JPS62182751A - Electrophotographic light receptive member - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic light receptive member especially excellent in humidity resistance, repeated successive use characteristics, use circumstance resisting characteristics, such as resistance to high voltage, durability, and the like by specifying the layer structure of said member having a photoconductive layer made of a-Si(H,X). CONSTITUTION:The light receptive layer 100 formed on a substrate 101 is made of an amorphous material composed of a layer structure of an electrostatic charge blocking layer 102, the photoconductive layer 103 made of a-Si(H,X), and the surface layer 104 of an amorphous material consisting of Si, C, and H atoms as the constituent elements, and the concentrations of these atoms are changed so as to obtain the optical band gap matching in the interfaces between them, and the surface layer 104 has the maximum concentration of the H atoms of 41-70atom%, preferably, 45-60atom%.

Description

[Description of the field to which the invention pertains] The present invention relates to electromagnetic waves such as light (here, light in a broad sense, meaning ultraviolet rays, visible rays, infrared rays, xvi, γ rays, etc.). The present invention relates to an electrophotographic light-receiving member that is sensitive to light.

[Description of conventional technology]

In the image forming field, high sensitivity, SN
The ratio [photocurrent (Ip)/dark current (Id)] is high, the absorption spectrum characteristics are compatible with the spectral characteristics of the electromagnetic waves to be irradiated, the photoresponsiveness is fast, and the desired dark resistance value is used. At times, properties such as being non-polluting to the human body are required. Particularly in the case of an electrophotographic light-receiving member incorporated into an electrophotographic apparatus used in an office as a business machine, pollution-free properties during use are important.

Based on this point, amorphous silicon (hereinafter referred to as @A-5i) is a photoconductive material that has recently attracted attention.
855718 describes its application as a light-receiving member for electrophotography.

However, the conventional electrophotographic light receiving member having a light receiving layer composed of A-St has electrical, optical, photoconductive properties such as dark resistance value, photosensitivity, and photoresponsiveness, and usage environment characteristics. Individual improvements have been made in terms of stability, stability over time, and durability, but there is still room for further improvement in terms of improving overall properties. is the reality.

For example, when applied to light-receiving materials for electrophotography, when trying to achieve high photosensitivity and high dark resistance at the same time, it has often been observed in the past that residual potential remains during use; When a light-receiving member is used repeatedly for a long period of time, it has many disadvantages such as the accumulation of fatigue caused by repeated use and the so-called ghost phenomenon in which an afterimage occurs.

In addition, when forming the photoreceptive layer with A-S+ material, in order to improve its electrical and photoconductive properties, 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. However, problems may arise in the electrical or photoconductive properties or voltage resistance of the formed layer.

That is, for example, the lifespan of photocarriers generated in the formed photoconductive layer by light irradiation is not sufficient, or the image transferred to the transfer paper has what is commonly called "white spots". Image defects that are thought to be caused by localized discharge breakdown phenomena, and image defects that are commonly referred to as "white streaks" that are thought to be caused by abrasion when a blade is used for cleaning; If the surface layer has a certain thickness and is substantially transparent to the light used, the reflection spectrum of the surface layer will change due to abrasion caused by long-term rubbing, which is particularly preferable in terms of sensitivity, etc. In many cases, there were no changes over time.

Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs.

Therefore, while efforts are being made to improve the properties of the A-Si material itself, when designing a light-receiving member, the layer structure, chemical composition of each layer, method of preparation, etc. must be adjusted so that all of the above-mentioned problems can be solved. It needs to be improved.

[Purpose of the invention]

The object of the present invention is to solve the various problems in electrophotographic light-receiving members having conventional light-receiving layers made of A-Si as described above.

That is, the main object of the present invention is to have electrical, optical, and photoconductive properties that are virtually always stable without depending on the usage environment, have excellent light fatigue resistance, and exhibit no deterioration phenomenon even after repeated use. 1. It has excellent durability and temperature resistance, and has no or almost no residual potential. A-3i
An object of the present invention is to provide a light-receiving member for electrophotography having a light-receiving layer composed of the following.

Another object of the present invention is to have excellent adhesion between a layer provided on a support and the support and between each layer of laminated layers,
A-, which is dense and stable in terms of structural arrangement and has high layer quality.
An object of the present invention is to provide an electrophotographic light-receiving member having a light-receiving layer composed of 5i.

Still another object of the present invention is that, when applied as a light-receiving member for electrophotography, the present invention has sufficient charge retention ability during charging processing for electrostatic image formation, making ordinary electrophotographic methods extremely effective. A-Si exhibits excellent electrophotographic properties that can be applied
An object of the present invention is to provide a light-receiving member for electrophotography having a light-receiving layer composed of the following.

Another object of the present invention is to easily obtain high-quality images with high density, clear halftones, and high resolution without any image defects or blurring during long-term use. An object of the present invention is to provide a light-receiving member having a light-receiving layer made of A-3t for electrophotography.

Still another object of the present invention is to provide an electrophotographic light-receiving member having a light-receiving layer made of A-5i and having high photosensitivity, high SN ratio characteristics, and high electrical voltage resistance. .

[Structure of the invention]

The light-receiving member for electrophotography of the present invention comprises a support, a charge injection blocking layer containing silicon atoms as a matrix and a substance for controlling conductivity, and a charge injection blocking layer containing silicon atoms as a matrix and containing hydrogen. An amorphous material containing at least one of an atom and a halogen atom (rA-3i (hereinafter referred to as rA-3i))
A photoconductive layer consisting of H, a photoreceptive layer, the surface layer having a degree distribution in the layer thickness direction of the constituent elements such that optical bandgap consistency is obtained at least at the interface with the photoconductive layer. is varied, and the maximum concentration of hydrogen atoms in the surface layer is 41 to 70 atomic %.

In the electrophotographic light-receiving member of the present invention, the surface layer may contain halogen atoms, or the photoconductive layer may contain at least one type of carbon, oxygen, or nitrogen atom in the center. May contain atoms.

The charge injection blocking layer, which has the function of blocking charge injection from the support during charging processing, contains a substance that controls conductivity as a constituent element, either uniformly in the layer thickness direction or distributed in a large amount on the support side. Contains.

Furthermore, the charge injection blocking layer may contain oxygen atoms and/or nitrogen atoms as constituent elements, either uniformly in the layer thickness direction or in a distributed state with a larger distribution on the support side. The oxygen atoms or nitrogen atoms in the charge injection blocking layer may reside on the support side.

Further, the photoconductive layer may contain at least one of oxygen atoms, nitrogen atoms, carbon atoms, and a substance that controls conductivity as constituent elements.

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

That is, when applied as a light receiving member for electrophotography, 1
It has no influence of residual potential on image formation, has stable electrical characteristics, high sensitivity, and a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and has high density.
It is possible to stably and repeatedly obtain high-quality images with clear halftones and high resolution.

Hereinafter, the electrophotographic light receiving member of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a schematic diagram schematically showing the structure of the electrophotographic light receiving member of the present invention.

The electrophotographic light-receiving member shown in FIG.
is provided on the +L layer 102 for charge injection.
, A-5i (H, The concentration of hydrogen atoms is changed in such a way that optical bandgap consistency is obtained at least at the interface with the photoconductive layer, and the maximum concentration of hydrogen atoms is 41 to 70.
It has a layer structure consisting of a surface layer 104 of atomic percent.

Each layer constituting the electrophotographic light-receiving member shown in FIG. 1 will be described below.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the electrically conductive support include NiCr, stainless steel, AC, Cr, Mo, Au
, Nb, Ta, V, Ti, Pt, Pd, or alloys thereof.

Examples of the electrically insulating support include polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride,
Films or sheets of composites and resins such as polystyrene, polyamide, glass, ceramics, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, NiCr, Ai
, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, P
t, Pd, I n203°S n02, ITO (I n
203+5no2), etc., or if it is a synthetic resin film such as polyester film, NiCr, A, Ag, P
b, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta
, V, Ti, Pt, or the like on the surface by vacuum evaporation, electron beam evaporation, sputtering, or the like, or by laminating the surface with the metal described above to impart conductivity to the surface. The shape of the support may be any shape such as cylindrical, belt-like, or plate-like, and the shape is determined depending on the need. For example, in the case of continuous high-speed copying,
The thickness of the support, which is preferably in the shape of an endless belt or a cylinder, is appropriately determined so as to form a desired electrophotographic light-receiving member. If this is required, it should be made as thin as possible within a range that allows it to fully function as a support. However, in such a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the number of pots is usually 10 or more.

In particular, when recording an image using coherent light such as a laser beam, unevenness may be provided on the surface of the support in order to eliminate image defects caused by so-called interference fringes that appear in visible images. good.

The unevenness provided on the surface of the support can be obtained by fixing a cutting tool having a 7-shaped cutting edge in a predetermined position on a cutting machine such as a milling machine or a lathe, and rotating the cylindrical support according to a program designed in advance as desired. However, by regularly moving in a predetermined direction, the surface of the support can be accurately cut to form a desired uneven shape, pitch, and depth. The inverted V-shaped linear protrusion created by the unevenness formed by such a cutting method has a chain line structure centered on the central axis of the cylindrical support. The chain line structure of the inverted V-shaped protrusion may be a double or triple multiple line structure, or a crossed chain line structure.

Alternatively, a slow line drawing along the central axis may be introduced in addition to the chain line structure.

The vertical cross-sectional shape of the uneven convex portions provided on the surface of the support is determined by the controlled non-uniformity of the layer thickness within the microcolumns of each layer formed, and by the difference between the support and the layer directly provided on the support. In order to ensure good adhesion and desired electrical contact between the two, the inverted V-shape is preferably used, but preferably the shape is substantially isosceles triangular, triangular in face, or non-triangular as shown in FIG. Preferably, it is an equilateral triangle. Among these shapes, isosceles triangles and right triangles are particularly desirable.

In the present invention, each dimension of the unevenness provided on the support surface in a -1τ treated state is L, which takes into consideration the following points, and the undeveloped f! It is set so that the purpose of H can be achieved as a result.

That is, firstly, the A-3i (H,

Therefore, it is safe to set the dimensions of the irregularities provided on the surface of the support so as not to cause deterioration in the layer quality of the A-3i (H,X) layer.

Secondly, if the free surface of the photoreceptive layer is extremely uneven, it becomes impossible to perform cleaning completely after image formation.

Further, when cleaning the blade, there is a problem that the blade becomes damaged quickly.

As a result of examining the above-mentioned problems in layer deposition, process problems in electrophotography, and conditions for preventing the interference T4 pattern,
The pitch of the recesses on the surface of the support is preferably 500 m to 500 m.
Desirably it is 0.3 gm, more preferably 200 μm to 1 μm, optimally 50 μm to 5 gm.

Further, the maximum depth of the recess is preferably 0.1 μm to 5 g.
m, more preferably 0.3 g m to 3 gm, optimally 0.6 μm to 2 Bm. When the pitch and maximum depth of the four parts of the support surface are within the above range, the slope of the slope of the recess (or linear protrusion) is preferably 1
degrees to 20 degrees, more preferably 3 degrees to 15 degrees, optimally 4 degrees
It is desirable that the temperature be between 10 degrees and 10 degrees.

Also, due to the non-uniform layer pressure of each layer deposited on such a support, the maximum difference in layer thickness is preferably 0.
1 gm to 2 pLm, more preferably 0.1 gm to
1.5 gm, optimally 0.2 p,m ~Igm.

Further, as another method for eliminating image defects caused by interference fringe patterns when coherent light such as laser light is used, an uneven shape formed by a plurality of spherical trace depressions may be provided on the surface of the support.

That is, the surface of the support has irregularities smaller than the resolving power required for electrophotographic light-receiving members, and the irregularities are caused by a plurality of spherical trace depressions.

Below, the shape of the surface of the support in the light-receiving member for electrophotography of the present invention and a preferred manufacturing example thereof will be explained with reference to FIG. What is its manufacturing method?

It is not limited to this.

FIG. 16 schematically shows a typical example of the surface shape of the support in the electrophotographic light-receiving member of the present invention, partially enlarging a part of the uneven shape. .

In FIG. 16, 1601 is a support, 1602 is a surface of the support, 1603 is a rigid pearl, and 1604 is a spherical trace depression.

Furthermore, FIG. 16 also shows an example of a preferred manufacturing method for obtaining the surface shape of the support. That is, it is shown that a spherical depression 1604 can be formed by allowing the rigid pearl 1603 to fall naturally from a predetermined height position from the support surface 1602 and collide with the support surface 1602. Then, by using a plurality of rigid pearls 1603 with a radius of curvature R' and dropping them from the same height h at the same time or at a later time, they are placed on the support surface 1602 with a radius of curvature R' that is approximately the same. A plurality of spherical trace depressions 1604 having the same width can be formed.

FIG. 17 shows a typical example of a support having an uneven shape formed by a plurality of spherical trace depressions on its surface as described above.

Incidentally, the radius of curvature R and the width of the uneven shape formed by the spherical trace depressions on the support surface of the electrophotographic light-receiving member of the present invention have the effect of preventing the occurrence of interference fringes in the light-receiving member of the present invention. This is an important factor to achieve efficiently. The present inventors have investigated the following points as a result of various experiments. That is, if the radius of curvature R and the width satisfy the following formula: 0.5 or more Newton rings due to shearing interference will exist in each trace depression. Furthermore, if the following equation is satisfied, one or more Newton rings due to shearing interference will exist in each trace depression.

For this reason, it is desirable to disperse the interference fringes generated over the entire light receiving member into each trace recess and to prevent the interference fringes from occurring in the light receiving member.

In addition, @D of unevenness due to trace depressions is at most 500g.
about m, preferably 200 m or less, more preferably 1
It is desirable to set it to 00 gm or less.

The charge injection blocking layer 102 in the two-layer invention is A-5i.
(H, Furthermore, if necessary, oxygen atoms and/or nitrogen atoms may be contained uniformly in the entire layer region or a part of the layer region of the layer 102, or preferably in a non-uniform state so that they are distributed more on the support side. It is possible to improve the adhesion between the layer 102 and the support 101 and to adjust the band gap.

Examples of the conductivity controlling substance contained in the charge injection blocking layer 102 include so-called impurities in the semiconductor field. (hereinafter referred to as "Group I atoms"), or atoms belonging to Group V of the periodic table (hereinafter referred to as "Group V atoms") that provide N-type conductivity characteristics. Specifically, as the group Ⅰ atoms, B
(boron), Ai (aluminum), Ga (gallium),
Examples include In (indium) and Ichibun (thallium), with B and Ga being particularly preferred. Specifically, Group V atoms include P (phosphorus), As (arsenic), and Sb (antimony).
, Bi (bismuth), etc., with P and AS being particularly suitable.

FIGS. 2 to 6 show typical examples of the distribution state of group (I) atoms or group (IV) atoms contained in the charge injection blocking layer 102 in the layer thickness direction. In the examples shown in FIGS. 2 to 6, the horizontal axis shows the distribution concentration C of group m atoms or group V atoms, the vertical axis shows the layer thickness of the charge injection blocking layer 102, and tB is the interface of the lot on the support side. tT indicates the position of the interface on the opposite side to the support side 101. That is, the charge injection blocking layer 102 is formed from the tB side toward the tT side.

FIG. 2 shows a first typical example of the distribution state of Group (1) atoms or Group (2) atoms contained in the charge injection blocking layer 102 in the layer thickness direction.

In the example shown in FIG. 2, from the interface position tB to the position tl, the content concentration C of group II atoms or group V atoms is 01.
The distribution concentration C gradually and continuously decreases from the position C2 until the interface position tT from the position t1. At the interface position 22, the angle of 4Ia degrees C becomes C3.

In the example shown in FIG. 3, the distribution concentration C of the group II atoms or group V atoms contained gradually and continuously decreases from C4 from position E to position atr, and then C5 at position tT. The distribution state is formed as follows.

In the example shown in FIG.
It is a constant value of 6, and is set to C7 in the first place T.

Between position t2 and position tT, the distribution density C is linearly decreased from position t2 to position t7.

In the example shown in FIG. 5, the distribution concentration C is at position tB.
From position t3 to position t3, C8 takes a constant value, and from position t3 to position a, the distribution state decreases linearly from C9 to C10.

In the example shown in FIG. 6, the minute ll1a degree C takes a constant value of C11 from the position of the sun to the end.

In the present invention, when the charge injection blocking layer contains group m atoms or group Ⅰ atoms in a distribution state in which they are distributed in large numbers on the support side, the maximum value of the distribution concentration value of group Ⅰ atoms or group V atoms is preferably 50 atomic ppm or more, more preferably 80
It is desirable that the layer be formed in such a manner that a distribution state of at least atomic ppm, optimally at least lOO atomic ppm, can be obtained.

In the present invention, the content of Group M atoms or Group V atoms contained in the charge injection blocking layer may be adjusted as desired so as to effectively achieve the object of the present invention, but preferably 30 ~50X104 atomic ppm, more preferably 50~1X104 atomic ppm, optimally 1X102~
Preferably, the amount is 5×10 3 atomic ppm.

The charge injection blocking layer 102 is made of oxygen atoms or/as described above.
By containing nitrogen atoms, the adhesion between the support 101 and the charge injection blocking layer 102 is primarily improved and the band gap between the charge injection blocking layer 102 and the photoconductive layer 103 is adjusted.

7 to 13 show typical examples of the distribution state of oxygen atoms and/or nitrogen atoms contained in the charge injection blocking layer 102 in the layer thickness direction. In the examples shown in FIGS. 7 to 13, the horizontal axis represents the distribution concentration C of oxygen atoms and/or nitrogen atoms,
The vertical axis indicates the layer thickness t of the charge injection blocking layer 102, t indicates the position of the interface on the support side 101, and tT indicates the position of the interface on the side opposite to the support side 101.

That is, the charge injection blocking layer 102 is formed from the t3 side toward the tT side.

FIG. 7 shows a first typical example of the distribution state of oxygen atoms and/or nitrogen atoms contained in the charge injection blocking layer 102 in the layer thickness direction.

In the example shown in FIG. 7, from the interface position Ht to the position t4, the content concentration C of oxygen atoms and/or nitrogen atoms is C1.
The distribution concentration C gradually and continuously decreases from position t4 to interface position tT from C13. At the interface position tT, the distribution concentration C is set to C14.

In the example shown in FIG. 8, the distribution concentration C of the contained oxygen atoms and/or nitrogen atoms is from the position tB to the position t7.
gradually and continuously decreases from C15 until reaching position tT.
The distribution state is such that C16 is formed at .

In the case of FIG. 9, the distribution concentration C of oxygen atoms and/or nitrogen atoms is constant at C17 from position tB to position t5, and gradually and continuously decreases between position t5 and position t7. It is said that at position 1, it is qualitatively zero.

In the case of FIG. 10, the oxygen atoms and/or nitrogen atoms change position from day to position tT, minute, /Ij concentration C becomes C.
19, it is gradually decreased continuously and becomes substantially zero at position tT.

In the example shown in FIG. 11, the concentration C of oxygen atoms and/or nitrogen atoms is C from position It to position t7.
It takes a constant value of 22, and C from position 7 to position jδtT
It is assumed that the molecule +j state decreases linearly from C23 to C24.

In the example shown in FIG. 11, the concentration C of oxygen atoms or /' and nitrogen atoms is a constant value of C20 at position t6, and C21 at position t6. . Between position Its and position E, the distribution concentration C is located linearly and is decreased from 6 to position tT.

In the example shown in FIG. 12, the distribution concentration C is at the position t
Take a constant value of 025 from B to D.

In the present invention, the charge injection blocking layer 102 is made of oxygen atoms or/
and nitrogen atoms are contained in a distributed state in a large amount on the support 101 side, the distribution concentration value of oxygen atoms and/or nitrogen atoms or the maximum value of the sum of both atoms is preferably 500.
It is desirable that the layer be formed in such a manner that it can form 15 states with a concentration of 1,000 atomic ppm or more, preferably 800 atomic ppm or more, and optimally 1,000 atomic ppm or more.

In the present invention, the amount of oil containing oxygen atoms and/or nitrogen atoms contained in the charge injection blocking layer 102, or the sum of both, may be adjusted as appropriate as desired so that the object of the present invention is effectively achieved. However, it is preferably 0,001 to 50 atom%, more preferably 0.0'02 to 4o atom%, and optimally 0,003 to 30 atom%.

In the present invention, the thickness of the charge injection blocking layer 1020 is determined from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
Preferably 0.01 to 10 l, more preferably 0.05
It is desirable that it be set to ~8 liters, optimally 0.1 to 5 liters.

Tatsumame Eij The photoconductive layer 103 in the present invention is A-3i(H,X)
It has photoconductive properties that satisfy the desired electrophotographic properties.

Note that the entire layer region of the layer 103 may contain a substance for controlling conductivity within a range that does not impair the properties required of the layer 103.

Further, the entire layer region of the layer 103 may contain a desired amount of at least one of carbon atoms, oxygen atoms, and nitrogen atoms within a range that does not impair the properties required of the layer 103.

As the substance for controlling the conductivity, group (I) atoms and V-group atoms can be used as in the charge injection blocking layer 102 described above.

In the case where the entire layer region of the photoconductive layer 103 in the present invention contains group (I) atoms or group V atoms, the conductivity type and/or
Alternatively, the content of the group (III) atoms or group V atoms is relatively small, and preferably lX
10-3 to 3X102 atomic ppm, more preferably 5X1
0-3 to 102 atomic ppm, optimally 1 x 10-2 to 5
It is desirable that the content be 0 atomic ppm.

In addition, when oxygen atoms or nitrogen atoms are contained in the entire layer region of the photoconductive layer 103 in the present invention, it is mainly possible to increase the dark resistance and improve the adhesion between the charge injection blocking layer and the photoconductive layer. Although the ring effect is exhibited, it is desirable that the content of oxygen atoms and carbon atoms be relatively small, especially in order not to deteriorate the photoconductive properties of the layer 103.

In the case of nitrogen atoms, in addition to the above-mentioned points, the photosensitivity can be improved by coexisting with, for example, group (I) atoms, especially B.

In order to effectively achieve the purpose of the present invention,
The photoconductive layer 103 formed on the support 101 and forming a part of the photoreceptive layer 102 has the semiconductor characteristics shown below,
A-3t(H,X
).

■ P-type A-5i (H, X) - Contains only 7 receptors. Or one that contains both a donor and an acceptor, with a high relative concentration of acceptor.

p-type A-3i (H,

(≧) n-type A-Si(H,X) --- Contains only a donor. or one that contains both donor and acceptor, with a high relative concentration of donor.

(2) n-type A-S i (H,

+Wl i type A -s i (H, X) -----N
aHNb0 or Na2Nd.

In the present invention, F, C1, and Br are preferable as the halogen atoms (X) contained in the charge injection blocking layer 102 and/or the photoconductive layer 103.

(2), with F and C1 being particularly desirable.

In the present invention, the charge injection blocking layer 102 and/or photoconductive layer 103 made of A-Si (H, This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon, such as a rating method. for example,
A-3i(H) was obtained by glow discharge method.

In order to form a layer composed of X), basically a raw material gas for Si supply that can supply silicon atoms (Si), and a material gas for introducing hydrogen atoms (H) and/or halogen atoms (
X) A raw material gas for introduction is introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber, and A-S
It is sufficient to form a layer consisting of L (H,
When sputtering a target composed of Si in an atmosphere of an inert gas such as or a mixed gas based on these gases, sputtering a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) It is sufficient to introduce it into a deposition chamber for use.

The raw material gas for Si supply used in the present invention includes SiH4, Si2H6, 5i3HB, Si4H10
Silicon hydride (silanes) in a gaseous state or which can be gasified, such as S f
H4.

Si2H6 is preferred.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, and halogen-substituted silane derivatives. Or a halogen compound that is easily gasified is preferably mentioned.

Further, silicon compounds containing halogen atoms, which are in a gaseous state or can be gasified and which have silicon atoms and halogen atoms as constituent elements, can also be mentioned as effective in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include halogen residues of fluorine, chlorine, bromine, and iodine, BrF, and CIF.

ClF3, BrF5, BrF3, IF3.

Interhalogen compounds such as IF7, ICu, and IBr can be mentioned.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF4,5i2FB, 340 sentences4. Preferred examples include silicon halides such as SiBr4.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride gas is not used as a raw material gas capable of supplying Si. In either case, a layer consisting of A-5i:H containing halogen atoms as a constituent element can be formed on a predetermined support.

When manufacturing a layer containing halogen atoms according to the glow discharge method, basically silicon halide gas, which is a raw material gas for supplying Si, and Ar are used.

By introducing gases such as H2 and He into a deposition chamber to form a desired layer at a predetermined mixing ratio and gas flow rate, and generating a glow discharge to form a plasma atmosphere of these gases. , a desired layer can be formed on a predetermined support, or in order to introduce hydrogen atoms, a predetermined percentage of a silicon compound gas containing a hydrogen atom T is added to these gases.
'11 may be combined to form a layer.

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

To form a layer consisting of A-Si(H,X) by a reactive sputtering method or an ion blating method,
For example, in the case of the sputtering method, a target made of Si is used and sputtered in a predetermined gas plasma atmosphere, and in the case of the ion blasting method, polycrystalline silicon or single crystal silicon is used as the evaporation source at the evaporation port. This silicon evaporation source is heated using a resistance heating method.
Alternatively, the evaporated material may be heated and evaporated by an electron beam method (CEB method) or the like, and the flying evaporated material may be passed through a predetermined gas plasma atmosphere (71).

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

Further, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H2 or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Good.

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

Hydrogen halides such as HCM, HBr, HI, SiH2F
2,5tH2I2,5iH2Cu2゜5iH(,Q3,
Halogen-substituted silicon hydrides such as 5iH2Br2 and 5iHBr3, and gaseous or gasifiable halides having hydrogen atoms as one of their constituents are also mentioned as effective starting materials for forming charge injection blocking layers and photoconductive layers. I can do things.

These halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer formed during layer formation, so the present invention It is used as a suitable raw material for introducing halogen.

To structurally introduce hydrogen atoms into the formed layer,
In addition to the above, H2 or SiH4゜Si2H6,5i3
This can also be achieved by causing a discharge by causing a silicon hydride gas such as HB or Si4H10 to coexist with a silicon compound for supplying St in the deposition chamber.

For example, in the case of the reactive sputtering method, a Si target is used, and a plasma atmosphere is created by introducing gas for introducing halogen atoms and H2 scum into the deposition chamber, including inert gases such as He and Ar as necessary. By forming and sputtering the Si target, A-
A layer consisting of 3i(H,X) is formed.

Furthermore, ice can also be produced by introducing a gas such as B2H6 which also serves as doping with impurities.

In the present invention, hydrogen atoms (H
), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms is preferably 1 to 40 atom %, more preferably 5 to 30 atom %.

To control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the formed layer, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X) can be controlled. The amount of the starting material used for inclusion into the volumetric apparatus system, the discharge power, etc. may be controlled.

In order to make the charge injection blocking layer or the photoconductive layer contain Group Ⅰ atoms or Group V atoms and carbon atoms, oxygen atoms, or nitrogen atoms, the charge injection blocking layer or the photoconductive layer can be formed by using a glow discharge method, a reactive sputtering method, etc. When forming a photoconductive layer, a charge injection blocking layer or a photoconductive layer containing a starting material for introducing group (I) atoms or group V atoms, and a starting material for introducing oxygen atoms, nitrogen, and carbon, respectively, is used. This is accomplished by its use in conjunction with the starting material for forming the layer, controlling its amount in the formed layer.

Such starting materials for introducing carbon atoms, for introducing oxygen atoms, and/or for introducing nitrogen atoms, or for group m atoms or group V atoms.
As a starting material for introducing group atoms, a gaseous substance or a gasified substance whose constituent atoms are at least one of carbon atoms, oxygen atoms, and nitrogen atoms, or group I atoms or group V atoms is gasified. Most of them can be used.

For example, if you want to include oxygen atoms, silicon atoms (
A raw material gas containing St) as a constituent atom, a raw material gas containing an oxygen atom (0) as a constituent atom, and a hydrogen atom (H
) or a raw material gas containing a halogen atom (X) as a constituent atom in a desired mixing ratio, or a raw material gas containing a silicon atom (Si) as a constituent atom and an oxygen atom (0) and a raw material gas whose constituent atoms are hydrogen atoms (H), also mixed at a desired mixing ratio, or,
Mixing and using a raw material gas containing silicon atoms (S i) as constituent atoms and a raw material gas containing three constituent atoms: silicon atoms (St), oxygen atoms (0), and hydrogen atoms (H). I can do it.

Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing oxygen atoms (0) as constituent atoms.

Specifically, starting materials for introducing oxygen atoms and for introducing nitrogen atoms include, for example, oxygen (02), ozone (
03), -nitrogen oxide (No), nitrogen dioxide (NO2),
-Nitrogen dioxide (N20), nitrogen sesquioxide (N203)
.

Nitrogen tetroxide (N 204), Nitrogen sesquioxide (N2
05), nitrogen trioxide (NO3), nitrogen (N2), ammonia (NM3), hydrogen azide (HN3), hydrazine (
NH2NH2), silicon atoms (St) and oxygen atoms (0
) and a hydrogen atom (H) as constituent atoms, for example, disiloxane (H3SiO9iH3), ) resiloxane 7 (
Examples include lower siloxanes such as H3S its 1H20s 1H3).

Examples of carbon atom-containing compounds that serve as raw materials for introducing carbon atoms include saturated hydrocarbons having 1 to 4 carbon atoms, and saturated hydrocarbons having 2 to 4 carbon atoms.
Examples include ethylene hydrocarbons, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (C2Hs), propane (C3H8), n
-Butane (n-C4Hto).

Pentane (C5H12), ethylene hydrocarbons include ethylene (C2H4), propylene (C3Hs)
, butene-1 (C4H8), butene-2 (C4H8),
Inbutylene (C4H8), Bear 77 (CsHlo)
, As the acetylenic hydrocarbon, acetylene (C2H
2).

Examples include methylacetylene (C3H4) and butyne (C4He).

As a raw material gas containing Si, C, and H as constituent atoms, S
i (CH3) 4. Alkyl silicides such as S t (C2H4) 4 can be mentioned.

When a glow discharge method is used to form a charge injection blocking layer and a photoconductive layer containing group Ⅰ atoms or group V atoms, the starting material that becomes the raw material gas for forming the layer is
- A starting material for introducing group II atoms or group V atoms is added to a starting material appropriately selected from among the starting materials for forming a charge injection blocking layer and a photoconductive layer composed of St(H, x). It is something that The starting material for introduction of such Group II atoms or Group V atoms may be a gasified substance containing Group II atoms or Group V atoms as a constituent atom, or a gasified substance that can be gasified. , any one may be used.

In the present invention, starting materials that can be effectively used for introducing group (III) atoms include B2H6, B4HIO, B5H9, B5H11, and
, B6H10, B6) (12, B61-114, etc.), boron halides such as BF3, BC3.BBr3, etc. In addition, AuCJ13
．． GaCl3. I nC, Q3. Mention may also be made of TlCl3 and the like.

In the present invention, the starting materials that are effectively used for the introduction of Group Ⅰ atoms are specifically for the introduction of phosphorus atoms:
Hydrogenated phosphorus such as PH3, P2H4, PH4I, PF3
, PFs , PCCS2PCus , PBr3. PBr
Examples include phosphorus halides such as s, PI3, and the like. In addition, A
sH3゜AsF3, AsCl3, AsBr3, A
sF5.

SbH3, SbF3, 5bFs, SbC cross 3° SbC cross 5. BiH3, BiC sentence 3, B1Br3, etc. can also be mentioned.

The inclusion of group M atoms or group II atoms introduced into the layer for charge injection and the photoconductive layer containing group II atoms or group V atoms is the introduction of the group III atoms introduced into the deposition chamber. Alternatively, it can be arbitrarily controlled by controlling the dregs flow 1 of the starting material for introducing Group V atoms, the gas flow rate ratio, the discharge power, the support temperature, the pressure in the deposition chamber, etc. 6. The support temperature for achieving
'O~350'100' more suitable than C2 0~300
It is desirable to set it to ℃1.

In the formation of the charge injection blocking layer and the photoconductive layer in the present invention, the glow discharge method is used because delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are easier than other methods. However, when forming a charge injection blocking layer and a photoconductive layer using these layer forming methods, the discharge power and gas during layer formation should be Pressure is an important factor that influences the characteristics of the charge injection blocking layer and photoconductive layer.

In order to efficiently and productively produce a charge injection blocking layer and a photoconductive layer having characteristics that can achieve the object of the present invention, the discharge power condition is preferably 10 to 10%.
tooow, more preferably 20 to 500 W, and the gas pressure in the volume chamber is preferably 0.01 to 1 Torr, more preferably 0.1 to 0.5
It is desirable to set it to approximately Torr.

In the present invention, the above-mentioned ranges are mentioned as preferable numerical ranges for the support temperature and discharge power for creating the charge injection blocking layer and the photoconductive layer, but these layer creation factors are usually determined independently and separately. However, in order to form a charge injection blocking layer and a photoconductive layer with desired properties, based on mutual and organic relationships,
It is desirable to determine the optimal value for each layer creation factor.

In the present invention, the amount of carbon, oxygen, or nitrogen contained in the photoconductive layer to be formed greatly influences the characteristics of the electrophotographic light-receiving member to be formed, and is appropriately determined as desired. However, the content as the sum of the three is preferably 05 to 30 at% of O,OO, more preferably 1 to 20 at% of O,OO, optimally 0.002
It is desirable that the content be 15 atomic %.

The layer thickness of the photoconductive layer 103 is determined as desired so that photocarriers generated by irradiation with light having desired spectra I/L characteristics are efficiently transported, and is preferably 1 to 100 g. More preferably, it is 2 to 50 liters.

Surface layer> The surface layer 104 formed on the photoconductive layer 103 has a free surface 105, and is mainly suitable for the present invention in terms of 1ifFt71 property, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability. established to achieve the purpose of

In the light-receiving member of the present invention, at the interface between the surface layer 104 and the photoconductive layer 103, the optical band gaps of both layers match, or the surface layer 104 and the photoconductive layer
It is extremely important that the structure be configured to match at least to an extent that substantially prevents reflection of incident light on the sea surface. At the same time, it is also an important point to be able to detect extremely specific favorable conditions in relation to the hydrogen content. Furthermore, in the present invention, the hydrogen content in the surface layer 104 must be set to a predetermined concentration in a region close to the surface of the surface layer 104, at least in the outermost surface. The distribution state of the components needs to be determined after strict condition control.

In addition to the above-mentioned conditions, at the end of the surface layer 104 on the free surface side, a sufficient amount of incident light can be ensured to reach the photoconductive layer 103 provided below the surface layer. In order to make the optical band gap Eopt of the surface layer 104
Another consideration is that it should be configured to be sufficiently large. The optical band gap Eopt is configured to match at the interface between the surface layer 104 and the photoconductive layer 103, and the optical band gap Eopt is made sufficiently sharp at the free surface side end of the surface layer. When configured, the optical bandgap of one surface layer is configured to include at least a region in which the optical bandgap of one surface layer changes continuously in the layer thickness direction of the one surface layer.

In order to control the value of the optical bandgap Eopt of the surface layer in the layer thickness direction as described above, carbon atoms (C), which are typically the main adjusting atoms of the optical bandgap, are added to the surface layer. This can be done by controlling the amount of hydrogen contained, and hydrogen, which has the function of matching other properties of the surface layer to optimal conditions in accordance with changes in the band gap, can be contained in a specific distribution state. Control quantity.

Hereinafter, some typical examples of the distribution state of carbon atoms and hydrogen atoms in the surface layer will be explained with reference to FIGS. 19 to 22, but the present invention is not limited to these examples.

In Figures 19 to 22, the horizontal axis represents atoms (C, Si).
and distribution concentration C1 of atoms (H). The vertical axis indicates the layer thickness of the surface layer. In the figure, tT is the interface position between the photosensitive layer and the surface layer, tF is the free surface position, and the solid line is the atom (C). The two-dot diagonal line indicates a change in the distribution concentration of silicon atoms (S i ), and the one-dot chain line indicates a change in the distribution concentration of hydrogen atoms (H).

FIG. 19 shows a first typical example of the distribution state of atoms (C), silicon atoms (St), and hydrogen atoms (H) contained in the surface layer in the layer thickness direction. On the chain side, from the interface position tT to the position t8, the distribution concentration C of atoms (C) increases linearly from zero until the concentration C26, and on the other hand,
The distribution concentration of silicon atoms is from concentration C27 to concentration C2B.
The distribution concentration of hydrogen atoms increases linearly from C29 to C30,
From position t8 to position tF, the distribution concentrations C of atoms (C), silicon atoms, and hydrogen atoms maintain constant values of concentration C25, concentration C2B, and concentration C30, respectively. Here, for convenience of explanation, the inflection point of the distribution state of each component is set at 78, but there is no substantial problem even if the points deviate from each other.

In the example shown in FIG. 20, from position a t T to position tF, carbon atoms (C) range from zero to concentration C31, silicon atoms (Si) range from C32 to C33, and hydrogen atoms (H) range from C34 to C34. to C35, the values are varied in the order of magnitude. In this example, since the components change over the entire surface layer, it is possible to further improve the adverse effects caused by discontinuity of the components.

Also, for example, patterns in which the rate of change of the components changes momentarily as shown in FIGS. 21 to 22, and patterns as shown in FIGS. 19 to 22
Combinations of the typical examples described in the figures are also possible, and can be selected as appropriate depending on desired film characteristics, conditions on the manufacturing equipment, etc. Furthermore, the consistency of the band gap at the interface only needs to be a sufficient value in actual value as described above, and in that sense, the carbon content at tT is not limited to O, but may have a certain finite value, and From this point of view, it may be acceptable for the change in the component to stagnate for a certain period in the distribution region.

The surface layer 104 can be formed by glow discharge method, microwave discharge method, sputtering method, ion implantation method,
This is accomplished by ion blating method, electron beam method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, equipment and capital investment load, manufacturing regulations, and desired characteristics of the electrophotographic light-receiving member to be manufactured. It is relatively easy to control the production conditions to produce an electrophotographic light-receiving member having desired properties, and carbon atoms and hydrogen atoms can be easily introduced into the surface layer 104 together with silicon atoms. The glow discharge method or the sputtering method is preferably employed because of its advantages such as:

Furthermore, in the present invention, the surface layer 104 may be formed using a glow discharge method and a sputtering method in the same system.

In order to form the surface layer 104 by the glow discharge method, the raw material gas for forming A-(SixC1-x)y:Hl-y, which is basically the same both in the distribution region of the constituent elements and in a certain region, is required. It is mixed with a dilution gas at a predetermined mixing ratio according to the conditions, and introduced into a deposition chamber for vacuum deposition where the support 101 is installed, and the introduced gas is turned into gas plasma by generating a glow discharge. A-(SixC1
-x)y:)1t-y may be deposited. Formation of the distribution region is easy by increasing or decreasing the components to be changed, such as carbon atom-containing gas, silicon atom-containing gas, hydrogen molecules, etc., according to a specific sequence set to obtain the desired distribution pattern from the starting flow rate. done to.

In the present invention, TE A −(S t xC1-x) y :)
(As the raw material gas for forming ty, St.

Almost any gaseous substance containing at least one of C and H as a constituent atom or a gasified substance that can be gasified can be used.

When using a raw material gas containing Si as one of Si, C, and H, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing C as a constituent atom, and a raw material gas containing H as a constituent atom. Alternatively, a source gas containing St as a constituent atom and a source gas containing C and H as constituent atoms may be mixed at a desired mixing ratio. Alternatively, a raw material gas containing St as a constituent atom and a raw material gas containing Si, C, and H as constituent atoms can be mixed and used.

Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing C as constituent atoms. Further, in the distribution region, the mixing ratio may be changed according to a predetermined sequence.

In the present invention, Si containing Si and H as constituent atoms is effectively used as the raw material gas for forming the surface layer 104.
Silicon hydride gas such as silanes (Siuane) such as H2, 5i2He, 5i3H3, Si4H10, etc., saturated hydrocarbons having C1 to C4 as constituent atoms, for example,
Examples include ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (C2H6), propane (C3H8), n
-Butane (n-C4Hxo).

Pentane (C5H12), ethylene hydrocarbons include ethylene (C2H4), ;/Robyrene (C3He)
, butene-1 (C4H8), butene-2 (C4H8)
, inbutylene (C4H6), pente7 (C5H10)
, As the acetylenic hydrocarbon, acetylene (C2H
2).

Examples include methylacetylene (C3H4) and butyne (C4He).

As a raw material gas containing Si, C, and H as constituent atoms, S
t (CH3) 4. Mention may be made of alkyl silicides such as Si (C2H5)4. In addition to these raw material gases, H2 is of course also used as an effective raw material gas for H introduction.

To form the surface layer 104 by the sputtering method, sputtering is performed in various gas atmospheres using a single crystal or polycrystal Si wafer, a C wafer, or a wafer containing a mixture of Si and C as a target. You can do it by doing.

For example, if a Si wafer is used as a target, the raw material gases for introducing C and H are diluted with diluting gas as necessary and introduced into the deposition chamber for sputtering. The Si wafer may be sputtered by forming plasma, and the distribution area in this case is as follows:
For example, the concentration of the raw material gas containing C may be changed according to a certain sequence.

Alternatively, Si and C can be sputtered using separate targets in a gas atmosphere containing at least hydrogen atoms. In this case, in the distribution region, it is necessary to use a gas containing at least one of C or Si, and to change the concentration of these gases according to a certain sequence.

As the raw material gas for introducing C or H, the raw material gas shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, so-called rare gases such as He, Ne, Ar, etc. can be preferably mentioned as the diluting gas used when forming the surface layer 104 by a glow discharge method or a sputtering method. .

As described above, the surface layer 104 of the present invention has a distribution area in accordance with the gist of the present invention, and is carefully formed so that the required properties are provided as desired from the viewpoint of the entire surface layer. Ru.

In other words, materials whose constituent atoms are Si, C, and H can have structural forms ranging from crystalline to amorphous depending on the conditions of their creation, and electrical properties ranging from conductive to semiconductive to insulating. , and exhibit properties ranging from photoconductive properties to non-photoconductive properties, so in the present invention, so that A-5ixC1-x having desired properties depending on the purpose is formed, The selection of the formation conditions is made strictly according to the desired conditions.

For example, in order to provide the surface layer 104 with the main purpose of improving voltage resistance, A-(SixC1-x)y:Ht-y is used as an amorphous material with remarkable electrically insulating behavior in the usage environment. , arranged.

In addition, when the surface layer 104 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 the layer has a certain degree of sensitivity to irradiated light. A-3 as an amorphous material
ixC1-x) are arranged.

A-(SixC1-x)yHx on the surface of the photoconductive layer 103
When forming the surface layer 104 consisting of It is desirable that the temperature of the support during layer formation be strictly controlled so that A-(S i xCt-x)y)Ii-y having the following properties can be formed as desired.

Surface layer 1 for effectively achieving the object of the present invention
As for the support temperature when forming the surface layer 104, an optimum range is selected as appropriate in accordance with the method of forming the surface layer 104.
4 is carried out, preferably between 50°C and 350°C.
℃, more preferably 100℃ to 300''C.To form the surface layer 104, delicate control of the composition ratio of the atoms constituting the layer and control of the layer thickness are more effective than other methods. It is advantageous to adopt a glow discharge method or a sputtering method because it is relatively easy to apply, but when forming the surface layer 104 using these layer forming methods, the temperature of the support is the same as that described above. A- where the discharge power and gas pressure during layer formation are created.
(SixC1-x)y: One of the important factors that influences the characteristics of Hl-y.

A-(
SixC1-x)y: The discharge power conditions for effectively creating Hx-y with good productivity are preferably l
It is desirable that the power is 0 to 1000W, more preferably 20 to 500W. The gas pressure in the deposition chamber is preferably 0. O1
~ITorr, more preferably about 0.1 to 0.5 Torr.

In the present invention, the values in the above-mentioned ranges are listed as the preferable numerical ranges for the support temperature and discharge power for creating the surface layer 104, but these layer creation factors can be determined independently and separately. A-
It is preferable that the optimum value of each layer formation factor be determined based on mutual organic relationship so that the surface layer 104 consisting of 5ixC1-x is formed.

The amount of carbon atoms and hydrogen atoms contained in the surface layer 104 in the electrophotographic light-receiving member of the present invention is determined according to the desired characteristics to achieve the object of the present invention, as well as the production conditions of the surface layer 104 as described above. is an important factor in forming the surface layer 104 obtained.

In the present invention, the amount of carbon atoms contained in the surface layer 104 is usually O to 90 atom%, preferably O to 85 atom%, optimally, based on the total amount of silicon atoms and carbon atoms in the distribution region. It is desirable to vary within the range of 0 to 80 atomic%, and in a certain range, it is usually lXl0-3 to 9
0 atomic %, preferably 1 to 90 atomic %, optimally 10 to 90 atomic %
It is desirable that the content be 80 atomic %. The content of hydrogen atoms is desirably constant or varied within the range of 1 to 70 atomic % based on the total amount of constituent atoms in the distribution region, and is usually 41 to 70 atomic % in a certain range or at least on the outermost surface. atomic %, preferably 45-6
It is desirable that the content be 0 atomic %.

A light-receiving member having a surface layer prepared under the above-mentioned amount range, the above-mentioned distribution state, and the above-mentioned manufacturing conditions can be sufficiently applied as a material that is far superior to anything previously available in practice. The effect will be explained below using an example in 2.3.

First, to explain the aspect of band gap consistency, for example, when a clear optical interface exists between a surface layer and a photoconductive layer as in the conventional case, reflection of incident light at the interface occurs. However, there is a phenomenon in which the amount of light incident on the photoconductive layer is influenced to some extent by interference between this and reflection on the free surface. This tendency is particularly noticeable when coherent light such as laser light is used as a light source. On the other hand, for example, in the case of a copying machine that uses a blade cleaning method, it is inevitable that the surface layer will wear out more or less due to long-term use, and changes in the thickness of the surface layer due to this wear will change the interference state. . That is,
This means that there is a phenomenon in which the amount of light incident on the photoconductive layer is influenced to some extent by wear.

The control of the consistency of the /Hend gap in the present invention has one aspect of minimizing reflection at the interface from the viewpoint of component continuity, and another aspect of controlling the consistency of the hend gap. This has a two-fold favorable effect of giving continuity to the light absorption property itself. Therefore, among the preferable electrophotographic properties already mentioned, the remarkable effect in this case is that it exhibits an outstanding effect in maintaining the properties particularly during long-term use.

Next, we will discuss the role of hydrogen in the surface layer. Defects existing in the surface layer (mainly dangling bonds of silicon atoms and carbon atoms) are known to have a negative effect on the properties of light-receiving materials for electrophotography. deterioration of characteristics, fluctuations in charging characteristics due to changes in surface structure under use environments such as high humidity, and charge injection into the surface layer from the photoconductive layer during corona charging or light irradiation, causing damage within the surface layer. Afterimage phenomenon occurs during repeated use due to charge being trapped in defects in the image.

However, by controlling the hydrogen content in the surface layer to 41 at. It is possible to make dramatic improvements in this area.

On the other hand, if the hydrogen content in the surface layer is 71 atomic % or more, the hardness of the surface layer decreases, making it impossible to withstand repeated use. Therefore, controlling the hydrogen content in the surface layer within the above range is one of the very important factors in obtaining the desired electrophotographic properties that are extremely excellent. can be controlled by the H2 gas flow rate, support temperature, discharge power, gas pressure, etc.

There is also a unique correlation between the bandgap consistency and the hydrogen-containing state, especially in the distribution region of carbon atoms (C), which is a typical change component of the bandgap. The hydrogen content is set so as to optimize the structure in that region or to minimize dangling bonds, and the role of hydrogen in the surface layer is determined. In other words, it is set in the most reasonable form so that the amount of hydrogen tends to increase at least toward the free surface side, so that it has the value necessary to achieve the effect described above.

Therefore, the hydrogen content state of the surface layer in the present invention has the additional effect of matching the effect of band gap matching and the effect of the hydrogen content itself so that both effects are maximized. It can be said that it has.

Halogen atoms may be contained in the surface layer.For example, 5EF4, 5iFH3, Si2F6, 5iF3S may be added to the raw material gas as a method for containing halogen atoms in the surface layer.
Mix halogenated silicon gas such as iH3, 5tC14, or/and CF4.00 sentence 4. CH3CF3
It may be formed by a glow discharge decomposition method or a sputtering method by mixing halogenated carbon gases such as the like.

The numerical range of the layer thickness in the present invention is one of the important factors for effectively achieving the object of the present invention.

The numerical range of the layer thickness of the surface layer 104 in the present invention is appropriately determined according to the desired purpose so as to effectively achieve the purpose of the present invention.

Furthermore, the layer thickness of the surface layer 104 can be appropriately determined as desired based on the organic relationship depending on the characteristics required for each layer region in relation to the layer thickness of the photoconductive layer 103. It is necessary to In addition, it is desirable to consider the economical aspects including productivity and mass production.

The thickness of the surface layer 104 in the present invention is preferably 0.003 to 30 JL, more preferably 0.004 to 20 JL, and most preferably 0.005 to 10 JL. be.

The layer thickness of the light-receiving layer of the electrophotographic light-receiving member 100 according to the present invention is suitably determined as desired in accordance with the purpose.

In the present invention, the layer thickness of the photoreceptive layer 102 is such that the characteristics imparted to the photoconductive layer 103 and the surface layer 104 that constitute the photoreceptive layer 102 are effectively utilized to achieve the object of the present invention. The layer thickness relationship between the photoconductive layer 102 and the surface layer 103 is appropriately determined as desired so that the thickness of the photoconductive layer 102 can be achieved. It is preferable that the thickness is several hundred to several thousand times greater.

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

FIG. 18 shows an example of an apparatus for manufacturing a light-receiving member for electrophotography.

In the gas cylinders 1102 to 1106 in the figure, raw material gases for forming the respective layers of the present invention are sealed.
．． 999%) cylinder, 1103 is B2 diluted with H2
H6 gas (purity 99.999%, hereinafter referred to as B 2 H6/
It is abbreviated as He. ), 1104 is H2 gas (purity 99°99
999%) cylinder, 1105 is No gas (purity 99.9
99%) cylinder, 1106 is CH4 gas (purity 99.9
9%) It is a cylinder.

In order to flow these gases into the reaction chamber 1101, valves 1122 to 112B of gas pumps 1102 to 1106 are used.
, check that the leak valve 1135 is closed, and also check that the inflow valves 1112 to 1116 and the outflow valve 11 are closed.
After confirming that auxiliary valves 17 to 1121 and auxiliary valves 1132 and 1133 are being heard, first open the main valve 1134 to exhaust the reaction chamber 1101 and the gas piping. Next, when the vacuum gauge 1136 reads approximately 5X10-6 torr, the auxiliary valves 1132 and 1133 and the outflow valve 111
Close 7-1121.

Next, to give an example of forming an electrophotographic light-receiving member having the layer structure shown in FIG.
Open the valves 1122 to 1125 to supply H6/B2 gas and No gas from the gas pump 1105, respectively, and check the outlet pressure gauge 1.
The pressures of 127 to 1130 are adjusted to IKg/cm', respectively, and the inflow valves 1112 to 1115 are gradually opened, respectively, to flow into the mass flow controllers 1107 to 1110, respectively. Subsequently, the outflow valves 1117 to 1120 and the auxiliary valve 1132 are gradually opened to supply each gas to the reaction chamber 1.
101. At this time, the SiH4 gas flow rate and B
Adjust the outflow valves 1117 to 1120 so that the ratio of the 2H6/B2 gas flow rate and the No gas flow rate becomes the desired value,
In addition, the vacuum gauge 11 is adjusted so that the pressure inside the reaction chamber reaches the desired value.
Adjust the opening of the main valve 1134 while checking the reading of 36. After confirming that the temperature of the base cylinder 1137 is set to a temperature in the range of 50 to 350°C by the heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. At the same time, the flow rate of B2H6/B2 gas and/or No gas is controlled by the valve 1118 manually or by an external drive motor, etc. according to a pre-designed rate of change curve.
Or/and 1120 is gradually changed to control the distribution concentration of boron atoms and/or oxygen atoms contained in the formed layer in the layer thickness direction.

As described above, when the charge injection blocking layer containing boron atoms and oxygen atoms is formed to a desired thickness, the outflow valves 1120 and 1118 are closed, and the B inflow into the reaction chamber 1101 is completed.
By blocking the inflow of 2H6/He gas and No gas and at the same time adjusting the outflow valves 1117 and 1119 to control the flow rates of SiH4 gas and B2 gas and subsequently forming a layer, light containing no oxygen atoms and boron atoms is produced. A conductive layer is formed on the charge injection blocking layer to a desired thickness.

In addition, when forming a photoconductive layer containing oxygen atoms and/or boron atoms, the outflow valve 1118 or/and 112
Instead of closing 0, just adjust it to the desired flowmeter.

When halogen atoms are contained in the charge injection blocking layer and the photoconductive layer, for example, SiF4 gas is further added to the above gas and the mixture is fed into the reaction chamber 1101.

Depending on the gas type selected when forming each layer, the layer formation speed can be further increased.For example, if layer formation is performed using Si2H6 gas instead of SiH4 gas, the productivity can be increased several times. will improve.

In order to form a surface layer on the photoconductive layer prepared as described above, for example, SiH4 gas is applied using the same valve operation as in the formation of the photoconductive layer.

This is accomplished by flowing CH4 gas and, if necessary, diluent gas such as B2 into the reaction chamber 1101 at a desired flow rate ratio to generate glow discharge according to desired conditions.

The amount of carbon atoms contained in the surface layer is, for example, SiH4
It can be controlled as desired by arbitrarily changing the flow rate ratio of gas and CH4 gas introduced into the reaction chamber 1101 as desired.

Further, the amount of hydrogen atoms contained in the surface layer is, for example, H2
It can be controlled as desired by arbitrarily changing the flow rate of gas introduced into the reaction chamber 1101 as desired.

Needless to say, all the outflows 7 except for the gases necessary when forming each layer are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow into the reaction chamber 1101.
Inner and outflow valves 1117 to 1121 to the reaction chamber ttot
In order to avoid remaining in the piping leading to the inside, close the outflow valves 1117 to 1121, open the auxiliary valve 1132, fully open the main/help 1134, and evacuate the system to a high vacuum as necessary. conduct.

Further, during layer formation, the base cylinder 1137 is constantly rotated at a desired speed by a motor 1139 in order to ensure uniform layer formation.

<Example 1> Using the manufacturing apparatus shown in FIG. 18, an electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the manufacturing conditions shown in Table 1. This light-receiving member (hereinafter referred to as a drum) was set in an electrophotographic device, and electrophotographic characteristics such as initial chargeability, residual potential, and ghost were checked under various conditions. We investigated the decrease in charging ability and deterioration in sensitivity and increase in image defects after actual machine testing. Furthermore, 35℃,
Image deletion of the drum in an atmosphere of high temperature and high humidity of 85% was also evaluated.

After the evaluation was completed, the drum was cut out from the parts corresponding to the upper part and the lower part of the image area to be used as samples, and the samples were subjected to quantitative analysis of hydrogen contained in the surface layer using SIMS.

The above evaluation results and the maximum hydrogen content in the surface layer are shown in Table 2. Significant superiority was observed in each item of sensitivity deterioration.

Comparative Example 1 A drum and sample for analysis were prepared using the same equipment and method as in Example 1, except that the preparation conditions were changed as shown in Table 3.
It was subjected to similar evaluation and analysis. The results are shown in Table 4.

As shown in Table 4, it was found that the sample was inferior to Example 1 in various items.

<Example 2> Using the manufacturing apparatus shown in FIG. 18, an electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the manufacturing conditions shown in Table 5. This light-receiving member (hereinafter referred to as drum) was set in an electrophotographic device, and electrophotographic characteristics such as initial chargeability, residual potential, and ghost were checked under various conditions. We investigated the decrease in charging ability, deterioration in sensitivity, and increase in image defects after a long period of time in actual machine 1#.

Furthermore, image deletion on the drum was also evaluated in an atmosphere of high temperature and high humidity at 35°C and 985%.

After the evaluation has been completed, the drum is cut out from the top, middle, and bottom of the image area as a sample, and is subjected to quantitative analysis of hydrogen contained in the surface layer using SIMS. Silicon atom (Si), carbon atom (C) in.

The component profile of hydrogen element (H) in the layer thickness direction was investigated. Furthermore, the structured profile of boron (B) and oxygen (0) in the layer thickness direction in the charge injection blocking layer was also investigated. The above evaluation results and the maximum hydrogen content contained in the surface layer are shown in Table 6, and the component profile of the element in the surface layer is shown in FIG. 25. The component profile of the element in question is shown in FIG.

As seen in Table 6, in particular, initial chargeability 2 image flow,
Residual potential, ghost.

Significant superiority was recognized in many items including light sensitivity unevenness in the generatrix direction, sensitivity deterioration, and increase in image defects.

<Example 3 (Comparative Example 2)> A plurality of drums and samples for analysis were prepared under the same conditions as in Example 1, except that the conditions for producing the surface layer were changed to several conditions shown in Table 7. .

These drums and samples were subjected to the same evaluation skewer analysis as in Example 1, and the results shown in Table 8 were obtained.

<Example 4> The conditions for producing the photoconductive layer were changed to several conditions shown in Table 9,
A plurality of drums were used under the same conditions as in Example 1 except for the above. These drums were subjected to the same evaluation as in Example 1, and the results shown in Table 10 were obtained.

<Example 5> A plurality of drums were prepared under the same conditions as in Example 1 except that the conditions for producing the charge injection blocking layer were changed to several conditions shown in Table 11. These drums were subjected to the same evaluation as in Example 1, and the results shown in Table 12 were obtained.

<Example 6> A plurality of drums were prepared under the same conditions as in Example 1 except that the conditions for producing the charge injection blocking layer were changed to several conditions shown in Table 13. These drums were subjected to the same evaluation as in Example 1, and the results shown in Table 14 were obtained.

<Example 7> The mirror-finished cylinders were further subjected to lathe processing using a sword tool with various angles to produce cylinders with cross-sectional shapes as shown in Figure 23 and various cross-sectional patterns as shown in Table 15. I prepared several books. The 18th cylinder
It was set in the manufacturing apparatus shown in the figure and subjected to drum manufacturing under the same manufacturing conditions as in Example 1. The drum created is 780
Various evaluations were carried out using an electrophotographic device with a digital exposure function using a semiconductor laser having a wavelength of nm as a light source, and the results shown in Table 16 were obtained.

<Example 8> The surface of the mirror-finished cylinder was then exposed to the falling of a large number of bearing balls, and a so-called surface dimple treatment was performed that produced countless scratches on the cylinder surface. A plurality of cylinders having a cross-sectional shape as shown in the figure and various cross-sectional patterns as shown in Table 17 were prepared. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 18 and subjected to drum manufacturing under the same manufacturing conditions as in Example 1. The produced drum was subjected to various evaluations using an electrophotographic device with a digital exposure function using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 18 were obtained.

[Summary of effects of the invention]

The light-receiving member of the present invention has a light-receiving member for electrophotography having a light guiding layer composed of A-3i (H,
It can solve all the problems with conventional electrophotographic light-receiving members composed of (H, It is something that has gender, etc. In addition, there is no influence of residual potential and its electrical characteristics are stable, and the images obtained using it are extremely excellent, with high density and vivid halftones. .

Particularly, in the electrophotographic light-receiving member of the present invention, by providing a charge injection blocking layer, a relatively low-resistance light guide that is sensitive to light of a relatively wide range of wavelengths can be obtained. It became possible to use the li layer. Furthermore, due to the specific layer structure mentioned above, a large number of charges excited by light irradiation and thermal excitation are swept out sufficiently quickly not only in the photoconductive layer but also in the charge injection blocking layer and the surface layer. Even under exposure conditions, no residual potential or ghost occurs, and high-quality images with high resolution can be stably and repeatedly obtained.

Furthermore, an extremely noteworthy effect of the present invention is that even when the surface layer is worn out during long-term use, the above-mentioned excellent properties are maintained exactly as they were at the initial stage.

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the electrophotographic light-receiving member of the present invention, and FIGS. 2 to 6 respectively show group An explanatory diagram for explaining the distribution state of group V atoms; FIGS. 7 to 13 are explanatory diagrams for explaining the distribution state of oxygen atoms and/or nitrogen atoms contained in the charge injection blocking layer, respectively; FIGS. 14 to 17 are schematic diagrams for explaining the uneven shape of the surface of the support and the method for producing the uneven shape, and FIG. 18 is a diagram showing the formation of the light-receiving layer of the electrophotographic light-receiving member of the present invention. FIGS. 19 to 22 are explanatory diagrams for explaining the distribution state of carbon atoms. Figures 23 and 24 are schematic diagrams showing the shape of the support, Figure 25 is a distribution diagram showing the distribution of silicon, carbon, and hydrogen in the layer, and Figure 26 is the distribution of boron and oxygen in the layer. FIG. Regarding FIG. 1, 1OO...photoreceptive layer, 101...support, 10
2... Charge injection blocking layer, 103... Photoconductive layer, 104... Surface layer. 105...Free surface. Regarding FIG. 15, 1500... Photoreceptive layer, 1501... Support, 1502-1... Charge injection blocking layer, 1502-2... Photoconductive layer, 1503... Surface layer, 1504...・Free surface. Regarding Figure 16.17 1601.1701...Support, 1602.1702...Support surface, 1603.17
03...Rigid pearl, 1604.1704...Spherical trace depression. Regarding FIG. 18, 1101... Reaction chamber, 1102-1106... Gas cylinder, 1107-11
11... Mass flow controller, 1112 to 1116
... Inflow valve, 1117-1121 ... Outflow valve, 1122-1126 ... Valve. 1127-1131...Pressure regulator, 1132.11
33...Auxiliary valve, 1134...Main valve, 1135...Leak valve, 1136...Vacuum gauge. 1137... Base cylinder, 1138... Heater, 1139... Motor, 1140... High frequency power supply. 1111-C-1〇□〇
−□−−−−0−−−−←CC □0
□C1q03 r'tot4 Cμm □ Surface layer ellipse ↓ Nobu J ≠ -) 19! r￥C,”]

Claims (11)

[Claims] (1) a support, and a charge injection blocking layer on the support that contains a substance that controls conductivity and has silicon atoms as a host;
A photoconductive layer that is composed of an amorphous material that has silicon atoms as a matrix and contains at least one of hydrogen atoms and halogen atoms as a component, and that exhibits photoconductivity, and silicon atoms, carbon atoms, and hydrogen atoms. a surface layer made of an amorphous material as an element; A photoreceptor for electrophotography, characterized in that the concentration distribution of the constituent elements in the layer thickness direction is changed in the form obtained, and the maximum concentration of hydrogen atoms in the surface layer is 41 to 70 atomic %. Element. (2) The electrophotographic light-receiving member according to claim 1, wherein the distribution region of the constituent elements of the surface layer is present on the support side of the surface layer. (3) The light-receiving member for electrophotography according to claim 1, wherein the distribution region of the constituent elements of the surface layer covers the entire area of the surface layer. (4) The electrophotography according to claims 2 and 3, wherein the surface layer contains carbon atoms in a distribution state in which carbon atoms are distributed more toward the surface side in the distribution region of the constituent elements. Light receiving member for use. (5) The electrophotography according to any one of claims 1 to 4, wherein the surface layer contains hydrogen atoms in a distribution state in which hydrogen atoms are distributed more toward the surface side in the distribution region of the constituent elements. Light receiving member for use. (6) The electrophotographic light-receiving member according to claim 1, wherein the surface layer contains halogen atoms. (7) Claim 1, wherein the photoconductive layer contains at least one of carbon atoms, oxygen atoms, and nitrogen atoms.
2. The electrophotographic light-receiving member described in 1. (8) The electrophotographic light-receiving member according to claim 1, wherein the charge injection blocking layer contains oxygen atoms and/or nitrogen atoms. (9) The electrophotographic light-receiving member according to Claims 1 and 8, wherein the charge injection blocking layer contains a substance that controls conductivity in a distribution state in which the charge injection blocking layer is mostly distributed on the support side. (10) The electrophotographic light-receiving member according to Claims 4 and 9, wherein the charge injection blocking layer contains oxygen atoms and/or nitrogen atoms in a distribution state in which the charge injection blocking layer is distributed in large numbers on the support side. (11) The electrophotographic light-receiving member according to claims 8 and 10, wherein the oxygen atoms and/or nitrogen atoms contained in the charge injection blocking layer are present on the support side.