JPS63201664A - Light receiving member for electrophotography - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

[Description of prior art]

In the image forming field, high sensitivity, SN
It has a high ratio [photocurrent (Ip) / dark current (Id)), has absorption spectral characteristics that match the spectral characteristics of the electromagnetic wave to be irradiated, has fast photoresponsiveness, has a desired dark resistance value, and when used In this field, characteristics 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, the above-mentioned non-polluting property during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as A-5i) is a photoconductive material that has recently attracted attention.
Application as a light-receiving member for electrophotography is described in Japanese Patent No. 55718 and the like.

However, an electrophotographic light-receiving member having a conventional pre-receiving layer made of A-3i has a dark resistance value.

Individual improvements have been made in terms of electrical, optical, photoconductive properties such as photosensitivity and photoresponsiveness, usage environment properties, as well as stability over time and durability. However, the reality is that there is room for further improvement in terms of improving overall characteristics.

For example, when applied to light-receiving members 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 used repeatedly for a long period of time, fatigue accumulates due to repeated use and there are few disadvantages such as afterimages and so-called ghost phenomena.

In addition, when forming a photoreceptive layer using A-3i material, in order to improve its electrical and photoconductive properties, hydrogen atoms (H) or halogen atoms (X) such as fluorine atoms and chlorine atoms are added. , boron atoms, phosphorus atoms, etc. to control the electrical conductivity type, or other atoms to improve other properties are contained in the photoconductive layer as constituent atoms, respectively.
Depending on the manner in which these constituent atoms are contained, problems may arise in the electrical or photoconductive properties or electrical withstand voltage of the formed layer.

That is, for example, the lifetime of photocarriers generated in the formed photoconductive layer due to light irradiation may not be sufficient, or the image transferred to the transfer paper may have localized areas commonly called "white spots". When a blade is used as a cleaning means, there are image defects that are thought to be due to discharge breakdown phenomena, and image defects that are commonly referred to as "white streaks" that are thought to be caused by the rubbing of the blade. Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of images often occurs.

Therefore, while efforts are being made to improve the properties of the A-5i material itself, when designing light-receiving members, 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]

An object of the present invention is to solve the various problems in electrophotographic light-receiving members having conventional light-receiving layers made of silicon-based materials as described above.

In other words, the main object of the present invention is to have electrical, optical, and photoconductive properties that are virtually independent of the usage environment (substantially always stable, have excellent light fatigue resistance, and do not deteriorate even after repeated use). To provide a light-receiving member for electrophotography, which has a light-receiving layer made of a silicon atom-based material that does not cause any phenomenon, has excellent durability and moisture resistance, and has no or almost no residual potential observed. be.

Another object of the present invention is to provide excellent adhesion between a layer provided on a support and the support, and between each layer of laminated layers.
It is an object of the present invention to provide a light-receiving member for electrophotography, which has a light-receiving layer made of a silicon-based material that is dense and stable in terms of structural arrangement and has high layer quality.

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. It is an object of the present invention to provide a light-receiving member for electrophotography, which has a light-receiving layer made of a material containing silicon atoms as a matrix and exhibits excellent electrophotographic properties that can be applied.

Another object of the present invention is to obtain high-quality images with high resolution and high density without image defects or blurring during long-term use. It is an object of the present invention to provide a light-receiving member for electrophotography having a light-receiving layer made of a material having silicon atoms as a matrix, which can be easily produced.

Still another object of the present invention is to provide a light-receiving member for electrophotography, which has a light-receiving layer made of a silicon-based material, which has high photosensitivity, high signal-to-noise ratio characteristics, and high electrical voltage resistance. It's about doing.

[Structure of the invention]

The electrophotographic light-receiving member of the present invention includes a support, a long wavelength light absorption layer (hereinafter abbreviated as "rlR absorption layer"), a charge injection blocking layer, and a charge transport layer (hereinafter referred to as rcTLJ) on the support. a photoreceptive layer having a layered structure in which a charge generation layer (hereinafter abbreviated as rCGLJ) is laminated in this order from the support side, and the CTL and the CGL have silicon atoms as their base material. and is composed of a non-single crystal material (hereinafter abbreviated as [Non-3i (H, It is characterized by containing at least one type of oxygen atom and at least a portion containing atoms belonging to Group V of the periodic table as a substance controlling conductivity in a non-uniform distribution state in the layer thickness direction. It is said that

[For production]

The electrophotographic light-receiving 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 properties.

Demonstrates optical, photoconductive properties, durability and usage environment properties.

In particular, the influence of residual potential on image formation is practically practically non-existent (its electrical characteristics are stable, high sensitivity, high SN
It has a light fatigue resistance.

Because it has excellent repeated use characteristics, moisture resistance, and electrical pressure resistance,
High-quality images with high density, clear halftones, and high resolution can be stably and repeatedly obtained.

Furthermore, the electrophotographic light-receiving member of the present invention has high photosensitivity in the entire visible light range and fast photoresponse.

Therefore, in order to be able to repeatedly obtain a large number of high-resolution, high-quality images in a stable state and at high speed, we have developed a system based on digital signals (suitable for image formation). By adopting a functionally separated structure using CGL and CGL, each layer can have the important functions for an electrophotographic light-receiving member: generation of charge (photocarrier) and transport of the generated charge. This allows a greater degree of freedom in layer design than having both functions in one layer, and can produce products with superior properties.Also, CTLs contain a small amount (or one type) of carbon atoms, nitrogen atoms, and oxygen atoms. The dielectric constant of the CTL can be lowered by using CTL, which can reduce the capacitance per layer thickness, improve the charging ability and sensitivity, and improve the withstand voltage against high voltage. , durability is also improved.In addition, by containing a substance that controls conductivity in the CTL in a non-uniform distribution state in the layer thickness direction, a CTL having an optimal charge transport ability can be designed as desired.

Furthermore, charge injection properties at the interface between CTL and CGL are improved, resulting in improved charging ability, sensitivity, and residual potential.

Ghosting, sensitivity unevenness, durability, resolution, etc. can be dramatically improved.

Furthermore, by providing an IR absorption layer between the support and the CTL, even if long-wavelength light such as a semiconductor laser is used as an exposure light source for an electrophotographic device, it is completely absorbed between the incident surface side and the support. Since the IR absorption layer absorbs the long-wavelength light with high efficiency, the occurrence of interference phenomenon due to reflection of long-wavelength light on the surface of the support can be significantly prevented, and the image quality can be dramatically improved.

Furthermore, since a charge injection blocking layer is provided between the support and the CTL, it is possible to effectively prevent charges from being injected from the support side into the CGL when subjected to charging treatment. , and the charging ability is dramatically improved.

[Detailed description of the invention]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic light-receiving member of the present invention will be described in detail below with reference to the drawings.

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

The electrophotographic light-receiving member 100 shown in FIG. 1 includes an IR absorption layer 103 on a support lot for use as an electrophotographic light-receiving member, and a substance (MO) for controlling conductivity over the entire layer area. Non-3i (H,X
) (hereinafter abbreviated as rNon-3iMo) (H,X));
i is composed of (H,X) and is a carbon atom.

A portion containing at least one of nitrogen atoms and oxygen atoms, and containing atoms (M) belonging to Group V of the periodic table as a substance controlling conductivity in a non-uniform distribution state in the layer thickness direction. CTL105 and No.
CGL 106 made of n-Si (H,X); and a photoreceptive layer 102 having a layered structure. C.G.L.
106 has a free surface 107.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, and Al.

Cr, Mo, Au, Nb, Ta, V,
Examples include metals such as Ti, Pt, and Pb, and alloys thereof.

Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide, glass, ceramic, paper, and the like. It is preferable that at least one surface of these electrically insulating supports is conductively treated, and a light-receiving layer is provided on the conductively treated surface side.

For example, if it is glass, N t Cr r on its surface
An! , Cr, Mo, Au, Ir, Nb,
Ta, V, Ti.

Conductivity is imparted by providing a thin film made of Pt, Pd, InO2, ITO (In203+Sn), etc., or if it is a synthetic resin film such as polyester film, NiCr, Aj', Ag, Pb, Zn,
Ni.

Au, Cr, Mo, Ir, Nb, Ta
, V, TI, Pt, etc., by vacuum evaporation or electron beam evaporation.

The surface is provided with sputtering or the like, or the surface is laminated with the metal to impart conductivity to the surface. The shape of the support can be a plate, an endless belt, or a cylinder with a smooth or uneven surface, and its thickness is determined as appropriate so as to form a desired electrophotographic light-receiving member. When flexibility is required as a light-receiving member for electrophotography, it can be made as thin as possible within a range that allows it to function as a support.

However, in view of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually 10 μm or more.

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

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 spiral structure centered on the central axis of the cylindrical support.

The spiral structure of the inverted ■-shaped protrusion may be a double or triple spiral structure, or a crossed spiral structure.

Alternatively, in addition to the spiral structure, a parallel line structure along the central axis may be introduced.

The vertical cross-sectional shape of the uneven convex portions provided on the surface of the support is designed to achieve controlled non-uniformity of the layer thickness within the microcolumns of each layer formed, and between the support and the layer directly provided on the support. In order to ensure good adhesion and desired electrical contact, the inverted V-shape is preferably used (A) and (B) as shown in Figure 2.
), (C), it is desirable that the shape is substantially an isosceles triangle, a right triangle, or a scalene triangle.

Among these shapes, isosceles triangles and right triangles are particularly desirable.

In the present invention, the dimensions of the irregularities provided on the surface of the support in a controlled manner are set in such a way that the object of the present invention can be achieved as a result, taking into account the following points.

That is, the first is Non-3i (H
, It is necessary to set the dimensions of the unevenness provided on the surface of the support so as not to cause a decrease in the surface resistance.

Secondly, if the free surface of the photoreceptive layer has extreme irregularities, it becomes impossible to perform cleaning completely after image formation.

In addition, when cleaning the blade, there is a problem that the blade gets damaged quickly.

After considering the above-mentioned problems in layer deposition, process problems in electrophotography, and conditions for preventing interference fringes, we found that:
The pitch of the recesses on the surface of the support is preferably 500 μm x
The thickness is preferably 0.3 μm, more preferably 200 μm to 1 μm, most preferably 50 μm to 5 μm.

Further, the maximum depth of the recess is preferably 0.1 μm to 5 μm.
m1 is preferably 0.3 μm to 3 μm, optimally 0.3 μm to 3 μm.
It is desirable that the thickness be 6 μm to 2 μm.

When the pitch and maximum depth of the recesses on the surface of the support are within the above range, the slope of the slope of the recesses (or linear protrusions) is preferably 1 degree to 20 degrees, more preferably 3 degrees to 15 degrees,
The optimum angle is preferably 4 degrees to 10 degrees.

Further, the maximum difference in layer thickness due to the non-uniformity of the layer thickness of each layer deposited on such a support is preferably 0.1 μm to 2 μm1, more preferably 0.1 p mN within the same pitch.
1.5 p ms, optimally 0.26 mNl p m.

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
This is due to multiple 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 FIGS. 3 and 4. The manufacturing method is not limited to this.

FIG. 3 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. 3, 301 is a support, 302 is a support surface,
303 indicates a rigid pearl, and 304 indicates a spherical trace depression.

Furthermore, FIG. 3 also shows one example of a preferred manufacturing method for obtaining the surface shape of the support. That is, it is shown that the spherical depression 304 can be formed by allowing the rigid true sphere 303 to naturally fall from a position at a predetermined height from the support surface 302 and collide with the support surface 302. Then, by using a plurality of rigid true spheres 303 having approximately the same diameter RO and dropping them simultaneously or sequentially from approximately the same height h, the support surface 302 has approximately the same radius of curvature R and Multiple spherical trace depressions 3 having the same width
04 can be formed.

As described above, FIG. 4 shows a typical example of a support having an uneven shape formed by a plurality of spherical trace depressions on its surface.

In FIG. 4, 401 is a support, 402 is a convex position of an uneven portion, 403 is a rigid true sphere, and 404 is a spherical trace depression.

Incidentally, the radius of curvature R and the width of the uneven shape formed by the spherical trace depressions on the surface of the support of the light-receiving member for electrophotography of the present invention serve to prevent the occurrence of interference fringes in the light-receiving member for electrophotography of the present invention. This is an important factor in achieving the effect efficiently. As a result of various experiments, the present inventors have discovered the following points. That is, when the radius of curvature R and the width satisfy the following formula: % formula %, 0.5 or more Newton rings due to shearing interference are present in each trace depression. Furthermore, if the following formula: % formula % is satisfied, one or more Newton rings due to shearing interference will exist in each trace depression.

For this reason, in order to disperse the interference fringes that occur throughout the electrophotographic light receiving member into each trace depression and to prevent the occurrence of interference fringes in the electrophotographic light receiving member, the above-mentioned - 0.035 or more,
Preferably, it is 0.055 or more.

In addition, the width of the unevenness due to the trace depression is at most 500
It is desirable that the thickness be about .mu.m, preferably 200 .mu.m or less, more preferably 100 .mu.m or less.

The example in FIG. 4 shows an example in which rigid true spheres with approximately the same radius Ro are used, but the support in the present invention is not limited to this, and the purpose of the present invention can be achieved. A plurality of types of rigid true spheres with different radii Ro may be used, with the number and type being managed within the range.

FIG. 5 shows that an IR
Absorbent layer 502. Charge injection blocking layer 503. CTL504
An example is shown in which a photoreceptive layer 500 made of CGL505 is formed. CGL 505 has a free surface 506.

1 or 1"Ll The IR absorption layer (103, 502) in the present invention has germanium atoms (Ge) and tin atoms (
8) and one of the hydrogen atoms (
H) and a halogen atom (X), and preferably also a silicon atom (Si) (hereinafter referred to as [Non-3i (Ge, Sn)
(H,X)J).

The germanium atoms and/or tin atoms contained in the IR absorption layer may be uniformly distributed in the IR absorption layer, or may be uniformly contained in the entire layer area of the IR absorption layer. However, in any case, in the in-plane direction parallel to the surface of the support, the distribution concentration is uniform (with no bias). This is necessary from the point of view of uniformity of properties in the in-plane direction.In other words, it is necessary to ensure that the IR absorption layer is evenly contained in the thickness direction of the IR absorption layer, and that it is contained evenly on the side where the support is provided. The IR absorbing layer is distributed so that it is more concentrated (distributed) on the support side than on the opposite side (the free surface side of the photoreceptive layer), or the IR absorbing layer is distributed in a reverse distribution state. contained within.

In the electrophotographic light-receiving member of the present invention, as described above, the distribution state of germanium atoms and/or tin atoms contained in the IR absorption layer takes the above-mentioned distribution state in the layer thickness direction, It is desirable to have a uniform distribution in the in-plane direction parallel to the surface of the support.

Further, in one of the preferred embodiments, the distribution state of germanium atoms and/or tin atoms in the IR absorption layer is such that germanium atoms and/or tin atoms are continuously and evenly distributed in the entire layer region, Since the distribution concentration of atoms and/or tin atoms in the layer thickness direction decreases from the support side toward the CGL, there is excellent affinity between the IR absorption layer and the CGL, and as will be described later. By making the distribution concentration of germanium atoms extremely thick at the edge of the support, the light on the long wavelength side that cannot be completely absorbed from CTL to CGL when using a semiconductor laser etc. is substantially absorbed in the IR absorption layer. can be completely absorbed, and interference can be prevented by reflection from the support surface.

6 to 11 show typical examples where the distribution state of germanium atoms and/or tin atoms contained in the IR absorption layer of the light-receiving member of the present invention in the layer thickness direction is non-uniform. It will be done.

In FIGS. 6 to 11, the horizontal axis shows the distribution concentration C of germanium atoms and/or tin atoms (hereinafter abbreviated as "atomic (GS) J"), and the vertical axis shows the layer thickness of the !R absorption layer, tB indicates the position of the end face of the IR absorption layer on the support side, and tT indicates the position of the end face of the !R absorption layer on the opposite side to the support side.

That is, the IR absorption layer containing atoms (GS) is tB
Layer formation is performed from the side toward the tT side.

FIG. 6 shows a first typical example of the distribution state of atoms (GS) contained in the IR absorption layer in the layer thickness direction.

In the example shown in FIG. 6, the contained I of the atom (GS)
From the interface position tB where the surface on which the R absorption layer is formed and the surface of the IR absorption layer contact to the position tl, atoms (GS)
While the distribution concentration C of takes a constant value C3, atoms (GS
) is contained in the formed IR absorption layer, and from the position t1, the concentration is gradually and continuously decreased from the concentration C2 to the interface position tT. At the interface position ft1tr, atoms (GS
) is assumed to be C3.

In the example shown in FIG.
) forms a distribution state in which the concentration C gradually and continuously decreases from the concentration C4 from the position tB to the position tT, and reaches the concentration C5 at the position ff1tr.

In the case of FIG. 8, the distribution concentration C of atoms (GS) is constant at the concentration C6 from position tB to position 'r2, and gradually and continuously decreases between position t2 and position tT. , at position tT, the distribution concentration C is substantially zero (substantially zero herein means the case where the amount is less than the detection limit; the meaning of "substantially zero" hereinafter is also the same). ).

In the case of FIG. 9, the distribution concentration C of atoms (GS) is at the position t
From B to position tT, the concentration is gradually decreased continuously from C8, and becomes substantially zero at position tT.

In the example shown in FIG. 10, the distribution concentration C of atoms (GS) is a constant value of concentration C9 between the position tB and the position t3, and the concentration C+ok at the position tr. Between the position ff1t3 and the position tT, the distribution density C is linearly decreased from the position t3 to the position tT.

In the example shown in FIG. 11, from position tB to position tr, the distribution concentration C of atoms (GS) decreases linearly from the concentration 01 position to substantially zero.

As described above with reference to FIGS. 6 to 11, some typical examples of the distribution state of atoms (GS) contained in the IR absorption layer in the layer thickness direction, in the present invention, silicon atoms on the support side and the distribution concentration C of atoms (GS)
It is preferable if the IR absorption layer is provided with a distribution state of atoms (GS) in which the distribution concentration C is considerably lower on the interface tT side than on the support side. This is one of the most important examples. in this case,
Atoms (GS) as the distribution state of atoms (GS) in the layer thickness direction
The maximum value Cmax of the distribution concentration of is preferably 1000 atomic ppm or more, more preferably 5000 atomic ppm or more, optimally I
It is desirable that the layer be formed in such a manner that it can have a distribution state of atomic ppm or more.

In the present invention, atoms (GS
) may be determined as desired so as to effectively achieve the purpose of the present invention, but preferably 1 to 1.
1oxlo' atom ppm5, preferably 100-9.
5X10' atoms p p m , optimally 500-8X
Preferably, the amount is 10' atoms ppm.

The above-mentioned IR absorption layer further includes a conductivity controlling material (M
R), an oxygen atom (0), a nitrogen atom (Nl), and a carbon atom (C).

Further, as the substance (MR) that controls conductivity, so-called impurities in the semiconductor field can be mentioned. (hereinafter referred to as "group ■ atoms")
, or an atom belonging to Group V of the periodic table (hereinafter referred to as "Group V atom") that provides n-type conductivity. Specific examples of Group Ⅰ atoms include B (boron), Al (aluminum), Ga (gallium), and In (indium).
, Tl (thallium), etc., with B and Ga being particularly suitable. Specifically, the Group V atoms include P (phosphorus), A
s (arsenic), Sb (antimony), Bi (bismuth)
etc., especially P.

As is preferred.

In the present invention, the content of the substance (M
．． 5~lXl0' atoms p p m , optimally 1~5×
It is desirable that the amount is lo3 atomic ppm.

In the present invention, Non-3i (Ge, Sn) (H
,
GL.

The film is created by a vacuum deposition film formation method similar to CTL, with numerical conditions for film formation parameters set appropriately so as to obtain desired characteristics. Specifically, for example, glow discharge method (alternating current discharge CVD such as low frequency CVD, high frequency CVD or microwave CVD, or direct current discharge CVD, etc.), sputtering method, vacuum evaporation method, ion blating method, photo CVD method, thermal CVD method, activated species (A) generated by decomposing raw material gas of non-single crystal material, and the active species (
Active species (B) generated from film-forming chemicals that chemically interact with A) are introduced into the film-forming space for forming deposited films separately, and these are caused to react chemically. A method of forming non-single crystal materials (hereinafter referred to as rHRC) by
VD method), a raw material gas for a non-single crystal material and a halogen-based oxidizing gas that has the property of oxidizing the raw material gas are separately introduced into a film forming space for forming a deposited film. However, it can be formed by various thin film deposition methods such as a method of forming a non-single crystal material by chemically reacting these materials (hereinafter abbreviated as "rFOcVD method"). These thin film deposition methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, equipment capital investment load, manufacturing scale 1, and desired characteristics of the light-receiving member to be produced. The glow discharge method and the sputtering method are used because it is relatively easy to control the conditions for manufacturing the receiving member and it is easy to introduce halogen atoms and hydrogen atoms together with silicon atoms.

The ion blasting method, HRCVD method, and FOCVD method are suitable. These methods may be used in combination within the same device system.

For example, Non-8i (Ge
.

5n) (H,
A raw material gas for supplying, a raw material gas for supplying Ge that can supply germanium atoms (Ge), a raw material gas for supplying Sn that can supply tin atoms (Sn), and a raw material gas for supplying Sn that can supply germanium atoms (Ge), hydrogen atoms ( H) A raw material gas for introduction and/or a raw material gas for introducing halogen atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber to generate a glow discharge at a predetermined level. Non-3i (Ge,
5n) (H.

It is sufficient to form a layer consisting of X). In addition, in order to contain germanium atoms and/or tin atoms in a non-uniform distribution state, non-3i (Ge , 5n) (H, X) may be formed. In addition, when forming by a sputtering method, for example, a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, or the target and Ge and/or Using two or three targets composed of Sn or Si and Ge and/or Sn
He as needed using a mixed target of
, Ar and other diluent gases for supplying Ge and/or Sn are added as necessary to hydrogen atoms (
This is accomplished by introducing a gas for introducing H) or/and halogen atoms (X) into a sputtering deposition chamber to form a plasma atmosphere of the desired gas. When the distribution of germanium atoms and/or tin atoms is made non-uniform, the target is sputtered while controlling the gas flow rate of the source gas for supplying Ge and/or supplying Sn according to a desired rate of change curve. Just do it.

In the case of the ion blating method, for example, polycrystalline silicon or single-crystal silicon, polycrystalline germanium or single-crystal germanium, and/or polycrystalline tin or single-crystalline tin are housed in a deposition board as evaporation sources, and the evaporation It can be carried out in the same manner as the sputtering method, except that the source is heated and evaporated by a resistance heating method or an electron beam method (EB method), and the flying evaporated material is passed through the desired gas plasma atmosphere. .

Non-5i (Ge, 5n) (
In order to form an IR absorption layer composed of H,
Alternatively, the gas may be activated by introducing the gas at the desired pressure into an activation space provided at the front stage of the deposition chamber where the internal pressure can be reduced, and causing a glow discharge or heating in the activation space. Species (A) is generated and hydrogen atoms (■ () are introduced into the raw material gas and or halogen atoms (
X) Introduce raw material gas for introduction into another activation space in the same way to generate active species (B), and activate species (A) and active species (B)
were separately introduced into the deposition chamber and placed on the surface of a predetermined support that had been set in advance at a predetermined position.
A layer consisting of (Ge, Sn) (H, X) may be formed. In addition, in order to contain germanium atoms and/or tin atoms in a non-uniform distribution state, Non-5i ( Ge, 5
A layer consisting of (H, X) may be formed.

Non-Si (Ge, 5n) (
In order to form an IR absorption layer composed of H, Introducing a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, further introducing halogen (X) gas into the deposition chamber separately from the source gas at a desired gas pressure,
These gases are chemically reacted in the deposition chamber, and No.
A layer consisting of n-3i (Ge, 5n) (H, X) may be formed. In addition, in order to contain germanium atoms and/or tin atoms in a non-uniform distribution state, non-3i (Ge
, 5n) (H,X) may be formed.

Substances that can be used as raw material gas for supplying Si used in the present invention include SiH4, Si2H6゜5i3H@
, 5i4H1 (1 grade) gaseous or gasifiable silicon hydride (silanes) is cited as one that can be effectively used, especially because of its ease of handling during layer creation work, good Si supply efficiency, etc. In this respect, SiH4 and Si2 H6 are preferred.

As a material that can be a source gas for supplying Ge, GeH
4, Ge2H6, Ge3lg, Ge4H, (,.

Ge5 H12+ Ge 6 H14+ Ge 7 H
Germanium hydride in a gaseous state or that can be gasified, such as 16+ Ge8 H18+GegH2o, is cited as one that can be effectively used.GeH4, Ge2
1-16°Ge 3 HB is preferred.

Substances that can be used as raw material gas for Sn supply include SnH.
4, 5n2H6, SSn3H, 5n4H+0+Sn5
H12+ Sn6 H14+ Sn 7 H16+ S
SnH4,5n2H6, 5n3HB
are listed as preferred.

Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into

Furthermore, silicon hydride compounds containing silicon atoms and halogen atoms in a gaseous state or containing gasifiable halogen atoms can also be mentioned as effective in the present invention.

Examples of halogen compounds that can be suitably used in the present invention include halogen gases of fluorine, chlorine, bromine, and iodine, BrF, CIF, CIF3. BrF
5. l3rF3. IF3. IF7. Ice
, IBr, and other interhalogen compounds.

Specifically, examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include SiF4. Si 2 F6+ 5i (14°SiB
Preferred examples include silicon halides such as r4.

When forming the characteristic electrophotographic light-receiving member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, Ge supply and/or S
Non-3i (Ge, Sn) containing halogen atoms on a desired support without using silicon hydride gas as a source gas that can supply Si together with the source gas for supplying n.
An IR absorption layer consisting of (H,X) can be formed.

When manufacturing an IR absorption layer containing halogen atoms according to the glow discharge method, basically, for example, silicon halide is used as a raw material gas for supplying Si, and germanium hydride and/or Sn are used as raw material gas for supplying Ge. Tin hydride, which serves as the raw material gas for supply, is introduced into the deposition chamber where the IR absorption layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. By doing so, an IR absorption layer can be formed on a desired support, but in order to more easily control the ratio of hydrogen atoms introduced, hydrogen gas or hydrogen atoms may be added to these gases. A layer may also be formed by mixing a desired amount of a silicon compound gas containing .

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

Sputtering method, ion blating method.

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

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as F2, or the above-mentioned silanes and/or germanium hydride, is introduced into the sputtering deposition chamber. It is sufficient to form a plasma atmosphere.

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

HCI! , HBr, hydrogen halides such as Hl, Si
H2F2.

5tH212, 5IH2C12, 5tHCA' 2 ,
SiH2Br2.

Halogen-substituted silicon hydride such as 5iHBr2, and Ge
HF3. GeF2 F2. GeH3F, G
eHBr3゜GeF2 (12, GeHBr3.GeHB
r3. GeF2Br2゜GeH3Br, GeHI3
, GeF212, halides containing hydrogen atoms as one of their constituent elements such as hydrogenated germanium halides such as GeH3r, GeF4゜GeCl4. GeBr4. Ge
14. GeF2. GeC12゜GeBr2, Ge
germanium halide such as 12, or/and 5n
HF3,5nH2F2,5nH3F.

5nHCj73.5nH2Cj? 2.5nH3CJ7.
5nHI3r3゜5nH2Br2.5nH3Br, 5
Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated tin halides such as nHI3.5nH212°5nH31, 5nF4°5nCj' 4. SnBr4,5n1
4. SnF2,5nCj! 2゜SnBr2, 5n12
Gaseous or gasifiable substances such as tin halides and the like may also be mentioned as useful starting materials for forming the IR absorbing layer. Among these substances, halides containing hydrogen atoms are used because when forming an IR absorption layer, hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time as halogen atoms are introduced into the layer. , is used as a suitable raw material for introducing halogen in the present invention.

In order to structurally introduce hydrogen atoms into the IR absorption layer, in addition to the above, F2, SiH4, Si2H6゜Si3
Hg, silicon hydride such as 5i4H1o with germanium or a germanium compound for supplying Ge, or GeH4, Ge 2 H6, Ge 3 HB.

Ge4II, 0. Ge5H,2,Gea ”+4+G
e7 F16゜Ge g H18+ Ge g F2
with tin or a tin compound for supplying germanium hydride and/or Sn, such as SnH4,
Sn 21115+Sn3 HBr Sn4 HIon
Sn5 H12+ Sn6 H14+Sn7'+
6+ S08 F118+ S19 "20, etc., and silicon or a silicon compound for supplying Si coexist in the deposition chamber to generate a discharge.

In a preferred example of the present invention, hydrogen atoms (■1) contained in the IR absorption layer of the electrophotographic light-receiving member to be formed
The amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H+ X ) is preferably 0.
It is desirable that the content be 0.01 to 40 atom %, more preferably 0.05 to 30 atom %, and optimally 0.1 to 25 atom %.

To control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the IR absorption layer, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X) contained What is necessary is to control the amount of starting material used for this purpose introduced into the deposition system, the discharge power, etc.

In the present invention, in order to contain nitrogen atoms and/or carbon atoms and/or oxygen atoms in the IR absorption layer, I
The starting materials for introducing nitrogen atoms and/or carbon atoms and/or oxygen atoms during the formation of the R absorption layer are
It may be used together with the starting material for forming the R-absorbing layer and contained in the formed layer while controlling its amount.

I by glow discharge method, HRCVD method, FOCVD method
In order to form the R absorption layer, as a starting material for introducing nitrogen atoms, a small amount (most of the gaseous substances whose constituent atoms are nitrogen atoms or gasified substances that can be gasified) are used. obtain.

For example, a raw material gas whose constituent atoms are silicon atoms (Si), a raw material gas whose constituent atoms are nitrogen atoms (N), and hydrogen atoms (■]) or halogen atoms (
A raw material gas having constituent atoms of X) is mixed at a desired mixing ratio, or a raw material gas having silicon atoms (Si) and nitrogen atoms (N) and hydrogen atoms (
(2) Either mix 1) with the raw material gas whose constituent atoms are also at a desired mixing ratio, or
) and silicon atoms (Si).
, a raw material gas having three constituent atoms: nitrogen atom (N) and hydrogen atom (H) can be used in combination.

Alternatively, a raw material gas containing nitrogen atoms (N) may be mixed with a raw material gas containing silicon atoms (Si) and hydrogen atoms (H).

A starting material that can be effectively used as a raw material gas for introducing nitrogen atoms (N) is, for example, nitrogen (N2) having N as a constituent atom or having N and ■] as constituent atoms.
, ammonia (NH3), hydrazine (H2NNH
2), hydrogen azide (HN3), ammonium azide (
Mention may be made of gaseous or gasifiable nitrogen such as NH4N3), nitrogen compounds such as nitrides and azides. In addition to this, nitrogen trifluoride (F 3 N) is used because it can also introduce halogen atoms (X) in addition to nitrogen atoms (N).

Examples include halogenated nitrogen compounds such as nitrogen tetrafluoride (F4N2).

I by glow discharge method, HRCVD method, FOCVD method
In order to form the R-absorbing layer, most of the starting materials for introducing carbon atoms may be used, including gaseous substances having at least carbon atoms as constituent atoms or gasified substances that can be gasified.

For example, a raw material gas containing silicon atoms (Si), a raw material gas containing carbon atoms (C), and hydrogen atoms (H) or/or halogen atoms (
A raw material gas having constituent atoms of
■])) at a desired mixing ratio, or silicon atoms (Si).
A raw material gas whose constituent atoms are silicon atoms (Si),
A raw material gas having three constituent atoms, carbon atoms (C) and hydrogen atoms (H), can be mixed and used.

Also, silicon atoms (Si) and hydrogen atoms (■])
You may mix and use the raw material gas which has a carbon atom (C) as a constituent atom with the raw material gas which has a carbon atom (C) as a constituent atom.

A starting material that can be effectively used as a raw material gas for introducing carbon atoms (C) has C and 1 as constituent atoms.

Examples include saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, the saturated hydrocarbon is methane (CI(4
), ethane (C2H6), propane (C31(8).

n-Butane (n C4H+o), pentane (C51-
112), ethylene (C2
H4).

Propylene (C3H6), butene-1 (C4H8).

Butene-2 (C4H8), isobutylene (c4HB
) + pentene (C3H11)), and examples of acetylene hydrocarbons include acetylene (c 2 H2), methylacetylene (C3H4), butyne (c a Ha ), and the like.

As a raw material gas containing Si, C, and H as constituent atoms, S
Examples include alkyl silicides such as i (CH3), s, and Si (C2H5)4.

In addition to this, CF4゜CCI
Examples include halogenated carbon gases such as 4+ CH3CF3.

I by glow discharge method, HRCVD method, FOCVD method
To form the R-absorbing layer, most of the starting materials for introducing oxygen atoms may be used, including gaseous substances containing at least oxygen atoms or gasified substances that can be gasified. .

For example, a source gas containing silicon atoms (Si), a source gas containing oxygen atoms (0), and hydrogen atoms (H) or halogen atoms (
A raw material gas having constituent atoms of
H) is also mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and silicon atoms (Si), oxygen atoms (0) are mixed. and a raw material gas containing three hydrogen atoms (H) as constituent atoms can be used in combination.

In addition, silicon atoms (Si) and hydrogen atoms (1-(
) may be mixed with a material gas containing oxygen atoms (0) as constituent atoms.

Starting materials that can be effectively used as raw material gases for introducing oxygen atoms (0) include, for example, oxygen (02), ozone (03), and nitrogen oxide (No).

Nitrogen dioxide (No 2 >, -nitrogen dioxide (N 2 o
).

Nitrogen sesquioxide (N203), trinitrogen tetraoxide (N204)
).

Nitrogen sesquioxide (N20s), nitrogen trioxide (NO2).

Silicon atom (Si), oxygen atom (0) and hydrogen atom (■
1) and constituent atoms, for example, disiloxane (F■3
SiO8i■]3), trisiloxane (H3SiO3i
Examples include lower siloxanes such as 1120SiH3).

To form an IR absorption layer by sputtering method,
■When forming the R absorption layer, use single-crystal or polycrystalline Si wafers or Si3N4 wafers, or wafers containing a mixture of Si and Si3N4 and/or SiO2 wafers, or Si and 5i02
This can be carried out by sputtering a wafer containing a mixture of SiC and/or a SiC wafer or a wafer containing a mixture of Si and SiC in various gas atmospheres as targets.

For example, if a Si wafer is used as a target to contain nitrogen atoms, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms or/and halogen atoms may be diluted with a diluent gas as necessary. These gases may be introduced into a deposition chamber for sputtering to form a gas plasma of these gases to sputter the Si wafer.

Alternatively, Si and Si 3 N 4 may be used as separate targets or by using a single mixed target of Si and Si 3 N 4 in an atmosphere of dilution gas as a sputtering gas or This is accomplished by sputtering in a gas atmosphere containing a small amount of hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms.

As the raw material gas for introducing nitrogen atoms, carbon atoms, and oxygen atoms, the raw material gas for introducing nitrogen atoms, carbon atoms, and oxygen atoms in the raw material gas shown in the example of the glow discharge method mentioned above can also be used when sputtering is used. Can be used as an effective gas.

In the present invention, when forming the IR absorption layer, the distribution concentration of nitrogen atoms and/or carbon atoms and/or oxygen atoms contained in the layer C(N) and/or C(C) and/or C( 0) in the layer thickness direction to form a layer having a desired depth profile in the layer thickness direction, glow discharge method, HRCVD method,
In the case of the FOCVD method, the starting material gas for introducing nitrogen atoms and/or carbon atoms and/or oxygen atoms to change the distribution concentration C(N) and/or C(C) and/or C(0). is introduced into the deposition chamber while changing the gas flow rate appropriately according to a desired rate of change curve.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be appropriately changed by any commonly used method such as manually or by using an externally driven motor.

When formed by a sputtering method, the distribution concentration C(N) and/or C(C) and/or C(0) of nitrogen atoms and/or carbon atoms and/or oxygen atoms in the layer thickness direction is changed in the layer thickness direction. In order to form a desired depth profile of nitrogen atoms and/or carbon atoms and/or oxygen atoms in the layer thickness direction, first, as in the case of the glow discharge method, nitrogen atoms are and/or by using a starting material for introducing carbon atoms and/or oxygen atoms in a gaseous state and appropriately changing the gas flow rate when introducing the gas into the deposition chamber as desired.

Second, the target for sputtering is, for example, S
If a target containing a mixture of i and Si 3 N 4 is used, this can be done by changing the mixing ratio of Si and Si 3 N 4 in advance in the layer thickness direction of the target.

When using SiC or S+02, the same procedure as for Si 3 N 4 may be used.

The amount of nitrogen atoms (N) contained in the IR absorption layer, or the amount of oxygen atoms (0), or the amount of carbon atoms (C), or the sum of the amounts of nitrogen atoms and oxygen atoms (N+0), or nitrogen The sum of the amounts of atoms and carbon atoms (N + C), the sum of the amounts of carbon atoms and oxygen atoms (C + O), or the sum of the amounts of nitrogen atoms, carbon atoms and oxygen atoms (N + C 〇) is preferably 0.
．． It is desirable that the content be 0.01 to 40 atom %, more preferably 0.05 to 30 atom %, and optimally 0.1 to 25 atom %.

a substance controlling conduction properties (MR) in the IR absorption layer;
For example, in order to structurally introduce a group II atom or a group V atom, a starting material for introducing a group II atom or a starting material for introducing a group V atom is placed in a gaseous state in a deposition chamber during layer formation. In addition, it may be introduced together with other starting materials for forming the IR absorption layer. As the starting material for such introduction of Group (I) atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, as starting materials for introducing such group III atoms, for introducing boron atoms,
B2 ■46+ 84 ”'IO+ B5 ”■11+
B5 ■(lI+B 6 I] 10, B 6
Boron hydride such as H12, B 7 II 14, BF
3. BCl2. Examples include boron halides such as BBr3. In addition, AlCl3. Ga C13,Ga(
C)13)3, InCl! 2, TIC13, etc. can also be mentioned.

In the present invention, effective starting materials for introducing Group V atoms include PH3,
Next to hydrogen ratio such as P2H4, PH41°PF3. PF5.
PCf3. PCI! 5. PBr3. Examples include halogen ratios such as PBr3°PI3. In addition, As1
13. AsF3. AsCj' 3. As
Br3. AsF5°SbH3, SbF3. Sb
F,, 5bCj73. 5bC15゜BiH3, B
iCj' 3 , B1Br 3 and the like can also be mentioned as effective starting materials for introducing Group V atoms.

Furthermore, the layer thickness of the IR absorption layer in the present invention is set to 0.0000.
05-25μ, preferably 0.07-20μ, optimally 0.1-15μ.

The charge injection blocking layer (104, 503) is composed of NoNon-3i (H,X) as described above. The charge injection blocking layer in the present invention has the function of blocking charges from being injected into the CTL from the support side when the surface of the photoreceptive layer is subjected to charging treatment with one polarity, and has the function of blocking charge injection into the CTL from the support side. Such functions will not be exhibited when subjected to electrostatic treatment.
It has a so-called rectifying property. In order to provide such a function, the charge injection blocking layer contains a relatively large amount of a conductivity controlling substance (Mo) that provides one conductivity type.

The substance that controls conductivity (MO) is uniformly contained in the layer interface direction of the charge injection blocking layer, but its distribution concentration C (MO) is uniform in the layer thickness direction. may also be non-uniform. However, in any case, it is contained in the entire layer region of the charge injection blocking layer.

When the distribution concentration C(MO) is non-uniform, it is preferable to contain it in a multi-distribution manner on the support side.

A substance that controls conductivity contained in the charge injection blocking layer (
MO) may have the same polarity as the atom (M) belonging to Group V of the periodic table contained in CTL, which will be described later, or may have a different polarity, or even be the same substance. may also be different substances.

These matters are appropriately determined in consideration of the purpose when designing the photoreceptive layer. Specifically, the conductivity controlling substance (MO) contained in the charge injection blocking layer includes the conductivity controlling substance (MR) mentioned above and the substance belonging to Group V of the periodic table described below. The same thing as atom (M) can be mentioned.

FIGS. 12 to 16 show typical examples of the distribution state of the conductivity controlling substance (MO) in the layer thickness direction when the charge injection blocking layer contains the substance (MO) with a non-uniform distribution concentration in the layer thickness direction. is shown.

In the examples shown in FIGS. 12 to 16, the horizontal axis represents the substance (Mo
), the vertical axis shows the layer thickness t of the charge injection blocking layer, tB shows the position of the interface on the support side, and tT shows the position of the interface on the side opposite to the support side. That is, the charge injection blocking layer is formed from the tB side toward the tT side.

FIG. 12 shows a substance (M) contained in the charge injection blocking layer.
A first typical example of the distribution state of O) in the layer thickness direction is shown.

In the example shown in FIG. 12, from the interface position tB side to the position I4, the concentration C (MO) of the substance (Mo) is C
The distributed concentration C(MO) is contained while taking a constant value I2, and is gradually and continuously decreased from the position CI3 from the position t4 to the interface position tT. At the interface position tT, the distribution concentration C is set to CI4.

In the example shown in FIG. 13, the contained substance (M
The distribution concentration C(MO) of O) forms a distribution state in which it gradually and continuously decreases from CI5 from position tB to position tT, and reaches CI8 at position tT.

In the example shown in FIG. 14, the distribution concentration C (Mo) of the substance (MO) is C1□ between the position tB and the position I5.
is a constant value, and is set to CI8 at position tT.

Between the position t5 and the position tT, the distribution concentration C(MO) is decreased in a negative order scale from the position t5 to the position tT.

In the example shown in FIG. 15, the distribution concentration C(MO)
takes a constant value of CI9 from position 1B to position t6,
From position t6 to position tT, the distribution state decreases in a linear function from C2Ill to C21.

In the example shown in FIG. 16, the distribution concentration C(MO)
takes a constant value of C22 from position tB to position tT.

In the present invention, when the charge injection blocking layer contains a conductivity controlling substance (MO) in a distributed state on the support side, the maximum value of the distribution concentration C(MO) of the substance (MO) is preferably 50 atomic ppm or more, more preferably 8
It is desirable that the layer be formed in such a manner that the distribution state can be such that the concentration is 0 atomic ppm or more, and optimally 100 atomic ppm or more.

In the present invention, the substance (M
The content of (1) may be determined as desired so as to effectively achieve the object of the present invention, but is preferably 30 to 5XIO4 atomic ppm.

More preferably, it is 50 to 1X10' atoms ppm, and most preferably 1X10'' to 5X103 atoms ppm.

The charge injection blocking layer mainly improves the adhesion between the support and the charge injection blocking layer and the bond between the charge injection blocking layer and the CTL by containing carbon atoms and/or nitrogen atoms and/or oxygen atoms. Adhesion is improved.

17 to 23 show the distribution in the layer thickness direction of carbon atoms and/or oxygen atoms and/or nitrogen atoms (these are collectively referred to as "atoms (Z)") contained in the charge injection blocking layer. Typical examples of conditions are shown.

In the examples shown in Figures 17 to 23, the horizontal axis is the atom (Z).
The vertical axis shows the layer thickness t of the charge injection blocking layer, tB shows the position of the interface on the support side, and tT shows the position of the interface on the side opposite to the support side. That is, the charge injection blocking layer is formed from the tB side toward tT.

Figure 17 shows atoms (Z) contained in the charge injection blocking layer.
A first typical example of the distribution state in the layer thickness direction is shown.

In the example shown in FIG. 17, from the interface position tB to the position t7, the distributed concentration Cz of atoms (Z) is contained with a constant value of C23, and from the position t7, the distributed concentration C is contained until the interface position tT. It is gradually and continuously decreased from C24. At the interface position tT, the distribution concentration C is set to C25.

In the example shown in FIG. 18, the contained atoms (Z
) distribution density Cz is C from position tB to position tT.
C2 gradually and continuously decreases from 26 at position tT.
A distribution state such as □ is formed.

In the case of FIG. 19, the distribution concentration Cz of atoms (Z) is set to a constant value C from position tB to position t8, and at position t8
It is gradually and continuously decreased between and the position tT, and becomes substantially zero at the position tiftT.

In the case of Fig. 20, the atom (Z) is at position tT from position tB.
The distribution concentration Cz gradually decreases continuously from C30 until reaching the position tT, and becomes substantially zero at the position tT.

In the example shown in FIG. 21, the distribution concentration C of atoms (Z)
z is a constant value of C31 between position ta and position 18, and is set to C32 at position tT.

Between position fit t s and position tT, the distribution concentration Cz
is decreased linearly from position t9 to position tT.

In the example shown in FIG. 22, the distribution concentration Cz of atoms (Z) takes a constant value of C33 from position 1B to position t10, and linearly changes from C34 to Cj from position t10 to position tT. The distribution state is said to be decreasing.

In the example shown in FIG. 23, the distribution concentration Cz of atoms (Z) takes a constant value of C38 from position tB to position tT.

In the present invention, when the charge injection blocking layer contains atoms (Z) in a distribution state in which the atoms (Z) are largely distributed on the support side, the atoms (
The maximum value of the distribution concentration Cz of Z) is preferably 500 atoms p
It is desirable that the layer be formed in such a manner that the distribution state can be such that the concentration is 1000 atomic ppm or more, more preferably 800 atomic ppm or more, and most preferably 1000 atomic ppm or more.

In the present invention, atoms (
The content of Z) may be determined as desired so as to effectively achieve the object of the present invention, but preferably 0.
001 to 50 atom%, more preferably 0.002 to 40
The content is desirably atomic %, most preferably 0.003 to 3o atomic %.

The hydrogen atoms and/or halogen atoms contained in the charge injection blocking layer in the present invention are Non-31M.

It is possible to compensate for the dangling bonds present in (H,X) and improve the layer quality.

The content of hydrogen atoms or halogen atoms, or the sum of hydrogen atoms and halogen atoms, is preferably 1 to 5 atomic %, more preferably 5 to 40 atomic %, most preferably 10 to 30 atomic %.

In the present invention, the layer thickness of the charge injection is preferred, and from the fact that the desired electronic photographic characteristics are obtained, and the economic effects, etc. Of ~lOμ, more preferably 0.0
It is desirable that the thickness be 5 to 8μ, most preferably 0.1 to 5μ.

The charge injection blocking layer is formed by a vacuum deposition film forming method similar to CGL and CTL, which will be described later, by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics.

CGL CGL (106,505) in the present invention is Non
-3i (H,X) and has desirable photoconductive properties, especially charge generation properties.

The CGL in the present invention includes a substance that controls conductivity,
Carbon atom (C), nitrogen atom (N) and oxygen atom (0)
Substantially none of these are contained.

Further, the hydrogen atoms and/or halogen atoms contained in the CGL of the present invention compensate for the dangling bonds of silicon atoms and are effective in improving layer quality, particularly photoconductive properties.

The content of hydrogen atoms, halogen atoms, or the sum of hydrogen atoms and halogen atoms is preferably 1 to 40 atoms96. The content is more preferably 5 to 30 atom %, most preferably 10 to 20 atom %.

In the present invention, the layer thickness of the CGL is determined depending on the light absorption coefficient of the light source used in the electrophotographic image forming apparatus in order to obtain desired electrophotographic characteristics and economical effects, especially to obtain sufficient charge generation ability. The thickness is determined as desired, preferably from 0.01 to 30 μm, more preferably from 0.1 to 20 μm.
μm1 Optimally, it is desirable to set it to 1-10 μm.

In the present invention, in order to form a CGL composed of Non-5i (H,
Or AC discharge CVD such as microwave CVD.

or direct current discharge CVD, etc.), ECR-CVD method, sputtering method, vacuum evaporation method, ion blating method,
It can be formed by various thin film deposition methods such as optical CVD, thermal CVD, HRCVD, and FOCVD.

These thin film deposition methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, equipment capital investment, manufacturing scale, and desired characteristics of the light-receiving member to be manufactured. The glow discharge method, sputtering method, Law.

Ion brating method, ECR-CVD method, HRCV
D method and FOCVD method are preferred. In some cases, these methods may be used in combination in the same device system.

For example, Non-5i (H,X
), basically a raw material gas for Si supply that can supply silicon atoms (Si) and a raw material gas for introducing hydrogen atoms (H) or/and halogen atoms (X). A raw material gas for introduction is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber, which is then deposited onto the surface of a predetermined support that has been placed at a predetermined position in advance. Non-3i (H,X)
What is necessary is to form a layer consisting of. In addition, when forming by sputtering, a target made of Si is used in an atmosphere of an inert gas such as Ar or He, or a mixed gas of these gases, as necessary. , hydrogen atom (H) or/and halogen atom (X)
This is accomplished by introducing a gas for introduction into a deposition chamber for sputtering to form a plasma atmosphere of the desired gas.

In the case of the ion blating method, for example, polycrystalline silicon or single crystal silicon is housed in an evaporation board as an evaporation source, and this evaporation source is heated and evaporated by a resistance heating method, an electron beam method (EB method), or the like. This can be carried out in the same manner as in the sputtering method, except that the flying evaporated material is passed through a desired gas plasma atmosphere. Non-3i (
For example, to form a CGL composed of
i. The raw material gas for supply is introduced at a desired gas pressure into the activation space provided at the front stage of the deposition chamber, the interior of which can be reduced in pressure, to cause glow discharge or overheating in the activation space. Activated species (A) are generated by Activated species (B) are generated, active species (A) and active species (B) are each separately introduced into the deposition chamber, and N'on is deposited on the surface of a predetermined support that has been placed at a predetermined position in advance. -8i (H.

It is sufficient to form a layer consisting of X). CGL composed of Non-3i (H,X) by FOCVD method
In order to form, for example, a raw material gas for supplying Si is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and halogen (X) gas is introduced into the deposition chamber separately from the raw material gas at a desired gas pressure. These gases are introduced under pressure and chemically reacted in the deposition chamber to form N on -S i (H
, X) may be formed.

Substances that can be used as raw material gas for supplying Si used in the present invention include SiH4, Si, 1-16,5i
Gaseous or gasifiable silicon hydride (silanes) such as 3HB, 5I4H1°, etc. are effectively used, and in particular, Si
5il (4°5i2H6) is preferred in terms of supply efficiency.

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 can be gasified is preferably mentioned.

Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, and bromine.

Iodine halogen gas, l3rF, CI! F, ClF3
゜BrF5. BrF3. HF3. IF7. ICI,
Interhalogen compounds such as IBr can be mentioned.

Examples of silicon compounds containing halogen atoms, so-called halogen atom-substituted silane derivatives include, for example, SiF4. Si2F6. Preferred examples include silicon halides such as SiCl 4°5iI3r 4 .

When forming the characteristic electrophotographic light-receiving member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride gas as a raw material gas capable of supplying Si is used. Even if it is not used, CGL consisting of Non-3i (H,X) containing a halogen atom can be formed on a desired support.

CGL containing halogen atoms according to the glow discharge method
When manufacturing CGL, for example, silicon halide, which serves as a raw material gas for supplying Si, is basically introduced into a deposition chamber where CGL is formed at a predetermined gas flow rate, and a glow discharge is generated to produce these materials. CGL can be formed on a desired support by forming a gas plasma atmosphere, but in order to more easily control the ratio of hydrogen atoms introduced, these gases may be further added. Hydrogen gas or a silicon compound gas containing hydrogen atoms may also be mixed as desired to form a layer.

In addition, each gas may be used not only as a single species, but also as a mixture of multiple species at a predetermined mixing ratio.

Sputtering method, ion blating method.

In order to introduce halogen atoms into the layer formed by either the HRCVD method or the FOCVD 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, and the gas is It is sufficient to form a plasma atmosphere of

In addition, 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 sputtering volume chamber to create a plasma atmosphere of the gases. All you have to do is form it.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, LIC1.

Hydrogen halides such as HB r and HI, 5jjl 2
F2, 5i) 1212, SiH2C12,
5iHC12, 5i)12Br2.

Gaseous or gasifiable materials such as halogen-substituted silicon hydrides such as 5iHBr 2 may also be mentioned as useful starting materials for CGL formation. Among these substances, halides containing hydrogen atoms are used because hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer at the same time as halogen atoms are introduced into the layer during CGL formation. In the invention, it is used as a suitable raw material for introducing halogen.

In order to structurally introduce hydrogen atoms into CGL, in addition to the above, H2, SiH4, Si. H6゜Si3H8,
This can also be carried out by causing a discharge by causing silicon hydride such as 5i4H,o and silicon or a silicon compound for supplying Si to coexist in a deposition chamber.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in CGL, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X) can be controlled. What is necessary is to control the amount of starting material used in the deposition system introduced into the deposition system, the discharge power, etc.

CTL The CTL (105,504) in the present invention contains silicon atoms, at least one of carbon atoms, nitrogen atoms, and oxygen atoms as constituent elements, and atoms belonging to Group V of the periodic table (M ) and N containing
on-5i (H,X) (rNon-3iM(C
,N,O) (abbreviated as (H,X)J), and has charge transport properties that satisfy desired electrophotographic properties. The carbon atoms, nitrogen atoms, or oxygen atoms contained in the CTL may be contained in the CTL in a uniformly distributed state, or may be contained in a non-uniformly distributed state in the layer thickness direction. The atoms (M) belonging to Group V of the periodic table may be contained in a non-uniformly distributed state in the layer thickness direction.In any case,
CT
It is contained in the entire layer region of L. The substance (M) is contained in the CTL so that the distribution concentration of atoms (M) belonging to Group V of the periodic table in the layer thickness direction of the CTL is small (and non-uniform in some layer regions). be done.

The distribution concentration of carbon atoms, nitrogen atoms, and oxygen atoms in the CTL in the layer thickness direction may be uniform (or, similar to the atoms (M) belonging to Group V of the periodic table), the distribution concentration of carbon atoms, nitrogen atoms, and oxygen atoms in the CTL may be uniform. The content may be non-uniform in the layer region.

FIGS. 24 to 39 show typical examples of the distribution state of atoms (M) belonging to Group V of the periodic table contained in CTL in the layer thickness direction.

In FIGS. 24 to 39, the horizontal axis indicates the contained atoms (
M), the vertical axis shows the layer thickness of CTL, and tB
indicates the position of the end face of the CTL on the support side, and tT indicates the position of the end face of the CTL on the opposite side to the support side.

That is, the CTL containing atoms (M) is formed in layers from the tB side toward the tT side.

FIG. 24 shows a first typical example of the distribution state of atoms (M) contained in the CTL in the layer thickness direction.

In the example shown in FIG. 24, from the interface position tB where the charge injection blocking layer and the CTL contact to the position t16, the distribution concentration C of atoms (M) takes a constant value of C57, and the atoms ( M) is contained in the formed CTL and located at position t
16, the concentration is gradually and continuously decreased from C58 to the interface position tT. At the interface position tT, the distribution concentration C of atoms (M) is set to a value C59.

In the example shown in FIG. 25, the contained atoms (M
) forms a distribution state in which the concentration C gradually and continuously decreases from the concentration C6o from the position to to the position tT, and reaches the concentration C61 at the position tT.

In the case of FIG. 26, from position tB to position tI7, the distribution concentration C of atoms (M) is a constant value of concentration C62,
Between position t17 and position tT, the distribution concentration C is gradually and continuously decreased from C63, and at position tT, the distribution concentration C is substantially zero (here, substantially zero means that the concentration is below the detection limit). (The meaning of ``substantially zero'' hereinafter is also the same.)

In the case of FIG. 27, the distribution concentration C of atoms (M) is at position t
From B to position tT, the concentration is gradually decreased continuously from C64, and becomes substantially zero at position tr.

In the example shown in FIG. 28, the distribution concentration C of atoms (M)
is the concentration C6 between position tB and position t111.
5, which is a constant value, and the density is C66 at position tT. Between the position [, 8 and the position tT, the distribution concentration C is linearly decreased from the position t+a to the position tT.

In the example shown in FIG. 29, from the position to to the position tT, the distribution concentration C of atoms (M) decreases linearly from the concentration C67 to substantially zero.

In the example shown in FIG. 30, the contained atoms (M
) is C6 from position tB to position tT.
C69 gradually decreases continuously from 8 at position tT.
The distribution state is formed as follows.

In the example shown in FIG. 31, the distribution concentration C of atoms (M) takes a constant value C70 from position tB to position t19, and from position t19 to position tT, it is a linear function from C71 to value C72. The distribution state is said to be decreasing.

In the example shown in FIG. 32, the distribution concentration C of atoms (M) gradually and continuously increases from the value C75 to C74 from position 1B to position t2o, and from position t2o, C
It takes a constant value of 73 and forms a distribution state that reaches position tT.

In the example shown in FIG. 33, the distribution concentration C of atoms (M) is from C77 to C7 from position tB to position tT.
A distribution state is formed that gradually and continuously increases up to 6.

In the example shown in FIG. 34, the distribution concentration C of atoms (M) increases gradually and continuously from position to to position t21, from substantially zero to C79, and from position [21 to C78. It takes a constant value and forms a distribution state that reaches position tT.

In the example shown in FIG. 35, the distribution concentration C of atoms (M) forms a distribution state in which it gradually and continuously increases from substantially zero to Cso from position ta to position fatr. .

In the example shown in FIG. 36, the distribution concentration C of atoms (M) is from C82 to C from position tB to position t2□.
increases linearly up to s+, and from position t2□ Cs+
A distribution state is formed in which a constant value of is reached and the position tT is reached.

In the example shown in FIG. 37, the distribution concentration C of atoms (M) forms a distribution state in which it substantially increases linearly from zero to C83 from position tB to position tT.

In the example shown in FIG. 38, the distribution concentration C of atoms (M) is from C85 to C3 from position tB to position tT.
A distribution state is formed that gradually and continuously increases up to A.

In the example shown in FIG. 39, the distribution concentration C of atoms (M) increases linearly from C88 to C87 from position tB to position t23, and from position t23 to C8
It takes a constant value of 6 and forms a distribution state that reaches position tT.

Figures 40 to 49 show carbon atoms and/or nitrogen atoms and/or oxygen atoms (hereinafter collectively abbreviated as "atoms (Y)") contained in the CTL in the layer thickness direction. A typical example of the distribution state is shown.

In FIGS. 40 to 49, the horizontal axis indicates the contained atoms (
Y), the vertical axis shows the layer thickness of CTL, and tB
indicates the position of the end face of the CTL on the support side, and tT indicates the position of the end face of the CTL on the opposite side to the support side.

That is, the CTL containing atoms (Y) is formed in layers from the tB side toward the tT side.

FIG. 40 shows a first typical example of the distribution state of atoms (Y) contained in the CTL in the layer thickness direction.

In the example shown in FIG. 40, from the interface position tB where the charge injection blocking layer and CTL contact to the position t24, the distribution concentration C of atoms (Y) takes a constant value of C89, and the atoms (Y) ) is contained in the formed CTL, at position t 24
The irradiance is gradually and continuously reduced from the concentration C90 to the interface position tT. At the interface position tT, atoms (
The distribution density C of Y) is assumed to be C91.

In the example shown in FIG. 41, the contained atoms (Y
) forms a distribution state in which the concentration C gradually and continuously decreases from the concentration C92 from the position 1itB to the position tT, and reaches the concentration C93 at the position tT.

In the case of FIG. 42, the distribution concentration C of atoms (Y) is kept at a constant value C94 from position tB to position t3, and gradually and continuously decreases from C95 between position t25 and position tT. , taffi[T, the distribution concentration C is substantially zero (here, substantially zero means that it is less than the detection limit amount).

In the case of FIG. 43, the distribution concentration C of atoms (Y) is at position t
From B to position tr, the concentration is gradually decreased continuously from C96, and becomes substantially zero at position gtT.

In the example shown in FIG. 44, the distribution concentration C of atoms (Y)
The concentration is C97 between position 10 and position tze.
is a constant value, and the concentration is C98 at position tT. Between the position ft t 26 and the position tT, the distribution concentration C is linearly decreased from the position t2I to the position tr.

In the example shown in FIG. 45, from position tB to position tT, the distribution concentration C of atoms (Y) decreases in a linear manner so as to reach substantially zero from the concentration C99.

In the example shown in FIG. 46, the contained atoms (Y
) is C+ from position tB to position tT.
It gradually decreases continuously from oo to C+ at position tT.
A distribution state such as o+ is formed.

In the example shown in FIG. 47, the distribution concentration C of atoms (Y) takes a constant value of C102 from position to to position t27, and from position t2□ to position d is a linear function from ClO3 to CIO2. The distribution state is said to be decreasing.

In the example shown in FIG. 48, the distribution concentration C of atoms (Y) takes a constant value of C1o5 from position tB to position tT.

The examples shown in FIGS. 40 to 48 are all t
We have shown an example where the distribution concentration C of atoms (Y) is higher on the tB side than on the T side, but if the tT side and tB side are completely reversed, t
The distribution concentration C of atoms (Y) may be larger on the tT side than on the B side (for example, in the example shown in Fig. 49, when the tT side and tB side are reversed in Fig. 40, the interface position t
Distribution concentration C of atoms (Y) from B to position t2Il
increases gradually and continuously from C+os to C107 at position t28, and reaches position 1. C+o from to interface position tT
It becomes a constant value s.

As the atom (M) belonging to Group Ⅰ of the periodic table, I
Mention may be made of the Group V atoms mentioned in the description of the R absorption layer.

In the present invention, by containing group V atoms as a substance (M) that controls conductivity in the entire layer region of CTL, the effect of controlling the conductivity type and/or conductivity and/or the interaction between CGL and CTL is achieved. Although it is possible to obtain the effect of improving the charge injection property during the period, its content is set to be relatively small. The content of the substance (M) is preferably I X 10-'' to lXl0' atoms p p m, more preferably 5 X 10'' to l X 10'' atoms p
pm.

Optimally, I x 10-'' to 50 atomic ppm is desirable.

Further, the entire layer region of the CTL in the present invention contains carbon atoms and/or oxygen atoms and/or nitrogen atoms, and is mainly used to increase dark resistance, control spectral sensitivity, and improve adhesion between the CGL and CTL. You can measure your improvement. The content of carbon atoms, oxygen atoms, or nitrogen atoms, or if at least two of these atoms are contained, the total content of these atoms is preferably 1 x 1 O'' to 5.
It is desirable that the content be XIO atomic %, more preferably 5XIO2 to 4 x IO atomic %, optimally IXlO-' to 3 x 10 atomic %.

Further, the hydrogen atoms and/or halogen atoms contained in the CTL of the present invention can compensate for the dangling bonds of silicon atoms and improve the layer quality.

The content of hydrogen atoms or halogen atoms, or the sum of hydrogen atoms and halogen atoms, contained in CTL is preferably 1 to 70 at%, more preferably 5 to 50 at%, and optimally 10 to 30 at%. It is preferable to set it as %.

In the present invention, the CTL layer thickness is preferably 5 to 50 μm, more preferably 10 to 40 μm, and most preferably 2 μm from the viewpoint of obtaining desired electrophotographic properties and economical effects.
It is desirable that the thickness be 0 to 30μ.

In the present invention, atoms (Y) can be introduced into the CTL by using them together with the starting materials for forming the CTL, and by controlling the amount of the atoms (Y) in the formed layer.

C by glow discharge method, HRCVD method, FOCVD method
To form a TL, as a starting material for introducing nitrogen atoms, a small amount (most of gaseous substances containing nitrogen atoms or gasified substances that can be gasified) can be used. .

For example, a raw material gas containing silicon atoms (Si), a raw material gas containing nitrogen atoms (N), and hydrogen atoms (H) or halogen atoms (X) as necessary. or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are nitrogen raw materials (N) and hydrogen atoms (H). , also at a desired mixing ratio, or silicon atoms (Si)
A raw material gas whose constituent atoms are silicon atoms (Si),
A raw material gas having three constituent atoms, nitrogen atom (N) and hydrogen atom (I()), can be mixed and used.

In addition, silicon atoms (Si) and hydrogen atoms (11)
You may mix and use the raw material gas which has a nitrogen atom (N) as a constituent atom with the raw material gas which has a nitrogen atom (N) as a constituent atom.

Starting materials that can be effectively used as raw material gases for introducing nitrogen atoms (N) have N as a constituent atom, or N and H as constituent atoms, such as nitrogen (N2
), ammonia (NH3), hydrazine (H2NN
H2), hydrogen azide (HN3), ammonium azide (
Mention may be made of gaseous or gasifiable nitrogen such as NH4N3), nitrogen compounds such as nitrides and azides. In addition to this, nitrogen trifluoride (
F3 N).

Examples include halogenated nitrogen compounds such as nitrogen tetrafluoride (F4 N2).

Glow discharge method, HRCVD method, FOCVD method
In order to form T L, most of the gaseous substances or gasified substances having at least carbon atoms as a constituent atom can be used as the starting material for introducing carbon atoms.

For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing carbon atoms (C) as constituent atoms, and hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms as necessary. or a raw material gas containing silicon atoms (Si) and a raw material gas containing carbon atoms (C) and hydrogen atoms (H). are also mixed at a desired mixing ratio, or a source gas containing silicon atoms (Si) and three atoms, silicon atoms (Si), carbon atoms (C), and hydrogen atoms (H), are mixed. It can be used in combination with a raw material gas as constituent atoms.

Alternatively, a raw material gas having carbon atoms (C) as constituent atoms may be mixed with a raw material gas having silicon atoms (Si) and hydrogen atoms (H) as constituent atoms.

Starting materials that can be effectively used as raw material gases for introducing carbon atoms (C) include C and H as constituent atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, and 2 carbon atoms.
-4 ethylene hydrocarbons, 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-C41(+o), pentane (C5H1
2) As the ethylene hydrocarbon, ethylene (C2H
4).

Propylene (C3H6), butene-1 (C41-18)
.

Butene-2 (C4H8), isobutylene (C4H8).

Pentene (C5H1O), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3
H4), butyne (C4H6), and the like.

As a raw material gas containing Si, C, and H as constituent atoms, S
i (CII3)4. Mention may be made of alkyl silicides such as Si (C2H5)4.

In addition to this, CF4゜CCl4
．． Examples include halogenated carbon gases such as CH3CF3.

Glow discharge method, HRCVD method, FOCVD method
As a starting material for introducing oxygen atoms when forming a TL, most of the gaseous substances containing oxygen atoms or the gasified substances that can be gasified can be used.

For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing oxygen atoms (0) as constituent atoms, and hydrogen atoms (H) or/and halogen atoms (X) as constituent atoms as necessary. or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are oxygen atoms (0) and hydrogen atoms (■1). gas, also at the desired mixing ratio, or silicon atoms (S
i) as a constituent atom and a silicon atom (Si
), an oxygen atom (0), and a hydrogen atom (1-r) as constituent atoms can be mixed and used.

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

Starting materials that can be effectively used as raw material gases for introducing oxygen atoms (0) include, for example, oxygen (0°),
Ozone (03), -nitric oxide (No).

Nitrogen dioxide (NO2), -nitrogen dioxide (N20).

Nitrogen sesquioxide (N203), trinitrogen tetraoxide (N204)
).

Nitrogen sesquioxide (N20S), nitrogen trioxide (NO2),
Silicon atom (S i), oxygen atom (0) and hydrogen atom (
For example, disiloxane (summer (3S r OS iH3) * F disiloxane (
Examples include lower siloxanes such as H3SiO5iH20SiH3).

To form CTL by sputtering method, CT
During L formation, single crystal or polycrystalline Si wafer or Si3N4 wafer, or Si and Si3N4
A wafer containing a mixture of SiO2 and/or a SiO2 wafer, a wafer containing a mixture of Si and SiO2 and/or a SiC wafer, or a wafer containing a mixture of Si and SiC. Sputtering may be performed using these as targets in various gas atmospheres.

For example, if a Si wafer is used as a target to contain nitrogen atoms, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms or/and halogen atoms may be diluted with a diluent gas as necessary. These gases may be introduced into a deposition chamber for sputtering to form a gas plasma of these gases to sputter the Si wafer.

Alternatively, by using Si and Si3N4 as separate targets or a single mixed target of Si and Si3N4, in an atmosphere of diluent gas as a sputtering gas or at least hydrogen atoms. This is accomplished by sputtering in a gas atmosphere containing (H) or/and halogen atoms (X) as constituent atoms.

As the raw material gas for introducing nitrogen atoms, carbon atoms, and oxygen atoms, the raw material gas for introducing nitrogen atoms, carbon atoms, and oxygen atoms in the raw material gas shown in the example of the glow discharge method mentioned above can also be used when sputtering is used. Can be used as an effective gas.

In the present invention, when forming a CTL, the distribution concentration c (y) of atoms (Y) contained in the layer is changed in the layer thickness direction to obtain a desired distribution state in the layer thickness direction (depthpro
Glow discharge method, H
RCVD method, FDCVD method (7) In the case of i: It, the gas of the starting material for introducing atoms (Y) whose distribution concentration c (y) is to be changed is suitably adjusted at the gas flow rate according to the desired rate of change curve. This is accomplished by introducing the substance into the deposition chamber while changing it.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be appropriately changed by any commonly used method such as manually or using an externally driven motor.

When forming by the sputtering method, the desired distribution state (depth) of atoms (Y) in the layer thickness direction is achieved by changing the distribution concentration c (y) of atoms (Y) in the layer thickness direction.
First, as in the glow discharge method, the starting material for introducing atoms (Y) is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is adjusted. This can be done by appropriately changing it as desired.

Second, the target for sputtering is, for example, S
If a target containing a mixture of i and Si 3 N 4 is used, this can be done by changing the mixing ratio of Si and Si 3 N 4 in advance in the layer thickness direction of the target.

When using SiC or SiO2, the same steps as for Si 3 N 4 may be used.

In order to structurally introduce group V atoms as a substance that controls conductivity into CTL, it is necessary to form a CTL in a deposition chamber using a starting material for introducing group V atoms in a gaseous state during layer formation. It may be introduced together with other starting materials. As a starting material for such introduction of Group V atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for such introduction of Group V atoms include:
For phosphorus atom introduction, hydrogen north neighbors such as PH3, P2H4, PH41, PF3. PF5. PCl3. PCl5. P
Examples include halogens adjacent to the north such as Br3゜PBr3 and PI3. In addition, AsH3, AsF3, As
Cj'3, AsBr3.

AsF6. SbH3, SbF3. SbF6,5bCj7
3゜5bCj' 5, BiI3, BiCj!
3, B1Br3, etc. can also be mentioned.

A CGL having characteristics that can achieve the object of the present invention.

A-3i containing a hydrogen atom or/and a halogen atom (hereinafter referred to as
In order to select and construct rA-3i (referred to as (H,X)J), it is necessary to appropriately set the temperature and gas pressure of the support as desired.

The support temperature (Ts) is appropriately selected in an optimal range according to the layer design, but it is usually 50°C to 400°C, preferably 100 to 300°C.

Similarly, the optimum range for the gas pressure in the deposition chamber is selected according to the layer design, but in normal cases I
0Torr1 preferably l x 101~3Torr,
Optimally, it is desirable to set l x 10-2 to 1 Torr.

In the present invention, the above-mentioned ranges are mentioned as preferable numerical ranges for the support temperature and gas pressure for creating each of the layers, but these layer creation factors are usually not determined independently and separately. (In order to form each layer with desired properties, it is desirable to determine the optimal value of each layer creation factor based on mutual and organic relationships.

Polycrystalline silicon containing hydrogen atoms and/or halogen atoms (rpoly-3i (H,X) J
It is called. ), there are various methods for forming the layer, including the following methods.

One method is to increase the support temperature to a high temperature, specifically 40°C.
In this method, the temperature is set at 0 to 600° C., and a film is deposited on the support by plasma CVD.

Another method is to first form an amorphous film on the surface of a support, that is, to form a film on the support at a temperature of about 250° C. by plasma CVD, and then annealing the amorphous film. By doing pol
This is a method of converting it into y. The annealing treatment is performed by heating the support to 400 to 600° C. for about 5 to 30 minutes, or by irradiating it with laser light for about 5 to 30 minutes.

Next, a method for manufacturing the electrophotographic light-receiving member of the present invention, which is formed by a high frequency (hereinafter abbreviated as RF) glow discharge decomposition method, will be described.

FIG. 50 shows an apparatus for manufacturing an electrophotographic light-receiving member using the RF glow discharge decomposition method.

1011 in the diagram. 1012. 1013. 1014
．． Gas cylinders 1015, 1016, and 1017 are sealed with raw material gases for forming the respective layers of the present invention.
II 4 gas (99.999% purity) cylinder, 1012
For lI2 gas (99.999% purity) cylinder, 101
3 contains PH3 gas diluted with lI2 gas (purity 99.
999%, hereinafter abbreviated as rPII3/H□) cylinder, 1
014 is No gas (99.5% purity) cylinder, 1015
is GeH4 gas (99.999% purity) cylinder, 101
6 is NH3 gas (purity 99.999%) cylinder, 101
7 is a CH4 gas (purity 99,999%) cylinder.

A method for producing an electrophotographic light-receiving member having the layer structure of the present invention on a base cylinder will be described based on a specific example.

That is, S i H4 gas, PH3/H2 gas, No gas, GeH4 gas was used as the gas for forming the IR absorption layer, and SiH4 gas was used as the gas for forming the charge injection blocking layer.

112 gas, PH3/H2 gas, No gas as the CTL forming gas; Si) I4 gas, C114 gas,
PH3/I (2 gases, SiH as CGL forming gas)
4 gas.

(Let's take the case where two gases are used.

In order to flow these gases into the reaction chamber 1001, valves 1051-1057 of gas cylinders 1011-1017,
Confirm that the leak valve 1003 of the reaction chamber 1011 is closed, and also check the inflow valves 1031 to 1037,
After confirming that the outflow valves 1041-1047 and the auxiliary valve 1070 are open, first open the main valve 1002.
is opened to exhaust the reaction chamber 1001 and gas piping.

Next, when the reading of the vacuum gauge 1004 becomes approximately 5X10-' Torr, the auxiliary valve 1070 and the outflow valve 1041
~Close 1047.

After that, 5il14 gas from gas cylinder 1011, H2 gas from gas cylinder 1012, PH3/H2 gas from gas cylinder 1013, No gas from gas cylinder 1014,
GeH4 gas from Kasu cylinder 1015, gas cylinder 10
NH3 gas from 16, C) I4 from gas cylinder 1017
Gas is introduced by opening valves 1051 to 1057, and the pressure of each gas is adjusted to 2 kg by pressure regulators 1061 to 1067.
/crrr.

Next, the inflow valves 1031-1037 are gradually opened to supply each of the above gases to the mass flow controllers 1021-1021.
It will be introduced within 27 days.

In addition, the base cylinder 1 installed in the reaction chamber 1001
The temperature of 007 is set to 50 to 35 by heating heater 1008.
Heat to desired temperature between 0°C.

After the preparation for film formation is completed as described above, an IR absorbing layer, a charge injection blocking layer, a CTL
, each layer of CGL is formed.

Outflow valve 1041.104 to form the IR absorption layer
3. Gradually open the 1044, 1045 and auxiliary valves 1070 to release S i H4 gas, P H3/H2
Gas, no gas.

Ge■■4 gas is allowed to flow into the reaction chamber 1001. At this time, 5iFI4 gas flow rate, PH3/H2 gas flow rate, N
.

Gas flow ff1. The outflow valve 1041. so that the GeH4 gas flow rate is at the desired value. 1043. 1044. 1
045 and the main valve 1002 while watching the vacuum gauge 1004 so that the pressure in the reaction chamber reaches the desired value.
Adjust the aperture. Thereafter, the power source 1010 is set to a desired power level to generate an RF glow discharge in the reaction chamber 1001, thereby starting to form an IR absorbing layer on the base cylinder.

After the desired film thickness has been formed, the RF glow discharge is stopped and the outflow valve 1041. 1043°1044.
1045 to stop the gas from flowing into the reaction chamber, and the IR
Finish forming the absorbent layer.

A charge injection blocking layer is formed on the IR absorption layer formed as described above.

To form the charge injection blocking layer, the outflow valve 1041.
1042, 1043.1044 and auxiliary valve 107
Gradually open 0 and add SiH4 gas + H2 gas.

PI(3/H2 gas and No gas are caused to flow into the reaction chamber 1001. At this time, the SiH4 gas flow filH
2 gas flow rate.

Outflow valves 1041, 1042, 1043 so that the PH3/Hz gas flow fi, No gas flow rate becomes the desired value.
1044, and while watching the vacuum gauge 1004, turn the main valve 10 so that the pressure inside the reaction chamber reaches the desired value.
Adjust the opening of 02. Thereafter, the power source 1010 is set to a desired power level to generate an RF glow discharge in the reaction chamber 1001 to begin forming a charge injection blocking layer on the base cylinder. After the desired film thickness has been formed, the RF glow discharge is stopped and the outflow valves 1041, 1042, 10
43.1044 is closed to stop the flow of gas into the reaction chamber, and the formation of the charge injection blocking layer is completed.

CTL on the charge injection blocking layer formed as described above.
form.

To form the CTL, the outflow valve 1041. 1043
1047 and the auxiliary valve 1070 gradually open,
SiH4 gas, PH3/H2 gas, and CH4 gas are introduced into the reaction chamber 1001. At this time, SiH4 gas flow fl
Outflow valve 1041. L PH3/H2 gas flow i, CH4 gas flow ah<desired value. 1043゜1
047, and while watching the vacuum gauge 1004, turn the main valve 100 so that the pressure inside the reaction chamber reaches the desired value.
Adjust the opening of 2. Thereafter, the power source 101O is set to a desired power to generate an RF glow discharge in the reaction chamber and begin forming CTLs on the base cylinder. After the desired film thickness has been formed, the RF glow discharge is stopped and the outflow valve 1041. 1043° and 1047 are closed to stop the gas from flowing into the reaction chamber, and the CTL formation is completed.

A CGL is formed on the CTL formed as described above.

To form a CGL on the CTL, an outflow valve 10
41.1042 and the auxiliary valve 1070 are gradually opened to allow SiH4 gas and H2 gas to flow into the reaction chamber 1001. At this time, the outflow valves 1041 and 104 are adjusted so that the SiH4 gas flow rate and H2 gas flow rate become the desired values.
2 and the opening of the main valve 1002 while watching the vacuum gauge 1004 so that the pressure in the reaction chamber reaches the desired value. Thereafter, the power supply 1oto is set to a desired power to generate an RF glow discharge in the reaction chamber, and the formation of CGI on the base cylinder is started. After the desired film thickness has been formed, an RF glow discharge is applied to the IE and an outflow valve 1041. 1042 is closed to stop the flow of gas into the reaction chamber, and the formation of CGL is completed.

Needless to say, when forming each layer, all outflow valves except for necessary gases are closed, and each gas is in the reaction chamber 1001 and outflow valves 1041-104.
In order to avoid remaining in the piping from 7 to the reaction chamber 1001, the outflow valves 1041 to 1047 are closed, the auxiliary valve 1070 is opened, and the main valve 1002 is fully opened to temporarily evacuate the system to a high vacuum. Perform operations as necessary.

Further, during layer formation, the base cylinder 1007 is rotated at a desired speed by a motor 1009 in order to ensure uniform layer formation.

Needless to say, the above-mentioned gas types and valve operations may be changed according to the conditions for forming each layer.

Next, a method for manufacturing an electrophotographic light-receiving member formed by a microwave (hereinafter abbreviated as μW) glow discharge decomposition method will be described.

FIG. 51 shows an apparatus for manufacturing a light receiving member for electrophotography using the μW glow discharge decomposition method.

2011 in the figure.・2012.2013.2014.2
The raw material gas for forming each layer of the present invention is sealed in the gas cylinders of 2015, 2016, and 2017. For example, in 2011, a SiH4 gas (purity 99.999%) cylinder was used, and in 2012, a SiH4 gas (purity 99.999%) cylinder was used. is a H2 gas (purity 99°999%) cylinder, and in 2013 is a PII3 gas diluted with H2 gas (purity 99.999%, hereinafter referred to as 1').
-PH3/H2J) cylinder, 2014 is No gas (purity 99.5%) cylinder, 2015 is GeH4 gas (abbreviated as
purity 99.999%) cylinder, 2016 is NH3 gas (
purity 99,999%) cylinder, 2017 is CH4 gas (
(purity 99.999%) cylinder.

As an example of forming an electrophotographic light-receiving member using the apparatus shown in FIG. 51, Si
I-14 gas, PH3/H, gas, No gas.

GeH4 gas was used as a charge injection blocking layer forming gas, and S
i H4 gas, H2 gas, PH3/H2 gas, No gas as CTL forming gas, S i H4 gas,
A case will be discussed in which CH4 gas and P113/H2 gas are used as CGL forming gases, and S i H4 gas and H2 gas are used as CGL forming gases.

In order to flow these gases into the reaction chamber 2001, valves 2051 to 2057 of gas cylinders 2011 to 2017,
Confirm that the leak valve 2003 of the reaction chamber 2011 is closed, and confirm that the inflow valves 2031 to 2037, the outflow valves 2041 to 2047, and the auxiliary valve 2070 are open, and first open the main valve 2002. The reaction chamber 2001 and gas piping are evacuated.

Next, when the vacuum gauge 2004 reads approximately 5810-'Torr, the auxiliary valve 2070. Outflow valve 2041
~Close 2046.

After that, SiH4 gas from gas cylinder 2011, H2 gas from gas cylinder 2012, and P from gas cylinder 2013.
H3/[■2 gas, No gas from gas cylinder 2014,
G e H4 gas from gas cylinder 2015, NH3 gas from gas cylinder 2016, CH from gas cylinder 2017
4 gases were introduced by opening the valves 2051 to 2057, and the pressure of each gas was adjusted to 2 K using the pressure regulators 2061 to 2067.
g/crd.

Next, gradually open the inflow valves 2031 to 2037 to supply each of the above gases to the mass flow controllers 2021 to 2020.
It will be introduced within 27 days.

In addition, the base cylinder 2 installed in the reaction chamber 2001
The temperature of 006 is set to 50 to 35 by heating heater 2005.
Heat to desired temperature between 0°C.

After the preparation for film formation is completed as described above, an IR absorbing layer, a charge injection blocking layer, a CTL
, each layer of CGL is formed.

To form the IR absorption layer, the outflow valve 2041°20
43.2044.2045 and the auxiliary valve 2070 to gradually open SiH4 gas, P113/H2 gas, No.
A gas, GeH4 gas, is caused to flow into the reaction chamber 2001.

At this time, S i H4 gas flow rate, PH3/H2 gas flow rate, N.

Adjust the outflow valves 2041.2043.2044.2045 so that the flow rate of the residue and GeH4 gas reach the desired values, and adjust the main valve 2002 while watching the vacuum gauge 2004 so that the pressure inside the reaction chamber reaches the desired value. Adjust the aperture. Thereafter, the microwave power source 2008 is set to a desired power, a μW glow discharge is generated in the reaction chamber through the waveguide 2009 and the dielectric window 201O, and the formation of an IR absorption layer on the base cylinder is started. After the desired film thickness is formed, the μW glow discharge is stopped, and the outflow valves 2041, 2043, 2044, and 2045 are closed to stop the gas from flowing into the reaction chamber, thereby completing the formation of the IR absorption layer.

A charge injection blocking layer is formed on the IR absorption layer formed as described above.

to form a charge injection blocking layer, an outflow valve 204];
2042, 2043.2044 and auxiliary valve 207
Gradually open 0 and add Si H4 gas + H2 gas.

PI (3/H. gas, No gas is flowed into the reaction chamber 2001. At this time, SiH4 gas flow rate, ) I2 gas flow rate.

P I3/H2 gas flow fi, No outflow valve 2041.2042.2043 so that the gas flow rate is at the desired value.
．． 2044, and while watching the vacuum gauge 2004, turn the main valve 2 so that the pressure inside the reaction chamber reaches the desired value.
Adjust the aperture of 002. After that, microwave power supply 20
08 to a desired power, a μW glow discharge is generated in the reaction chamber 2001 through the waveguide 2009 and the dielectric window 201O, and the formation of a charge injection blocking layer on the base cylinder is started. After the desired film thickness is formed, the μW glow discharge is stopped, and the outflow valve 2041. 204
2. 2043 and 2044 are closed to stop the gas from flowing into the reaction chamber 2001, and the formation of the charge injection blocking layer is completed.

CTL on the charge injection blocking layer formed as described above.
form.

To form the CTL, the outflow valve 2041.2043
Gradually open ゜2047 and auxiliary valve 2070,
SiH4 gas, PH3/H2 gas, and CH4 gas are introduced into the reaction chamber 2001. At this time, S i I-I 4
gas flow rate.

PI-13/H2 gas flow fi, CH4 gas flow rate to desired value, outflow valve 2041.2043.20
47, and while watching the vacuum gauge 2004, turn the main valve 200 so that the pressure inside the reaction chamber reaches the desired value.
Adjust the opening of 2. After that, microwave power supply 2008
, is set to the desired power and a μW glow discharge is generated in the reaction chamber through the waveguide 2009 and the dielectric window 201O to initiate the formation of CTLs on the substrate cylinder. After the desired film thickness is formed, the μW glow discharge is stopped, the outflow valves 2041, 2043, and 2047 are closed to stop the gas from flowing into the reaction chamber, and the CTL formation is completed.

A CGL is formed on the CTL formed as described above.

To form a CGL on the CTL, an outflow valve 204
1, 2042 and the auxiliary valve 2070 are gradually opened to allow SiH4 gas + H2 gas to flow into the reaction chamber 2001. At this time, the SiH4 gas flow rate,
2, and the opening of the main valve 2002 while watching the vacuum gauge 2004 so that the pressure inside the reaction chamber reaches the desired value. After that, the microwave power source 2008 is set to the desired power, and the waveguide 2009 and dielectric window 201 are
A μW glow discharge is generated in the reaction chamber through O to initiate the formation of CGL on the substrate cylinder. After the desired film thickness is formed, the μW glow discharge is stopped and the outflow valve 2 is closed.
041. 2042 is closed to stop the flow of gas into the reaction chamber, and the formation of CGL is completed.

Needless to say, all the outflow valves for gases other than those required for forming each layer are closed, and each gas is in the reaction chamber 2001 and the outflow valves 2041 to 204.
In order to avoid remaining in the piping from 7 to the reaction chamber 2001, the outflow valves 2041 to 2047 are closed, the auxiliary valve 2070 is opened, and the main valve 2002 is fully opened to temporarily evacuate the system to a high vacuum. Perform as necessary.

Further, during layer formation, the base cylinder 2006 is rotated at a desired speed by a motor 2007 in order to ensure uniform layer formation.

Needless to say, the above-mentioned gas types and valve operations may be changed according to the conditions for forming each layer.

Next, a method for manufacturing an electrophotographic light-receiving member formed by the II RCV D method will be described.

FIG. 52 shows an apparatus for manufacturing an electrophotographic light-receiving member using the HRCV D method.

In FIG. 52, 3001 is a film forming chamber, 3002 is an activation chamber (A), 3003, 3018 is a microwave plasma generator, 3004 is a raw material gas introduction tube for active species (A),
3005 is an active species (A) introduction tube, 3006 is a motor,
3007 is a heater that heats a cylindrical base;
008.3009 is a blowout pipe, 3010 is a cylindrical base, and 3011 is a main exhaust valve.

Further, 3012 to 3016 are cylinders for supplying raw material gas, 3017 is an activation chamber (B), 3019 is a raw material gas introduction pipe, and 3020 is an active species introduction pipe generated from the activation chamber (B). A method for producing an electrophotographic light-receiving member having a layer structure according to the present invention on a cylindrical substrate using this apparatus will be specifically described.

- For example, A1 is used as the cylindrical substrate, and SiH4, G
eH4, PH3/H2, No, H2, and SiH4, PI (3/H2) as charge injection blocking layer forming gas.

NO, H2, and SiH4 as CTL forming gas.

SiF4, CH4, H2, P H3/H2, C
SiH4 and H2 were used as the GL forming gas.

First, an Af cylindrical substrate 3010 is suspended in a film forming chamber 3001, and a heating heater 3007 is provided inside it so that it can be rotated by a motor 3006.
It was evacuated to lO-'Torr.

To form the IR absorption layer, l■2 from the cylinder 3012
Guide the gas into the activation chamber (A) through the introduction pipe 3004,
Activation treatment was performed using a microwave plasma generator 3003, and active hydrogen was introduced into the film forming chamber 3001 through an inlet pipe 3005 and a blowout pipe 3008. On the other hand, cylinder 3
5it (4 gas from 013, PH3/H2 from 3014)
Gases, No gas from 3015, CH4 gas from 3016, GeH4 gas, and SiF4 gas from unillustrated cylinders are introduced into the activation chamber (B) 3017 from the introduction pipe 3019,
After being activated by a microwave plasma generator 3018, it was introduced into a film forming chamber 3001 through an introduction pipe 3020 and a blowoff pipe 3009. At this time, the gas flow rate, internal pressure,
and the microwave power is set to the desired value.

The A1 cylindrical substrate 3010 was heated and maintained at a desired temperature by a heater 3007, and the exhaust gas was exhausted by appropriately adjusting the opening of the main exhaust valve 3011. In this way, an IR absorption layer was formed.

Similarly, on the IR absorption layer, H
2 gas, SiH4 gas from 3013, PH from 3014
3/H2 gas and No gas were supplied from 3015 to form a charge injection blocking layer.

To form a CTL on the charge injection blocking layer, H2 gas is introduced from the cylinder 3012 through the introduction pipe 3004 into the activation chamber (A), and the microwave plasma generator 3003
Activation treatment was carried out by , and active hydrogen was introduced into the film forming chamber 3001 through the introduction pipe 3005 and the blowoff pipe 3008 .

On the other hand, S i H4 gas from cylinder 3013, cylinder 3
PH3/H2 gas from 014, CH from cylinder 3016
4 gases are introduced into the activation chamber (B) 3017 through the introduction pipe 3019 and activated by the microwave plasma generator 3018, and then passed through the introduction pipe 3020 into the blowout pipe 3.
009 to the film forming chamber 3001. At this time, the gas flow rate, internal pressure, and microwave power are set to desired values.

The kl cylindrical substrate 3010 was heated and maintained at a desired temperature by a heater 3007, and the exhaust gas was exhausted by appropriately adjusting the opening of the main exhaust valve 3011. CTLs were formed in this way. Similarly, on top of the above CTL, H2 gas from cylinder 3012 and Si from 3013
CGL was sequentially formed by supplying H4 gas and SiF4 gas from a cylinder (not shown) to form a light-receiving member for electrophotography.

Next, a method for manufacturing an electrophotographic light-receiving member formed by the FOCVD method will be described.

FIG. 53 shows a method of manufacturing a light receiving member for electrophotography using the FOCVD method.

4011.4012.4013.4014.40 in the diagram
15° 4016 and 4017 are sealed with raw material gases for forming the respective layers of the present invention. For example, 4011 is a SiH4 gas (purity 99.999%) cylinder, 4012 is 4013 is a H2 gas (purity 99.999%) cylinder, and 4013 is a PH3 gas diluted with H2 (purity 99.999%, hereinafter referred to as PH3/H2
J) cylinder, 4014 is No gas (purity 99.5
%) cylinder, 4015 is GeH4 gas (purity 99,99
9%) cylinder, 4016 is CH4 gas (purity 99.99
9%) cylinder, 4017 is F2 gas (10% He diluted,
Purity: 99.99%).

5jl-14 gas, PH3 as IR absorption layer forming gas
/H2 gas, No gas, GeH4 gas, F2 gas, and SiH4 gas as charge injection blocking layer forming gas.

H2 gas, PH3/H2 gas, No gas, F2, CT
The gas for L formation is SiH4 gas and CH4 gas.

PH3/H2 gas A case will be discussed in which p2 gas is used as CGL forming gas, and S i H4 gas, H□ gas, and F2 gas are used.

The raw material gases filled in the cylinders 4011 to 4016 are supplied to the respective valves 4031 to 4036 and 4053 to 4.
It passes through the mask row controller 058 and is introduced into the vacuum chamber 4020 to 4001.

The F2 gas filled in the cylinder 4017 is introduced into the vacuum chamber 4001 through 4021 in the same manner as described above.

The vacuum chamber 4001 is evacuated via a main vacuum valve 4002 by a vacuum evacuation device (not shown).

4061 heats the base cylinder 4060 to an appropriate temperature during film formation, or heats the base cylinder 4060 before film formation.
This is a heater for heating the substrate for preheating the film 60 or for annealing the film after film formation.

Electric power is supplied to the substrate heater from a power source (not shown) via a conductive wire (not shown).

Further, the base cylinder 4060 is rotated by a rotation mechanism 4062 in order to form a uniform film.

To introduce gases 4011 to 4017 into 4001,
When the inside of the chamber of 4001 reaches approximately 5×10 Torr, it is necessary to slowly introduce it by operating various valves.

Further, the temperature of the base cylinder 4060 installed in the chamber 4001 is controlled by the heater 4061 to 50°C.
What is necessary is just to heat to the desired temperature between -350 degreeC.

After the preparation for film formation is completed as described above, an IR absorption layer, a charge injection blocking layer; a CTL,
Film formation is performed in the order of CGL.

To form an IR absorption layer, use valves 4046.4048~
Open 4050 and outflow valve 4031.4033.40
34° 4035 and the auxiliary valve 4060 gradually open S i H4 gas, PH3/H2 gas, No gas,
G e H4 gas is allowed to flow into the reaction chamber 4001 . At this time, the outflow valve 4031.4033.403 is adjusted so that the S i H4 gas flow rate, PH3/H2 gas flow rate, No gas flowff1l GeH4 gas flow rate becomes the desired value.
4. Adjust main valve 4002 while watching the vacuum gauge (not shown) until the pressure inside the reaction chamber reaches the desired value.
Adjust the aperture.

Next, open valve 4052, and while watching the mass flow meter 4059, gradually open the valve 4037 until the desired flow rate is reached.After the flow rate has been set and the fR absorption layer has been formed to the desired thickness, The formation of the IR absorption layer is completed.

A charge injection blocking layer is formed on the IR absorbing layer created as described above by the same operation as above. For each layer, the necessary gas is flowed, and the IR
Just operate the valve in the same way as for the absorption layer.

To form a CTL on the charge injection blocking layer, open the valves 4046.4048.4051.4052, gradually open the outflow valves 4031, 4033, 4036.4037 and the auxiliary valve 4060 to inject S i H4 gas, P
H3/[I2 gas, CH4 gas, F2 gas is supplied to the reaction chamber 40.
01. At this time, each outflow valve is adjusted so that the respective gas flow rates reach the desired values, and the opening of the main valve 4002 is adjusted while watching the vacuum gauge (not shown) until the pressure inside the reaction chamber reaches the desired value. .

Once the flow rate has been set and time has elapsed to form the CTL to a desired thickness, the CTL formation is completed.

A CGL is formed on the CTL created as described above by the same operation as above. For each layer, the necessary gases may be flowed and the valves may be operated in the same manner as in the CTL.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

<Example I> Using the manufacturing apparatus shown in Fig. 50, the first
An electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the preparation conditions shown in Tables 2, 3, and 4.

The produced electrophotographic light-receiving member was set in an electrophotographic device using a halogen lamp as a light source and an electrophotographic device using a semiconductor laser having a wavelength of 780 nm as a light source, and subjected to initial charging under various conditions. Check the electrophotographic characteristics such as performance, sensitivity, residual potential, ghost, etc.
Decrease in charging ability after accelerated endurance running test equivalent to 00,000 sheets 1
Surface scraped.

We investigated the increase in image defects.

In addition, the dielectric strength was investigated by applying a DC high voltage to the drum. Furthermore, scratch resistance was examined by applying a constant load to a needle with a spherical tip and scratching the drum surface. The above comprehensive evaluation results are shown in Table 5.

As shown in Table 5, good results were obtained for all items. In particular, remarkable superiority was recognized in terms of initial charging ability and durability.

<Example 2> Using the manufacturing apparatus shown in FIG.
Drums were produced in the same manner as in Example I under the production conditions shown in Tables 2, 6, and 7, and the same evaluations were performed.

The results are shown in Table 8.

As shown in Table 8, good results were obtained for all items.

<Example 3> Using the manufacturing apparatus shown in FIG.
Example 1 under the preparation conditions shown in Tables 2, 9, and 10.
A drum was made in the same manner as above, and the same evaluation was conducted.

The results are shown in Table 11.

As seen in Table 11, good results were obtained for all items.

<Example 4> Using the manufacturing apparatus shown in FIG.
Drums were produced in the same manner as in Example 1 under the production conditions shown in Tables 2, 12, and 13, and the same evaluations were performed.

The results are shown in Table 14.

As seen in Table 14, good results were obtained for all items.

<Example 5> Using the manufacturing apparatus shown in FIG.
Drums were produced in the same manner as in Example 1 under the production conditions shown in Tables 2, 15, and 16, and the same evaluations were performed.

The results are shown in Table 17.

As seen in Table 17, good results were obtained for all items.

<Example 6> Using the manufacturing apparatus shown in FIG.
Drums were produced in the same manner as in Example 1 under the production conditions shown in Tables 2, 18, and 19, and the same evaluations were performed.

The results are shown in Table 20.

As seen in Table 20, good results were obtained for all items.

<Example 7> Using the manufacturing apparatus shown in FIG.
Drums were produced in the same manner as in Example 1 under the production conditions shown in Tables 2, 21, and 22, and the same evaluations were performed.

The results are shown in Table 23.

As seen in Table 23, good results were obtained for all items.

<Example 8> Using the manufacturing apparatus shown in Fig. 51, electrophotography was performed on an aluminum cylinder that was mirror-finished using the microwave CVD method according to the preparation conditions shown in Tables 24, 25, 26, and 27. A light receiving member for use was formed.

The produced electrophotographic light-receiving member was set in an electrophotographic device using a halogen lamp as a light source and an electrophotographic device using a semiconductor laser having a wavelength of 780 nm as a light source, and subjected to initial charging under various conditions. Noh 9. Check the electrophotographic characteristics such as sensitivity, residual potential, ghost, etc.
Charging ability decreased after accelerated durability running test equivalent to 1,000,000 sheets.1 Surface scraping.

We investigated the increase in image defects.

In addition, the dielectric strength was investigated by applying a DC high voltage to the drum. Furthermore, scratch resistance was examined by applying a constant load to a needle with a spherical tip and scratching the drum surface. The above comprehensive evaluation results are shown in Table 28.

As seen in Table 28, good results were obtained for all items. In particular, remarkable superiority was recognized in terms of initial charging ability and durability.

<Example 9> Using the manufacturing apparatus shown in FIG. 52, an electrophotographic light-receiving member was formed on an aluminum cylinder which had been mirror-finished by the HRCVD method according to the preparation conditions shown in Tables 29 to 32. The produced electrophotographic light-receiving member was set in an electrophotographic device using a halogen lamp as a light source and a semiconductor laser having a wavelength of 780 nm as a light source, and the initial chargeability was measured under various conditions. The electrophotographic characteristics such as sensitivity, residual potential, and ghost were checked, and the decrease in charging ability, surface scraping, and increase in image defects after an accelerated durability running test equivalent to 2 million sheets were also investigated.

In addition, the dielectric strength was investigated by applying a DC high voltage to the drum. Furthermore, the scratch resistance was examined by applying a constant load to a needle with a spherical tip and scratching the drum surface. The above comprehensive evaluation results are shown in Table 33.

As seen in Table 33, good results were obtained for all items. In particular, remarkable superiority was recognized in terms of initial charging ability and durability.

<Example 10> Using the manufacturing apparatus shown in FIG. 53, the 34th
An electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the preparation conditions shown in Tables 37 to 37.

The prepared electrophotographic light-receiving member was set in an electrophotographic device using a halogen lamp as a light source and a semiconductor laser having a wavelength of 780 nm as a light source, and the initial chargeability, The electrophotographic characteristics such as sensitivity, residual potential, and ghost were checked, and also the decrease in charging ability, 9 surface scraping, 9 increase in image defects, etc. after accelerated durability equivalent to 2 million sheets were investigated.

In addition, the dielectric strength was investigated by applying a DC high voltage to the drum. Furthermore, scratch resistance was examined by applying a constant load to a needle with a spherical tip and scratching the drum surface. The above comprehensive evaluation results are shown in Table 38.

As shown in Table 38, good results were obtained for all items. In particular, remarkable superiority was recognized in terms of initial charging ability and durability.

<Example 11> The mirror-finished cylinders were further subjected to lathe processing using a sword bit with various angles to produce cylinders with cross-sectional shapes as shown in Figure 58 and various cross-sectional patterns as shown in Table 40. I prepared several books. The 50th cylinder
It was set in the manufacturing apparatus shown in the figure and subjected to drum manufacturing under the manufacturing conditions shown in Table 39. The produced drums were subjected to various evaluations using an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 41 were obtained.

<Example 12> The surface of the mirror-finished cylinder was subsequently exposed to the dropping of many bearing applications, and a so-called surface dimple treatment was performed to produce countless dents on the cylinder surface, as shown in Fig. 59. A plurality of cylinders having a cross-sectional shape as shown in Table 43 and various cross-sectional patterns as shown in Table 43 were prepared. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 50 and subjected to drum manufacturing under the manufacturing conditions shown in Table 42. The prepared drums were subjected to various evaluations using an electrophotographic device using a halogen lamp as a light source and 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 44 were obtained.

<Example 13> Tables 44 and 45 using the manufacturing apparatus shown in FIG.

Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables 46 and 47, and the same evaluations were conducted.

The results are shown in Table 48.

As shown in Table 48, all items are good Table 1 CGL film formation conditions Table 2 CTL film formation conditions Table 3 Table 4 Table 5 Continuation of Table 5 ◎: 1 ○: Good △・Not a practical problem ◎ New to rainbow disorders O: Good △: Can't hold onto practical nails X: Practical 1: j5iI
Yes, continuation of Table 8 ◎ Niji-tai ○: Good △:: Not very useful ×: Practical g, jjW
1st Table 9th Table 10th Table 11 Continuation of Table 11 ◎: l Incredibly good ○: Good ∆: No practical problem ×: Continuation of Table 11 ◎" Very good ○ : Good △ : Not a problem in practical use Good for No. 1 O: Good △: No problem ×: Practically problematic Table 15 Table 16 Table 17 Continuation of Table 17 ◎ Good for 2 No. 4 ○: Good △: No problem for practical use × : Practical + 3'li - Continuation of Table 17 ◎ New to rainbow O: Good △: Not a problem for practical purposes X: Practical j, J','
ll Yes Table 18 Table 19 Table 20 Table Continuation of Table 20 ◎: In the I ball ○: Good Δ: Not a problem for practical use ×: Practical + s'rns
Continuation of Table 20 ◎ Rice cake on the verge of rainbow ○: Good △: Not suitable for practical use X: Practical 1. Ji,'
With D Table 21 Table 22 Table 23 Continuation of Table 23 ◎: IF! Part of 1g ○: Good Δ: Actual size is acceptable Table 24 Table 25 Table 26 CGL film forming conditions Table 27 CTL film forming conditions Table 28 Continuation of Table 28 ◎, Immediately ○: Good △, practically no problem × Practically problematic Continuation of Table 28 ◎・lIt is poor O: Good △: Cannot be used in practical use ×: Practical 1ヰ■ With suspension Table 29 Table 30 Table 32 CGL film formation conditions Table 33 Continuation of Table 33 @ Good for rainbow squads O: Good △: Not a problem in practical terms
@Yes Table 34 Table 35 Table 36 CGL film forming conditions Table 37 CTL film forming conditions Table 38 Table 38 continued ◎: Approximately 1 ○: Good Δ: Not a problem for practical use X: Practical 1 $”jlM
Yes Continuation of Table 38 ◎: J Sui group 0: Good △: Not practical ×: Practical problem Table 39 Table 40 Table 41 Table ◎□ Very good ○□ Good Δ□ Cannot be used for practical purposes Table 46 Table 47 CGL film formation conditions Table 48 CTL film formation conditions Table 49 Continuation of Table 49 ◎: I ■ O: Good Δ: No problem if the actual month ×: Practically L% dust Continuation of Table 49 ◎ Always good O: Good △: Poor in practical use ×: 41 wins in practical fishing books [Summary of the effects of the invention] The electrophotographic light receiving member of the present invention was used as described above. By adopting a specific layer structure, all the problems in conventional electrophotographic light-receiving members made of A-3i can be solved, and in particular, extremely excellent initial charging ability, continuous repeated use characteristics, and pressure resistance.

It has usage environment characteristics and durability.

In addition, its electrical properties are stable, and the images obtained using it are of excellent quality, with high density and clear halftones.

In particular, in the present invention, a functionally separated structure using CTL and CGL is used, and (M) is added unevenly or partially in the layer thickness direction as an atom belonging to group V of the periodic table as a substance that controls conductivity. By containing a small amount (or at least one kind) of carbon atoms, nitrogen atoms, and oxygen atoms in a non-uniformly distributed state, it is possible to design freely according to the characteristics of each layer, and the charge generation, injection and transport from CGL to CTL are carried out quickly, it has particularly excellent chargeability sensitivity, and there are few residual potential ghosts (also, images have high resolution and high quality images can be stably and repeatedly produced). You can get it.

[Brief explanation of the drawing]

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 5 show the uneven shape of the surface of the support and the method for producing the uneven shape, respectively. FIGS. 6 to 11 are schematic diagrams for explaining the distribution of atoms (GS) contained in the IR absorption layer, and FIGS. 12 to 16 are schematic diagrams for explaining the
The figures are explanatory diagrams of the distribution state of the substance (Mo) that controls conductivity contained in the charge injection blocking layer, respectively. Figures 24 to 39 are explanatory diagrams of the distribution states of Y), respectively, and Figures 40 to 49 are diagrams of carbon atoms and/or oxygen atoms and/or substances that control conductivity constituting the CTL, respectively. FIG. 50 is an explanatory diagram for explaining the distribution state of nitrogen atoms, and FIG.
A schematic explanatory diagram of a manufacturing device using a glow discharge method using
FIG. 51 is an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography according to the present invention, and is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method using microwaves. Fig. 53 is an example of an apparatus for forming the light-receiving layer of the electrophotographic light-receiving member of the present invention, and is a schematic explanatory diagram of a manufacturing apparatus using the HRCVD method. FIG. 54 is a schematic explanatory diagram of a manufacturing device using the FOCVD method, which is an example of a device for forming the CTL of the electrophotographic light-receiving member of the present invention.
, F A diagram showing flow rate changes during film formation of impurity gas and doping gas when formed using glow discharge. Figure 56 is a diagram showing the flow rate changes of impurity gas and doping gas during film formation when forming a film.
Figure 57 shows the flow rate changes of impurity gas and doping gas during film formation when formed using the RCVD method.
,0. Figure 58 shows the flow rate changes of impurity gas and doping gas during film formation when forming the film using the CVD method. FIG. 59 is an enlarged view of the cylinder cross section when the cylinder is V-shaped. FIG. FIG. 60 is a diagram showing changes in the flow rates of impurity gas and doping gas during film formation in an example in which the CTL of the electrophotographic light-receiving member of the present invention is formed using RF glow discharge. Regarding FIG. 1, 101...Support 102...Photoreceptive layer 103...IR absorption layer 104...Charge injection blocking layer 105...CTL 107...Free surface FIGS. 3 and 4 Regarding the figure, 301, 401...Support 302, 402...Support surface 303, 403...Rigid true sphere 304, 404...Spherical trace depression Regarding Fig. 5, 500...Light receiving layer 501...Support 502...IR absorption layer 503...Charge injection blocking layer 504...CTL 505...CGL 506...Free surface In FIG. 50, 1001...Reaction chamber 1002... Main exhaust valve 1003 Reaction chamber leak valve 1004 Vacuum gauge 1007 Cylinder base 1008 Base heating heater 1009 Cylinder base rotation motor 1010
... R, F power supply 1011-1017 ... Raw material gas cylinder 1021 ~
1027... Mass flow controller 1031
-1037...Gas inflow valve 1041-1047.
... Gas outflow valves 1051 to 1057 ... Raw material gas cylinder valves 1061 to 1067 ... Pressure regulator Regarding Fig. 51, 2001 ... Reaction chamber 2002 ... Main exhaust valve 2003 ... Reaction chamber Leak valve 2004...Vacuum gauge 2005...Heater for heating the substrate 2006...Cylindrical substrate 2007...Motor for rotating the substrate 2008...Microwave power source 2009...Waveguide 201O... Dielectric window 2011~2017... Raw material gas cylinder 2021~
2027...Mass Flow Controller "2031"
~2037...Gas inflow valve 2041~2047・
...Gas outflow valves 2051-2057...Valves 2061-1267 of raw material gas cylinder...Pressure regulator Regarding Fig. 52, 3001... Film-forming chamber 3002... Activation chamber (A) 3003. 3018... Microwave plasma generator 3004, 3019... Raw material gas introduction pipe 3005.3
020...Active species introduction pipe 3006...Motor 3007...Cylinder base heating heater 3008
, 3009... Blowout pipe 3010... Cylindrical base 3011... Main exhaust valves 3012-3016... Raw material gas pump 3017...
...Activation chamber (B) Regarding Fig. 53, 4001...Reaction chamber 4002...Main exhaust valves 4011 to 4017...Material gas cylinders 4020, 4
021... Raw material gas introduction pipes 4031 to 4037...
Outflow valves 4046-4052...Inflow valves 4053-4059...Mass flow controller 4
060... Cylindrical base 4061... Heater 406 for heating the cylindrical base
2...Cylinder base rotation motor No. 750
No. 770 L C Ka/Figure 8
Figure 20, Figure 77.

Claims (1)

[Claims] (1) A support and a photoreceptive layer having a layer structure in which a long wavelength light absorption layer, a charge injection blocking layer, a charge transport layer, and a charge generation layer are laminated in this order from the support side on the support. wherein the charge transport layer and the charge generation layer are made of a non-single crystal material containing silicon atoms as a host and at least one of hydrogen atoms and halogen atoms; , a portion containing at least one of carbon atoms, nitrogen atoms, and oxygen atoms, and containing atoms belonging to Group V of the periodic table as a substance controlling conductivity in a non-uniform distribution state in the layer thickness direction. A light-receiving member for electrophotography, characterized in that it has at least the following.