JPS60143358A - 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. O, from the substrate side. The layer 104 contains Ge in a concn. distribution nonuniform in this layer 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 relates to a method that is sensitive to electromagnetic waves such as light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.). It relates to a certain photoconductive member.

[Prior Art] 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.
German Publication No. 2,855,718 describes an application to an electrophotographic image forming member, and German Publication No. 2,933,411 describes an application to a photoelectric conversion/reading device.

However, photoconductive members having a photoconductive layer composed of conventional a-9i have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are problems that need to be further improved in terms of environmental characteristics and furthermore, stability over time, which requires comprehensive improvement of 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 long wavelength region compared to the short wavelength region in the visible light region, making it difficult to match with semiconductor lasers currently in practical use. However, there is still room for improvement in the sense that when a commonly used halogen lamp or fluorescent lamp is used as a light source, it is not possible to effectively use light on the longer wavelength side. Alternatively, if the irradiated light is not sufficiently absorbed in the photoconductive layer and the amount of light that reaches the support increases, the support itself has a high reflectance to the light that passes through the photoconductive layer. In this case, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes larger as the illumination spot is made smaller in order to increase the resolution, and is a serious problem especially when a semiconductor laser is used as the light source.

Furthermore, when the photoconductive layer is composed of a-9i material,
In order to improve its electrical and photoconductive properties, hydrogen atoms or halogen atoms such as fluorine atoms and chlorine atoms are added, and boron atoms and phosphorus atoms are added to control the electrical conductivity type, or other properties are improved. Therefore, other atoms are contained in the photoconductive layer as constituent atoms, but depending on the manner in which these constituent atoms are included, problems may arise in the electrical or photoconductive properties of the formed layer. There are cases.

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-Si material itself, it is necessary to take measures to obtain the desired electrical and optical properties as described above when designing photoconductive members.

The present invention has been made in view of the above points, and relates to a-5i, an electrophotographic image forming member, a solid-state imaging device, and a reading device δ.
As a result of comprehensive research and consideration from the viewpoint of applicability and applicability as a photoconductive member used in an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X), i.e., so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to collectively as a-3i(H,X)] and a silicon atom (
An amorphous material having a matrix of Sl) and germanium atoms (Ge), especially an amorphous material having these atoms as a matrix and hydrogen atoms (H)
or an amorphous material containing at least one of halogen atoms (X), that is, 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-3iGe ( A photoconductive member made by specifying the layer structure of the photoconductive member consisting of (denoted as H, , it is superior in all respects to conventional photoconductive materials, has particularly excellent properties as a photoconductive material for electrophotography, and has absorption spectrum characteristics on the long wavelength side. This is based on the fact that it has been found to be superior in

[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, has excellent matching with semiconductor lasers, and has fast photoresponse.

Another object of the present invention is to provide a charge retention capacity during the charging process for electrostatic image formation to such an extent that ordinary electrophotography can be applied to an extremely high charge rate 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 use a photoconductive material for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution, without image defects or image deletion. It is to provide parts.

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 (I) made of an amorphous material containing silicon atoms and oxygen atoms, and germanium atoms contained in the second layer (II) , is characterized by being non-uniformly distributed in the thickness direction of the layer. It is desirable that at least one of the first layer (r) and the second layer (II) contain hydrogen atoms and/or halogen atoms, and the first layer (I) middle and said second layer (II)
It is preferable that at least one of them 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 electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical properties are stable, and it has high sensitivity and a high signal-to-noise ratio. Therefore, high-quality images with high light fatigue resistance and repeated use characteristics, high image density, clear halftones, and high resolution can be repeatedly obtained stably.

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

[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.

Figure ff51 is a diagram schematically showing the layer structure for explaining the layer structure of the photoconductive member of the present invention.

As shown in FIG. 1, the photoconductive member 100 of the present invention has a photoreceptive layer 102 having sufficient volume resistance and photoconductivity on a support 101 for the photoconductive member. Photoreceptive layer 102
is the first layer consisting of a-3i(H,X) from the support side.
layer (I) 103, a second layer (II) 104 made of a-3iGe(H,X), and a third layer (m) 105 made of a-3iO(H,X). Ru. Photoconductivity may be imparted to either the first layer (I) or the second layer (II); needs to be designed.

Moreover, in this case, the first layer (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, at least one of the first layer (I) and the second layer (II) contains a substance (C) that controls conductivity. conductivity can be controlled as desired. The substance (G) has a first layer (I) and a second layer (II).
) are contained in either a uniform or non-uniform distribution state in the layer thickness direction. In addition, the layer region (P) containing the substance (C)
In N), the substance (C) is continuously uniform or non-uniform in the layer thickness direction! It is contained so that it is in the σ state.

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

On the other hand, the layer thickness of the first layer (I) is made thicker than the layer thickness of the second layer (II), and the second layer (II) is mainly used as a charge generation layer, and the first layer (I) is made thicker than the second layer (II). When used to function as a charge transport layer, a substance that controls conductivity (
It is desirable that C) be contained so as to be more distributed on the support side of the first layer (I).

As described above, in the present invention, at least one of the first layer (I) 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 and improve electrical withstand voltage.

Examples of the substance (C) that governs conductivity include so-called impurities in the semiconductor field, and in the present invention, p-type impurities that give p-type conductivity to Sl or Ge Mention may be made of impurities and n-type impurities that provide n-type conduction properties. Specifically, the P-type impurities include 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 Group V of the periodic table (Group V atoms), such as P, As, Sb, Bi, etc., with P and As being 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 conductive properties required for the layer region (PN), 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. 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 substance that governs the conductivity. The content of (C) is appropriately selected.

In the present invention, the content of the substance (C) controlling conductivity contained in the layer region ('PN) is preferably 0.001 to 5X104 atomic ppm, more preferably 0.5 to IX10 ' atomic ppm
, most preferably 1 to 5×103103ato ppm.

In the present invention, the content of the substance (C) that controls conductivity in the layer region (PN) is preferably 30 atoms.
ic ppm or more, more preferably 50 atomic
ppm or more, optimally 1oOatoIIlic ppm
By doing the above, for example, the substance (C) can be
In the case of type impurities, when the free surface of the photoreceptive layer is charged to Φ polarity, injection of electrons from the support side into the photoreceptor layer can be effectively prevented; When the substance (C) is the n-type impurity, the (''
When the outer surface is subjected to charging treatment to have θ polarity, injection of holes from the support side into the photoreceptive layer can be effectively 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 the amount contained in .

In such a case, the content of the substance (C) 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 to 1001000ato ppm, more preferably 0
．． 05-500 atomic ppm, optimally 0.1
~200 atomic ppm T7)

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 30 atomic ppm or less. In addition to the above-mentioned cases, in the present invention, a layer region containing a substance (C) that controls conductivity having one polarity in the photoreceptive layer, and a layer region controlling conductivity having the other polarity. It is also possible to provide a so-called depletion layer in the contact region by providing a layer region containing a substance CG) in direct contact with the contact region. That is, for example, the layer region containing the n-type impurity and the layer region containing the n-type impurity are provided in the photoreceptive layer so as to be in direct contact with each other to form a so-called p-n junction, thereby forming a depletion layer. can be provided.

In the present invention, specific examples of the halogen atom (X) contained in the layer (I) of tfJl as necessary include fluorine, chlorine, bromine, and iodine. It can be mentioned as a suitable one.

In the present invention, a-9i()1. In order to form the first layer (I) composed of X), for example, a glow discharge method,
A vacuum deposition method using a discharge phenomenon such as a sputtering method or an ion blating method is applied.

For example, in order to form the first layer (I) composed of a-9i (H, At the same time, the raw material scraps for introducing hydrogen atoms (I) and/or the raw material scraps for introducing halogen atoms (X) are introduced into a deposition chamber whose interior can be depressurized at a predetermined mixing ratio and gas flow rate. By generating a glow discharge in the deposition chamber and forming a plasma atmosphere of these scum, a-S is deposited on the surface of the support previously placed at a predetermined position.
A first layer (I) composed of i(H1×) is formed.

In addition, when forming by sputtering method, for example, A
When sputtering a target composed of Si in an atmosphere of inert gas such as r, He, or a mixed gas containing these gases, a 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 (1).

First, the starting materials that will become the raw material gas for supplying Si are as follows:
SiH4, Si2H6, 5i3HB, 514H10
Gaseous or gasifiable silicon hydrides (silanes) such as
S in terms of ease of handling layer creation work, good Si supply efficiency, etc.
Preferred examples include iH4 and Si2H6.

Effective starting materials that serve as raw material scraps for supplying Si 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, SiF4.5i2F 6 , 5
Silicon halides (7) such as iCI4, SiBr4, etc. can be mentioned as preferred, and furthermore,
S i B2 F2.5iH212, 5iH2CI2
, 5iHC13, 5iH2Br2, 5iHBr3, and other halogen-substituted silicon hydrides, gaseous or gasifiable halides containing hydrogen atoms as one of their constituent elements are also effective as starting materials for forming the first layer (I). can be mentioned.

Even when using a silicon compound 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 the raw material gas for introducing halogen atoms (X) used to form the first layer CI) include, in addition to the above, for example, fluorine,
Halogen gas such as chlorine, bromine, iodine, CIF, Cl
F3, BrF, BrF3, BrF5, IF3, I
Interhalogen compounds such as F7, IH, IBr, HF,
) l'cl, HBr, Hl, and other hydrogen halides.

In order to structurally introduce a substance (C) that controls conductivity into the layer region constituting the first layer (I), for example, a group Ⅰ atom or a group V atom, it is necessary to The starting material for introducing atoms of group M or the starting material for introducing atoms of group V 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 m atoms, it is desirable to use a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions.

Specifically, starting materials for the introduction of Group Ⅰ atoms include B2H6, B4 for the introduction of boron atoms,
Hlo, BS B9, ESHll, B6HIO, B6
Boron hydride such as H12, B&H14, BF3. B.C.
Examples include boron halides such as 13 and BBr3.

In addition, for the introduction of other group Ⅰ atoms, AlCl
3. GaCl3, Ga (CH3)3, InC13T
ICh etc. can be mentioned.

In the present invention, effective starting materials for introducing Group Ⅰ atoms are PH3 for introducing phosphorus atoms.
, phosphorus hydride such as P2H4, PH41, PF3, PF5
, PCl3, PCl5, PBr3, PBr5, PI3, and other phosphorus halides. In addition, AsH3,
AsF3, AsCl3, AsBr3, AsF5
．． 5bH3, SbF3, SbF5, SbC: 13, 5
bGI9, SiH3, BiCl3, B1Br3, etc. can also be mentioned as effective starting materials for the introduction of the V# atom.

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 (I) or the layer (I). It is appropriately selected based on organic relationships such as the characteristics of other layers provided in direct contact with I) and the characteristics of the contact interface with the base layer.

In the present invention, the content of the substance controlling conductivity contained in the first layer (1) is preferably 0.00
It is desirable to set it to 1-5XIO4 atomic ppm, more preferably 0.5-LX10'at, omic 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 (HlX) that may be contained in the first layer (I) is , preferably 1 to 40 atomic%, more preferably 5 to 30a
It is desirable to set it to tomic%.

Water that may be contained in the first layer (1),
) and/or to control the amount of halogen atoms (X),
For example, support temperature, hydrogen atom (H) or halogen atom (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 (I) of the present invention is determined depending on whether the first layer (I) mainly functions as an adhesive layer between the support and the second layer (If), or whether the first layer (I) 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 1ooOx to 50Iin, more preferably 2000A to 30IiIn, optimally 200A
It is desirable that it be 0A to 10μ. In the latter case,
Preferably 1 to 100 tiles, more preferably 1 to 80 tiles,
The optimal number is preferably 2 to 50.

In the photoconductive member of the present invention, the first layer (I) 103
A second layer (II) 104 is formed on top. First layer (
I) and the second layer (II) are each mainly composed of an amorphous material having a common constituent atom, silicon atoms, so that chemical stability is maintained at the laminated interface. Sufficiently secured.

In the photoconductive member of the present invention, the distribution state of germanium atoms contained in the layer (II) of $2 is non-uniform in the layer thickness direction, but the distribution state is non-uniform with respect to the surface of the support. 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 different from that in the first layer (II). ), the distribution decreases from the boundary with the third m (m), the first layer (I)
A layer structure in which the distribution increases from the boundary with the third layer (m) toward the boundary with the third layer (m), or a layer structure that has the characteristics of both layers is allowed.

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

In FIGS. 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 (H), and tB shows the distribution concentration C of germanium atoms. The position of the interface with the second layer (II), t, is the position of the interface between the second layer (II) and the third layer (m
) indicates the position of the interface with That is, the second layer (II) containing germanium atoms is formed from the tB side toward the tT 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, from the interface position tB with the first layer (I), where the second layer (II) containing germanium atoms is formed, to the position tl, there is a distribution of germanium atoms. It is contained in the second Je (II) with the concentration C taking a constant value of 01, and from the position t1, the concentration C2 gradually continues until the interface with the third layer (m) reaches the has been reduced to

At the interface t1, the 1r5 concentration C of germanium atoms is 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 from the position tB to the position t1, and reaches the concentration C5 at the position 11tr. It forms a distribution state.

In the case of Fig. 4, the distribution concentration C of germanium atoms is kept at a constant value C6 from position ta to position t2, and gradually and continuously decreases between position t2 and position d. , at position 0, the distribution e2 claw 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 gradually decreased from the concentration CB from position F(tB to position 1), and becomes substantially zero at position 1. ing.

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is C9 between position fitB and position 13.
It is a constant value, and the density at one position is C1°. Between position mL3 and position 1, the distribution concentration C is linearly decreased from position L3 to mL.

In the example shown in FIG. 7, the distribution concentration C is located at B
The density C11 takes a constant value up to position 4, and at position t
From position 4 to position 1, the distribution state is such that the concentration decreases linearly from concentration C12 to concentration CI3.

In the example shown in FIG. 8, from position tB to position D, the distribution concentration C of germanium atoms decreases linearly from the concentration C14 to substantially zero.

In FIG. 9, from position tB to position t, the distribution concentration C of germanium atoms decreases linearly from concentration CI5 to concentration CI6, and between position t5 and position 1, In this example, the concentration C1F is set to a constant value.

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration C17 at a position tB, and the concentration decreases slowly from this concentration C17 until reaching a position t6, and then near the position t6. , the concentration is rapidly decreased to a concentration CI8 at a position E6.

Between position t6 and position t7, the concentration is initially decreased rapidly, then slowly and gradually decreased to reach CI9 at position t7, and between position t7 and position t8, it is extremely slowly decreased. The concentration is gradually decreased to reach the concentration C2° at position t8. Between position t8 and position tT,
The concentration is decreased from C20 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 the germanium concentration is 0 at position Wtr.
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 1 position t
The germanium concentration is constant at C24 from lo to position t.

In addition, the germanium concentration distributions shown in FIGS. 2 to 13 show a distribution in which the germanium concentration is high near the interface with the first layer (I) in FIGS. 2 to 10, and
Although FIGS. 1 to 13 show a distribution in which the germanium concentration is high near the interface with the third layer (m), a germanium concentration distribution may be obtained by combining these.

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

The second layer (II) constituting the photoreceptive layer constituting the photoconductive member in the present invention is preferably the first layer as described above.
near the interface with the layer CI) and/or the third layer (I[I
) 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 it in a region within five corners from the boundary surface position tB or Ll.

In the present invention, the localized region (A) may be located at the interface B or the entire layer region (Ll) from 1 to 5 tiles thick, or may be a layer region (L layer). ).

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

The localized region (A) has a distribution state of germanium atoms contained therein in the layer thickness direction, such that the maximum distribution concentration CIIIax of germanium atoms is preferably +000 atomic ppm or more, more preferably more than +000 atomic ppm relative to silicon atoms. 5000 atomic'ppm or more, optimally I
It is desirable that the layers be formed so that a distribution state of X 10' atomic-1 sieve m or more can be obtained.

That is, in the present invention, the second J'# (II) containing germanium atoms is a layer from the first layer (I) side or from the free surface of the second amorphous layer (II). It is preferable to form the layer so that the maximum value Cmax of the distribution Is degree exists within 5 scales in thickness (layer region of 5 scales from tB).

In the present invention, the content of germanium atoms contained in the second layer (II) may be determined as desired so as to effectively achieve the object of the present invention.
Preferably 1-9.5X 10'atomic ppm
, more preferably 100 to 8×lO5105ato p
pm, optimally 500-7XI05atomic 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 (TI) 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, when the free surface of the photoreceptive layer is subjected to polar charging treatment, the photoreceptor is removed from the support side. Injection of electrons into the layer can be effectively blocked, and in the case of the contained substance (C) or the n-type impurity, the free surface of the photoreceptive layer is charged to O 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 (Zll) of the second layer (11) excluding the layer region (PM),
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) that controls the conductivity contained in the layer region (211) depends on the polarity and content of the substance (C) contained in the layer region (PN). Although it is determined as appropriate depending on the amount, preferably 0.
001-1001000 atomic ppm, more preferably 0.05-500 atomic ppm, optimally o
, preferably 1 to 200 atomic ppm.

In the present invention, when the layer region (PN) and the layer region (ZII) provided in the second layer (II) contain the same type of substance (C) that controls conductivity, the layer region (
Substance controlling the conductivity contained in ZII) (C)
The content is preferably 30ato++ icpp
It is desirable that it be less than m. In addition to the above-mentioned case, in the present invention, a layer region containing a substance (C) controlling conductivity having one polarity and a conductivity controlling substance (C) having one polarity is included in the second layer (II). It is also possible to provide a so-called depletion layer in the contact region by directly contacting a layer region containing a substance (C) that controls conductivity. That is, for example, the second M! The layer region containing the p711 impurity and the layer region containing the n-type impurity are provided in direct contact in j(II) to form a so-called p-n junction,
A depletion layer can be provided.

In the present invention, specific examples of the halogen atom (X) contained in the second layer (II) as necessary 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-5iGe (H, Deposition method is applied.

For example, by glow discharge method, a-9iGe(H,X)
In order to form the second layer (II), basically, a raw material gas for S1 supply that can supply silicon atoms (Sl) 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. The second curve composed of a-3iGe(H,X) is controlled so that the curve becomes a desired rate of change curve.
A layer (II) is formed.

In addition, when forming by sputtering method, for example, A
A target made of Si, two targets made of Si and a target made of Gie, or a target made of Si in an atmosphere of an inert gas such as r or l (e) or a mixed gas based on these gases. Using a mixed target of (X
) Introducing the raw material gas for introduction into the deposition chamber for sputtering to form a desired gas plasma atmosphere,
The target may be sputtered while controlling the gas flow rate of the raw material gas for supplying Ge 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 respectively accommodated as evaporation sources in the evaporation port, and these 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 flying evaporated material is heated and evaporated by EB method or the like and passed through a predetermined gas plasma atmosphere.

In the present invention, the starting materials that serve as the raw material gas used to form the second layer (II) include:

The following are valid:

First, the starting materials that will become the raw material gas for supplying Si are as follows:
Gaseous or gasifiable silicon hydrides (silanes) such as SiH4, S1□H6, 5i3H6, 5i4H1゜, etc. can be used effectively, especially for ease of handling in layer creation work and Si supply. SiH in terms of efficiency etc.
, s, and Si2H6 are preferred. G
The starting material that becomes the raw material gas for e supply is GeH4.
,Ge2H6,Ge3HB,Ge4H16,Ge5
H12, Ge6H14, Ge7H16, GeBH1g,
Gaseous forms such as Ge4H16! (7) Or germanium hydride, which can be gasified, can be effectively used, and GeH4, Ge2H&, Ge3HB are particularly preferred in terms of ease of layer creation work, good Ge supply efficiency, etc. Can be mentioned.

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 suitably used to form the second layer (rl) include halogen gases such as fluorine, chlorine, bromine, and iodine, CIF
, ClF3, BrF , BrF3, BrF5, IF
Examples include interhalogen compounds such as s, IF7, ICI, and IBr.

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

The second embodiment of the photoconductive member of the present invention is produced by a glow discharge method using such a silicon compound containing a halogen atom (X). In the case of forming (II), the first layer (I) was formed on the surface without using silicon hydride gas as a raw material gas capable of supplying Si together with the raw material gas for supplying Ge. A second layer (II) composed of a-5iGe(H,X) can be formed on the support.

According to the glow discharge method, the second one containing a halogen atom (X)
When forming a layer (IT), basically, for example, Si
Silicon halide, which will be the raw material gas for supply, germanium hydride, which will be the raw material gas for Ge supply, ^r, H
Gases such as e and the like are introduced at a predetermined mixing ratio and gas wave amount into a deposition chamber where the second layer (II) is formed, and a glow discharge is generated to remove these gases. By forming a plasma atmosphere, a second layer (II) can be formed on the support on whose surface a first layer CI) has been formed. In addition, in order to more easily control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is further mixed with these gases to form the second layer (II). Good too. Moreover, each gas may be used not only as a single species but also as a plurality of them at a predetermined mixing ratio.

In both the sputtering method and the ion plate ink 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. The gas may be introduced to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a gas for introducing hydrogen atoms, such as F2, or the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering, and a plasma atmosphere of the gas is introduced. All you have to do is form it.

In the present invention, the above-mentioned halides or silicon compounds containing halogen atoms are effectively used as the raw material gas for introducing halogen atoms when forming the second layer (II). , HF, HCI, HB
r, old hydrogen halide, S i F2 F2.5
iH2h, 5iH2CI2.5iHC13, 5iH2B
Halogen-substituted silicon hydride such as r2.5iHBr3, and GeHF3, GeF2F2, GeH3F, G
eHCl3, GeF2012, GeHBr3. G
eHBr3, GeF2Br2, GeHBr3GeF
212, halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides such as GeH3I,
GeF4, GeCl4, GeBr4, GeI4
, GeF2, GaCl2', GeBr2, GeI
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituents, such as germanium halides such as No. 2, can also be mentioned as effective starting materials for forming the second layer (■).

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 into the layer at the same time as halogen atoms are introduced into the layer. is used as a suitable raw material for introducing halogen atoms.

In order to structurally introduce hydrogen atoms into the $2 layer (n), in addition to the above, F2, SiH4, Si2H6,5i
Silicon hydride such as 3HB, 5i4H+o with germanium or a germanium compound for supplying Ge, or GeH4, Ge2H6, G, e3HB,
GeaHIo, Ge5H+2, Ge6H14, Ge7H
It can also be carried out by coexisting germanium hydride such as +r, , GeBHIB, ce9) 120 with silicon or a silicon compound for supplying Si in the deposition chamber to generate a discharge.

In a preferred example of the present invention, hydrogen atoms () that may be contained in the second layer (II) of the photoconductive member to be formed
Measure l), the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 0.0
1-40 atomic%, more preferably 0.05-30
ato+nic%, optimally 0.1-25atomic
It is preferable to set it as %.

Hydrogen atoms (H
) and/or to control the amount of halogen atoms (X),
For example, support temperature, hydrogen atom (H) or halogen atom (X
), the amount of the starting material introduced into the deposition system, the discharge power, etc. may be controlled.

In the second layer (II), 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 way as in the case of explaining the method for forming the first layer (I), the above-mentioned introduction of a group ① atom is carried out during layer formation. The starting material for or for the introduction of Group V atoms may be introduced in gaseous form into the deposition chamber together with other starting materials to form the second W(II).

The layer thickness of the second layer (II) in the photoconductive member of the present invention is such that when the second layer (II) is mainly used as a photocarrier generation layer, It is determined as appropriate in consideration of the absorption coefficient of layer (II) of No. 2, and is preferably 10008 to 50u+, more preferably 100OA to 30U+, most preferably 1000A to 20U.

In addition, when the second layer (II) is used mainly as a layer for generating and transporting photocarriers, the layer is appropriately determined as desired so that photocarriers can be transported efficiently, and preferably has a layer of 1 to 100 scales. , more preferably 1-80
The number is preferably 2 to 50.

The third layer (m) 105 formed on the second layer (II) 104 of the photoconductive member of the present invention has a free surface, and mainly has temperature resistance, continuous repeated use characteristics, electrical breakdown voltage. This is provided to achieve the objectives of the present invention in terms of performance, use environment characteristics, and durability. 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 the present invention consists of silicon atoms (Si
), an oxygen atom (0), and, if necessary, a hydrogen atom (H) and/or /\\rogen atom (X) (hereinafter, a-(SiXO+ -X)) y
It is written as (H2X)+-a, provided that 0<x, y<1).

The third layer (III) composed of a-(SlxO+-x)y(H, XL-y) can be formed by glow discharge method, suba-interring method, ion implantation method, ion plate ink method, electron It is carried out by a beam method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, degree of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. ,
It is relatively easy to control the conditions for producing a photoconductive member having desired characteristics, and it is easy to introduce oxygen atoms and halogen atoms together with silicon atoms into the third layer (m) to be produced. The glow discharge method or the sputtering method is preferably employed because of its advantages such as being able to perform the following steps. Also,
The third layer (m) may be formed by using a glow discharge method and a sputtering method in the same device system.

To form the third layer (m) by the glow discharge method,
a-(Sjx O+ -x)y (H,X) ly
The raw material gas for formation is mixed with a diluent gas as necessary at a predetermined mixing ratio, and introduced into a deposition chamber for vacuum deposition where the support on which the second layer (It) is formed is installed, The introduced scum is turned into scum plasma by causing glow discharge, and a-
(St, o, -X)y (H, XL-y may be deposited.

In the present invention, a-(SlxO+-x)y(H,X)
The raw material residue for +-y formation is silicon atoms (Si
), most of the scum-like substances containing at least one of oxygen atoms (0), hydrogen atoms (H) and halogen atoms (X) as constituent atoms, or gasified substances that can be gasified. can be used.

When using a raw material gas having Si as a constituent atom as one of Si, 0, H, and X, for example, a raw material gas having Si as a constituent atom, a raw material gas having 0 as a constituent atom,
Source gas containing H as a constituent atom and/or X as necessary
A raw material gas containing 0 and H as constituent atoms and/or a raw material gas containing 0 and H and/or 0 and Alternatively, a raw material gas containing Sl as a constituent atom and a raw material gas containing three constituent atoms of Si, 0, and H or Sl , 0 and X as constituent atoms are mixed at a desired mixing ratio.

Alternatively, as a side method, a raw material gas containing Si and H as constituent atoms and a raw material gas containing 0 as constituent atoms may be used in combination, or a raw material gas containing Si and X as constituent atoms may be used. and a raw material gas having 0 as its constituent atoms may be used in combination.

In the present invention, suitable halogen atoms (X) that may be contained in the third layer (III) include F,
CI, Br, and I, with F and C1 being 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 atoms.
i H4, Si2H6, 5i3HB, 5i4H1O
Gaseous or gasifiable silicon hydrides (silanes) such as S1 can be effectively used, and S
Preferred examples include iH4 and Si2H6.

If these starting materials are used, S can be added in the third layer (m) to be formed by appropriately selecting the layer forming conditions.
H may also be introduced along with i.

Effective starting materials that serve as raw material scraps 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 (7) such as iG14, SiBr4, etc. can be mentioned as preferable ones, and furthermore, S
i H2F2.5iH2I2.5iH2C12, 5i
Halogen-substituted silicon hydrides such as HCI3.5iH2Br2.5iHBr, etc., and halides having two hydrogen atoms in a gaseous state or which can be gasified, are also effective starting materials for forming the third layer (m). can be mentioned.

Even when using a silicon compound containing these halogen atoms (X), as described above, by appropriately selecting the layer forming conditions, the halogen atoms (X) together with 81 can be added to the third layer (m) to be formed. 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, C
IF3, BrF, BrF3, BrF5IF5,
Interhalogen compounds such as IF7, [1, IBr.

Examples include hydrogen halides such as HF, HCI, Her, and old.

In the present invention, starting materials that are effectively used as a raw material gas for supplying oxygen atoms (0) used to form the third layer (III) include those having 0 as a constituent atom, or 0 and H as constituent atoms, for example oxygen (02)
, ozone (03), -nitrogen oxide (NO), nitrogen dioxide (
NO2), mnitric oxide (N20), nitric oxide (8
203), trinitric oxide (N20), mininitric oxide (N
20S), nitrogen dioxide (NO3), silicon atoms (S
i), an oxygen atom (0), and a hydrogen atom (H) as constituent atoms, for example, disiloxane (!(3s+09iH3),
Examples include lower siloxanes such as trisiloxane (H3SiO3iH20SiH3).

These third layer (m) forming substances contain silicon atoms, oxygen atoms, and optionally halogen atoms and/or hydrogen atoms in a predetermined composition ratio in the third layer (III) to be formed. In the formation of the third layer (m), it is selected and used as desired.

In order to form the third layer (III) by the subinterning method, for example, the following method can be adopted.

The first method is to process Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these residues.
When sputtering a target made of
It may be introduced into the deposition chamber where sputtering 1) 7 is performed together with the raw material gas for introduction.

In the second method, the sputtering target is a target made of Si, a target made of Si and a target made of 5i02, or a target made of Si and 8102. I
By using *, oxygen atoms (0) can be introduced into the third layer (m). At this time, if the above-mentioned raw material gas for introducing oxygen atoms (0) is also used, the amount of oxygen atoms (0) introduced into the third layer (III) can be controlled as desired by controlling the flow rate. It is easy to control.

The material that becomes the raw material residue for introducing 0, H and X is the third layer (III) shown in the glow discharge example mentioned above.
Forming substances can also be used as effective substances in sputtering methods.

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, 0, H and/or In the present invention, a- In order to form (SixO+-x)y(H, If provided for the main purpose, a-(si
, o, -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. As an amorphous material with sensitivity, a-
(SiXO+-x), (H,X),-.

is created.

On the surface of the second layer (II) a-(Sxx o, -
X )y (HlX)! - When forming the third layer (m) consisting of (A), the temperature of the support during layer formation is one of the important factors that influences the structure and properties of the formed layer, and in the present invention, , a-(SiX
It is desirable that the temperature of the support during layer formation be tightly controlled so that O+ -x )y (H,X) 1-y 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
For the formation of the third layer (III), which is preferably kept at an optimal temperature of 100 to 300°C, delicate control of the composition ratio of the atoms constituting the layer is relatively easy compared to other methods. For certain reasons, it is advantageous to adopt the glow discharge method or sputtering method, but when forming the second layer using these layer formation methods, the temperature of the layer formation as well as the support temperature described above must be adjusted. The actual discharge power is created a−(Six o, −X )y
(H,X) can be cited as one of the important factors that influence the characteristics of ry.

The discharge power conditions for effectively producing a-(SlxO+-x)y(H,XL-y with good productivity) are as follows: Preferably 10-300W, more preferably 20-2
It is desirable that the power be 50W, most preferably 50 to 200W.

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

In the present invention, the above-mentioned values are listed as the preferable numerical ranges for the support temperature and discharge power for creating the third layer (m), but these layer creation factors can be determined independently. a of the desired characteristic, rather than one that can be determined separately.
It is preferable that the optimum value of each layer creation factor is determined based on mutual organic relationships so that the third layer (m) consisting of -(StXO, -X )y (HlXL-7) is formed.

The amount of oxygen atoms contained in the third layer (I[I) in the light guide member of the present invention is such that the objective of the present invention can be achieved as well as the conditions for forming the third layer (m). This is one of the important factors for forming the third layer (m) that provides desired characteristics. The amount of oxygen atoms contained in the third layer (m) in the present invention is appropriately determined as desired depending on the characteristics of the amorphous material constituting the third layer (m).

That is, the general formula &-(Slx O+ -x)y (
H,
An amorphous material composed of silicon atoms and oxygen atoms (hereinafter referred to as a-9ilOl-a, where O<a<
1) An amorphous material composed of silicon atoms, oxygen atoms, and hydrogen atoms (hereinafter a-(Si, OB-b)
) cH+-c. However, 0 < b, c < 1
), an amorphous material composed of silicon atoms, oxygen atoms, halogen atoms, and optionally hydrogen atoms (hereinafter a)
7 (Start-a)a (H,X), written as -8. However, it is classified as 0<d, e<1).

In the present invention, the third layer (m) is a-9iH01-&
, the amount of oxygen atoms contained in the third layer (m) is preferably 0.33 to 0.99999.
, more preferably 0.5-0.98, optimally 0.6-0
．． It is 9.

On the other hand, in the present invention, the third layer (I[[) is '-(S
When composed of tb O+ -b )c H+-0,
The amount of oxygen atoms contained in the third layer (I [ 0.9, C is preferably o, e~0.98, more preferably 0.65~0,
98, optimally 0.7 to 0.85.

The third layer (III) is a-(Si, 1 o, -a
)e (H,X) When composed of I-e, the third
The content of oxygen atoms contained in the layer (m) is:
d is preferably 0.33-0.99999, more preferably 0.5-0.99, optimally 0.6-0.9.
e is preferably 0.8 to 0.9θ, more preferably 0.8
It is desirable that it is between 2 and 0.89, most preferably between 0.85 and 0.88.

Further, the amount of hydrogen atoms (H) is preferably 80a with respect to the sum (H+X) of halogen atoms (X) and hydrogen atoms (H).
atomic% or less, more preferably 80 atomic%
What is the best option below? It is desirable that it be less than Oatomic%.

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.

Further, the layer thickness of the third layer (III) is the same as that of the third layer (II).
I) The amount of oxygen atoms contained in the organic layer and the thickness of the first layer (I) and second layer (II) are determined according to the characteristics required for each layer. It needs to be determined appropriately based on the relevance and desire. In addition, it is desirable to consider the economical aspects including productivity and mass production.

The thickness of the third layer (m) in the present invention is preferably 0.003 to 30 units, more preferably 0.004 to 30 units.
・It is desirable to set the time to 20 seconds, optimally 0.005 to IO μs.

The support lot used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, AI, Cr,
KO, Au, Nb, τa, 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, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

That is, for example, if it is glass, NiC is applied to the surface of the glass.
r, AI, Cr, No, Au, Tr, Nd, Ta,
V, Ti, Pt, In2O3,5n02, ITO (1
Conductivity is imparted by providing a thin film consisting of ++203→-9n02), or if it is a synthetic resin film such as polyester film, NiCr, AI,
Ag, Pb, Zn, Ni, Au, Cr, Mo,
A thin film of metal such as 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 to make the surface conductive. Granted.

The shape of the support is determined as desired, but for example, if the photoconductive member lOO shown in 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 cases, from the viewpoint of manufacturing and handling of the support, as well as mechanical strength, it is usually set to 1O- 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 sealed with raw material gas for forming the photoconductive layer of the photoconductive member of the present invention.
1103 is a cylinder of SiH4 gas (purity 99.999%, hereinafter referred to as SiH4/He scum) diluted with Hete gas (purity 99.899%, hereinafter referred to as G
1104 is a SiF4 gas diluted with He (purity 99.999%, hereinafter referred to as S
iF4/He gas) cylinder, 1105 is H
B2H6 gas diluted with e (purity! 39.999%,
(hereinafter abbreviated as E2 H6/He gas) cylinder, 1106
is a He dregs (purity SS, 9a%) cylinder. Although not shown in the drawings, it is possible to add cylinders of desired gas types in addition to these as needed.

In order to flow these gases into the reaction chamber 1101, each valve 1122 to 112 of the gas cylinders 1102 to 1108 is opened.
6 and leak valves 1135 are closed, and also inlet valves 1112-1118, outlet/nine valves 1117-1121 and auxiliary valves 1132.11.
33 is opened, first, the main valve 1134 is opened to exhaust the inside of the reaction chamber 1101 and each gas pipe. Next, the reading of vacuum gauge 1136 is about 5 x 10° 6t
The auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed at the last point when the condition becomes orr.

First, an example of forming the first layer (I) on the cylindrical substrate 1137 is shown.
Open the H6/He gas valves 1122 and 1125 and adjust the pressure on the outlet pressure gauges 1127 and 1130 to IKg.
/ cm2, inlet valve 1112.1115
Gradually open the mass flow controller 1107.11.
10 respectively. Subsequently, outflow valve 1
117, 1120 and the auxiliary valve 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 between the SiH4/He gas flow rate and the 82H6/ )He gas flow rate becomes a desired value.
7. Adjust the opening of the main valve 1134 while checking the reading of the vacuum gauge 1136 so that the pressure inside the reaction chamber reaches the desired value. Then, the temperature of the base cylinder 1137 is increased to 50°C by the heating heater 1138.
After confirming that the predetermined temperature of ~400°C is set, the power supply 1140 is set to the desired power and the reaction chamber 11 is heated.
A glow discharge is generated in the base cylinder 11.
A first layer (I) is formed on 37. Further, during layer formation, the base cylinder 1137 is rotated at a constant speed by a motor 1138 in order to ensure uniform layer formation. Close all gas operation valves that were last used.
The reaction chamber 1101 is once evacuated to high vacuum.

Next, to show an example of forming the second layer (II) on the first layer (I) formed in this way, when the reading of the vacuum gauge 1136 becomes approximately 5X 10' torr, Repeat the same operations as above.

That is, SiH4/He gas is supplied from the gas pump 1102, GeH4/He gas is supplied from the gas pump 1103, and B7 H(,/)He gas is supplied from the gas pump 1105 by opening the valves 1122, 1123, and 1125, respectively, and adjusting the pressure on the outlet pressure gauges 1127, 1128, and 1130. IKg
/ cm2, inlet valve 1112.1113.
Gradually open 1115, mass flow control, 11
07.1108.1110 respectively. Subsequently, the outflow valves 1117, 1118, and 1120 and the auxiliary valve 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, SiH4/He gas flow rate, GeH4/He gas flow rate, and B2 H6/H
e Adjust the outflow valve 1 so that the ratio with the gas flow rate is the desired value.
117.1118.1120 and the second layer (II
) is controlled so that the germanium atom concentration distribution in the layer thickness direction becomes a desired distribution. Further, the opening of the main valve 1134 is adjusted while checking the reading on the vacuum gauge 1136 so that the pressure in the reaction chamber reaches a desired value. Then, the temperature of the base cylinder 1137 is raised to 50~50 by heating heater 1138.
After confirming that the predetermined temperature of 400° C. is set, the power source 1140 is set to the desired power and the reaction chamber 110 is heated.
1 to generate a glow discharge in the base cylinder 113.
A layer (II) of $2 is formed on the layer (II) in the same manner as the formation of the first layer (I).

Next, when forming the third layer (III) on the second layer (II) formed in this way, close all the waste operation system valves used as in the previous case. Once the reaction chamber 1101 is evacuated to a high vacuum and the reading of the vacuum gauge 1136 becomes approximately 5X 10" torr, Si
H4/He dregs, SiF4/H from Kasponbe 1104
e-gas, NO gas is supplied from the gas cylinder 1106,
A third layer (m) is formed by generating a glow discharge. The amount of carbon atoms in the third layer (]I[) is controlled by adjusting the supply flow rate of NO gas.

Examples will be described below.

Example 1 Using the manufacturing apparatus shown in FIG. 18, a photoreceptive layer was formed on an AI cylinder according to the manufacturing conditions shown in Table 1 by the glow discharge decomposition method detailed above. Each sample (samples 1-1 to 1e-6, 06 types in total) as an image forming member was prepared.

The distribution states of boron atoms and germanium atoms contained in the photoreceptive layer of each sample at this time are shown in FIGS. 14A and 14.
They are shown in Figure B and Figure 15, respectively.

The distribution state of boron atoms and germanium atoms in each sample is determined by adjusting the flow rate of B2H6 and GeF4 residue by automatically opening and closing the corresponding valves according to a predetermined gas flow rate change rate curve. Formed by. 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. Corona charging was performed for 0.3 seconds using OKV, and a light image was immediately irradiated.

The optical image is 0.21ux using a tungsten lamp light source.
A light amount of ssec was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading an e-chargeable developer (including toner and carrier) over the imaging member surface. 5. Toner image on the surface of the image forming member. When the images were 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.

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 using an 810 nm GaAs semiconductor laser (10 mW). As in the previous case, clear, high-quality images with good gradation reproducibility were obtained.

Example 2 Using the manufacturing apparatus shown in FIG. 18, a cylindrical substrate made of A1 was fabricated in the same manner as in Example 1 except that the manufacturing conditions shown in Table 3 were changed to produce an image forming member for electrophotography. Each sample (
A total of 48 types of samples (J21-1 to J28-6) were prepared.

The distribution state of boron atoms and germanium atoms contained in the photoreceptive layer of each sample at this time is shown in Fig. 16 and 1.
They are shown in Figure 7. The distribution state of boron atoms and germanium atoms in each sample can be determined by adjusting the gas flow rates of B2 H68 and GeF4 by automatically opening and closing the corresponding valves according to a predetermined rate of change curve of gas flow rates. Formed by. The distribution state of boron atoms and germanium atoms in each sample and the first
The correspondence with FIG. 6 and FIG. 17 is shown in Table 4 as a list.

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 Using the manufacturing apparatus shown in FIG. 18, the samples of Example 1, J 12-5, and Example 1 were used, except that the conditions for producing the third layer (III) were as shown in Table 5. 2 samples, 1
Electrophotographic imaging members (Samples! 1.2-5-1 to 12-5-8.24-4-1) were prepared according to the same conditions and procedures as those used to prepare 1L24-4 and 2day-2, respectively. ~2
A total of 24 samples (4-4-8.2B-2-1 to 28-2-8) 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 (I [ Sample #6.3- of Example 1 except that the content ratio of silicon atoms and oxygen atoms in 3.a (m) was changed.
A photoreceptive layer was formed on a cylindrical Al substrate in the same manner as in 1 to obtain an electrophotographic image forming member (sample #1lL3-
1-1 to 3-1-7) were produced.

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 The same procedure was carried out except that when forming the third layer (Cm), the flow rate ratio of SiH4 gas and NO gas was changed to change the content ratio of silicon atoms and oxygen atoms in the third layer (m). A light-receiving layer was formed on a cylindrical Al substrate in exactly the same manner as Sample Acid 3-1 in Example 1, and an image forming member for electrophotography (Sample Acid 3-1) was formed on a cylindrical Al substrate.
-1-11 to 3-1-18) were produced, 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 6 When forming the third layer (m), the content ratio of silicon atoms and oxygen atoms in the third layer (III) was changed by changing the flow rate ratio of SiH4 scum, SiF4 scum and NO gas. A light-receiving layer was formed on a cylindrical Al substrate in exactly the same manner as Sample Acid 3-1 of Example 1, except for the above, to obtain electrophotographic image forming members (Samples, 63-1-21 to 3-3). 1-27, total 7
) 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 A light-receiving layer was formed on a cylindrical Al substrate in the same manner as in Example 1, except that the thickness of the third layer (m) was changed. Image forming members for electrophotography (a total of four sample acids 3-1-31 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: When forming the first and third layers Approximately 250°C When forming the S2 layer Approximately 200'0 Discharge frequency: 13.58 MHz Reaction chamber pressure during reaction: 0.3 Toor Table 10

[Brief explanation of the drawing]

FIG. 1 is a diagram schematically showing the layer structure for explaining the structure of the photoconductive member of the present invention. 2 to 13 are schematic diagrams for explaining the distribution state of germanium atoms in the second layer ('II) of the photoconductive member of the present invention, respectively. FIG. 14A, FIG. 14B, and FIG. 16 are diagrams schematically showing the concentration distribution of boron atoms in the photoreceptive layer in an example of the photoconductive member of the present invention, respectively, and FIGS. FIG. 17 is a diagram schematically showing the concentration distribution of germanium atoms in the second layer (II) in each example of the photoconductive member of the present invention. 81
FIG. 8 is a diagram showing an apparatus for manufacturing a photoconductive member using a glow discharge decomposition method. 100: Photoconductive member 101: Support 102: Photoreceptive layer 103. First layer (I) 104 + second layer (II) lQ5: third layer (m) 1101:
Reaction chambers 1102 to 110 fl: gas cylinders 1107 to 1111 + mass flow controller 1112
~l1lf (: Inflow valve 1117-1121': 1 & Output valve 1122-112Ei: Pressure regulator 1132 for valve 1127-113: Auxiliary pulse;)' 1133: Main valve 1134: Gate valve 1135: Leak valve 11
36: Vacuum gauge 113? :Base Schilling -1138°
Heater 1139: Motor 1140: High frequency power supply (matching box) Fig. 1 Fig. 2 Fig. 3 Fig. 4 Fig. 5 Fig. 0 Fig. 7 Fig. 8 Fig. 9 Fig. 1 IO Fig. (301) (302) (303) (3014)(
++m) Iku j'' distribution concentration (atomic ppm) containing pure substances (atomic ppm) No. (305), (306) (307) (308)!
! Figure 6 (401) (402) (403) (atomic X) (4014) (405) (406) Figure B7

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 formed of silicon from the support side. a first layer (I) composed of an amorphous material containing atoms;
A second layer (II) made of an amorphous material containing silicon atoms and germanium atoms, and a third layer (III) made of an amorphous material containing silicon atoms and oxygen atoms.
), and germanium atoms contained in the second Je(II) are non-uniformly distributed in the thickness direction of the layer. (2) The light according to claim 1, wherein at least one of the first layer (I) and the second layer (II) contains a Li-hyung atom and/or a rogen atom. conductive member. (3) The photoconductive material according to claim 1 or 2, wherein at least one of the first layer (I') and the second layer (II) contains a substance that controls conductivity. Element. (4) The photoconductive member according to claim 3, wherein the substance that governs 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.