JPS62183466A - Light receiving member - Google Patents

Abstract

PURPOSE:To enhance durability and humidity resistance by forming on a substrate a light receiving layer composed of the first photoconductive layer made essentially of Si, and the second layer made essentially of Si and containing C. CONSTITUTION:The light receiving member 100 is composed of a substrate 101 and the light receiving layer obtained by laminating on the substrate 101 the first photoconductive layer 102 made of an amorphous material composed essentially of Si, and the second layer 103 of an amorphous material composed essentially of Si and containing C. The first layer 102 contains a conductivity governing substance in a nonuniform distribution, and the second layer 103 contains it in a uniform distribution, and an element included in group III or V of the periodic table is used for said substance, thus permitting durability and humidity resistance to be enhanced.

Description

[Detailed Description of the Invention] [Technical Field to which the Invention Pertains] The present invention relates to the use of light such as light (here, light in a broad sense, meaning ultraviolet rays, visible light, infrared rays, X-rays, γ-rays, etc.). The present invention relates to a light-receiving member sensitive to electromagnetic waves.

[Description of prior art]

As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it has high sensitivity and a high signal-to-noise ratio [photocurrent (Ip)].
/dark current (Id)': has a high value of 1, has a high absorption spectrum that matches the spectral characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, and has a desired dark resistance value.
Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use and being able to easily dispose of afterimages within a predetermined time. Especially,
In the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is important.

Based on this point, amorphous silicon (hereinafter referred to as a-81) is a photoreceptive material that has recently attracted attention.
No. 55718 describes its application as an image forming member for electrophotography, and German Published Publication No. 293!1411 describes its application to a photoelectric conversion/reading device.

However, the conventional photoreceptive member having a photoreceptive layer composed of a-8i has poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and usage environment characteristics. , and in terms of stability and durability over time, respectively.
Although individual characteristics have been improved, the reality is that there is still room for further improvement in terms of overall characteristics improvement.

For example, when applied to electrophotographic image forming members, 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 the occurrence of a ghost phenomenon, which is an afterimage.

When the photoreceptive layer is made of a-8i 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 included for control purposes, and other atoms are included as constituent atoms in the photoreceptive layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, However, 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 by light irradiation in the photoreceptive layer after formation is not sufficient, or the injection of charge from the support side in a dark area is not sufficiently prevented, or Images transferred to transfer paper may have image defects commonly called "white spots," which are thought to be caused by localized discharge breakdown, and when a blade is used for cleaning, there may be "white streaks," which may be caused by rubbing. Image defects that are said to 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.

Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes after it is left in the air after being removed from the vacuum deposition chamber for skin formation. This tends to cause phenomena such as This phenomenon often occurs particularly when the support is a drum-shaped support commonly used in the field of electrophotography, and there are issues that need to be resolved in terms of stability over time.

Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing a light-receiving member.

[Purpose of the invention]

The present invention aims to solve various problems in a light receiving member having a light receiving layer made of a-Si as described above.

In other words, the main object of the present invention is to have electrical, optical, and photoconductive properties that are essentially stable at all times without depending on the usage environment, have excellent light fatigue resistance, and are durable even after repeated use. The object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-Si, which does not cause deterioration, has excellent durability and moisture resistance, and has no or almost no residual potential observed.

Another object of the present invention is that when applied as an electrophotographic image forming member, it has sufficient charge retention ability during charging processing for electrostatic image formation, and ordinary electrophotographic methods can be applied extremely effectively. An object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-Si and having excellent electrophotographic properties.

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

Still another object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-Si and having high photosensitivity, high signal-to-noise ratio characteristics, and high electrical voltage resistance.

[Structure of the invention]

The present invention achieves the above-mentioned objects, and provides product feasibility and applicability of a-Si as a light-receiving member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc.
As a result of comprehensive and intensive research, including matters such as applicability, we have discovered an amorphous material with a silicon atom as its matrix, especially a silicon atom as its matrix, and at least one of a hydrogen atom (6) or a halogen atom. an amorphous material containing
Light that has a photoreceptive layer composed of so-called hydrogenated amorphous silicon, halogenated a7alphasic silicon, aluminum or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "a-8i (H,X)J"]. A light-receiving member designed and produced with a specific layer structure as described below not only exhibits significantly superior properties in practical use, but also exhibits superior properties compared to conventional light-receiving members. It was completed based on the discovery that it is superior in all respects, and has particularly excellent properties as a light-receiving member for electrophotography.

That is, the light-receiving member of the present invention includes a support, a photoconductive first layer made of an amorphous material containing silicon atoms as a matrix, and a photoconductive first layer on the support. a second layer made of an amorphous material containing carbon atoms; The second layer is characterized in that the second layer contains a substance that controls conductivity in a uniform distribution state.

In particular, the amorphous material having silicon atoms as a matrix constituting the first layer is silicon atoms (Sl).
an amorphous material containing at least either a hydrogen atom (6) or a halogen atom (3),
That is, a-8i (H+X) is used, and the amorphous material containing silicon atoms as a matrix and containing carbon atoms, which constitutes the second layer, is particularly composed of silicon atoms ($1) as a matrix and carbon atoms (C) and a hydrogen atom) or a halogen atom■
[hereinafter referred to as ra-8iC(H,X)J]
Le. ] Use it.

The substances that control conductivity include so-called impurities in the semiconductor field, which include atoms belonging to group I of the periodic law (hereinafter referred to as group II atoms) that give P-type conductivity. , or periodic table item ■ giving n-type conductivity.
Atoms belonging to the group (hereinafter referred to as cylindrical group atoms) are used.

Specifically, the m-th group atoms include B (boron), At(
Particularly preferably B,
Ga is used. In addition, as group V atoms, P (phosphorus),
As (arsenic), sb (antimony), Bi (bismuth), etc. are used, particularly preferably P%A, 9. and a substance that controls conductivity contained in the first layer;
The substance that controls conductivity contained in the second no is
They may be the same or different.

In the light-receiving member of the present invention, these conductivity-controlling substances are contained in the first layer in a non-uniform distribution in the entire layer region or in a part of the layer region, and the second layer The layer is uniformly distributed throughout the entire layer area.

The purpose and effect of containing the conductivity controlling substance in the first layer vary depending on the state in which it is distributed and contained in the second layer, as described below.

That is, when the first layer contains a relatively large amount of a substance that controls conductivity on the side in contact with the support, the first layer is effective as a charge injection blocking layer. In this case, t of the substance controlling conductivity to be contained is relatively large, and is generally 30 to 5X 1
04 atomic ppm, preferably 50~
IX1lX104ato ppm s optimally lX10
2-5×105 atomic ppm.

Also, contrary to the above case, when a relatively large amount of the substance that controls conductivity is contained on the side of the first layer that is in contact with the second layer, the first layer and the second layer If the conductivity type of the substance controlling the conductivity contained in is the same,
The effect of improving the energy level matching between the first layer and the second layer and increasing the charge transfer between the two layers is achieved, and this effect is achieved when the second layer is thick and dark. This is especially noticeable when the resistance is high.

Furthermore, in the case where a substance that controls conductivity is contained in a relatively large amount on the side of the first layer that is in contact with the second layer, the substance that controls conductivity is contained in the first layer and the second layer. If the conductivity of the substances differs, the region of the T-layer containing a large amount will actively serve as the junction between the first layer and the second layer, and the apparent increase in dark resistance during the charging process will occur. It has the effect of measuring.

When a relatively large amount of a substance that controls conductivity is contained on the side of the first layer that is in contact with the second layer,
In either case, a relatively small amount of itf'i is required, and a typical VC is I X 10-5 to I X 10' a
tomic ppm, preferably 5X10-2
~5 X 102 atomic ppm, optimally lX
10-1 to 2 x 102 atomic ppm.

Next, the purpose of containing carbon atoms and a substance that controls conductivity in the second layer will be explained.

The second layer of the light-receiving member of the present invention is provided on the first layer for the purpose of improving moisture resistance, continuous repeated use characteristics, electrical pressure resistance, usage environment characteristics, durability, and the like. This objective can be achieved by structurally introducing carbon atoms into the amorphous material constituting the second layer.

When carbon atoms are structurally introduced into the second layer, the aforementioned properties improve with the increase in the amount of carbon atoms, but too large an amount of carbon atoms deteriorates the layer quality and increases the electrical and Mechanical properties are also reduced.

From these facts, the content t of carbon atoms is usually I
10-5 to 90 atomic %, preferably 1 to 9 Q atomic %, optimally 10 to 80 a
tomic%.

Furthermore, in order to improve the characteristics and durability of continuous repeated use, it is preferable to increase the thickness of the second layer.
If the thickness is increased, residual potential may be generated. For these reasons, a substance that controls conductivity is added to the second layer, that is,
By containing a group atom or a group V atom, the generation of the residual potential described above can be prevented or suppressed to the extent that it has no substantial effect.

Normally, this kind of second layer has excellent mechanical durability, but if the surface of the layer is rubbed or pressed with something with a sharp tip, the optical surface will be damaged. Even if they do not remain as so-called scratches, they often appear as electrostatic trace scratches during the charging process, resulting in a deterioration in the image quality of the fz toner transfer image. Even in such cases, these problems can be prevented from occurring by making the second 1- contain a substance that controls conductivity.

Specific examples of the halogen atom (3) to be included in the first layer and the second layer of the present invention, if necessary, include chlorine, bromine, and iodine, but particularly preferred are These are fluoride and chlorine.

In addition, the amount of hydrogen atoms (6) contained in the first layer and the second layer of the present invention, the amount of hydrogen atoms (3), or the amount of hydrogen atoms (a) and The sum of the quantities is
The content is generally 0.01 to 40 atomic %, preferably 0.05 to 30 atomic %, and optimally 0.1 to 25 atomic %.

The layer thickness of the first layer and the layer thickness of the second layer in the present invention are one of the important factors for efficiently achieving the purpose of the present invention, and are determined as appropriate depending on the intended purpose. Although it is determined, the oxygen atoms contained in each type, Group II atoms,
It is also necessary to determine the amount of Group Ⅰ atoms, carbon atoms, hydrogen atoms, hydrogen atoms, and the thickness of each layer based on mutual and organic relationships depending on the required properties. be. Furthermore, it is necessary to consider economic efficiency, which also takes into account productivity and mass production. For this reason, the layer thickness of the first layer is usually 1 to 100 μm, preferably 1 μm.
~80μ, optimally between 2 and 50μ, and the layer thickness of the second layer is typically between 3X10-5 and 50μ, preferably 4X10-5
~20μ, optimally 5X10-5~10μ.

By having the above-described layer structure, the light-receiving member of the present invention can solve all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon, and has extremely excellent electrical and optical properties. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, and its electrical properties are excellent. It is stable, has high sensitivity, has a high 8N ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably produce high-quality images with high density, clear halftones, and high resolution. can be obtained repeatedly.

Further, in the light-receiving member of the present invention, the light-receiving layer formed on the support is strong and can be repeatedly used at high speed and continuously for a long time.

Hereinafter, the specific layer structure of the light-receiving member of the present invention will be explained in detail with reference to the drawings.

FIG. 1 is a diagram schematically showing the layer structure of the light-receiving member of the present invention. In the figure, 100 is the light-receiving member, 101 is the support, 102 is the first layer, and 103 is the first layer. The second layer, 104, represents the free surface.

The support 101 used in the present invention may be electrically conductive or electrically insulating, and examples of the electrically conductive support include Ni
Cr, stainless steel, kA, cr, Mo, Au, N
Examples of the electrically insulating support include metals such as b, Ta, V, T1, pt, and pb, and alloys thereof, and examples of the electrically insulating support include polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, A film or sheet of synthetic resin such as polystyrene or polyamide, glass, ceramic, paper, etc. is used. 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, NiCr is applied to its surface.

At, CrS Mo, Au, Ir, Nb, Ta, v,'
ri, PtS Pd.

Engineering n204, Sn○2, ITO (In20g +8nO
2) Conductivity can be imparted by providing a thin film consisting of NiCr5At, Ag5Pb, Zn, etc., or if it is a synthetic resin film such as a polyester film.
Ni, Au.

Cr, Mo, Ir5Nb, Ta, V, Ti, pt
Conductivity is imparted to the surface by providing a thin film of metal such as by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. The shape of the support can be any shape, such as a cylinder, a belt, or a plate, and the shape is determined depending on the need. For example, if it is used as an electrophotographic image forming member, a continuous In the case of high-speed copying, it is desirable to use an endless belt or a cylindrical shape. The thickness of the support is appropriately determined so as to form a desired light-receiving member, but if flexibility is required as a light-receiving member, the thickness of the support should be determined within a range that can sufficiently function as a support. can be made as thin as possible.

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

The first layer 102 is provided on the support 101 and is made of a material that controls conductivity, that is, a-8i (H, Hereinafter, it will be written as ra-8iM(H,X)J (where M represents a group m atom or a group V atom). ] and is a photoconductive layer. mth layer in the -th layer
Group atoms or Group V atoms are distributed so that the distribution concentration in the layer thickness direction is non-uniform, but the distribution state in the plane parallel to the support surface is uniform. are doing.

The distribution state of group m atoms or group V atoms when the distribution concentration C of group m atoms or group V atoms is nonuniform in the layer thickness direction will be described below.

2 to 10 show that a relatively large amount of group m atoms or group V atoms is contained on the support side, and the content of group m atoms or group V atoms is changed from the support side to the second layer. A typical example is shown in which the amount is gradually decreased toward the adjacent side. In the figure, the horizontal axis shows the distribution concentration C of group (I) or group V atoms, and the vertical axis shows the layer thickness t of the first layer. Further, tB indicates the interface position where the support surface and the first layer are in contact, and tT indicates the interface position between the first layer and the second layer.

FIG. 2 is a diagram illustrating a first typical example of the distribution state of group (I) atoms or group V atoms contained in the first layer in the layer thickness direction. In this example, from the interface position tB where the first layer containing Group Ⅰ atoms or Group V atoms and the surface of the support are in contact with each other, to the position tl, the distribution concentration of Group Ⅰ atoms or Group Ⅰ atoms is C takes a constant value of 01, and from position t1 to interface position tT where the first layer contacts the second layer,
The distribution concentration C of group atoms or group V atoms decreases continuously from the concentration C2, and the distribution concentration of group m atoms or group V atoms becomes 03 at the interface position tT.

FIG. 3 shows another typical example, and in the example shown in FIG. Up to 1T,
The concentration decreases continuously from C4 and reaches C5 at position tT.

In the example shown in FIG. 4, from position tE to position t2, the distribution concentration C of group (III) atoms or group (III) atoms maintains a constant value of concentration C6, and from position t2 to position tT, the concentration The distribution density C decreases continuously from C7 and becomes substantially zero at the position tT. (Here, "substantially zero" is used when the value is below the detection limit.) In the example shown in FIG. 5, the distribution concentration C of group II atoms or group V atoms is from position tB to position #tT Until then, the concentration decreases continuously from C8, and the distribution concentration is substantially zero at position tT.

In the example shown in FIG. 6, the distribution concentration C of Group II atoms or Group V atoms is a constant value of concentration C9 between position tB and position #ts, and between position t3 and position t4, The concentration decreases continuously from C9 to substantially zero, and the manner of decrease shows a linear function decrease.

In the example shown in FIG. 7, the distribution concentration C of group (IV) atoms or group V atoms is the concentration C11 from position tB to position t4.
The concentration CI2 is kept constant between the position t4 and the position station.
It decreases in a linear manner from to the concentration C13.

In the example shown in FIG. 8, the distribution concentration C of group m atoms or group
It decreases linearly until it becomes substantially zero.

In the example shown in FIG. 9, the distribution concentration C of the melon group atoms or group (Ⅰ) atoms decreases linearly from the concentration C15 to the concentration C16 from the position tB to the position t5, and from the position t5 to the position C16. Until tT, the concentration C16 is maintained at a constant value.

Finally, in the example illustrated in FIG.
7, from position tB to position t6, the concentration initially decreases slowly from C17, rapidly decreases near position t6, and reaches the concentration 01B at position t6. Further, between position t6 and position t7, the concentration decreases rapidly at first, and then decreases slowly and gradually, and reaches the concentration C19 at position t7. Further, the concentration decreases very slowly and gradually between the positions t7 and t8, and the concentration reaches 0 at the position t8.
It becomes 20. Furthermore, from position t8 to position t2, the concentration gradually decreases from C18 until it becomes substantially zero.

As in the examples shown in FIGS. 2 to 10, the distribution concentration C of group II atoms or group V atoms is on the side closer to the support side of the first layer.
Preferably, the distribution concentration C has a portion where the concentration is considerably low or a portion where the concentration is substantially close to zero on the interface side of the first layer with the second layer. As mentioned above, there is a localized region A in which the distribution concentration of Group V atoms or Group V atoms is relatively high in a portion close to the support side.
Particularly preferably, when the localized region A is provided within 5μ from the interface position in contact with the support surface,
The layer region in which the distribution concentration of group (I) or group V atoms is high is responsible for the effect as a charge injection blocking layer.

As mentioned above, in the present invention, the distribution state of group (I) atoms or group (I) atoms can be freely determined depending on the purpose, and FIGS. 2 to 10 are only examples. it is obvious. That is, in other distribution states, for example, when the distribution concentration of group (III) atoms or group (III) atoms at the interface side of the first layer with the second layer is relatively high, or when the distribution concentration of group (III) atoms is relatively high, In the case where the distribution concentration of Group Ⅰ atoms or Group V atoms in the part is relatively high,
The distribution state shown in the figure can be applied and used as appropriate.

The second layer 103 of the present invention is provided on the first layer 102, and contains carbon atoms and a substance that controls conductivity, that is, a group (III) atom or a group (III) atom. −
sl(a,x) l:Hereinafter, ra-slcM(H,X)
It is written as J (where M represents a Group Ⅰ atom or a Group V atom). ] Consists of.

The carbon atoms and Group I atoms or Group V atoms in the second layer are distributed so as to be uniform in the layer thickness direction and in the plane parallel to the support surface. be.

The second layer 103 must be carefully formed to obtain the desired properties. In other words, substances whose constituent atoms are silicon atoms, carbon atoms, hydrogen atoms, and/or halogen atoms, and group II atoms or group V atoms have crystalline forms depending on the content of each constituent atom and other conditions of creation. electrical properties range from conductivity to semiconductivity to insulating properties, and photoelectric properties range from photoconductive properties to non-photoconductive properties. It is important to select the content of each constituent atom, production conditions, etc. so that the second layer 103 having desired characteristics can be formed.

For example, when the second layer 103 is provided with the main purpose of improving electrical withstand voltage, the amorphous material constituting the second layer 106 has a remarkable electrically insulating behavior under the usage conditions. Form. In addition, when the second layer 103 is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the amorphous material constituting the second layer 103 has the above-mentioned degree of electrical insulation. Although it alleviates it to some extent,
It is formed to have a certain degree of sensitivity to the irradiating light.

Next, a method for forming the photoreceptive layer of the present invention will be explained.

The amorphous material constituting the photoreceptive layer of the present invention is deposited by a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blasting method. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level of equipment capital investment, manufacturing scale, and desired characteristics of the light-receiving member to be manufactured. The glow discharge method or the sputtering method is preferable because it is relatively easy to control the conditions for manufacturing the receiving member, and carbon atoms and hydrogen atoms can be easily introduced together with silicon atoms. be.

Further, the glow discharge method and the sputtering method may be used together in the same apparatus system.

For example, to form a layer composed of a-8i (H, 6) A raw material gas for introduction or/and \rogen atoms ■ is introduced into a deposition chamber whose interior can be made to have a reduced pressure, and a glow discharge is generated in the deposition chamber. A layer consisting of a-8i(H,X) is formed on the surface of the support.

Specific examples of the atomic atom that may be included in the layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

The raw material gas for supplying S1 includes SiH4, Si2
Gaseous or gasifiable silicon hydride (silanes) such as H6,81sHs, 814H10, etc. may be mentioned, and in particular,
81 in terms of ease of layer creation work, good S1 supply efficiency, etc.
H4 and Si2H6 are preferred.

Further, as the raw material gas for introducing halogen atoms, there are many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen compounds in a gaseous state such as halogen-substituted silane derivatives, or halogen compounds that can be gasified. is preferred.

Furthermore, silicon compounds containing silicon atoms and halogen atoms, which are in a gaseous state or can be gasified, can also be mentioned as effective compounds. Specifically, halogen compounds include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CLF, and ClF.
3, BrF5, BrF3, IFg, IF7, ICt,
Examples include halogen compounds such as IBr, and examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include SiF4, E3i2F,
Preferable examples include silicon halides such as 6.5iCta and B1Br4.

When forming by glow discharge method using such a silicon compound containing halogen atoms, halogen atoms can be formed on a predetermined support without using silicon hydride gas as a raw material gas that can supply Sl. A layer consisting of a-8i containing a-8i can be formed.

When forming a layer containing halogen atoms using the glow discharge method, basically, silicon halide gas, which is a raw material gas for supplying Si, and gases such as Ar, H2, He, etc. are mixed at a predetermined mixing ratio. A layer can be formed on a predetermined support by introducing a gas into a deposition chamber at a certain flow rate and causing a glow discharge to form a plasma atmosphere of these gases. In order to measure the introduction of atoms, a predetermined amount of a silicon compound gas containing hydrogen atoms may be mixed with these gases.

Moreover, each gas may be used not only singly but also in a mixture of multiple types at a predetermined mixing ratio.

To form a layer of a-8i (H, Sputtering is performed in an atmosphere, and in the case of the ion blating method, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is used by a resistance heating method, an electron beam method (EB method), etc. This can be carried out by heating and evaporating the flying evaporated material and passing it through a predetermined gas plasma atmosphere.

At that time, in order to introduce hydrogen atoms into the layer formed by either the sputtering method or the ion blasting method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. A plasma atmosphere of the gas may be formed by introducing the gas into the gas.

Further, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H2 or the above-mentioned 7Ran gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Bye.

When forming a layer by glow discharge method, sputtering method, ion blating method, etc., the above-mentioned halogen compounds or halogen-containing silicon compounds can be effectively used as the raw material gas for introducing halogen atoms. In addition, HF, He2. HBr5H
Hydrogen halides such as I, 81H2F2.5iH2I2,
SiH+CL2.5iHCLs, 81H2Br 2.8
Halogenated compounds having hydrogen atoms as one of their constituents, such as halogen-substituted silicon hydrides such as iHBrs, which are in a gaseous state or can be gasified, can also be mentioned as effective starting materials.

These halides containing hydrogen atoms can 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.
It can be used as a suitable raw material for introducing halogen atoms.

In order to structurally introduce hydrogen atoms into the layer, in addition to the above, H
2, or SiH4, 512Hs, 5i3Ha, Si4
This can also be carried out by causing a discharge by causing a silicon hydride gas such as H10 to coexist with a silicon compound for supplying 81 in the deposition chamber.

For example, in the case of the reactive sputtering method, an S1 target is used, and a plasma atmosphere is created by introducing a gas for introducing halogen atoms and H2 gas, including an inert gas such as He5Ar as necessary, into the deposition chamber. , a skin of a-8i (H,X) is formed on the support by sputtering the S1 target.

The amount of hydrogen atoms, the amount of halogen atoms, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the light-receiving layer of the light-receiving member of the present invention is usually 1 to 40a.
tomIC%, preferably 5 to 60 atomic%.

In order to control the amount of hydrogen atoms (6) and/or halogen atoms (3) contained in the light-receiving layer, for example, the support temperature and/or the amount of hydrogen atoms can be controlled, or the amount of halogen atoms (3) can be controlled. The amount of starting material introduced into the deposition system, the discharge force, etc. may be controlled.

The first layer is a-8i (H,
H, X) containing a carbon atom and a group 1 atom or a group When forming a layer of a-8i (H, ,

For example, the second layer is a-5iC(H,X) [hereinafter referred to as a-8iCM(H,
, ], but in order to form the second skin by the glow discharge method, a-8iCM
The raw material gas for forming (H, A-8iCM is formed on the first layer already formed on the support by turning the gas into gas plasma by generating a glow discharge.
(H,X) may be deposited.

As the raw material gas for a-8iCM(H,X) formation, S
i.

Any substance made by gasifying a gaseous or gasifiable substance containing at least one of CSE and/or a halogen atom, and a Group I atom or a Group V atom. There may be.

When using a raw material gas containing Sl as a constituent atom of Sl, C, H and/or a halogen atom, a group (Ⅰ) atom, or one of group (Ⅰ) atoms, for example, a raw material gas containing Sl as a constituent atom and , a raw material gas containing C as a constituent atom, a raw material gas containing H and/or a halogen atom as a constituent atom, and a raw material gas containing a Group Ⅰ atom or a Group Ⅰ atom in a desired mixing ratio. Or, a raw material gas containing Sl as a constituent atom, a raw material gas containing C and H and/or halogen atoms as constituent atoms, and a raw material gas containing Group Ⅰ atoms or Group Ⅰ atoms as constituent atoms. are also mixed at a desired mixing ratio, or a raw material gas containing Sl as a constituent atom and S
It is possible to use a mixture of a raw material gas having three constituent atoms: 1, C, H, and/or halogen atoms, and a raw material gas having group Ⅰ atoms or group V atoms as constituent atoms.

Alternatively, a raw material gas containing Sl, H and/or halogen atoms as constituent atoms, a raw material gas containing C as constituent atoms, and a raw material gas containing group m atoms or group (Ⅰ) atoms as constituent atoms are mixed. You may also use it as

SiH4, 812H6, 5i5H8, 5i4H1o, whose constituent atoms are 8i and H, can be effectively used as a raw material gas for forming a layer composed of a-stc (a, x).
silicon hydride gas such as silanes (5ilane),
For example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like, which have C and H as constituent atoms, can be mentioned.

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (C2H6), propane (C3HB), n-
Methane (n-C4H1oχ pentane (C5H12), ethylene hydrocarbons include ethylene (C2H4), propylene 7 (C3H6), buf y-1 (C4H8),
Buti 7-2 (C4H8).

Isobutyne (CaHa), Pentene (CsHlo)
), acetylene hydrocarbons include acetylene (C2
H2), methylacetylene (C3H4), butyne (C4
H6) and the like.

As a raw material gas whose constituent atoms are Sl, C, and H, 5
Examples include alkyl silicides such as x(cH3)4 and si(C2H5)4. In addition to these raw material gases, H
Of course, H2 can also be used as the raw material gas for introduction.

When a glow discharge method is used to form a layer containing @■ group atoms or a group V atom, the starting material serving as the raw material gas for forming these layers or layer regions is a-8i (H,
A starting material selected from among the starting materials for forming X) or a-8iC(H,

As a starting material for introducing a melon group atom or a group II atom,
Any gasified substance that is a gaseous substance that is a group M atom or a group V atom or a substance that can be gasified can be used.

Specifically, starting materials for the introduction of group Ⅰ atoms include B2H6, B4H10, B5H9, B2H6, B4H10, B5H9,
Examples include boron hydrides such as 5H11, B6H10SB6H12, and B6H14, and boron halides such as BF3, BCl2, and BBr3. In addition, kLcLs, GaCl2
, oa(cH3)2, InCl3, TtCL5, etc. can also be mentioned.

As starting materials for introducing Group V atoms, specifically for introducing phosphorus atoms, hydrogen ratios such as PH5, P2H4, PH
4 engineering, PF5, PF5, pct3, PCl5, PBr!
Examples include halogen ratios such as S, PBrs, and PI5.

In addition, AsHs, AsF3, kscts, A3Br3
, ASF5, SbH,, 5bFs, SbF5, F3bC
Ls, 5bcts, BiH5, B1CAs, B1Br
s and the like can also be mentioned as effective starting materials for introducing Group V atoms.

When forming the first layer and second layer of the present invention by glow discharge method, sputtering method, etc., a-8i(H,
) The content of carbon atoms, group II atoms, or group V atoms introduced into the deposition chamber depends on the gas flow rate of the starting material introduced into the deposition chamber, the gas flow rate ratio, the discharge power, the support temperature, the deposition It can be controlled arbitrarily by controlling the indoor pressure, etc.

The support temperature is normally desirably 500 to 350C, preferably 100 to 250C. The discharge power conditions are appropriately selected taking into consideration the function of each layer, and specifically, 0.005 to 50" II
It is normal to set the range to /cs2.

However, preference is given to the range from 0.01 to 30 W/32, particularly preferably from 0.01 to 20 W/32. In addition, the gas pressure in the deposition chamber is usually 0.01 to ITorr,
It is desirable that the pressure is preferably about 0.1 to 0.5 Torr.

Desirable numerical ranges for the support temperature and discharge power include the values in the above ranges, but these layer creation factors are usually not determined independently and separately;
It is desirable to determine optimal values for each layer formation factor based on their mutual and organic relationships in order to form an amorphous layer with desired properties.

In the present invention, when forming the first layer, the distribution concentration of group (III) atoms or group (III) atoms contained in the layer is changed in the layer thickness direction to obtain a desired distribution state in the layer thickness direction. To form the first layer, if a glow discharge method is used, the gas flow rate when introducing the gas of the starting material for introducing group M atoms or group V atoms into the deposition chamber is adjusted to the desired value. It is formed by changing it appropriately according to the rate of change curve and keeping other conditions constant. Specifically, to change the gas flow rate,
For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manual operation or an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a rate-of-change curve designed in advance to obtain a desired content rate curve.

In addition, when forming the first layer using a sputtering method, ``distribution of group Ⅰ atoms or group Ⅰ atoms in the layer thickness direction + 1
In order to form a desired distribution state in the layer thickness direction by changing the concentration in the layer thickness direction, as in the case of using the glow discharge method, the starting material for introducing group m atoms or group The gas flow rate at which the gas is introduced into the deposition chamber is varied as desired.

In the present invention, the carbon atoms and group (I) atoms or group V atoms contained in the second layer are uniformly distributed in the layer, and in order to form the second layer, , it is necessary to keep the above-mentioned conditions constant.

〔Example〕

Hereinafter, the present invention will be explained in more detail according to Examples 1 to 8, but the present invention is not limited thereto.

In each example, the first layer and the second layer were formed using a glow discharge method. FIG. 11 shows an apparatus for manufacturing a light-receiving member of the present invention using a glow discharge method.

In the gas cylinders 202, 205, 204, 205, 206 in the figure, raw material gases for forming the respective layers of the present invention are sealed.
2 is 5iHa gas diluted with He (purity 99.999
%, hereinafter abbreviated as SiH4/He) cylinder, 203 is He
PHs gas (purity 99.999%, hereinafter abbreviated as PH5/'He) diluted with He gas (purity 99.999%, hereinafter referred to as PH5/'He) cylinder, 204 is B2H6 gas diluted with He (purity 99.999%, hereinafter referred to as B2
It is abbreviated as H6/'He. ) cylinder, 205 is a C2H4 gas (purity 99.999%) cylinder, 206 is a Si2H6 gas diluted with He (purity 99.999%, hereinafter 512
It is abbreviated as H6/He. ) It is a cylinder.

When introducing halogen atoms into the layer to be formed, 8
Instead of 1H4 gas or S i 2H6 gas, for example,
The cylinder may be changed to use SiF4 gas.

To allow these gases to flow into the reaction chamber 201, make sure that the valves 222 to 226 of the gas cylinders 202 to 206 and the leak valve 235 are closed, and also close the inflow valves 212 to 216, the outflow valves 217 to 221, and the auxiliary valve. 252. Confirm that 235 is open, and first open the main valve 234 to exhaust the reaction chamber 201 and gas piping. Next, the vacuum gauge 236 reads approximately 5 x 10''.
6 torr, the auxiliary valve 232.21
Close the outflow valves 217-221.

An example of forming the first layer 102 on the base cylinder 237 will be given. SiH4/H from gas cylinder 202
e gas and B2Hs/Me gas from the gas cylinder 204 by opening the valves 222 and 224 and checking the outlet pressure gauge 227.
．． Adjust the pressure of 229 to IKf/ff12, and
/ Flow 212.214't Gradually open to allow flow into mass flow controller 207.209. Subsequently, the outflow valves 217 and 219 and the auxiliary valve 232 are gradually opened to allow gas to flow into the reaction chamber 201.

BIH4/) at this time (e gas flow rate, B 2H6/)
(e) Set the outflow valve 2 so that the gas flow ratio is the desired value.
17S219 and the opening of the main valve 234 while checking the reading on the vacuum gauge 2'56 so that the pressure inside the reaction chamber 201 reaches the desired value. Then, the temperature of the base cylinder 257 is increased to 50 to 4
After confirming that the temperature is set to 00C, the power supply 240 is set to the desired power to generate glow discharge in the reaction chamber 201, and a microcomputer (not shown) is used to generate a glow discharge. , B 2H6/Me gas flow rate, s i
First, a layer region containing boron atoms and silicon atoms is formed on the base cylinder 237 while controlling the ratio of H4/He gas flow rate.

Next, after a predetermined period of time has passed, the reaction chamber 2 of B2H6/He gas
A layer containing no boron atoms is formed by closing the valves of the corresponding gas introduction pipes and continuing glow discharge for a predetermined period of time.

When halogen atoms are contained in the first layer, for example, SiF4/He gas may be further added to the above gas and then fed into the reaction chamber.

In order to form a second layer on the first layer formed on the base cylinder 237 by the above operation, for example, S
By diluting each of iH4 gas, C2H4 gas, and PH3 gas with a diluent gas such as He as necessary, and flowing them into the reaction chamber 201 at a desired flow rate ratio to generate a glow discharge according to desired conditions. will be accomplished.

Needless to say, all outflow valves other than those required for forming each layer are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow into or out of the reaction chamber 201. From valves 217 to 221 to reaction chamber 201
In order to avoid gas from remaining in the gas piping leading to the system, close the outflow valves 217 to 221 as necessary, open the auxiliary valves 232 and 233, and fully open the main valve 234 to once evacuate the system to a high vacuum. Perform operations.

Further, while forming the second layer, the base cylinder 237 is constantly rotated by the motor 259 at a desired speed in order to ensure uniform layer formation.

Example 1 Using the manufacturing apparatus shown in FIG. 11, a layer was formed on a drum-shaped aluminum substrate which had been washed in a conventional manner according to the layer forming conditions shown in Table 1. At this time, B2H6/
The change in the gas flow rate ratio of SiH4 is controlled by the microcomputer according to the flow rate ratio change line designed in advance as shown in FIG.
Adjusted automatically by control.

The drum-shaped light-receiving member for electrophotography thus obtained was
A copying test was conducted using a Canon high-speed copying machine that had been modified for experiments, using a Canon exhibition test chart as a manuscript, and selecting appropriate image forming process conditions (a tungsten lamp was used as the light source). We were able to obtain high quality images.

Example 2 A drum-shaped light-receiving member for electrophotography was obtained in the same manner as in Example 1, except that the B2HliH4 gas flow rate ratio was controlled according to the flow rate ratio change line shown in FIG. 13 in accordance with the layer forming conditions shown in Table 2. When the same copying test as in Example 1 was conducted, high-quality images with excellent resolution could be obtained.

Example 6 According to the layer formation conditions shown in Table 3, B2H6/SiH4
A drum-shaped light-receiving member for electrophotography was obtained in the same manner as in Example 1, except that the gas flow rate ratio was controlled according to the flow rate ratio change line shown in FIG. 13, and the same copying test as in Example 1 was conducted. We were able to obtain high-quality images with excellent resolution.

Example 4 A drum-shaped light-receiving member for electrophotography was prepared in the same manner as in Example 1, except that the B2H6AlH4 gas flow rate ratio was controlled according to the flow rate ratio change line shown in FIG. 14 in accordance with the layer forming conditions shown in Table 4. When the same copying test as in Example 1 was carried out, high-quality images with excellent resolution could be obtained.

Example 5 A drum-shaped light-receiving member for electrophotography was obtained in the same manner as in Example 1, except that the B2H6A1H4 gas flow rate ratio was controlled according to the flow rate ratio change line shown in FIG. 15 in accordance with the layer forming conditions shown in Table 5. When the same copying test as in Example 1 was conducted, high-quality images with excellent resolution could be obtained.

Example 6 A drum-shaped light-receiving member for electrophotography was obtained in the same manner as in Example 1, except that the B2H7SiH4 gas flow rate ratio was controlled according to the flow rate ratio change line shown in FIG. 16 in accordance with the layer forming conditions shown in Table 6. When the same copying test as in Example 1 was conducted, high-quality images with excellent resolution could be obtained.

Example 7 When forming the second layer (n) in Table 1, the procedure was roughly the same as in Example 1, except that the thickness of the 70 layer was varied as shown in Table 7. Each light-receiving member (sample 7) under similar conditions.
01 to 707) were prepared and evaluated by applying the same image forming process as in Example 1 to each of them, and the results shown in Table 7 were obtained.

Table 7 ◎: Extremely excellent ○: Excellent Δ: Practically sufficient Example 8 When forming the second layer (n) in Table 1, the gas flow rate ratio C2H4/51H4 was Each light-receiving member (sample &801 to 807) was created using the same procedure and substantially the same conditions as in Example 1, except that the values were set to the values shown in Table 8, and the same evaluation as in Example 1 was performed. However, in each case, the reproducibility of halftones was good, and high-quality images could be obtained.

Furthermore, in a durability test involving repeated and continuous use, it was possible to obtain images of a quality that was comparable to the initial image quality, and it was demonstrated that the image quality was excellent in durability.

Table 8 ◎: Extremely excellent ○: Excellent Δ: Practically sufficient [Summary of the effects of the invention] The light-receiving member of the present invention has a light-receiving layer composed of a-8i (H,X) By making the layer structure of the light-receiving member specific as described above, a-8i
All of the problems associated with the conventional light-receiving member constructed with the above structure can be solved. That is, the light-receiving member of the present invention has particularly excellent moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, etc.
It also has improved photosensitivity and dark resistance.

When the light-receiving member of the present invention is applied as an electrophotographic image-forming member, there is no influence of residual potential, its electrical characteristics are stable, and images obtained using it are
The image quality is extremely high, with high density and clear halftones.

[Brief explanation of drawings]

FIG. 1 is a diagram schematically showing the layer structure of the light-receiving member of the present invention, and FIGS. FIG. 11 is a concentration distribution diagram showing a typical example of the distribution state of atoms, and FIG. 11 is an example of an apparatus for manufacturing the light-receiving member of the present invention, and is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge decomposition method. Yes, 12th
Figures 1 to 16 are diagrams showing changes in gas flow rate ratio during layer formation according to the present invention. 100... Light receiving member, 101... Support, 102
...First layer, 103...Second layer, 104...
Free surface, 201... Reaction chamber, 202-206...
Gas cylinder, 207-211...Mass flow control-y, 212-216...Inflow valve, 217-22
1...Outflow valve, 222-226...Valve, 2
27~231...Pressure regulator, 232°233...
Auxiliary valve, 234... Main valve, 235...
Leak valve, 266... Vacuum gauge, 237... Basic cylinder y+, 238... Heater, 239...
Motor, 240...High frequency power supply, C, (d~CI?
...Distribution concentration of group ■ atoms or group V atoms, t, t2
~t4...layer thickness, tB...interface position between the support surface and the first layer, tr...interface position between the first 1- and the second layer. Fig. 2 Fig. 3 □C Fig. 8 = C Fig. 12 Fig. 13 Gas flow rate ratio "Zooo ' Fig. 15 Fig. 16 Gas flow rate ratio (xy4ooo)

Claims (1)

[Claims] a support, a photoconductive first layer made of an amorphous material containing silicon atoms as a matrix, and an amorphous material containing carbon atoms containing silicon atoms as a matrix on the support; a second layer, and the first layer contains a substance that controls conductivity in a non-uniform distribution in the layer; A light-receiving member characterized in that the second layer contains a substance that controls conductivity in a uniformly distributed state in the layer.