JPS62195673A - Photoreceptive member for electrophotography - Google Patents

Abstract

PURPOSE:To improve moisture resistance and electrical breakdown strength by providing a photoconductive layer and photoreceptive layer having a surface layer constituted of a polycrystalline material contg. silicon atoms, carbon atoms and hydrogen atoms as a constituting element. CONSTITUTION:This photoreceptive member 100 for electrophotography is provided with a photoreceptive layer 102 on a substrate 101 for a photoreceptive member. The photoreceptive layer 102 is constituted of a long wavelength light photosensitive layer 106 which is constituted of the polycrystalline material contg. the silicon atoms and germanium atoms, the photoconductive layer 103 which consists of an amorphous atoms as the constituting element and has photoconductivity and the surface layer 104 consisting of a polycrystalline material contg. the silicon atoms, carbon atoms and hydrogen atoms as the constituting element. Both conductive and electrically insulating materials are used for the substrate. The moisture resistance and electrical durability are thus improved.

Description

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

[Description of conventional technology]

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 waves to be irradiated, has fast photoresponsiveness, and has a desired dark resistance value, Characteristics such as being non-polluting to the human body during use are required. Particularly in the case of an electrophotographic light-receiving member that is incorporated into an electrophotographic apparatus used in an office, the above-mentioned non-polluting property during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as A-3i) is a photoconductive material that has recently attracted attention.
855718 describes its application as a light-receiving member for electrophotography.

However, electrophotographic light-receiving members having a light-receiving layer composed of conventional A-3i have electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and use environment characteristics. Individual improvements have been made in terms of stability, stability over time, and durability.
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, resulting in a so-called ghost phenomenon, which causes an afterimage.

In addition, when forming a photoreceptive layer using A-3i material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms to control the properties of the photoconductive layer, and other atoms are included in the photoconductive layer to improve properties. However, problems may arise in the electrical or photoconductive properties or voltage resistance of the formed layer.

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

Therefore, while efforts are being made to improve the properties of the A-5i material itself, when designing light-receiving members, the layer structure, chemical composition of each layer, 9 preparation method, etc. must be adjusted in order to solve all of the above-mentioned problems. It needs to be improved.

[Purpose of the invention]

The object of the present invention is to solve various problems in electrophotographic light-receiving members having conventional light-receiving layers made of A-3t as described above.

That is, the main object of the present invention is to have electrical, optical, and photoconductive properties that are virtually always stable without depending on the usage environment, have excellent light fatigue resistance, and exhibit no deterioration phenomenon even after repeated use. To provide a light-receiving member for electrophotography, which has a light-receiving layer made of A-3i and polycrystalline silicon, which has excellent durability and wettability, 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.
A- has a dense and stable structure and high layer quality.
An object of the present invention is to provide a light-receiving member for electrophotography having a light-receiving layer made of Si and polycrystalline silicon.

Still another object of the present invention is that, when applied as a light-receiving member for electrophotography, the present invention has sufficient charge retention ability during charging processing for electrostatic image formation, making ordinary electrophotographic methods extremely effective. A-3i exhibits excellent electrophotographic properties that can be applied
Another object of the present invention is to provide a light-receiving member for electrophotography having a light-receiving layer made of polycrystalline silicon.

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

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

[Structure of the invention]

The light-receiving member for electrophotography of the present invention includes a support, a long-wavelength photosensitive layer that is made of a polycrystalline material containing silicon atoms and germanium atoms and is sensitive to long-wavelength light, and silicon atoms on the support. An amorphous material containing at least one of a hydrogen atom and a halogen atom as a constituent element (hereinafter abbreviated as rA-3i (H,X) J)
It has a photoconductive layer that exhibits photoconductivity, and a photoreceptive layer that is made of a polycrystalline material containing silicon atoms, carbon atoms, and hydrogen atoms as constituent elements. It is characterized by things.

Further, the surface layer may contain halogen atoms,
Further, the photoconductive layer includes carbon atoms.

At least one type of atom such as an oxygen atom or a nitrogen atom may be contained in the center.

Furthermore, the long wavelength photosensitive layer may contain at least one of a conductivity controlling substance, an oxygen atom, and a nitrogen atom.

The electrophotographic light-receiving member of the present invention designed to have the above-described layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, and photoconductive properties. , durability and use environment characteristics.

In particular, it has no influence of residual potential on image formation, has stable electrical characteristics, high sensitivity, and high S/N ratio, and has excellent light fatigue resistance, repeated use characteristics, moisture resistance, and pressure resistance. As a result, high-quality images with high density, clear halftones, and high resolution can be stably and repeatedly obtained.

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

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

In the electrophotographic light receiving member 100 shown in FIG. 1, a light receiving layer 102 is provided on a support 101 for the light receiving member, and the light receiving layer 102 includes silicon atoms and germanium atoms. Long wavelength photosensitive layer 106 A-3i (H, X) composed of polycrystalline material containing
A photoconductive layer 103 having photoconductivity, silicon atoms,
It has a layer structure including a surface layer 104 made of a polycrystalline material whose constituent elements are carbon atoms and hydrogen atoms.

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

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. .

Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, NtCr, AI
, Cr, Mo, Au, Ir, Nb, Ta, ■, Ti, P
t, Pd, In2O3, S n02, I To (I
Conductivity is imparted by providing a thin film consisting of NiCr, A, Ag, etc., or if it is a synthetic resin film such as a polyester film.
Pb, Zn, Ni, Au, Cr,
A thin film of a metal such as Mo, Ir, Nb, Ta, ■, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam welding, sputtering, etc., or the surface is laminated with the above metal. Provides electrical conductivity. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, in the case of continuous high-speed copying, it may be an endless belt or a cylinder. It is desirable to do so. The thickness of the support is appropriately determined so that a desired electrophotographic light-receiving member is formed.
When flexibility is required as a light-receiving member for electrophotography, it is made as thin as possible within a range that allows it to sufficiently function as a support. However, in such a case, from the viewpoints of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 1 Lop or more.

Particularly when image recording is performed using coherent light such as laser light, it appears in visible images. In order to eliminate image defects caused by so-called interference fringe patterns, irregularities may be provided on the surface of the support.

FIG. 9 shows a light-receiving member in which a light-receiving layer is provided on a support 1501 having an uneven shape and along the slope of the unevenness.

In FIG. 15, 1502-1 is a long wavelength photosensitive layer, 150
2-2 is a photoconductive layer, and 1503 is a surface layer. At this time,
Since the degree of inclination at the interface formed between the free surface 1504 and the photoreceptive layer 1500 is different, the free surface 1504
In addition, the reflection angles of the reflected light at the interfaces formed in the light-receiving layer 1500 are different.

Therefore, shearing interference similar to the so-called Newton's ring phenomenon occurs, and the interference fringes become dispersed within the depression. As a result, even if microscopic interference fringes appear in the image appearing through such a light-receiving member, they are of such a degree that they cannot be visually perceived. In other words, the use of a support having such a surface shape is for a light-receiving member having a multi-layered light-receiving layer formed thereon, and the light that has passed through the light-receiving layer is transmitted to the layer interface and the support. This effectively prevents the formed image from having a striped pattern due to reflection on the surface and interference.

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 pattern centered on the central axis of the cylindrical support. The spiral structure of the inverted V-shaped protrusion may be a double or triple spiral structure, or a crossed spiral structure.

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

The vertical cross-sectional shape of the uneven convex portions provided on the surface of the support is determined by the controlled non-uniformity of the layer thickness within the microcolumns of each layer formed, and by the difference between the support and the layer directly provided on the support. In order to ensure good adhesion and desired electrical contact between the parts, the inverted V-shape is used, but preferably the shape is substantially isosceles triangular, right-angled triangular, or not, as shown in FIG. It is preferable that the shape is an equilateral triangle, and particularly an isosceles triangle or a right triangle.

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, firstly, the A-5t(H, do.

Therefore, it is necessary to set the dimensions of the irregularities provided on the surface of the support so as not to cause deterioration in the layer quality of the A-5i(H,X) and polycrystalline silicon layers.

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

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

As a result of examining the above-described problems in layer deposition, process problems in electrophotography, and conditions for preventing interference fringes, the pitch of the recesses on the surface of the support is preferably 500) Lm-
0.3 pm, more preferably 200 JLm ~ Igm,
Optimally 50 gm to 5 pm is desirable.

1. The maximum depth of the recess is preferably O0lKm~
5 lm, more preferably 0.34 m to 3g1n, /i
It is desirable that the thickness be 0.6 μm to 2 pm. 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.

Also, due to the non-uniform layer pressure of each layer deposited on such a support, the maximum difference in layer thickness is preferably 0.
1 JLm to 2 gm, more preferably 0. ip,,
m −1.5 pm, most preferably 0.2 pm to lJLm.

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

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

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 are shown in FIGS. 10 and 1 below.
Although this will be explained with reference to FIG. 1, the shape of the support in the light-receiving member of the present invention and the manufacturing method thereof are not limited thereto.

FIG. 1O shows a typical example of the surface shape of the support in the electrophotographic light-receiving member of the present invention.

This diagram schematically shows a partially enlarged portion of the uneven shape.

In FIG. 10, 1601 is a support, 1602 is a surface of the support, 1603 is a rigid pearl, and 1604 is a spherical trace depression.

Furthermore, FIG. 10 also shows one example of a preferred manufacturing method for obtaining the surface shape of the support.

That is, it is shown that a spherical depression 1604 can be formed by allowing the rigid pearl 1603 to fall naturally from a position at a predetermined height from the support surface 1602 and collide with the support surface 1602. And 16 rigid pearls with the same diameter
By using a plurality of 03 and dropping them from the same height h simultaneously or sequentially, the support surface 1602
A plurality of spherical trace depressions 1604 having approximately the same curve radius R and the same width can be formed.

A typical example of a support having an uneven shape formed by a plurality of spherical trace depressions on one surface as described above is shown in FIG.
1701 is a support, 1702 is a convex surface of an uneven portion, 17
03 is a rigid true sphere, and 1704 is the surface of the concave portion.

By the way, 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 efficiently prevent the occurrence of interference fringes in the light-receiving member of the present invention. The present inventors have investigated the following points as a result of repeated various experiments. That is, when the radius of curvature R and the width satisfy the following formula: % formula %, there are 0.5 or more Newton rings due to shearing interference 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 occurring throughout the light receiving member into each trace recess and to prevent the occurrence of interference fringes in the light receiving member, the above ratio should be set to 0.035.
Preferably, it is 0.055 or more.

In addition, the width of the unevenness due to the trace depression is at most 500 mm.
gm, preferably 200 JLm or less, more preferably 100 gm or less.

The long-wavelength photosensitive layer in the present invention is composed of a polycrystalline material containing silicon atoms and germanium atoms, and the germanium atoms contained in the layer are uniformly distributed throughout the layer. The concentration may be distributed evenly in the layer thickness direction, but the distribution concentration may be non-uniform. In the in-plane direction, the content is uniform and evenly distributed.
This is also necessary from the point of view of making the characteristics uniform in the in-plane direction. That is, it is uniformly contained in the layer thickness direction of the long-wavelength photosensitive layer, and the above-mentioned content is uniformly contained in the layer thickness direction of the long-wavelength photosensitive layer, and the above-mentioned It is contained in the long-wavelength photosensitive layer so that it is distributed in a larger amount on the support side, or in the opposite distribution state.

In the light receiving member of the present invention, as described above, the distribution state of germanium atoms contained in the long wavelength photosensitive layer is as follows.
In the layer thickness direction, it is desirable to have the above-mentioned distribution state, and to have a uniform distribution state 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 in the long wavelength photosensitive layer is such that germanium atoms are continuously and evenly distributed over the entire layer region, and the layer thickness of germanium atoms is Since the distribution density C in the direction decreases from the support side toward the charge injection blocking layer, there is excellent affinity between the long wavelength photosensitive layer and the charge injection blocking layer, and as will be described later. Similarly, by extremely increasing the distribution concentration C of germanium atoms at the edge of the support, light on the long wavelength side, which is almost completely absorbed by the photoconductive layer when using a semiconductor laser, etc., can be absorbed by the photoconductive layer. In the photosensitive layer, the light can be absorbed substantially completely, and interference due to reflection from the support surface can be prevented.

7frJz to FIG. 7 show typical examples where the distribution state of germanium contained in the long-wavelength photosensitive layer of the light-receiving member of the present invention in the layer thickness direction is non-uniform.

In FIGS. 2 to 7, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the layer thickness of the long wavelength photosensitive layer.
tT is the position of the end surface of the long wavelength photosensitive layer on the support side.
indicates the position of the end face of the long wavelength photosensitive layer on the side opposite to the support side, that is, the long wavelength photosensitive layer containing germanium atoms is formed from the tB side toward the tT side.

52 shows a first typical example of the distribution state of germanium atoms contained in the long wavelength photosensitive layer in the layer thickness direction.

In the example shown in FIG.
A long-wavelength photosensitive layer is included in which germanium atoms are formed while the distribution concentration C of germanium atoms takes a constant value C1, gradually and continuously from the concentration C2 from position 1 to the interface position t7. has been reduced, the interface position 7τ
In this case, the distribution concentration C of germanium atoms is C3.

In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms is such that the concentration C4 gradually decreases from the position tB to the position M, and reaches the concentration C5 at the position t7. forming a state.

In the case of FIG. 4, the distribution concentration C of germanium atoms is kept at a constant value C6 from position tB to position t2, and gradually and continuously decreases between position t2 and position tT, until position Zttr In the above, the 1-distribution concentration C is substantially zero (substantially zero here means less than the detection limit amount).

In the case of FIG. 5, the distribution concentration C of germanium atoms is continuously gradually decreased from the concentration C8 from the position tB to the position tT, and becomes substantially zero at the position t7.

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is a constant value C9 between the 1st position and the position t3, and the concentration C10 is the concentration C10 at the 0th position t3 and the position t7 at the position t7. In between, the distribution concentration C is linearly decreased from position t3 to position 11tr.

In the example shown in FIG. 7, the distribution concentration C of germanium atoms from the position tB side to the position D is the concentration C11.
It decreases in a linear function so as to substantially reach zero.

As described above with reference to FIGS. 2 to 7, some typical examples of the distribution state of germanium atoms contained in the long wavelength photosensitive layer in the layer thickness direction, in the present invention, on the support side , the distribution state of germanium atoms has a part where the distribution concentration C of germanium atoms is high, and the distribution state of germanium atoms has a part where the distribution concentration C is considerably lower on the interface tT side than on the support side. If provided, it is cited as one of the preferred examples.

As for the distribution state of germanium atoms in the layer thickness direction, the maximum value CmaX of the distribution concentration of germanium atoms is preferably 1000 atomic ppm or more, more preferably 5000 atomic ppm or more, and optimally lX10
It is desirable to configure the layers so that a distribution state of 4 atomic ppm or more can be obtained.

In the present invention, the content of germanium atoms contained in the long wavelength photosensitive layer is determined as desired so as to effectively achieve the object of the present invention, but it is preferably 1 to 10 x 105 atomic ppm, preferably 100 to 9.5 x 105 atomic ppm
m, preferably 500 to 8XLO5 atomic ppm.

The long wavelength photosensitive layer further includes a substance that controls conductivity;
It may contain at least one of an oxygen atom and a nitrogen atom.

In addition, the substance that controls conductivity can be exemplified by so-called impurities in the semiconductor field, and in the present invention, atoms belonging to group m of the periodic table (hereinafter referred to as "m-th ), or N
Atoms belonging to Group V of the periodic table (hereinafter referred to as "Group V atoms") that provide type conductivity characteristics are used. Specifically, as group Ⅰ atoms, B (boron), A (aluminum)
, Ga (gallium), In (indium), TJ
Examples include J (thallium), and B and Ga are particularly preferred.

Specifically, the Group V atoms include P (phosphorus), As (arsenic), sb (antimony), Bi (bismuth), etc., with P and As being particularly preferred.

In the present invention, the content of the substance that controls conduction characteristics contained in the long wavelength photosensitive layer is as follows.

Preferably 0.01 to 5 x 105 atomic ppm.

More preferably 0.5 to 1 X I O4 atomic ppm.

The optimum content is 1 to 5 x 103 atomic ppm.

In the present invention, in order to form a long wavelength photosensitive layer made of a polycrystalline material containing silicon atoms and germanium atoms, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blating method is used. For example, to form a long-wavelength photosensitive layer by a glow discharge method, a raw material gas for Si supply that can supply silicon atoms (Si) and a germanium atom (Ge ) and, if necessary, a raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) into a deposition chamber whose interior can be reduced in pressure. The gas may be introduced at a desired gas pressure to generate a glow discharge within the deposition chamber, thereby forming a layer on the surface of a predetermined support that has been placed at a predetermined position. Further, in order to contain germanium atoms in a non-uniform distribution state, the layer may be formed while controlling the distribution concentration of germanium atoms according to a desired rate of change curve. In addition, when forming by sputtering method, for example, Ar
, using a target made of Si in an atmosphere of an inert gas such as He or a mixed gas based on these gases, or using two targets made of the target and Ge, or Using a target containing a mixture of Si and Ge, a source gas for supplying Ge diluted with a diluent gas such as He or Ar is added as necessary.
This is accomplished by introducing a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) into a deposition chamber for sputtering to form a plasma atmosphere of the desired gas.

In order to make the distribution of germanium atoms uniform, the above G
The target may be sputtered while controlling the gas flow rate of the raw material gas for e supply according to a desired rate of change curve.

In the case of the ion blating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in base ports as evaporation sources, and these evaporation sources are heated using resistance heating or electron beam heating. Except for heating and evaporating by beam method (EB method) etc. and passing the flying particles through the desired gas plasma atmosphere,
This can be done in the same manner as in the sputtering method.

Substances that can be used as raw material gas for supplying Si used in the present invention include SiH4゜Si2H6,5i3HB
Silicon hydride (silanes) in a gaseous state or that can be gasified such as SiH4,5i2Hs is preferred.

As a material that can be a source gas for supplying Ge, GeH
4,Ge2H(3,Ge3)19,Ge4Hto,Ge
5Ht2. Ge4Hto, Ge7Hts.

GeHte, Ge 9H20 and other gaseous or gasifiable germanium hydrides are effectively used, especially for their ease of handling during layer formation work,
In terms of Ge supply efficiency, etc., GeHa, Ge2H6
, Ge3HB are 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, and halogen-substituted silane derivatives. Preferable mention may be made of halogen compounds in the state or which can be gasified.

Furthermore, it can be in a gaseous state or gasified, which contains silicon atoms and halogen atoms as constituent elements. Silicon hydride compounds containing halogen atoms are also effective in the present invention.

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

Bromine, iodine halogen gas, BrP, C1F.

CuF2, BrF5, BrF3, IF
3.

IF7. Interhalogen compounds such as ICJl and IBr can be mentioned.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF4. Si2F6,5iCJ14. Silicon halides such as SiBr4 are preferred.

When a photoconductive member characteristic of the present invention is formed by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying Si together with a raw material gas for supplying Ge. A long wavelength photosensitive layer containing halogen atoms can be formed on a desired support without using silicone gas.

When manufacturing a long-wavelength photosensitive layer containing halogen atoms according to the glow discharge method, basically, for example, silicon halide, which is a raw material gas for supplying Si, germanium hydride, which is a raw material gas for supplying Ge, and Ar are used. , H2, He, etc. are introduced into a deposition chamber in which a long wavelength photosensitive 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, a long wavelength photosensitive layer can be formed on a predetermined support, but in order to make it easier to control the ratio of hydrogen atoms introduced, hydrogen gas or A desired amount of silicon compound gas containing hydrogen atoms may also be mixed to form a layer.

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.

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

In addition, when introducing hydrogen atoms, a raw material gas for hydrogen atom introduction, such as F2, or the above-mentioned silanes or/
A gas such as germanium hydride or the like may be introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gas.

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, halogen compounds such as HF, GCfL, HBr, and HI Hydrogen chloride, SiH2F2, 5iH2I2, 5fH2C 2゜5
Halogen-substituted silicon hydrides such as iHCJ13, 5iH2Br2, 5iHBr2, and GeHF3゜GeF2F2
, GeH3F, GeHCl3.

GeH2C12, GeHBr3. GeHBr3゜GeF
2Br2, GeF2Br, GeHI2.

GeF2I2. Hydrogenated germanium halides such as GeH3I, halides containing hydrogen atoms as one of their constituent elements, GeF4. GeC sentence 4°GeBr4. GeIa,
GeF2. Germanium halides such as GeC12°GeBr2, GeI2, and other gaseous or gasifiable substances can also be cited as effective starting materials for forming the long wavelength photosensitive layer.

Among these substances, /X rogides containing hydrogen atoms are:
When forming a long-wavelength photosensitive layer, 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. used.

In order to structurally introduce hydrogen atoms into the long wavelength photosensitive layer,
In addition to the above, F2 or SiH4゜5t2H6,5i3
Silicon hydride such as Hs, 5iaH1o, etc. with germanium or a germanium compound for supplying Ge, or with G
eHa.

Ge2H6, Ge2HB, Ge4H10, Ge
5Ht2. Ge5Ht4. Ge7Hts, GeBHle
.

This can also be achieved by causing germanium hydride such as Ge9H2o and silicon or a silicon compound for supplying Si to coexist in a deposition chamber to generate a discharge.

In a preferred example of the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms ( H+X) is preferably 0.01 to 40 atom%
, more preferably 0.05 to 30 atomic %, optimally 0.05 to 30 atomic %.
The content is preferably 1 to 25 atomic %.

To control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the long wavelength photosensitive layer, for example, the support temperature and/or hydrogen atoms (H) or halogen atoms (X) can be controlled. What is necessary is to control the amount of the starting material used to contain the material introduced into the deposition system, the discharge force, etc.

In the present invention, in order to incorporate nitrogen atoms into the long-wavelength photosensitive layer, the starting material for introducing nitrogen atoms when forming the long-wavelength photosensitive layer is the starting material for forming the long-wavelength photosensitive layer described above. It may be used in conjunction with the above, and the amount thereof may be controlled and contained in the formed layer.

To form a long-wavelength photosensitive layer by the glow discharge method, the starting material for introducing nitrogen atoms is most of the gaseous substances containing at least nitrogen 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 nitrogen atoms (N) as constituent atoms, and hydrogen atoms (H) or halogen atoms (X) as necessary as constituent atoms. Either a raw material gas is mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material whose constituent atoms are nitrogen atoms (N) and hydrogen atoms (H) are used. Alternatively, a raw material gas containing silicon atoms (Si) and silicon atoms (Si), nitrogen atoms (
It is possible to use a mixture of a raw material gas having three constituent atoms: N) and hydrogen atoms (H).

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).

Starting materials that can be effectively used as raw material gases for introducing nitrogen atoms (N) include those having N as a constituent atom or N and H as constituent atoms, such as nitrogen (N2) and ammonia (NH3). .

Hydrazine (H2NNH2), hydrogen azide (HN'3)
, gaseous or gasifiable nitrogen such as ammonium azide (NH4N3), nitrogen compounds such as nitrides and azides. In addition to this, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so nitrogen trifluoride (F3N), nitrogen tetrafluoride (F4N2
) and other halogenated nitrogen compounds.

In the present invention, the long wavelength photosensitive layer may contain nitrogen atoms and/or oxygen atoms. Examples of raw material gases for introducing oxygen atoms into the long wavelength photosensitive layer include oxygen (02), ozone (03), -nitrogen oxide (No), nitrogen dioxide (NO2), and -nitrogen dioxide. (N20), nitrogen sesquioxide (N203), trinitrogen tetraoxide (N 20 a ), nitrogen sesquioxide (N205).

Lower siloxanes such as nitrogen trioxide (NO3), silicon atoms (St), oxygen atoms (0), and hydrogen atoms (H) such as disiloxane (H3SiO3LH3) and )disiloxane (H3SiO5iH20S 1H3) etc. can be mentioned.

In order to form a long wavelength photosensitive layer by sputtering, single crystal or polycrystalline Si is used when forming the long wavelength photosensitive layer.
Wafer or 5t3N4 wafer or St and Si
The sputtering may be carried out by using a wafer containing a mixture of 3N4 as a target and sputtering the wafer in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluting gas as necessary, and then the material gas for introducing nitrogen atoms and hydrogen atoms and/or halogen atoms as necessary is diluted with a diluent gas and used in a deposition chamber for sputtering. The Si wafer may be sputtered by introducing the gas into the Si wafer and forming a gas plasma of these gases.

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

As the raw material gas for introducing oxygen atoms, the raw material gas for introducing nitrogen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, when forming a long wavelength photosensitive layer, the distribution concentration C(N) of nitrogen atoms contained in the layer is changed in the layer thickness direction to obtain a desired layer thickness direction distribution state ( depth
In the case of a glow discharge, to form a layer with a profile of 100%, the starting material gas for nitrogen atom introduction whose distribution concentration C(N) is to be changed is adjusted by adjusting the gas flow rate to the desired rate of change curve. This is accomplished by introducing the material into the deposition chamber while changing it accordingly.

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 forming by a sputtering method, the distribution concentration C(N) of nitrogen atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (depth p) of nitrogen atoms in the layer thickness direction.
rofile), firstly, as in the case of the glow discharge method, the starting material for the introduction of nitrogen atoms is used in a gaseous state, and the gas stoichiometry when introducing the gas into the deposition chamber is This can be done by appropriately changing as desired.

Second, the target for sputtering is, for example, S
If a target containing a mixture of i and 5t3Na is used, this can be done by changing the mixing ratio of Si and 5t3Na in advance in the layer thickness direction of the target.

The amount of nitrogen atoms (N), the amount of oxygen atoms (0), or the sum of the amounts of nitrogen atoms and oxygen atoms (S+O) contained in the long wavelength photosensitive layer is preferably.

0.01 to 40 at%, more preferably 0.05 to 30
The atomic % 2Nk is desirably 0.1 to 25 atomic %.

In order to structurally introduce a substance 1 for controlling conduction characteristics into a long-wavelength photosensitive layer, for example, a group Ⅰ atom or a group V atom, a starting material for introducing a group ① atom is added during layer formation. Alternatively, the starting material for introducing Group V atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the long wavelength photosensitive 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 a starting material for introducing a group Ⅰ atom, B2H6 is used for introducing a boron atom.

B4HLO, B5H9, BS) (11, BS) (10° Boron hydride such as B6H12, B6H14, BF3.

Examples include boron halides such as BCC20BBr3. In addition, AlCl3. GaCl3.

Ga(CH3)3, IncfL3. TiCl3 etc. can also be mentioned.

In the present invention, effective starting materials for the introduction of Group V atoms include PH3,
Hydrogenated phosphorus such as P2H4, PH4I, PF3, PF5
, PC standing 3. PCM5. PBr3. PBr3. PI3
(7) Examples include halogenated phosphorus. In addition, A5H
3°AsF3. AsCf13. AsBr3. AsF5S
bH3, SbF3. SbF5,5bC13.

SbCM5. BiH3, B1C13, B1Br etc. are also part V
It can be mentioned as an effective starting material for introducing group atoms.

In the present invention, the layer thickness of the long wavelength photosensitive layer is preferably:
30 people to 50 gm, more preferably 40 people to 40 gm
, the optimal number is preferably 50 people to 30 JLm.

In order to effectively achieve the object of the present invention, the photoconductive layer formed on the long wavelength photosensitive layer and constituting a part of the photoreceptive layer is a semiconductor shown below. It is composed of A-5i (H,

(2) pfJA-3i (H,

■ P-type A-S i (H, X) ---■ tie,
(3) n-type A-S i (H,X) ---containing only donors. or includes both a donor and an acceptor;
Those with a high relative concentration of donor.

(2) n-type A-3f (H,

■ Type i A-3i (H,X)---Na; Nb 20 or NazNd.

In the present invention, preferred halogen atoms (X) contained in the photoconductive layer are F, C1°Br, and I, with F and Cl being particularly preferred.

In the present invention, in order to form a photoconductive layer composed of A-St (H, For example, A-3t (H,X
) In order to form an amorphous layer made up of (X) A raw material gas for introduction is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber, and a glow discharge is caused to occur on the surface of a predetermined support that has been placed in a stirrup at a predetermined position.
A layer consisting of -Si (H,X) may be formed. In addition, when forming by sputtering method, for example, Ar,
When sputtering a target made of Si in an atmosphere of an inert gas such as He or a mixed gas based on these gases, hydrogen atoms (H) or The gas may be introduced into a deposition chamber for sputtering.

The raw material gas for Si supply used in the present invention includes SiH4,5i2He, 5i3He, Si4H10
Silicon hydride (silanes) in a gaseous state or which can be gasified, such as SiH
4, Si2H6 is preferred.

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

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

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

Iodine halogen gas, BrF, ClF, ClF3,
BrF5. BrF3. IF3. IF7゜IC1, IBr
Examples include interhalogen compounds such as.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF4. Si2F6,5tCQ4. Silicon halides such as SiBr4 are preferred.

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

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

By introducing gases such as H2, He, etc. into a deposition chamber in which a photoconductive layer is formed at a predetermined mixing ratio and gas flow rate, and generating a glow discharge to form a plasma atmosphere of these gases. , a photoconductive layer can be formed on a predetermined support, but in order to introduce hydrogen atoms, a predetermined amount of a silicon compound gas containing hydrogen atoms is further mixed with these gases to form a layer. It's okay.

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.

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

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

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

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

HCI, HBr, HI, etc. (7) Hatff Hydrogenide,
SiH2F2, 5iH2I2, 5iH2Ci2゜5iH
C-3, halogen-substituted silicon hydride such as 5iH2Br2, 5iHBr3, etc., in a gaseous state or capable of being gasified,
Halides containing hydrogen atoms as one of their constituents can also be cited as effective starting materials for forming the photoconductive layer.

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

In order to structurally introduce hydrogen atoms into the layer, in addition to the above, H
2, or SiH4,5i2Hs.

Silicon hydride gas such as 5i3Hs, Si4H10, etc.
This can also be done by causing discharge to occur by coexisting in the deposition chamber with a silicon compound for supplying.

For example, in the case of reactive sputtering method, St metal
A gas for introducing halogen atoms and H2 gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere. By sputtering, A-
A layer consisting of 3i(H,X) is formed.

Furthermore, a gas such as B2H6 can also be introduced to also serve as impurity doping.

In the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms contained in the photoconductive layer of the electrophotographic light-receiving member to be formed is The content is preferably 1 to 40 atom %, more preferably 5 to 30 atom %.

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

In the present invention, the diluent gas used when forming the photoconductive layer by a glow discharge method or a sputtering method is a so-called rare gas, such as He.

Suitable examples include Ne, Ar, and the like.

In order to obtain the desired semiconductor properties of the photoconductive layer from (1) to (3), when forming the layer, an n-type impurity or a p-type impurity,
Alternatively, this can be achieved by doping both impurities into the layer to be formed while controlling their amounts. Such impurities include atoms belonging to group m of the periodic table as p-type impurities, such as B, A! ;L, Ga, In.

Examples of n-type impurities include atoms belonging to Group V of the periodic table, such as N, P, and A.
S, Sb, and Bff are preferred, with B, Ga, and P being particularly preferred.

sb etc. are optimal.

In the present invention, the amount of impurity doped into the photoconductive layer in order to have a desired conductivity type is appropriately determined depending on the desired electrical and optical properties, but it is determined according to the desired electrical and optical properties. In the case of an impurity of 3X10-3 atomic % or less, the impurity may be doped in an amount of 3X10-3 atomic % or less, and in the case of an impurity in Group V of the periodic table, it may be doped in an amount of 5XlO-3 atomic % or less.

In order to dope impurities into the photoconductive layer, the raw material for impurity introduction may be introduced in a gaseous state into the deposition chamber together with the main raw material for forming the photoconductive layer during layer formation.
As the raw material for introducing such impurities, it is desirable to use a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions.

Specifically, as a starting material for introducing such impurities, P
H3, P2) (4, PF3, PFs.

PCC10, AsH3, AsF3, AsF5゜AsC
J13, SbH3, SbF3. SbF3.

SbF5. B1G3. BF3. BCM3°BBr3. B
2 Hs, B 4 Hlo, B5H9゜B 5
Hll, B 8H12, B6H14, A cross C standing 3
.

Examples include GaC9,3, I ncJ13, and T-text CI3.

In order to make the photoconductive layer contain at least one type of atom among carbon atoms, oxygen atoms, and nitrogen atoms, for example, when forming the photoconductive layer by a glow discharge method, at least one kind of atom among carbon atoms, oxygen atoms, and nitrogen atoms can be contained in the center of the photoconductive layer. The photoconductive layer may be formed by introducing a compound containing one type of element into a deposition chamber that can be made to have a reduced pressure together with a raw material gas for forming the photoconductive layer, and causing glow discharge within the deposition chamber.

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

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (02H6), propane (C3HB), n-buty (n-C4H10), pentane (C5H12), and ethylene hydrocarbons include ethylene (C2H4) and propylene (03H6).

Butene-1 (C4H8), Butene-2 (C4H8).

Inbutylene (C4H8), Pentey (CsHto).

Examples of acetylene hydrocarbons include acetylene (C2H2
), methylacetylene (C3H4).

Examples include butyne (C4H6).

As a raw material gas containing Si, C, and H as constituent atoms, S
Examples include alkyl silicides such as i(CH3)4.5i(C2H4)4.

Examples of the oxygen atom-containing compound serving as a raw material for introducing a fluorine atom include oxygen (02), -carbon oxide (Co), carbon dioxide (CO2), -nitrogen oxide, and nitrogen dioxide 1.

Further, examples of the nitrogen atom-containing compound serving as a raw material for introducing nitrogen atoms include nitrogen (N2).

- Examples include carbon oxide, nitrogen dioxide, ammonia, etc.

For example, when forming a photoconductive layer by a sputtering method, the desired mixing ratio may be, for example, (Si+5i3N
4) Use a sputtering target made of a mixture of (Si+5iC) or (Si+5i02), or use two Si wafers and Si3N4 wafers, two Si wafers and Si wafers, or a Si wafer and 5T.
Sputtering is performed using two targets of 02 wafers, or sputtering is performed using a carbon-containing compound gas, a nitrogen-containing compound gas, or an oxygen-containing compound gas such as Ar gas. The photoconductive layer may be formed by introducing the photoconductive layer into the deposition chamber together with a suitable gas and performing sputtering using Si or a target.

In the present invention, the amount of carbon, oxygen, or nitrogen contained in the photoconductive layer to be formed greatly influences the characteristics of the electrophotographic light-receiving member to be formed, and can be adjusted as desired. It must be determined appropriately, but preferably 0.00
It is desirable that the content be 0.05 to 30 atom %, more preferably 0.001 to 20 atom %, most preferably 0.002 to 15 atom %.

When forming a photoconductive layer, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. It is desirable that the temperature of the support during layer formation be tightly controlled so that the layer can be formed as desired.

In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the photoconductive layer is selected in an appropriate range in accordance with the method of forming the photoconductive layer, and The temperature is preferably 50°C to 350°C, more preferably 100°C to 300°C.

The glow discharge method and sputtering method are used to form the photoconductive layer, as it is relatively easy to finely control the composition ratio of the atoms that make up the layer and control the layer thickness compared to other methods. However, when forming a photoconductive layer using these layer forming methods, the discharge power and gas pressure during layer formation, as well as the support temperature described above, will vary depending on the photoconductive layer being created. It is one of the important factors that influence the characteristics.

The discharge power conditions for effectively producing a light guiding f-layer having characteristics for achieving the object of the present invention with good productivity are usually 10 to iooow, preferably 20 to
It is desirable that the power be 500W. The gas pressure in the deposition chamber is usually 0.01 to 1 Torr, preferably 0.1 to 0.5 Torr.
It is desirable that it be about rr.

In the present invention, the above-mentioned ranges are mentioned as preferable numerical ranges for the support temperature and discharge power for creating the photoconductive layer, but these layer creation factors cannot be determined independently and separately. It is desirable that the optimum value of each layer forming factor be determined based on the mutual organic relationship so that a photoconductive layer having desired characteristics is formed.

The layer thickness of the photoconductive layer is determined as desired so that photocarriers generated by irradiation with light having desired spectral characteristics are efficiently transported, and is preferably l-
It is desirable that the amount is 100 liters, more preferably 2 to 50 liters.

The surface layer formed on the photoconductive layer has a free surface and meets the objectives of the present invention mainly in terms of moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability. established to achieve.

The surface layer is formed of a polycrystalline material composed of silicon atoms, carbon atoms, and hydrogen atoms.

The surface layer can be formed by gummy discharge method, sputtering method, ion implantation method, ion blating method,
This is accomplished by an electron beam method or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, the level of equipment capital investment, manufacturing scale, and the desired characteristics of the electrophotographic light-receiving member to be manufactured. The advantages include that it is relatively easy to control the production conditions for producing a light-receiving member for electrophotography, and that it is easy to introduce carbon atoms and hydrogen atoms together with silicon atoms into the surface layer to be produced. Since the glow discharge method or the sputtering method is preferably employed, in the present invention, the surface layer may be formed by using both the glow discharge method and the sputtering method in the same apparatus system.

To form a surface layer by the glow discharge method, the raw material gas for surface layer formation is mixed with a dilution gas at a predetermined mixing ratio as necessary, and the deposition process for vacuum deposition, which is the installation of a support, is performed. A surface layer may be deposited on the photoconductive layer already formed on the support by introducing the gas into a chamber and generating a glow discharge to turn the introduced gas into gas plasma.

In the present invention, the raw material gas for forming the surface layer is St
, C, and H as a constituent atom, or gasified substances that can be gasified can be used.

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

Separately, C is added to the raw material gas containing Si and H as constituent atoms.
A mixture of raw material gases having constituent atoms may be used.

In the present invention, SiH4 whose constituent atoms are Si and H is effectively used as the raw material gas for forming the surface layer.
, Si2H6, 5i3H3゜Si4H10 etc.
silicon hydride gases such as C and H, for example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and acetylene hydrocarbons having 2 to 3 carbon atoms. Examples include hydrocarbons.

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (C2H6), propane (C3H9, n-butane (n-C4H10), pentane (C5HL2),
Ethylene hydrocarbons include ethylene (C2H4),
Propylene (C3H6).

Butene-1 (C4H8), Butene-2 (C4H8).

inbutylene (C4H8), pentene (C5HIO),
Examples of acetylene hydrocarbons include acetylene (C2H2
), methylacetylene (C3H4), butyne (CaH
s) etc.

As a raw material gas containing St, C, and H as constituent atoms, S
Examples include alkyl silicides such as i(CH3)4.5i(C2Hs)4. In addition to these raw material gases, H2 is of course also used as an effective raw material gas for H introduction.

To form the surface layer by the sputtering method, a single crystal or polycrystalline Si wafer, a C wafer, or an S
The sputtering may be carried out by using a wafer containing a mixture of i and C as a target and sputtering them in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gases for introducing C and H are diluted with diluting gas as necessary and introduced into the deposition chamber for sputtering. The Si wafer may be sputtered by forming plasma.

Alternatively, sputtering can be performed in a gas atmosphere containing at least hydrogen atoms by using Si and C as separate targets or by using a single mixed target of Si and C.

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

In the present invention, the diluent gas used when forming the surface layer by the glow discharge method or sputtering method is a so-called rare gas, such as He.

Suitable examples include Ne and Ar.

The surface layer in the present invention is carefully formed to provide the desired properties.

In other words, substances whose constituent atoms are Si, C, and H can have structural forms ranging from crystalline to amorphous depending on the conditions of their creation, and electrical properties ranging from conductive to semiconductive to insulating. and exhibit properties ranging from photoconductive properties to non-photoconductive properties, so in the present invention, as desired, so as to form a surface layer having desired properties depending on the purpose, The conditions for its creation are strictly selected.

For example, if the surface layer is provided primarily for the purpose of improving pressure resistance, the surface layer is made of an amorphous material with significant electrically insulating behavior in the environment of use.

In addition, if a surface layer is provided with the main purpose of improving the characteristics of continuous repeated use or the characteristics of the usage environment, the above-mentioned degree of electrical insulation will be moderated to some extent, and the surface layer will have a certain degree of sensitivity to the irradiated light. A surface layer of crystalline material is created.

When forming a surface layer made of a polycrystalline material on the surface of a photoconductive layer, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. It is desirable that the temperature of the support during layer formation be strictly controlled so that a surface layer having desired properties can be formed as desired.

In order to effectively achieve the purpose of the present invention, the optimal range of the support temperature when forming the surface layer is selected according to the method of forming the surface layer, and the formation of the surface layer is carried out. However, the temperature is preferably 50°C to 350°C, more preferably 100°C to 300'O.

Glow discharge and sputtering methods are used to form the surface layer, as it is relatively easy to finely control the composition ratio of the atoms that make up the layer and control the layer thickness compared to other methods. However, when forming a surface layer using these layer formation methods, the characteristics of the surface layer created are influenced by the discharge power and gas pressure during layer formation, as well as the support temperature described above. This is one of the important factors.

Preferably, the discharge power conditions are too
It is desirable that the power is 0 to 5000W, more preferably 200 to 2000W. The gas pressure in the deposition chamber is preferably
lXl0-3 to 0.8 Torr, more preferably 5x10
It is desirable to set it to about -3 to 0.5 Torr.

In the present invention, the support temperature for creating one surface layer,
Desirable numerical ranges for discharge power include the values in the above range, but these layer creation factors cannot be determined independently and separately, and a surface layer made of polycrystalline material with desired characteristics is formed. It is desirable that the optimum value of each layer forming factor be determined based on the mutual organic relationship.

The amounts of carbon atoms and hydrogen atoms contained in the surface layer of the electrophotographic light-receiving member of the present invention are determined to be the same as the conditions for forming the surface layer, such that the surface layer has the desired characteristics to achieve the object of the present invention. This is an important factor in the formation of layers.

In the present invention, the amount of carbon atoms contained in the surface layer is preferably lXl0 with respect to the total amount of silicon atoms and carbon atoms.
'-3 to 90 atomic %, most preferably 10 to 80 atomic %. The content of hydrogen atoms is preferably 1X10-3 to 7 with respect to the total amount of constituent atoms.
0 atom %, more preferably I X 10-2 to 60 atom %
, and the light-receiving member formed when the hydrogen content is within these ranges can be sufficiently applied as a material that is far superior to anything previously seen in practice. .

In other words, it is known that defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer composed of polycrystalline materials have a negative effect on the properties of light-receiving materials for electrophotography. Deterioration of charging characteristics due to charge injection from the surface, fluctuations in charging characteristics due to changes in the surface structure in the usage environment, such as high humidity, and charge on the surface layer from the photoconductive layer during corona charging or light irradiation. is injected into the surface layer, and charges are trapped in defects in the surface layer, resulting in an afterimage phenomenon during repeated use.

However, by making the surface layer a polycrystalline material, the defects in the surface layer are greatly reduced, and as a result, all of the above problems are solved, especially in terms of electrical characteristics and high-speed continuous use. You can make dramatic improvements in your sexuality.

Furthermore, halogen atoms may be contained in the surface layer. As a method for containing halogen atoms in the surface layer, for example, SiF 4 +Si'FH3, Si
2F6,5iF3S iH3.

It may be formed by a glow discharge decomposition method or a sputtering method by mixing a halogenated silicon gas such as 5iC14 or/and a halogenated carbon gas such as CF4.00 4°CH3CF3.

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

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

In addition, the thickness of the surface layer needs to be appropriately determined as desired in relation to the thickness of the photoconductive layer based on the organic relationship depending on the characteristics required for each layer region. There is. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production.

The thickness of the surface layer in the present invention is preferably 0.
003-307t, more preferably 0,004-20l,
The optimum value is 0.005 to 10 JL.

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

In the present invention, the layer thickness of the photoreceptive layer is such that the characteristics imparted to the photoconductive layer and the surface layer constituting the photoreceptor layer are effectively utilized to effectively achieve the object of the present invention. The thickness relationship between the photoconductive layer and the surface layer is determined as desired, so that the thickness of the photoconductive layer is preferably several hundred to several thousand times that of the surface layer. It is preferable that the above conditions be met.

The specific value is preferably 3 to 100 microns, more preferably 5 to 70 microns, and preferably 5 to 50 microns.

In the electrophotographic light-receiving member of the present invention, there is an eye 1111e for further improving the adhesion between the support and the photoconductive layer.
For example, an adhesion layer made of Si3N4,5i02°Sin, an amorphous material containing at least one of hydrogen atoms and halogen atoms, at least one of nitrogen atoms and oxygen atoms, and silicon atoms may be provided. good.

Next, a method for manufacturing a photoconductive member formed by a glow discharge decomposition method will be described.

FIG. 12 shows an apparatus for manufacturing a light receiving member for electrophotography using a glow discharge decomposition method.

1102, 1103, 1104°1105.11 in the diagram
The raw material gas for forming each layer of the present invention is sealed in the gas cylinder 06. For example, 1102 is a 5iH4 (purity 99.999%) cylinder, and 1103 is a gas diluted with H2. B2H6 gas (purity 9
9.999%, hereinafter abbreviated as B 2 H6/H2. ),
Cylinder 1104 is a GeH4 gas (purity 99, 99%) cylinder, 1105 is H2 gas (purity 99.999%), and 1108 is a cH4 gas cylinder.

In order to flow these gases into the reaction chamber 1101, the valves 1122-1126 of the gas cylinders 1102-1106.
Make sure the leak valve 1135 is closed,
In addition, inflow valves 1112 to 1116 and outflow valve 111
After confirming that 7 to 1121 and auxiliary valves 1132 to 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and gas piping. Next, when the vacuum gauge 1136 reads approximately 5XlO-6 torr, the auxiliary valves 1132 and 1133,
Close 7-1112.

To give an example of forming a long wavelength photosensitive layer on the base cylinder 1137, SiH
4 gas, GeH4 gas from gas pump 1104, open valve 1122.1124 and outlet pressure gauge 1127-1
129(7) Adjust the pressure to I K g/cm';
Gradually open inlet valves 1112.1114 to allow flow into mass flow a controllers 1107.1109.

Subsequently, the outflow valves 1117 and 1119 and the auxiliary valve 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. The outflow valve 1117 is adjusted so that the ratio of the SiH4 gas flow rate and the GeH4 gas flow rate at this time becomes a desired value.
1119, and adjust rAo of the main valve 1134 to 3A while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber reaches the desired value.

Then, the temperature of the base cylinder 1137 becomes higher than that of the heating heater 1.
After confirming that the desired temperature is set by 138, the power supply 1140 is set to the desired power and the reaction chamber 1 is turned on.
A glow discharge is generated in 101 to form a long wavelength photosensitive layer on the base cylinder.

When containing halogen atoms in the long wavelength photosensitive layer,
For example, SiF4 gas is further added to the above gas and fed into the reaction chamber 1101.

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

To form a photoconductive layer on the long wavelength photosensitive layer prepared as described above, for example, SiH4 gas, B 2 He gas, B 2 He gas, etc.
/ This is accomplished by flowing H2 gas and, if necessary, diluting gas such as H2 into the reaction chamber 1101 at a desired flow rate ratio to generate glow discharge according to desired conditions.

The amount of boron atoms contained in the photoconductive layer is, for example, SiH
4 gas and B 2 H6/H2 gas introduced into the reaction chamber 1101 can be controlled as desired by arbitrarily changing the flow rate ratio as desired.

Further, the amount of hydrogen atoms contained in the photoconductive layer is, for example, H
It can be controlled as desired by arbitrarily changing the flow rates of the two gases introduced into the reaction chamber 1101 as desired.

To form a surface layer on the photoconductive layer prepared as described above, for example, 5IH4 gas, CH4 gas, and if necessary, This is accomplished by flowing a diluent gas such as H2 into the reaction chamber 1101 at a desired flow rate and generating glow discharge according to desired conditions.

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

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

Needless to say, all outflow valves for gases other than those required for forming each layer are closed.

In addition, when forming each layer, in order to prevent the gas used for forming the previous layer from remaining in the reaction chamber 1101 and in the piping leading from the outflow valves 1117 to 1121 to the reaction chamber 1101, the outflow valve 1117 is closed. - 1121 are closed, the auxiliary valve 1132 is opened, and the main valve 1134 is fully opened to temporarily evacuate the system to a high vacuum, as necessary.

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

<Example 1> Using the manufacturing apparatus shown in FIG. 12, an electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the manufacturing conditions shown in Table 1. Also, using the same type of device as in Figure 12,
Cylinders with the same specifications on which only a surface layer was formed and those on which only a long wavelength photosensitive layer were formed were separately prepared as samples for analysis. The light-receiving member (hereinafter referred to as drum) is set in an electrophotographic device with a digital exposure function using a semiconductor laser with a wavelength of 780 nm as a light source, and the initial chargeability and residual Electrophotographic characteristics such as electric potential and ghosting were checked, and a decrease in charging ability, deterioration in sensitivity, and an increase in image defects after 1.5 million copies were actually processed were investigated. Furthermore, image deletion on the drum was also evaluated in a high temperature φ high humidity atmosphere of 35° C. and 85%. And the drums that have been evaluated.

Cut out the parts corresponding to the top, middle, and bottom of the image area and insert the SIM
The hydrogen contained in the surface layer was quantitatively analyzed using S. For samples with only the surface layer or only the wavelength-sensitive layer, after cutting out the portions corresponding to the upper, middle, and lower portions of the sample in the generatrix direction, use an X-ray diffraction device to obtain 5i ( A diffraction pattern corresponding to 111) was obtained, and the presence or absence of crystallinity was investigated. The above evaluation results, the hydrogen content in the surface layer, and the presence or absence of crystallinity in the surface layer and long-wavelength photosensitive layer are summarized in Table 2. 1. Significant superiority was observed in each of the following items: image deletion, residual potential, ghost, and increase in image defects.

Comparative Example 1> Drums and samples were produced using the same apparatus and method as in Example 1, except that the production conditions were changed as shown in Table 3, and were subjected to the same evaluation and analysis. The results are shown in Table 4.

As can be seen in Table 4, it was found to be inferior to Example 1 in various items.

<Example 2> Using the manufacturing apparatus shown in FIG. 12, an electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the manufacturing conditions shown in Table 5. Also, using the same type of device as in Figure 12,
Cylinders with the same specifications on which only a surface layer was formed and those on which only a long wavelength photosensitive layer were formed were separately prepared as samples for analysis. The light receiving member (hereinafter referred to as drum) has a wavelength of 780 nm.

It was set in an electrophotographic device with digital exposure function using a semiconductor laser as a light source, and electrophotographic characteristics such as initial charging ability, residual potential, and ghost were checked under various conditions. Deterioration of charging ability and sensitivity after drinking sake 2
The increase in image defects was investigated. Furthermore, image deletion on the drum was also evaluated in a high temperature, high humidity atmosphere of 85% at 35°C. After the evaluation was completed, the drum was cut out into parts corresponding to the upper middle and lower part of the image area and subjected to quantitative analysis of hydrogen contained in the surface layer using SIMS. The component profile of germanium (Ge) in the layer thickness direction was investigated. On the other hand, for samples with only the surface layer and only the long wavelength photosensitive layer, after cutting out the parts corresponding to the top, middle, and bottom of the sample ff1 line direction, the 5i ( A diffraction pattern corresponding to 111) was obtained, and the presence or absence of crystallinity was investigated. The above evaluation results, the hydrogen content in the surface layer, and the presence or absence of crystallinity of the surface layer and long wavelength photosensitive layer are summarized in Table 6. or,
FIG. 15 shows the component profile of the element in the long wavelength photosensitive layer.

As seen in Table 6, especially the initial charging capacity.

Significant superiority was observed in many items including residual potential, ghost, increase in image deletion, 1 image defect, 9 image defects, and interference fringes.

<Example 3 (Comparative Example 2)> The conditions for forming the surface layer were changed to several conditions shown in Table 7, and only a plurality of drums and the surface layer were formed under the same conditions as in Example 1 except for the following. Samples for analysis were prepared. These drums and samples were subjected to the same evaluation and analysis as in Example 1, and the results shown in Table 8 were obtained.

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

<Example 5> The conditions for producing the long wavelength photosensitive layer were changed to several conditions shown in Table 11, and only the plurality of drums and the long wavelength photosensitive layer were formed under the same conditions as in Example 1 except for the above conditions. A sample for analysis was prepared. These drums and samples were subjected to the same evaluation and analysis as in Example 1, and the results shown in Table 12 were obtained.

<Example 6> Only the plurality of drums and the long wavelength photosensitive layer were formed under the same conditions as in Example 1, except that the conditions for producing the long wavelength photosensitive layer were changed to several conditions shown in Table 13. A sample for analysis was prepared. These drums and samples were subjected to the same evaluation and analysis as in Example 1, and the results shown in Table 14 were obtained.

<Example 7> An adhesive layer was formed on the base cylinder under several manufacturing conditions shown in Table 15, and a light-receiving member was further formed on the adhesive layer under the same manufacturing conditions as in Example 1. was formed. Separately, a sample was prepared in which only an adhesive layer was formed. The light-receiving member was evaluated in the same manner as in Example 1, and a portion of the sample was cut out and measured at a diffraction angle of 2 using an X-ray diffraction device.
A diffraction pattern corresponding to 5i (111) around 7° was obtained to examine the presence or absence of crystallinity.

The above results are shown in Table 16.

<Example 8> An adhesive layer was formed on the base cylinder under several manufacturing conditions shown in Table 17, and a light-receiving member was further formed on the adhesive layer under the same manufacturing conditions as in Example 1. Formed. Separately, a sample was prepared in which only an adhesive layer was formed. The light-receiving member was evaluated in the same manner as in Example 1, and a portion of the sample was cut out and measured at a diffraction angle of 27° using an X-ray diffraction device.
A diffraction pattern corresponding to nearby 5i(111) was obtained to examine the presence or absence of crystallinity. The above results are shown in Table 18.

<Example 9> The mirror-finished cylinder was further subjected to lathe processing using a sword bit with various angles, and a plurality of cylinders with cross-sectional shapes as shown in Fig. 13 and various cross-sectional patterns as shown in Table 19 were obtained. I have prepared a book. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 12 and subjected to drum manufacturing under the same manufacturing conditions as in Example 1. The produced drum has a wavelength of 780 nm.
Various evaluations were carried out using an electrophotographic device with a digital exposure function using a semiconductor laser having a wavelength of 1 as a light source, and the results shown in Table 20 were obtained.

Example io The mirror-finished cylinder surface is subsequently subjected to multiple bearing drops, resulting in numerous dents on the cylinder surface.

A plurality of cylinders were prepared which had been subjected to a so-called surface dimple treatment and had a cross-sectional shape as shown in FIG. 14 and various cross-sectional patterns as shown in Table 21. 1 of the cylinders in sequence
It was set in the manufacturing apparatus shown in FIG. 2 and subjected to drum manufacturing under the same manufacturing conditions as in Example 1. The produced drum is 78
Various evaluations were conducted using an electrophotographic apparatus with a digital exposure function using a semiconductor laser having a wavelength of 0 nm as a light source, and the results shown in Table 22 were obtained.

[Summary of effects of the invention]

The light-receiving member of the present invention has a photoconductive layer composed of A-3t (H, It can solve all the problems with conventional electrophotographic light-receiving members composed of
It has characteristics such as continuous slight reversal use characteristics, electrical pressure resistance, use environment characteristics, and durability. In addition, there is no influence of residual potential, and its electrical characteristics are stable, so the images obtained using it are stable.

The density is high and the halftones come out clearly, making it extremely outstanding.

[Brief explanation of drawings]

Figure t51 is a schematic layer configuration diagram for explaining the layer configuration of the electrophotographic light-receiving member of the present invention. FIGS. 2 to 7 are explanatory diagrams explaining the distribution state of contained atoms in the layer, FIGS. 8 to 11 are uneven shapes on the surface of the support, and FIG. 12 shows the uneven portions according to the present invention. FIG. 2 is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method, which is an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography. FIG. 13 and FIG. 14 are explanatory diagrams showing the cross-sectional shape of one embodiment of the present invention, respectively. Figure 15 is. FIG. 3 is an explanatory diagram showing the distribution state of germanium atoms contained in a layer. Regarding FIG. 1, 100---------1----electrophotographic light-receiving member;
10 L-----1--Support, 102--
--------One photoreceptive layer, 103---------
- one photoconductive layer, 104--- one--- surface layer,
↓05--------One free surface, 106----
~-11---Long wavelength photosensitive layer. 1500 for FIG. 3 - one photoreceptive layer. Light-receiving member for electrophotography, 1501---------Ichisho Tokutai, 1! '; Q 9-1---- JXmJ#half jl
$l141502-2---One photoconductive layer, 1503---One surface layer, 1504---One free surface. Regarding Figures 4 and 5, 1601.1701----Ichisho Special, 1602.1
702-----One support surface, 1603.1703-
----One rigid true sphere, 1604.1704---One spherical trace depression, 1101 for FIG. 6---One reaction chamber. 1102~1106------Gas cylinder, 1107~
l 111---Mass flow controller. 1112~t i i 5----First-class valve, 11
17~1121---First outlet valve, 1122~l
126----- Valve, 1127-1131----
- Pressure regulator, 1132, 1133 - - Auxiliary valve, 1134 - Main valve, 1135 - -Leak valve, 1136--------Vacuum gauge, 1137-----Base cylinder, 1138-- ---------Heating heater, 1139------------
Motor, 1140-------------High frequency power supply. Silk 8

Claims (4)

[Claims] (1) a support; a long-wavelength photosensitive layer made of a polycrystalline material containing silicon atoms and germanium atoms on the support and sensitive to long-wavelength light; and a matrix made of silicon atoms;
A photoconductive layer composed of an amorphous material containing at least one of hydrogen atoms and halogen atoms as a constituent element and exhibiting photoconductivity, and a polycrystalline material containing silicon atoms, carbon atoms, and hydrogen atoms as constituent elements. 1. A light-receiving member for electrophotography, comprising: a surface layer comprising a surface layer; and a light-receiving layer comprising: (2) The electrophotographic light-receiving member according to claim 1, wherein the surface layer contains halogen atoms. (3) The photoconductive layer contains at least one of carbon atoms, oxygen atoms, and nitrogen atoms.
The electrophotographic light-receiving member according to Items 1 and 2. (4) The photoreceptor for electrophotography according to claims 1 to 3, wherein the long wavelength photosensitive layer contains at least one of a substance controlling conductivity, an oxygen atom, and a nitrogen atom. Element.