JPS6068675A - Photoconductive member - Google Patents

Abstract

PURPOSE:To always stabilize electrical and optical photoconductive characteristics by containing a substance for controlling conductive type in the first layer, and irregularly forming the distributed state of germanium atoms in the first layer in the thicknesswise direction. CONSTITUTION:A photoconductive member 100 has the first layer 102 and the second layer 103 having photoconductivity made of a-SiGe(H,X) on a support 101. Germanium atoms contained in the layer 102 are continuous in the thicknesswise direction of the layer 102, and container in the layer 102 to become more in the distributed state to the side of the support 102 to the opposite side to that provided with the support 101. The distributed state of the germanium atoms contained in the layer 102 are as shown in the thicknesswise direction, and preferably in regularly distributed state in the planar direction parallel to the surface of the support.

Description

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

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

Based on these points, amorphous silicon (hereinafter referred to as 35) is a photoconductive material that has recently attracted attention.
, for example, German Publication No. 2746967, German Publication No. 28
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

A photoconductive member having a conventional photoconductive layer composed of a-8i has excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and furthermore, stability over time, which requires a comprehensive improvement in characteristics.

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

Furthermore, a-8i has a relatively small absorption coefficient 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, when conventionally used fluorocarbon lamps and fluorescent lamps are used as light sources, there remains room for improvement in that they cannot effectively use light on the longer wavelength side.

In addition, if the amount of irradiated light that reaches the support without being sufficiently absorbed in the photoconductive layer increases, the support itself will absorb the light passing through the photoconductive layer. When the reflectance is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images.

This effect becomes larger as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source.

Alternatively, when the photoconductive layer is made of a-8t material, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms to control the properties of the photoconductive layer, and other atoms are included in the photoconductive layer to improve properties. In other words, for example, photocarriers generated in the formed photoconductive layer due to light irradiation may cause problems with the electrical or photoconductive properties or electrical withstand voltage of the formed layer. This may be due to insufficient lifespan, insufficient prevention of charge injection from the support side in dark areas, or local discharge breakdown phenomenon commonly referred to as "white spots" in the image transferred to the transfer paper. For example, when a blade is used for cleaning, so-called image defects commonly referred to as "white streaks" that are thought to be caused by the rubbing of the blade have occurred.
Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called image blurring often occurs. There are issues that need to be resolved in terms of stability over time, as often occurs in the case of ram-shaped supports.Therefore, while efforts are being made to improve the properties of the A-8i material itself, it is important to design photoconductive members. When doing so, it is necessary to devise ways to solve all of the problems mentioned above.

The present invention has been made in view of the above-mentioned points, and is characterized by its applicability and applicability to a-8T as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive and intensive research studies from various viewpoints, we found that an amorphous material containing at least either hydrogen atoms or halogen atoms So-called hydrogenated amorphous silicon germanium,] halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to as the generic notation ra-8iGe (H,X) J
The structure of the photoconductive member having the photoconductive photoreceptive layer composed of [using] the structure of the photoconductive member designed and produced under the specification as explained hereinafter is not suitable for practical use. It is not a fool's errand and has superior properties in all respects when compared with conventional photoconductive materials, especially as a photoconductive material for electrophotography. This is based on the discovery that it has excellent absorption spectrum characteristics on the long wavelength side.

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

Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, is particularly good in matching with a semi-integrated laser, and has a fast photoresponse.

Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having sufficient performance.

Still another object of the present invention is to provide a photoconductive member for electrophotography, which can easily produce high-quality images with high density, clear foottones, and high resolution. 0 Yet another object of the present invention is high photosensitivity.

It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics.

Still another object of the present invention is to easily obtain high-quality images with no image defects or image blurring, high density, clear halftones, and high resolution during long-term use. An object of the present invention is to provide a photoconductive member for electrophotography that can be used in electrophotography.

The photoconductive member of the present invention includes a support for the photoconductive member, a photoconductive first layer made of an amorphous material containing silicon atoms and germanium atoms, and silicon atoms and oxygen atoms. and a second layer made of an amorphous material including: the first layer contains a substance that controls conductivity; It is characterized by the fact that the distribution of germanium atoms in the layer is non-uniform in the layer thickness direction.

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

Indicates optical properties, electrical pressure resistance, and usage environment characteristics.

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

Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with a conductor laser, and has a fast optical response.

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

FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention.

The photoconductive member 100 shown in FIG. 1 has a-S iGe (H,
The first photoconductive material consisting of )'gI(I)102
and a second layer (II) 103. First (7)
The germanium atoms contained in the layer (1) 102 are continuous in the thickness direction of the layer (1) 1020 and on the side opposite to the side where the support 101 is provided (layer ( II) The layer (1) 10 is distributed more on the support side than on the 103 side.
Contained in 2.

In the photoconductive member of the present invention, the distribution state of germanium atoms contained in the first layer (1) is as described above in the layer thickness direction, and is parallel to the surface of the support. It is desirable to have a uniform distribution state in the in-plane direction.

In the photoconductive member of the present invention, the first layer (I) containing germanium atoms contains a substance that controls conduction properties, thereby improving the characteristics of the layer. 11 sex 1tsui
It can be controlled arbitrarily as desired.

Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-8iGe (H,X) constituting the first layer (I) to be formed.
On the other hand, a P-type impurity that provides P-type conduction characteristics and an n-type impurity that provides N-type conduction characteristics can be mentioned. Specifically, P-type impurities include atoms belonging to Group ■ of the periodic table (Group ■ atoms), such as B (boron), A/(aluminum), Ga (gallium), In (indium), and T.
7? (thallium), among others, B, and Ga are particularly preferably used.

Examples of n-type impurities include atoms belonging to Group V of the periodic table (Group V atoms), such as P (phosphorus), As (arsenic), Sb (anti-sulfur), Bi (bismuth), etc. , P and As are preferably used.

In the present invention, the content of the substance that controls the conduction properties contained in the layer (1) depends on the conduction properties required for the layer (I) or the layer (I) directly. It can be selected as appropriate based on the organic relationship, such as the relationship with the properties at the contact interface with the support provided in contact with it.

In addition, when the substance controlling the conduction properties is contained in the first layer (1) locally in a desired layer region of the layer (1), in particular, the first layer (1) When it is contained in the support side end layer region of layer (I), the characteristics of other layer regions provided in direct contact with the layer region and the contact interface with the layer region of the layer The content of the substance that controls the conduction characteristics is appropriately selected in consideration of the relationship with the conduction characteristics.

In the present invention, the content of the substance that controls conduction properties contained in the first layer (I) is preferably 0.
01~5 X 10' atomic flIll
, preferably (L 5 ~ I X 10' atoms
c l1pffi , optimally 1-5 X 103at
It is preferable to use omic n.

In the present invention, the content of the substance controlling conduction properties in the layer region containing the substance is preferably 30 at.
omic book or more, preferably 50 atomic books
11 or more, optimally 100 atomic pIm or more, it is difficult to locally contain the substance in some layer regions of the first layer (I), especially in the body ↓- It is preferable that the layer (1) is unevenly distributed in the support side end layer region.

Among the above, the support side end layer region (t') of the first layer (1)
For example, when the substance to be contained is the P-type impurity, the second layer (n ) can effectively prevent the injection of electrons from the support side into (1) when the free surface of In the case that the substance to be formed is the above-mentioned impurity, when the free surface of the second layer (II) is charged to e polarity, there is no positive charge from the support side into the first layer (■). Pore injection can be effectively prevented.

In this way, when the first end layer region (E) contains a substance that controls the conductivity of one polarity, the first layer (
The remaining layer region of 1), that is, the layer region (Z) excluding the end layer region fE) may contain a substance that controls conduction characteristics of other polarity, or The substance controlling the same polar conduction properties may be contained in an amount much smaller than the actual amount contained in the end layer region (E).

In such a case, the content of the substance controlling the conduction characteristics contained in the layer region fZl is as follows:
It is determined as desired depending on the polarity and content of the substance contained in E), but preferably o
,ooi~1000 atomic folding, preferably 0
．． 05-500 atomic KKA, optimally 0
．． It is desirable that it be 1 to 200 atomic e.

In the present invention, when the end layer region (E) and the layer region (Z) contain the same type of substance governing conductivity, the content in the layer region (Zl) is preferably 3
It is desirable that it be less than 0 atomic m. In addition to the above-described case, in the present invention, there is a layer region containing a substance controlling conductivity having one polarity in the first layer (1), and a layer region containing a substance controlling conductivity having one polarity. It is also possible to provide a layer region immediately in contact with a layer region containing a substance controlling the conductivity, and to provide a depletion layer in the contact region.

For example, in the layer (1) of 85-, there is a layer region f containing the above-mentioned P-type impurity and 1 containing the above-mentioned N-type impurity.
A depletion layer can be provided by providing a so-called P-n junction by providing the 6 regions in direct contact with each other.

2 to 10 show typical examples of the distribution state of germanium atoms contained in the first layer (1) of the photoconductive member of the present invention in the layer thickness direction.

In FIGS. 2 to 10, the horizontal axis represents the amount C of germanium atoms, and the vertical axis represents the first layer (1) exhibiting photoconductivity.
, tB is the surface position of the first layer (1) on the support side, and tT is the surface position of the first layer (1) on the opposite side to the support side.
indicates the position of the surface. That is, the layer (I) containing germanium atoms is formed from the tB side toward the ptT side.

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

In the example shown in FIG. 2, up to the interface position tB to the position t, where the surface on which the first layer (1) containing germanium atoms is formed and the surface of the layer (1) are in contact with each other, The distribution concentration C of germanium atoms is contained in the first layer (1) in which germanium atoms are formed while taking a constant value C8, and the distribution concentration C is maintained from the position t1 to the interface position tT.
It has been gradually and continuously decreased since 2. In the interface position, the distribution concentration C of germanium atoms is C8.

In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C4 from the position tB to the position tT, and reaches the concentration C3 at the position t7. is formed.

In the case of FIG. 4, the distribution concentration C of germanium atoms is a constant value of concentration C6 from the position sieve up to multiple positions t2, and
The distribution +1:c is gradually and continuously decreased between tz and position t, and at position 1T, the distribution +1:c is substantially zero (substantially zero here refers to the case where the amount is below the detection limit). Dechiru).

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

In the example shown in FIG. 6, the distribution grade C of germanium atoms is
is a constant value, and the concentration is CIO at position tT. Between the position t and the position 1T, the distribution density C is located linearly and is decreased until reaching the position tT.

In the example shown in FIG. 7, the distribution concentration C is at the position tB.
The concentration C1l takes a constant value up to the position t4, and the position et
4 and up to multiple positions tT, the distribution state is such that the concentration decreases linearly from the concentration CI2 to the concentration ILC,s.

In the example shown in FIG. 8, from position tB to position tT, the distribution concentration C of germanium atoms decreases linearly from the concentration CI4 to substantially zero.

In FIG. 9, from position tB to multiple positions t, the distribution concentration C of germanium atoms decreases linearly from the concentration CIJ to the concentration Cta, and from the position t5 to the position t.
, an example is shown in which the density C16 is set to a constant value.

In the example shown in FIG. 1θ, the distribution concentration C of germanium atoms is the concentration CIt at position tB, and up to position t6, /:! At first, the concentration is slowly decreased from the concentration CI7, and around the position t6, it is rapidly decreased to the concentration CI8 at the position t6.

Between position t, the concentration is first rapidly decreased, and then gradually decreased until the concentration C is reached at position t, and then between position t7 and position t.

is gradually decreased very slowly to the position t
At 8, the concentration C2° is reached. Position t, position Rt? In between, the concentration of CZO is reduced to substantially zero according to a curve shaped as shown in the figure.

As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of germanium atoms contained in the first layer (1) in the layer thickness direction, in the present invention, , on the support side, there is a part where the distribution linearity C of germanium atoms is high, and at the interface tTflll, the distribution state of germanium atoms has a part where the distribution concentration C is considerably lower than that on the support side. layer (I).

The first layer (1) constituting the photoconductive member of the present invention preferably has a localized area map in which germanium atoms are contained at a relatively high concentration on the support side as described above. desirable.

In the present invention, it is preferable that the localized region diagram be provided within 5 μm from the interface position tB, if explained using the symbols shown in FIGS. 2 to 10.

In the present invention, the localized region diagram may be the entire layer region (LT) up to 5μ thick from the interface position tB, or may be a part of the layer region (LT). 0 Whether the local region map is a part or all of the layer region (LT) is appropriately determined according to the characteristics required of the first layer (1) to be formed.

The localized area diagram shows the state of distribution of germanium atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of germanium atoms is preferably 1000 atomic ppm or more with respect to the sum with silicon atoms, and more preferably is 5000 atomic pp111 or more, optimally I
It is desirable that the layers be formed in such a manner that a distribution state of X 10' atomic P or more can be obtained.

That is, in the present invention, the first layer (I) containing germanium atoms has a layer thickness of 5 μm or less from the support side (
The maximum value Cmax of the distribution concentration in the layer region with a thickness of 5μ from tn)
It is preferable that it be formed so that there is.

In the present invention, the content of germanium atoms contained in the first layer (1) is appropriately determined as desired so as to effectively achieve the object of the present invention, but preferably 1 to 9.5 x 10
'atomic pIB z more preferably 100~
8. OX 105 atomic splints, optimally 500
A ~7×105 atomic solution is desirable.

In the present invention, halogen atoms (specifically, fluorine,
Examples include chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

In the present invention, to form the first layer (1) composed of a-8iGe (H,X), for example, a glow discharge method,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon such as a sputtering method or an ion blating method. For example, a-8iGe (H+
) In order to form the first layer (1), basically, a source gas for Si supply that can supply silicon atoms (Si) and a Ge
The raw material gas for supply and, if necessary, the raw material gas for introducing hydrogen atoms (If) and/or the N-phase gas for introducing halogen atoms (X) are kept at a desired gas pressure in a deposition chamber whose interior can be reduced in pressure. A- A layer consisting of 8iGe (H,X) may be formed. In addition, when forming by sputtering method, for example, a target made of Si, or a target made of Si and Ge in an atmosphere of an inert gas such as Ar' or He, or a mixed gas based on these gases. using two of the targets, or
Using a mixed target of Si and Ge, a source gas for supplying Ge diluted with a diluent gas such as He or Ar is added as necessary to hydrogen atoms (or
A gas for introducing halogen atoms (Xl) is introduced into a deposition chamber for sputtering to form a desired gas plasma atmosphere, and the flow rate of the source gas for supplying Ge is controlled according to a desired rate of change curve. , the above-mentioned target may be sputtered.

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 an evaporation boat as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam method. This can be carried out in the same manner as in the case of 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 desired gas plasma atmosphere.

Substances that can be used as the raw material gas for Si supply used in the present invention include 5IH4t 5i2I(a)Si
Silicon hydride (silanes) in a gaseous state or which can be gasified as 3H, 1, Si, HlolJr is used effectively, especially ease of handling during layer preparation work, 5
SiH4 in terms of i4A supply efficiency, etc.

51 gM is preferred. As a material that can be a raw material gas for supplying Ge, GeH4゜Ge
2Ha p Ge5Ha + GeaHa t Ge5
H1,,l Ge6HI4 + Ge7H1,+Qe@
[1B, Ge, H2O, and other germanium hydrides in a gaseous state or that can be gasified are listed as being effectively used, especially in terms of ease of handling during layer creation work, good Ge supply efficiency, etc. So, Ge1-L, .

Preferable examples include Ge2Ha and GeaHa.

Effective raw material gases for the introduction of (used in the present invention) log atoms include many log compounds, such as log gas, log compounds, interhalogen compounds, and halogen-substituted silane derivatives. Gaseous or gasifiable halogen compounds such as the like are preferably used.

Further, silicon hydride compounds containing halokene atoms, which are in a gaseous state or can be gasified and whose constituent elements are silicon atoms and -logen atoms, can also be mentioned as immobile compounds in the present invention. Specifically, halogen compounds that can be suitably used include fluorine, chlorine,
Bromine, iodine halogen gas l BrF, CtF,
ClF5 tBrFs l BrF3 t IF3 ,
Interhalogen compounds such as IF', , ICt, and IBr can be eliminated.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF'< + 5i2Fa r 5iC4t SiBr
Silicon halides such as No. 4 are preferred.

When forming the characteristic photoconductive part of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, it is necessary to use a silicon compound containing a halogen atom as a raw material gas that can supply Si together with a raw material gas for supplying Ge. The first layer (I) consisting of a 5iGe containing halogen atoms can be formed on a desired support without using silicon hydride gas.

According to the glow discharge method, the first 1θ containing a halogen atom
When creating (I), basically, for example, silicon halide is used as a raw material gas for supplying Si, germanium hydride is used as a raw material gas for supplying □□□, and Ar l & t He
These gases are introduced into the deposition chamber for forming the first layer (1) at a predetermined mixing ratio and flow rate of 7 menos, and a glow discharge is generated to form a plasma atmosphere of these gases. By this, the first layer (1) is formed on the desired support, but in order to make it easier to control the ratio of hydrogen atoms introduced, hydrogen is added to these gases. A desired amount of gas or a silicon compound gas containing hydrogen atoms may be mixed to form a layer.

In addition, each gas may be used as a single species in a mixture of multiple species at a predetermined mixing ratio. To introduce a halokene atom,
What is necessary is to introduce a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms into the deposition chamber to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, hydrogen, or a gas such as the above-mentioned shida silanes and/or germanium hydride is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases.

In the present invention, the above-mentioned norogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for introducing halogen atoms.
In addition, HF, HCA.

I (I31-, HI tongue hydrogen halide, 5xH
2Fz + 5iH2L tS lH2C4+ S I
HCAs + SiBrt + 5iHBrs, etc.), rogane-substituted silicon hydrides, and GeHF5, Ge
B2C4tGeHsF.

GeHC! -s + GeH2C4+ GeHsCA,
GeHBr5 + GeHBr5 JGeaaBr
, GeHIs, hydrogenated norogenated germanium such as GeB2C4, GeHsI, etc./%0 genides with hydrogen atoms as one of the constituent elements, GeF4, GeC
k.

GeBr, , Ge1. + GeFt + GeC
1, GeBr2. Gaseous or gasifiable substances such as germanium halides such as GeL can also be mentioned as useful starting materials for forming the first layer (I).

Among these substances, chlorides containing hydrogen atoms are
When forming the first layer (1), at the same time hydrogen atoms are introduced into the layer, hydrogen atoms, which are extremely effective in controlling electrical or electrical intelligibility, are also introduced, which is preferable in the present invention. It is used as a raw material for the introduction of norogen.

To structurally introduce hydrogen atoms into the first layer (1),
In addition to the above, B2 or 5IH4+ 512H6+5i
Silicon hydride such as 3Hal 5i4H+o with germanium or a germanium compound for supplying Ge, or GeL, Ge2Ha, 'Ge5Hs,
Ge4H+o, Ge5H+2゜GeeHn l G
This can also be achieved by causing discharge to occur by coexisting Ge/L/manium hydride such as e7H1a l Ge4H+o l GegHs and silicon or a silicon compound for supplying St in the deposition chamber.

In a preferred example of the present invention, the amount of hydrogen atoms (H) contained in the first layer (1) of the photoconductive member to be formed, or the amount of -Nts or hydrogen atoms of・
The sum of the amounts of rogen atoms (H+X) is preferably 0.01
~40 atomic%, more preferably 0.05-30
Atomic% s Optimally 0.1~'25atom
It is desirable to set it as ic%.

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

In order to structurally introduce a substance that controls conduction characteristics, such as a group 1 atom or a group Ⅰ atom, into the first layer (I), during layer formation, a substance for introducing a group ① atom is used. or a starting material for introducing group (III) atoms in a gaseous state into a deposition chamber,
It may be introduced together with other starting materials for forming the first layer (I). Possible starting materials for introducing such Group 1 atoms include those that are gaseous at room temperature and pressure, or
It is desirable to use a material that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such Group (I) atoms include B2H6, B4HI(+, B-He), and B2H6, B4HI(+, B-He).

B= Hio, B6H1O, BeH+4, B6HI4
Boron hydride, BFs etc.

BCtB y BBrs, etc.], boron chloride, and the like.

In addition, AICt3. GaC41Ga (CH, 3)
31 InCt3+T&t3 etc. can also be mentioned.

In the present invention, effective starting materials for introducing Group V atoms include PHs for introducing phosphorus atoms.
, PH4I, hydrogen north neighbor such as P2H4.

PF3 t PF5 * PO2+ PO2+ PBr
Examples include halogen ratios such as s l PBrs l PIs. In addition, ASI-L3゜AsF5 l ASC
! -s t AsBr5 I A8Fs + 5bfI
s + SbF3+ SbF++ +5bC4H5bC
ts r BIHs y B1C4HB1Br5 and the like can also be mentioned as effective starting materials for the introduction of Group (I) atoms.

The layer thickness of the first layer (1) in the photoconductive member of the present invention is:
In order to efficiently transport the photocarriers generated in the first layer (1), the method is appropriately adjusted as desired, preferably 1 to 100μ, more preferably 1 to 80μ, most preferably 2
It is desirable that the thickness be ~50μ.

In the present invention, the layer thickness of the η region that constitutes the first layer (1), contains a substance that controls the paper texture, and is unevenly distributed on the support side is as follows: The lower limit is preferably 30 Å or more, more preferably 30 Å or more. is desirably 40 Å or more, optimally 50 Å or more.

Further, when the content of the substance that inhibits the conductive properties contained in the layer region is 30 atomic pprr+ or more, the upper limit of the layer thickness of the layer region is preferably 5 μ or less, more preferably It is desirable that the thickness be 4 μ or less, and optimally 3 μ or less.

In the photoconductive member 100 shown in FIG. 1, a second layer (if) 10 is formed on a first layer (1) 102.
3 has a free surface and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, and 1 (L pressure resistance, use environment characteristics, and durability).

Furthermore, in the present invention, since each of the amorphous materials forming the first layer (1) 102 and the second layer ([) 103 has a common constituent element of silicon atoms, , chemical stability is sufficiently ensured at the laminated interface.

The second layer (II) in the present invention consists of silicon atoms (S
i), oxygen atom (0), and hydrogen atom (H
) or/and an amorphous material (hereinafter referred to as r a −(SixO+−x)y(H,X)+
It is written as -yj. However, % 0 <x's Y < 1)
It is composed of.

The second layer (F) composed of a-(SixO+ z)y(H%X)+ -y is formed by a glow discharge method, a sputtering method, an electron beam method, or the like. These manufacturing methods depend on the manufacturing conditions, the level of capital investment,
It is selected and adopted as appropriate depending on factors such as the manufacturing scale and the characteristics desired for the light guide member to be manufactured, but it is relatively easy to limit the manufacturing conditions to manufacture the photoconductive member having the desired characteristics. The glow discharge method or the sputtering method is preferably employed because of the advantages of easily introducing oxygen atoms and halogen atoms together with silicon atoms into the second layer (n) to be produced.

Furthermore, in the present invention, the second layer (II) may be formed by using a glow discharge method and a sputtering method in the same apparatus system.

To form the second layer (n) by glow discharge method a
-(5IXOI-x)y(HsX)+y
The raw material gas for formation is mixed with a dilution gas at a predetermined mixing ratio if necessary, and introduced into the vacuum deposition chamber where the support is installed, and the introduced gas is used to generate glow discharge. a (5iXOI-x) y on the first layer (1) already formed on the support.
(Hs X )+-y may be deposited.

In the present invention, a (5i)(0+ -x) y
The raw material gases for forming (Hs
Most gaseous substances or gasified substances containing at least one of the halogen atoms can be used.

When using a raw material gas having Si as a constituent atom as one of SiS2, H%X, for example, a raw material gas having Si as a constituent atom, a raw material gas having 0 as a constituent atom, and A raw material gas containing H as a constituent atom and/or a raw material gas containing X as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing Si as a constituent atom and 0 and A raw material gas containing atoms and/or a raw material gas containing O and (2) It is possible to mix and use a raw material gas having three constituent atoms of () or a raw material gas having three constituent atoms of 5xsO and X.

Alternatively, a raw material gas containing St and H as constituent atoms may be mixed with a raw material gas containing O as constituent atoms (7), or a raw material gas containing Si and X as constituent atoms may be mixed with O. A mixture of raw material gases having constituent atoms may be used.

In the present invention, F and ct are preferable as the halogen atoms (X) contained in the second layer (It).

Br and I are preferred, especially F%Ct.

In the present invention, raw material gases that can be effectively used to form the second layer (II) include those that are in a gaseous state at room temperature and normal pressure or that can be easily gasified. Can list substances.

When the second layer (n) is made of the above-mentioned amorphous material, the layer forming method may be a glow discharge method, a sputtering method, or an ion implantation method.

Examples include ion brating method and electron beam method. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, the level of equipment capital investment, and the desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing conductive members, and it is easy to introduce oxygen atoms and, if necessary, hydrogen atoms and halogen atoms into the 20th layer (n) to be manufactured along with silicon atoms. The glow discharge method or the sputtering method is preferably employed because of its advantages such as being able to perform the following steps.

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

In order to form the second layer (n) composed of a-8iO(H, A raw material gas for introducing oxygen atoms (0), a bridge for introducing hydrogen atoms (H) as needed, and a raw material gas for introducing halogen atoms (X) are introduced into a deposition chamber whose interior can be reduced in pressure. Then, a glow discharge is generated in the deposition chamber, and a-8iO is deposited on a predetermined first layer (I) that has been placed in a predetermined position in advance.
The second layer (II) consisting of (H,X) may be formed.

In addition, when forming a second layer (ribs) by a sputtering method, the first layer may be formed using, for example, kr,
When a target made of Si is subjected to snorting in an atmosphere of an inert gas such as He or a mixed gas based on these gases, the raw material gas for introducing oxygen atoms (0) may be added as necessary. It may be introduced into a vacuum deposition chamber in which sputtering is performed together with a source gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X).

Secondly, a 5 inch target is used as a sputtering target.
2, or a target made of Si and a target made of 5i02, or a second target made of Si and SiOt. Oxygen atoms (0) can be introduced into the layer (I[). At this time, if the above raw material gas for introducing oxygen atoms (0) is also used, its flow rate can be controlled.The amount of oxygen atoms (0) introduced into the second layer (II) can be controlled arbitrarily. It is easy to do.

The content of oxygen atoms (0) introduced into the second layer (IT) can be determined by controlling the flow rate when the raw material gas for introducing oxygen atoms (0) is introduced into the deposition chamber, or by controlling the flow rate when the raw material gas for introducing oxygen atoms (0) is introduced into the deposition chamber. Adjust the proportion of oxygen atoms (0) contained in the target for introducing atoms (0) when creating the target, or
By doing both, you can control W as desired.
You can do RI.

The starting material used as the raw material gas for supplying Si used in the present invention is s5izH4tSi2.

Silicon hydride (silanes) in a gaseous state or which can be gasified, such as 5iaI(s?SLH+o), can be cited as one that can be effectively used.
SiL + 5i2He is preferred from the viewpoint of good supply efficiency.

Using these starting materials, a second active layer (II) can be formed by appropriately selecting the layer forming conditions.
), H may also be introduced together with St.

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 no-rogen atom (X), so-called silane derivatives substituted with a no-rogen atom, specifically, for example, SiF + + 512F6
Preferred examples include silicon halides such as + 5iC4t and 5iBrn.

Furthermore, s 5xH2Ft t Si It + 5iH
tC4r 5iHC4+5iH2Br2+ 5iHBr
Si for the formation of the second layer (II) also effective is a gaseous or gasifiable halide having a hydrogen atom as one of the M# components, such as halogen 1% silicon hydride, etc.
It can be used as a starting material for supply.

As described above, by appropriately selecting the layer forming conditions, xf is formed together with Si in the second layer (n) formed by appropriately selecting the layer forming conditions in addition to these additives using a silicon compound containing a halogen atom (X').
It can be introduced.

The silicon halide compound containing a hydrogen atom in the above-mentioned starting material is used to control electrical or photogravitational properties at the same time as introducing halogen atoms (X) into the layer during the formation of the second layer (II). Since the highly available hydrogen atom (H) is also compromised, it is used in the present invention as a preferred starting material for the introduction of the halogen atom (X).

In addition to the above-mentioned materials, effective starting materials that serve as raw material gas for introducing halogen atoms (X) used in forming the second layer (n) in the present invention include, for example, fluorine, chlorine, and bromine. , iodine halogen gas, BrF I C
tF, CtF3, BrFa l BrF51IF3
Examples include interhalogen compounds such as yIF7H■cz and IBr, and hydrogen halides such as ■2゜Hctl HBr t HI.

Oxygen atoms (0
) Starting materials that can be effectively used as raw material gases for introduction include oxygen (0□), ozone (Oa), etc. whose constituent atoms are 0 or N and O.
-nitrogen oxide (NO), nitrogen dioxide (NO2), -nitrogen dioxide (N20), nitrogen sesquioxide (N203), trinitrogen tetraoxide (N20<) nitrogen sesquioxide (N! 05
), nitrogen trioxide (NO, ), silicon atoms (St
), an oxygen atom (0), and a hydrogen atom (H) as constituent atoms, for example, disiloxane (I(s S i O31)
(s).

Tridoxane (I(3S i O8lH2O5In2
) etc. In the present invention, the diluting gas used when forming the second layer ωn by the glow discharge method or the svatutaringe method is a so-called rare gas, such as I-fe.
, Ne, Ar, etc. can be mentioned as suitable examples.

The second layer (n) in the present invention is carefully formed so that the required properties are provided in nine different ways.

That is, Sl, 0, H or/and X as required (1-
Substances with y-component atoms have structural [
takes forms ranging from crystalline to amorphous, and in terms of electrical properties, it has properties ranging from conductivity to semiconductivity to insulating properties.
In addition, since they each exhibit photoconductive properties to non-photoconductive properties, in the present invention, a-
The formation conditions are strictly selected as desired so that (81XO1-x)y(HlX)+-y is formed.

For example, the second layer ω) is provided with the main purpose of improving the electrical pressure property as Vcl”t a −(8ixO□=x
)y(H,nX),y is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

In addition, when a second layer ω) is provided for the main purpose of improving the characteristics of continuous use and the environment of use, B1 is relaxed to the extent that the electrical insulation is as described above, and J! 1'l is created as an amorphous material having a certain degree of sensitivity to the reflected light.

On the surface of the first layer (I) a"xOs-x, )y(H
lx), -.

a-(S+, O, -x
) y (Hl In the present invention, the desired characteristic i wart a-(Sixo, -e)7
(H,,X) H−y is created as desired 4]ζ
It is desirable that the temperature of the support during the preparation of the film is strictly controlled.

In the present invention, the optimum range is selected as appropriate in accordance with the method of forming the second layer a1) for achieving the desired purpose effectively #/lC'3, and the second layer (II) is is carried out, preferably at 20-400°C, more preferably at 50
The temperature is preferably 100 to 300°C, most preferably 100 to 300°C. On the day of the formation of the second Hoken II),
Jf layer! The atomic composition J:f: is strange! li
For example, it is advantageous to adopt the glow discharge method or the Suba Sotaringe method because the control of the thickness is relatively difficult compared to other methods. The layer of
When forming the second layer (II) by the method 5, the above 5 P$Pt-humidity and γ must be combined with the radiation
/gwa is created a-(S i xol-x )y
(H%X), -,' (is one of the important factors that influences the

A-(SixOl-x)y('-I,X)+-y is highly productive and effective 2! - The discharge power conditions for creating a
~25QW, optimally 50~200W is desirable.

The gas pressure in the cypress chamber is preferably o, 6t~ITorr,
More preferably, CL is about 1 to 0.5 Torr.

In the present invention, the values in the above-mentioned ranges are listed as the preferable numerical ranges of the support temperature and discharge power for creating the second 0M (M), but these layer creation factors are independent of each other. The desired characteristics a−(S i xo,;)y(Hs X )1− y
It is desirable that the optimum value of each layer forming factor be determined based on the mutual organic relationship so that the second layer side consisting of is formed.

The content of oxygen atoms contained in the second layer in the photoconductive part of the present invention is determined by the formation of the second layer. A second layer (n) which obtains the desired properties that achieve the objectives of the invention as well as conditions.
is an important factor in the formation of

In the present invention, the number of oxygen atoms contained in the second layer ω) may be determined as desired depending on the type and characteristics of the amorphous material constituting the second layer ω). It can be decided.

That is, the general formula a-(81x01-x)y(HX)1
Amorphous materials represented by -y can be broadly classified into silico/
Amorphous material composed of atoms and oxygen atoms (hereinafter referred to as "a")
It is written as -8ia O, -aJ. However, O(a (1
), non-ot'la 'AA + i'r (hereinafter, ra
(SxbO+-b)cH+-cl. However, O<b
lC〈1), silicon atom and b2 '';8
Amorphous tough material that forms i) (hereinafter, [a-(S+
d 01- (1) c(',E(%X)1-6J
It is written. However, O(d.

e<1), divided into L;

In the main wall, the second /X7 (If) is a S+
When composed of a01-2, the acidic additive contained in the second glue 01) is n S 1aO (if expressed as a of -a, a is preferable -, i: L ( 'm 0.33~
0.99999, more preferably 0.5 to 0.99, optimally (d06 to 09).

In the present invention, the second M(IT) is a (SibO+
-b).

n, -o, H>H of k51 atoms contained in the second layer (Ji) is a (SibO+-
b) In the display of cIL-c, b is preferably 0.3 to 0.99999, preferably 05 to 09, optimally 0.6 to 0.9, and C or 06. -099, more preferably 065-098, optimally 0.7-0.95.

The second layer ([1) is a−(S idO+−d )e(
HlX)+-e, the content of oxygen atoms not included in the second layer is a(S+(
10+-d)(!(H-X) 1-d of e, d is preferably 0.33 to 0.99999
, more preferably 0.5-099, optimally 0.6-0.9
, e is preferably 0.8 to 0.99, more preferably 0.
It is desirable that it is between 82 and 099, most preferably between 0.85 and 0.98.

The range of thickness of the second layer (II) 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, regarding the layer lifting of the second layer ω), the amount of oxygen atoms contained in the layer (II), and the relationship with the layer thickness of the first layer (1), there are differences in each layer region. It is necessary to appropriately determine the desired characteristics based on the organic relationship depending on the required characteristics.

In addition, it is desirable to take into consideration productivity and mass production.

The thickness of the second layer (11) in the jJ produced by this invention is as follows:
Preferably 0.003 to 30 μ, more preferably 0.00
4, 20μ, optimal 2, o, oo5-10μ.

The support used in the present invention may be of any type, such as den'chu, shi, keisho, or keisho. [Military conductive support] 14 and C are, for example, NlCr or stainless steel.

M+Cr, 4o, Au, Nb, Ta, V,
Examples include Ti, PL, Pd'J (D stack), and alloys thereof.

It has two air fibers, one of which is polyester.

Polyethylene, polycarbonate, cellulose.

Acetate, holly fin/, polyvinyl chloride.

Synthetic F, FJ'rt films or sheets of polyhynylidene chloride, polystyrene, polyamide, etc., and glass.

Ceramink, paper, etc. are commonly used. These electrical conductors have at least one surface treated with electrical conductivity, and the electrically conductive surface is exposed to the surface of the surface! It is desirable that f be provided.

For example, a sword lath has NiCr on its surface.

AJj, Cr, Mo, Au, Ir, Nb, Ta, V, T
i, Pi.

Pd, In2O3,5n02', ITO(In2
03+ SnO, ) : ; 41f property is improved by providing a thin film consisting of 7, or A of polyester film formation.
:, if it is a film, NiCr, IJ, i~
g, Pd, Zn, Ni, Au.

Cr, Mo, Ir, Nb, Ta, V, Ti
, Pi and other gold fl;: vacuum evaporation of WgA film,
By applying electron beam evaporation and sputtering to the surface, or by laminating the surface with the above-mentioned vertical strips, 97K14I: is obtained on the surface. The shape of the support is d.

Any shape such as belt or plate? 4% IJI”1
Therefore, its shape is determined by, for example, t'+1
The photosensitive member 100 shown in the figure can be used.
The five notes () used as paulownia are Ren PIi'i',
4j h ``For the threaded connection of γ, it is preferable to use an endless belt or a cylindrical loop. However, in the case of υ no 1, which requires the ability to be used as a guide or king, it is possible as long as it is within the range where the function as '4' is fully demonstrated. However, in terms of manufacturing and handling of such a metal support, mechanical strength, etc., I'i is preferably set to 10 μ or more.

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

FIG. 11 shows an example of a photoconductive member manufacturing apparatus.

The gas cylinders 1102 to 1106 in the south contain raw material gas for forming the photoconductive member of the present invention. Gas (purity 99.999%, hereinafter referred to as SiH)
,/He ToM? S. ) cylinder, Ge1. ', Gas (purity 99.999%, hereinafter Gen4/He To#t', Jsu.) To the Hon, 11o4
diluted with Hen7e: SiF, gas (pure &99.
99%, hereinafter abbreviated as SiF,/He. ) cylinder, 110
5 is B2 diluted with He)]6 gas (purity 99.99
9%, hereinafter abbreviated as B2H6/He. ) ho/he, 110
61j: No dregs (99.999% Ni) cylinder.

In order to flow these gases into the reaction chamber 1]ol, gas K
], 1.02~1106 (ID valve 11
22 to 1126, confirm that the leak valve 1135 is closed, and also check that the inflow valves 1112 to 1116,
Outflow valves 1117-1121 Auxiliary valves 1132.1
133 is open, first open the main valve 1134 to open the reaction chamber 1101. and exhaust the inside of each gas pipe. Next, the reading on the vacuum gauge 1136 is approximately 5 x 1
When the pressure reaches 0-'torr, the auxiliary valve 1132
, 1133, close the outflow valves 1117-1121.

Next, taking an example of forming the first layer (1) on the cylindrical substrate 1137, 8iH,/He gas is formed from the gas cylinder 1102, GeH, /He gas is formed from the gas cylinder 1103,
/) (e gas, B2H from gas cylinder 1105.

/He gas valve 1122, 1123.1125 k
Husband open outlet pressure gauge 1127, 1128.1130
Adjust the pressure to 1”9/cut and inlet valve 11
12°1113 and 1115 are gradually opened to allow them to flow into squares 70/draw 21107, 1108 and 1110, respectively. Subsequently, the outflow valves 1117, 1118
.

1120, the auxiliary valve 1132 is gradually opened to allow each gas to flow into the reaction chamber 1101; 5rIl at this time
</)Te gas flow rate and GeH, /He gas flow rate and B2H
,,/Hetwyscallr',(((power with() outflow pulp 1117 to the desired value, ], ],
18 and 1120, and also adjust the opening of the main pulp 1134 while checking the reading of the vacuum chamber 1136 so that the pressure inside the reaction 1g 1101 reaches the desired value. After confirming that the temperature of the base 1137 is set to a temperature in the range of 50 to 400°C by the heating heater 1138, the power supply 1140 is set to the desired power and a glow discharge is caused in the chamber 1101. , and at the same time GeI (
.

/I-Ie gas flow H; manually or by using an external V-motor (k4), the pulp l] contained in the layer formed by performing an operation of changing the opening of 18 from time to time.
The distribution concentration of germanium atoms is controlled.

In this way, the first layer (1) is formed on the substrate 137.

When halogen atoms are contained in the first layer (1), a gas such as SiF, for example, may be further added to the above gas to cause glow discharge to occur completely.

Moreover, when a halogen atom is contained in the first 0M(I) without a hydrogen atom, the above 5it(.

/He gas and GeH, /He gas instead of SiF,
/He gas and GeF4/He gas may be used.

In order to completely form the second layer (II) on the first layer <1) formed to the desired layer thickness as described above, the same pulp operation as in the formation of the first layer (1) is performed. For example, this is accomplished by diluting Si gas and NO gas with a diluent gas such as He as necessary to generate glow discharge according to desired conditions.

In order to contain a halogen atom in the second M ("), for example, 8iF gas and NO gas, or 5iI (,
This is done by adding a gas and forming the second layer (Il) in the same manner as above.

Needless to say, all the outflow valves other than the pulp valves are closed for the outflow of gas necessary for forming each layer.Also, when forming each layer, the gas used to form the previous layer is allowed to flow out into the reaction chamber 1101. Pulp 1117-i i 21 , B
In order to avoid residue from remaining in the CC pipe leading to the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary knobs 1132 and 1133 are opened, and the main pulp 1134 is fully opened to completely drain the system. , jk Exhaust the air as necessary.

Second problem (1) The amount of atoms contained in the inside 1 is, for example, in the case of glow discharge, the flow of SiH, gas, and NO scum in the reaction chamber 1]-01. When forming the target, the silicon/wafer and S
The fuiJ can be controlled as desired by changing the sputtering area ratio of iO□ or by changing the mixing ratio of silicon powder and Si02 powder and molding the target. The amount of halogen atoms (3) contained in the second y-coat (11) is adjusted by adjusting the flow rate when the raw material gas for introducing halogen atoms, for example, 5IF4 gas, is introduced into the reaction chamber 1101. Furthermore, during layer formation, it is desirable that the base 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation.

Examples will be described below.

Example 1 A cylindrical AQ was manufactured using the manufacturing apparatus shown in Fig. 11.
On the substrate, Get'I4/He gas and
forming a first layer (I) on the M substrate by changing the gas flow rate ratio of i1-(,/He gas with the elapsed layer formation time;
Next, a second layer (If) was formed on the first layer (1) under the conditions shown in Table 1 to obtain an electrophotographic image forming member.

The image forming member thus obtained is installed in a charging exposure experiment apparatus; 5. Corona charging was carried out for 0.3 seconds using OKV, and a light image was immediately irradiated using a tungsten lamp, and a light amount of 21 ux'sec was irradiated through a transmission type test chart.

A good toner image was then obtained on the imaging member surface by cascading an e-containing developer (containing toner and carrier) over the imaging member surface. The toner image on the image forming member is processed by 5. When transferred onto transfer paper using OKV's corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 2 Using the manufacturing apparatus shown in FIG. 11, Ge
The first layer (I) was formed by changing the gas flow rate ratio of H,/He gas and Si[I4/He gas with the elapsed layer formation time, and using the other conditions as in Example 1. An electrophotographic image forming member was formed in the same manner as in Example 1 except for this.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 3 Using the manufacturing apparatus shown in FIG. 11, Ge
The layer formation of the first layer (I) was performed by changing the flow rate ratio of H,/He gas and SiH4/)le gas (7) gas with the elapsed layer formation time, and using the other conditions as in Example 1. An image forming member for a 1L child photograph was formed in the same manner as in Example 1 except for the following steps.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 4 The first layer (I) was prepared using the manufacturing apparatus shown in FIG. 11, changing the gas flow rate ratio with the elapsed layer formation time in Table 4, and keeping the other conditions the same as in Example 1. An electrophotographic image forming member was formed in the same manner as in Example 1 except that layer formation was performed.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 5 Using the manufacturing apparatus shown in FIG. 11, Ge
The flow rate ratio of H4/He gas and S i H,/He gas was changed with the elapsed layer formation time, and the other conditions were the same as in the example process, except that the first layer (L) was formed. An electrophotographic image forming member was formed in the same manner as in Example 1.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 6 Using the manufacturing apparatus shown in FIG. 11, Ge
The flow rate ratio of m4/He gas and SiH4/1-Ie gas was changed with the elapsed layer formation time, and the other conditions were the same as in Example 1, except that the first layer (I) was formed. An electrophotographic imaging member was formed in the same manner as in Example 1.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 7 Using the manufacturing apparatus shown in FIG. 11, Ge
The gas flow ratio of H4/He gas and S i H4/He gas was changed with the elapsed layer formation time, and the other conditions were the same as in Example 1, except that the first Id (I) layer was formed. An electrophotographic image forming member was formed in the same manner as in Example 1.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, only a clear image quality was obtained.

Example 8 Using the manufacturing apparatus shown in FIG. 11, G
The first layer (r) was formed by changing the gas flow-i ratio of eF,/He gas and SiF4/He gas with the elapsed layer formation time, and using the other conditions as in Example 1. Except for this, an image forming member for L-child photography was formed in the same manner as in Example 1.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 9 In Example 1, SiH,/He gas was replaced with Si
The first layer (I) was prepared using 2H,,/He gas under the conditions shown in Table 9, and under the same conditions as in Example 1.
An electrophotographic image forming member was formed in the same manner as in Example 1 except that layer formation was performed.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 10 The first layer ( An electrophotographic image forming member was formed in the same manner as in Example 1 except that layer I) was formed.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 11 In Example 1, (S
The first layer (I') was formed using iH4/He + SiF, /He ) gas under the conditions shown in Table 11, and under the same conditions as in Example 1. An electrophotographic image forming member was obtained in the same manner as in Example 1.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 12 A cylinder-shaped AA was produced using the manufacturing apparatus shown in FIG.
GeH,/He gas and S
i H4/He gas (7) An electrophotographic image forming member was formed in the same manner as in Example 1, except that the first layer (I) was formed by changing the gas flow rate ratio with the elapsed layer formation time. did.

The image forming member thus obtained was placed in a charging exposure experiment device.5. Corona charging was performed between 0.3 SCe with OKV, and a light image was immediately irradiated using a tungsten lamp light source, and the light image was 2t! The amount of light of uX-Qi 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 charged developer (including toner and carrier) over the surface of the imaging member. The tonneau image of the imaging member is transferred to e5. When transferred onto transfer paper using OKV's corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 13 Gef (4/Lie gas and S
An electrophotographic image forming member was formed in the same manner as in Example 1, except that the first layer (') was formed by changing the gas flow rate ratio of iH4/He gas with the elapsed layer formation time. The obtained image forming member was placed in a light beam i1r, g light 9 test device e5. Corona zone jJi was performed for Q, 3 seconds with OKV, and a light image was immediately irradiated using a tungsten lamp light source, 21! A light amount of α·(8) was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the image forming member by cascading a charged developer (including toner and carrier) over the surface of the image forming member. Toner image on the imaging member: 05. When transferred onto transfer paper using OKV's corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 14 Using the manufacturing apparatus shown in FIG. 11, G
The first layer (1) was formed by changing the gas flow rate ratio of e1-I4/He gas and SiH,/He gas with the elapsed layer formation time, and using the other conditions as in Example 12. Except for this, an electrophotographic image forming member was formed in the same manner as in the example.

Using the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 12, and an extremely clear image quality was obtained.

Example 15 Using the manufacturing apparatus shown in Fig. 1J, G was produced according to the rate of change curve of the gas flow rate ratio shown in Fig. 14 under the conditions shown in Table 15.
The gas flow rate ratio of eH, /He gas and SiH, /He gas was changed with the elapsed layer formation time, and the other conditions were the same as in Example 12, except that the first layer (I) was formed. An electrophotographic image forming member was formed in the same manner as in Example 1.

An image was formed on the image forming member thus obtained on a transfer paper under the same conditions and procedures as in Example 12, and an extremely clear image quality was obtained.

Example 16 Using the manufacturing apparatus shown in FIG. 11, the change rate of gas flow rate ratio shown in FIG. 15 was obtained under the conditions shown in Table 16.
The gas flow rate ratio of GeH4/He gas and SiH4/1-Le gas was changed with the elapsed layer formation time, and the other conditions were the same as in Example 12, except that the first layer (I) was formed. An electrophotographic image forming member was formed in the same manner as in Example 1.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 12, an extremely clear image quality was obtained.

Example 17 Using the manufacturing apparatus shown in FIG. 11, the gas flow rate ratio was changed according to the curve shown in FIG. 16 under the conditions shown in Table 17.
The gas flow rate ratio of CkI-1, /He gas and SiH, /He gas was changed with the elapsed time of production, and the other conditions were the same as in Example 12, and the first layer (1) was of'
Electrophotography (
An imaging member was formed.

When an image was formed on a transfer paper using the image forming member prepared in this way under the same conditions and procedures as in Example 12, an extremely clear image quality was obtained.

Example 18 Using the manufacturing apparatus shown in FIG. 11, under the conditions shown in Table 18, the G
eH,/i (the gas flow rate ratio of e gas and 5il-I4/He gas was changed with the elapsed layer formation time, and the conditions for the first layer (i) were the same as in Example 12). An electrophotographic image forming member was formed in the same manner as in Example 1 except that layer formation was performed.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 12, an extremely clear image quality was obtained.

Example 19 Using the manufacturing apparatus shown in FIG. 11, under the conditions shown in Table 39, the G
The gas flow rate ratio of eH,/He gas and SiH4/He gas was changed with the elapsed layer formation time, and the other conditions were the same as in Example 12, except that the first layer (I') was formed. Example 1. ! - An electrophotographic imaging member was formed in the same manner.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 12, an extremely clear image quality was obtained.

Example 20 In Example 12, 8i instead of SiH4/He gas
The 10th layer (I
) An electrophotographic image forming member was formed in the same manner as in Example 1, except that the layer was formed.

Using the thus obtained image forming area, an image was formed on a transfer paper under the same conditions and procedures as in Example 12, and an extremely clear image quality was obtained.

21 In Example 12, 5il (S instead of 4/He gas)
i F, / [(Same as Example 1 except that the first jJ rI) layer was formed using e gas and under the conditions shown in Table 21, and under the same conditions as Example 12. A single image forming member for electrophotography was obtained.

With respect to the sickle forming member thus obtained, an image was entirely formed on a transfer paper under the same conditions and procedure as in Example 12, and an extremely clear image quality was obtained.

Example 22 In Example 12, instead of C, S 1f-I, /14e gas (Sit-14/1-ie +Sin'4/He
) An electrophotographic image forming member was formed under the same conditions as in Example 12, except that gas was used and the conditions shown in Table 22 were used.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 12, an extremely clear image quality was obtained.

Example 23 Using the manufacturing apparatus shown in FIG. 11, GeH,/I4e gas and Si were deposited on a cylindrical U substrate under the conditions shown in Table 23 and according to the rate of change curve of the gas flow rate ratio shown in FIG.
H, /f(e) An electrophotographic image forming member was formed in the same manner as in Example 1, except that the first 16 (i) layer was formed by changing the nogas flow and parking ratio with the elapsed layer formation time. .

The image forming member thus obtained is installed in the band'a exposure experiment apparatus; 5. Corona charging was performed for 0.3 ff with OKV, and immediately after the light image was irradiated, 2 Jtix-ses of light was also irradiated through a transmission type test chart I using a tungsten lamp light source.

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

Example 24 In Examples 1 and 12, the light source was an 81Qnm OGaAS semiconductor laser (IQ
An electrophotographic image forming member prepared under the same toner image forming conditions as in Examples 1 and 12, except that an electrostatic image was formed using +nW). When the image quality of the toner-transferred image was evaluated, it was found that a clear, high-quality image with good resolution and good gradation reproducibility was obtained.

Example 25 Each of the electrophotographic image forming members (sample Oboro 25-2
01-25-208.25-301-25-308. −
-・・-=-z5-1ooi ~25-1oo9o72
samples) were prepared.

Each of the electrophotographic image forming members obtained in this way was individually placed in a copying machine, corona charged twice at 5KV''''cO, and irradiated with a light image.A tungsten lamp was used as the light source. The light intensity was 1.Q 13ux.The latent image was developed with an e-chargeable developer (containing toner and carrier) and transferred to ordinary paper.The transferred image f7 was extremely good. The toner remaining on the electrophotographic imaging member without being transferred was cleaned with a rubber blade.Even after repeating this process more than 100,000 times, no image deterioration was observed in any case. .

Table 24A shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability through repeated and continuous use.

Example 26 When forming layer (11), the target area ratio of Ar and NO mixed gas, silicon wafer, and 5io2 was changed to form layer (I).
Each of the image forming members was prepared in the same manner as in Example 1 except that the ratio of silicon atoms to oxygen atoms contained in T) was changed. For each of the image forming members thus obtained, the working, developing, and cleaning steps as described in Example 1 were repeated about 50,000 times, and then image evaluation was performed, and the results shown in Table 25 were obtained.

Example 27 When forming the layer (If), the following steps were carried out except that the flow rate ratio of the 5iI-1 gas and the No gas was changed to change the content ratio of silicon atoms and oxygen atoms in the layer (■). Each of the imaging members was made in exactly the same manner as in Example 1. For each image forming member thus obtained, the process up to transfer was repeated approximately 50,000 times using the method described in Example 1, and then image evaluation was performed, and the results shown in Table 26 were obtained. .

Example 28 When forming layer (II), 5s) (4 gases, SiF4 gas, N.

Each of the image forming members was produced in the same manner as in Example 1, except that the content ratio of silicon atoms and oxygen atoms in layer (1) was varied by changing the gas flow rate ratio. Each image forming member thus obtained was imaged and developed as described in Example 1.

After repeating the cleaning process about 50,000 times, the image 1'9
When the evaluation was carried out, the results shown in Table 27 were obtained.

Example 29 Each of the imaging members was prepared in exactly the same manner as in Example 1 except that the thickness of the layer (') was changed. The steps were repeated to obtain the results shown in Table 28. Common layer-forming moxibustion conditions in the above embodiments of the present invention are shown below.

Substrate temperature: Germanium atom (Ge) containing company...
・Contains no atoms (Ge) in gel manila at approximately 200℃...
・Approximately 250℃ (K)? jJ wave a: 13.56
Chamber pressure during MHz reaction: 0.3 Torr

[Brief explanation of the drawing]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are illustrations for explaining the distribution state of germanium atoms in the amorphous layer, respectively. 11 are schematic explanatory diagrams of the apparatus used in the present invention, and FIGS. 12 to 19 are explanatory diagrams showing variations in the gas flow rate ratio in the embodiments of the present invention, respectively. . lOO...Photoconductive member 101...Support 102,
...First layer (I) 1o, 3...Second layer (H)
Applicant: Canon Co., Ltd., a relative of 111 relatives, at the end of the 1st century, rflj'EL, 1,000N amendments (spontaneous) Patented October 25, 1980 Manabu Shiga, Commissioner of the Agency, Indication of the case Patent Application No. 155335 dated back to 1982, Name of the invention Photoconductive member 3, Relationship with the Nagisa case to be amended Patent applicant address 3-30 Shimomaruko, Ota-ku, Tokyo -2 name (+00
) Canon Co., Ltd. Representative Ryu Kaku Part 4, Agent address: 3-30-25 Shimomaruko, Ota-ku, Tokyo 146, Specification subject to amendment 6, Contents of amendment (1) Specification, page 45, No. 18 Correct “0.5 to 0.9” in the row to “0.5 to 0.994.” (2) Condition 25-4.25- in the column “Used waste” in Table 24, page 91 of the specification. 5.25-6.25-7.25-8
``NH3'' is corrected to ``NO'' in each location.

Claims (1)

[Claims] a support for a photoconductive member; a first layer exhibiting photoconductivity composed of an amorphous material containing silicon atoms and germanium atoms; and an amorphous material containing silicon atoms and oxygen atoms. The first layer contains a substance that controls conductivity, and the distribution state of germanium atoms in the first layer is Photoconductive member 0 characterized by being non-uniform in the thickness direction