107.
1108 and 1110 respectively. Subsequently, the auxiliary valves 117, 1118, 1120 and the auxiliary valves 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, the outflow valve 111 is adjusted so that the ratio of the SiH4/He gas flow rate, the GeH4/He gas flow rate, and the B2 H6/He gas flow rate becomes a desired value.
Adjust 7.1118.1120 and make the second layer (rr)
The germanium atom concentration distribution in the layer thickness direction is controlled to be a desired distribution. Further, the opening of the main valve 1134 is adjusted while checking the reading of the vacuum gauge 1138 so that the pressure in the reaction chamber reaches a desired value. and base cylinder 1
The temperature of 137 is set to 50 to 40 by heating heater 113B.
After confirming that the specified temperature of 0℃ is set,
A glow discharge is generated in the reaction chamber 1101 by setting the power source 1140 to the desired power to form the second layer (I) on the substrate cylinder 1137 in the same manner as in the formation of the first layer (I).
II).

Next, when forming the third layer (m) on the second layer (II) formed in this way, close all gas operating system valves used as in the previous case. , reaction chamber +
Once 101 is evacuated to a high vacuum and the reading on the vacuum gauge 1138 is approximately 5 x 10'' torr, do the same as in the case of J2, and connect S+H4 from 1102 to a gas phone, for example.
/He gas, SiF4/1-1 from gas pump 1104
E gas and NH3/He dregs are supplied from 1106 to the cassette to generate glow discharge and form the third layer (III). The amount of nitrogen atoms in the third layer Cm) is NH3/
This is carried out by adjusting the supply flow rate of He gas.

Examples will be described below.

Example 1 Using the manufacturing apparatus shown in FIG. 18, a photoreceptive layer was formed on an Al cylinder according to the manufacturing conditions shown in Table 1 by the glow discharge decomposition method described in detail above. Each sample (a total of 96 types of samples 1-1 to 16-6) was prepared as an image forming member.

The distribution states of boron atoms and germanium atoms contained in the photoreceptive layer of each trial 1 at this time are shown in FIG. 14A1Δ, FIG. 14B, and FIG. 15, respectively.

The distribution state of boron atoms and germanium atoms in each sample can be determined by automatically opening and closing the corresponding valves according to a predetermined change rate curve of the waste flow rate.
It was formed by adjusting the gas flow rates of B2H6 and GeF4. Table 2 lists the correspondence between the distribution states of boron atoms and germanium atoms in each sample and FIGS. 14A, 14B, and 15.

Set each of the image forming members obtained in this manner in a charging exposure experiment apparatus; 5. OKV"C' 17j+corona charging was performed for 0.3 seconds, and a light image was immediately irradiated.

The optical image is 0.21ux using a tungsten lamp light source.
A light amount of esec 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-chargeable developer (including toner and carrier) over the surface of the imaging member. 5. Toner image on the surface of the image forming member. When transferred onto transfer paper using OKV's corona charging, clear, high-density images with excellent resolution and good gradation reproducibility were obtained for all image forming members.

Next, replace the light source with a tungsten lamp using an 810n
m using a GaAs-based semiconductor laser (10 mW),
When the image quality of toner transfer images was evaluated under the same toner image forming conditions as above except that an electrostatic image was formed, the same results were found for all image forming members as in the previous case.
A clear, high-quality image with good gradation reproducibility was obtained.

Example 2 Using the manufacturing apparatus shown in FIG. 18, an image forming member for electrophotography was produced in the same manner as in Example 1, except that the manufacturing conditions shown in Table 3 were changed on a cylindrical aluminum substrate. Each sample (
A total of 48 types of sample notifications (21-1 to 28-6) were prepared.

The distribution of boron atoms and germanium atoms contained in the photoreceptive layer of each sample at this time is shown in FIGS. 16 and 17, respectively. The distribution state of boron atoms and germanium atoms in each sample can be determined by adjusting the gas flow rates of B2H6 and GeF4 by automatically opening and closing the corresponding valves according to a predetermined rate of change curve of gas flow rates. Formed. Table 4 shows the correspondence between the distribution of boron atoms and germanium atoms in each sample and FIGS. 16 and 17.

Using the image forming members thus obtained, the image quality of toner transfer images was evaluated in the same manner as in Example 1. All of the image forming members had excellent resolving power, clear high-definition images with good gradation reproducibility. A quality image was obtained.

Example 3 C±, the sample of Example 1, 112-5, and Example 1, respectively, except that the production equipment of FIG. 18 was used and the conditions for producing the third M (m) were as shown in Table 5 Sample 2//6
．． Electrophotographic imaging members were prepared according to the same conditions and procedures as those used to prepare 24-4 and 28-2 (Samples fi/EL12-5-1 to 12-5-8, 24-4-1), respectively.
~24-4-8.2B-2-1~28-2-8 total 2
4 samples) were prepared.

Using each of the image forming members thus obtained, image quality was evaluated under the same conditions as in Example 1, and durability through repeated and continuous use was evaluated.

The evaluation results for each of these samples are shown in Table 6.

Example 4 The third layer (m) was prepared by sputtering, and during its formation, the target area ratio of the silicon wafer and silicon nitride wafer was variously changed, and Ar and N)
A cylindrical aluminum plate was prepared in the same manner as Sample 3-1 of Example 1, except that the mixing ratio of No. 13 was changed and the content ratio of silicon atoms and nitrogen atoms in the third layer (Ill) was changed. An image forming member for electrophotography by forming a light-receiving layer on a substrate (
A total of 7 samples /L3-11 to 3-1-7) were prepared.

Using each of the image forming members thus obtained, the image forming, developing, and cleaning steps similar to those in Example 1 were repeated approximately 50,000 times, and then image quality was evaluated.
Table evaluation results were obtained.

Example 5 Except that when forming the third layer (DI), the IT ratio of SiH4 gas and NH3 gas was changed and the content ratio of silicon atoms and nitrogen atoms in the third layer (m) was changed. A light-receiving layer was formed on a cylindrical Al substrate in exactly the same manner as Sample No. 3-1 of Example 1 to produce image forming members for electrophotography (Sample No. 3-1-1f to 3-1-18). A total of 8 pieces) were prepared.

Using each of the image forming members thus obtained, the same image forming, developing, and cleaning steps as in Example 1 were repeated approximately 50,000 times, and then image quality was evaluated.
Table evaluation results were obtained.

Example 6 When forming the third layer (m), the content ratio of silicon atoms and nitrogen atoms in the third layer (m) was changed by changing the flow rate ratio of SiH4 gas, SiF4 gas, and NH3 gas. Except for the above, a light-receiving layer was formed on a cylindrical Al substrate in exactly the same manner as Sample J3-1 of Example 1, and electrophotographic image forming members (Samples J3-1-21 to 3) were prepared. -1-28, total 8
) were prepared respectively.

Using each of the image forming members thus obtained, the same image forming, developing, and cleaning steps as in Example 1 were repeated approximately 50,000 times, and then image quality was evaluated.
Table evaluation results were obtained.

Example 7 Example 1 except that the layer thickness of the third layer (III) was changed.
A photoreceptive layer was formed on a cylindrical Al substrate in exactly the same manner as Sample 3-1, and an electrophotographic image forming member (
A total of four samples (63-1-31 to 3-1-34) were prepared.

Using each of the image forming members thus obtained, the image forming, developing, and cleaning steps similar to those in Example 1 were repeated approximately 50,000 times, and then image quality was evaluated.
Table 0 evaluation results were obtained.

Common layer forming conditions in the above embodiments of the present invention are shown below.

Support temperature: Approximately 250°C when forming the first and third layers Approximately 200°C when forming the second layer Discharge frequency: 13.58 M)lz Reaction and reaction chamber pressure 0.3 Torr conversion method Table 10

[Brief explanation of the drawing]

FIG. 1 shows P:! for explaining the structure of the photoconductive member of the present invention. : A diagram schematically showing the structure. Figure 2 - 1st
Figure 3 shows layers (I) and (I) of the photoconductive member of the present invention, respectively.
I) This is a schematic diagram for explaining the distribution of kermanium atoms at 1. +4A (< Figures 14B and 7ffjle are diagrams each schematically showing the concentration distribution of boron atoms in the photoreceptive layer in an example of the photoconductive member of the present invention, and Figures 15 and 1?[A is 12/l which schematically shows the concentration distribution of germanium in the second layer (II) of the embodiment of the light guide 11Σ member of the present invention.No. 18 The figure is a diagram showing the main structure of a manufacturing apparatus for a lead main member using a glow discharge decomposition method. 100. Photoconductive member 101・Support 102: Photoreceptive layer 103. First layer (1) 104: Second layer Layer (II) 105: Third layer (m) 1101
: Anti-Evil Room 1102-1108: Kashonpe 1107-1111: Mass Flow Controller 1112
~1116 Inflow valve 1117~1121 Outflow valve 1122~11213: Valve 127~1131: Pressure regulator 1132: Auxiliary/Help 1133° Main valve 1
134: Kate Valve! 135 Leak valve 11
36: Vacuum gauge 1137 Base Zolintar 11'38:
Power II Thermal Heater 1139 Motor 1140/High frequency power supply (Manching Ho, Kusu) Fig. 1□C Fig. 2 Fig. 3 Fig. 4rlA Fig. 5 Fig. 6 Fig. 7'C Fig. 8 Fig. 9 Fig. 1O Fig. ) (302)(303) (3014)(a
tomi, c ppm) No. (305) (306) (307) (308) (1
Figure 6 (Ql) (402) (403) (aomicχ) :404) (405) (406)

Claims (5)

[Claims] (1) In a photoconductive member having a support for a photoconductive member and a photoreceptive layer provided on the support and having photoconductivity, the photoreceptor layer is on the side of the support. A first layer (I) made of an amorphous material containing silicon atoms, a second layer (II) made of an amorphous material containing silicon atoms and germanium atoms, and silicon atoms. A third layer (II
A photoconductive member characterized in that the germanium atoms contained in the second layer (xi) are non-uniformly distributed in the thickness direction of the layer. (2) The photoconductive member according to claim 1, wherein at least one of the first layer (Z) and the second layer (II) contains hydrogen atoms and/or halogen atoms. (3) The photoconductive member according to claim 1 or 2, wherein at least one of the first layer (1) and the second layer (II) contains a substance that controls conductivity. . (4) The photoconductive member according to claim 3, wherein the substance that controls conductivity is an atom belonging to Group Ⅰ of the periodic table. (5) The photoconductive member according to claim 3, wherein the substance that controls conductivity is an atom belonging to Group V of the periodic table.