JPS58108542A - Photoconductive material - Google Patents

Abstract

PURPOSE:To obtain superior characteristics on the whole, by forming a photoconductive amorphous silicon layer consisting of 2 layers on a substrate, and using a material contg. 40mol% silicon and 60mol% carbon for the second layer. CONSTITUTION:An amorphous material layer 102 contg. silicon atoms as a main component, and at least one of hydrogen and halogen as an element is formed on a substrate 101 to fabricate a photoconductive material 100. The layer 102 consists of the first photoconductive layer 103 and the second layer 104 contg. silicon atoms, and carbon atom up to 60 atomic % as constituent elements of amorphous materials, thus permitting the obtained photoconductive material to be enhanced in comprehensive characteristics of electrical, optical, and photoconductive characteristics, durability, etc.

Description

Detailed Description of the Invention The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, r-waves, etc.). As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the field of image forming, or a document reading device, it has a high sensitivity and a high signal-to-noise ratio [photocurrent (Ip
)/dark current (Id) ), has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has a certain dark resistance value, and has high resistance to the human body during use. The solid-state imaging device is required to have characteristics such as being non-polluting and being able to easily dispose of leftover residue within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, pollution-free properties during use are important.

Based on these points, amorphous silicon (hereinafter referred to as a-8i) is a photoconductive material that has recently attracted attention.
No. 55718 describes an image forming member for electrophotography, and German Patent Publication No. 2933411 describes its application to a photoelectric conversion/reading device.

However, the photoconductive member having the conventional photoconductive layer composed of a-8i has electrical characteristics such as dark resistance, photosensitivity, and photoresponsivity.
Efforts have been made to improve optical and photoconductive properties, but there is still room for improvement in IJ in order to improve overall properties.

For example, when applied to an electrophotographic image forming member, when attempting to simultaneously increase photosensitivity and dark resistance, it has often been observed that residual potential remains during use, and this type of photoconductive When a member is used repeatedly for a long period of time, fatigue due to repeated use may accumulate, resulting in a number of disadvantages such as the appearance of a ghost phenomenon.

In order to improve the electrical and photoconductive properties of the photoconductive layer, when a photoconductive layer is constructed using an a-8i material, hydrogen atoms, fluorine atoms, chlorine atoms, and halogen atoms, as well as electrically conductive Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, However, problems may arise in the electrical, optical or photoconductive properties, use environment properties, and pressure resistance of the formed layer.

That is, for example, the lifespan of photo stains generated in the formed photoconductive layer due to 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 winds and phenomena, and so-called image defects commonly called "white streaks" that are thought to be caused by the rubbing of a blade when a blade is used for cleaning, for example, occur. 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-8i material itself, when designing photoconductive members, it is necessary to devise ways to solve all of the above-mentioned problems. This was developed in view of the above points, and from the viewpoint of the applicability of a-8i as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, gunsmith equipment, etc. As a result of comprehensive research and study, we have developed an amorphous material that uses silicon atoms as its base material and contains at least one of hydrogen atoms (H) or norogen atoms (X), so-called hydrogenated amorphous silicon and halogenated amorphous silicon. , or halogen-containing hydrogenated amorphous silicon [hereinafter referred to generically as [
a-8i(H, Not only does it have excellent properties for practical use, but it also surpasses conventional photoconductive materials in every respect, especially as a photoconductive material for electrophotography. It is based on the heading dead center.

The electrical, optical, and photoconductive properties of the present invention are almost always stable regardless of the usage environment, and are resistant to light fatigue and do not deteriorate even after repeated use. The main object of the present invention is to provide a photoconductive member that has excellent durability and moisture resistance, and in which no or almost no residual potential is observed.

Another object of the present invention is that, when applied as an image forming member for electrophotography, the present invention has sufficient charge retention ability during banding treatment for electrostatic image formation, making ordinary electrophotographic methods extremely effective. It is an object of the present invention to provide a photoconductive member for electrophotography, which can easily produce high-quality images with clear and high resolution.

Yet another object of the present invention is to provide a photoconductive member having high photosensitivity, high signal-to-noise ratio characteristics, and higher pressure resistance.

The photoconductive member of the present invention includes a support for the photoconductive member, and an amorphous material provided on the support and having silicon atoms as a matrix and at least one of hydrogen atoms or halogen atoms as a constituent element. A first layer region exhibiting photoconductivity, and a second layer region composed of an amorphous material containing silicon atoms and carbon atoms as constituent elements. .

The photoconductive member of the present invention, which is designed to have the above-mentioned layer structure, can solve all of the problems mentioned above, and has extremely excellent electrical, optical, and photoconductive properties. - Indicates electrical conductivity and usage environment characteristics.

In particular, when applied as an electrophotographic image forming member, it has no influence of residual potential on image formation, has stable electrical characteristics, is highly sensitive, and has a high 8N ratio. Because of its excellent light resistance, repeated use characteristics, moisture resistance, and pressure resistance, it has a high density, clear halftones, and a high degree of decomposition. - The photoconductive member of the present invention will be described in detail below with reference to the drawings.

FIG. 1 is a schematic structural diagram schematically shown to explain the layer structure of the photoconductive member of the present invention.

A photoconductive member 100 shown in FIG. 1 includes an amorphous layer 102 (X) on a support 101 for photoconductive members, a first layer region 103 having photoconductivity, and silicon atoms. The support used in the present invention may be conductive or electrically insulating.

Examples of the conductive support include NiCr and stainless steel.

A#, Or, Mo, Au, Nb, Ta, V, Ti, Pt
, Pd, or alloys thereof.

Polyester is used as the electrically insulating support.

Polyethylene, polycarbonate, cell μm acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, etc., and glass.

Ceramics, paper, etc. are usually used. These electrically insulating supports preferably have at least one surface conductively treated, and are preferably provided with another layer of rfJIIIK on the conductively treated surface.

For example, if it is glass, its surface K, NiCr.

A/, Or, Mo, Au, Ir, Nb, Ta, V, T
i, Pt, Pd.

In, 0. ,8nO,,ITO(In,0.+8n
Conductivity can be imparted by providing a thin film consisting of NiCr, A/, Ag, etc., or a synthetic resin film such as a polyester film.
Pb, Zn, Ni, Au.

A thin film of metal such as Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, sub-beam evaporation, sputtering, etc., or the surface is laminated with the above metal. , imparts conductivity to its surface.

The shape of the support is cylindrical.

The photoconductive member 1 shown in FIG.
If 00 is used as an electrophotographic image forming member for continuous bulk copying, it is preferably in the shape of an endless belt or a cylinder. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within the range.

However, in such cases, from the viewpoint of manufacturing and handling of the support and mechanical strength, it is usually set to 10μ or more.

In the present invention, in order to effectively achieve the object, the first layer region 103 formed on the support 101 and forming a part of the amorphous layer 102 has the semiconductor characteristics shown below. a-8i (H
,X).

(Op type a-8i (to

(z3 p-type a-8i (H,

■ Fi-type a-84 (H,X): Contains only a donor.

Or one that contains both donor and acceptor and has a high relative concentration of donor.

■ n″fI1m-8i (H,

In the present invention, nitride 1 composed of a-84(H,X)
The zero layer region 103 is formed by, for example, a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blating method. For example, in order to form an amorphous layer composed of a-8i (H, or/and nologe/atom (X) for introducing hydrogen atom (H)
A raw material gas for introduction 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, thereby causing a droplet of K a -8 on the surface of a predetermined support that has been previously installed at a predetermined position.
It is sufficient to form a layer consisting of i (H,X). In addition, when forming by sputtering method, for example, Ar, He
When sputtering a target composed of Si in an atmosphere of an inert gas such as or a mixed gas based on these gases, the hydrogen atoms (H) are/and the gas for introducing halogen atoms (X). may be introduced into the deposition chamber for sputtering.

The raw material gas for supplying Si used in the present invention includes 8iH4, Si, H,, 8! ,H,,8! ,H,.

Silicon hydride (silanes) in a gaseous state or that can be gasified are mentioned as those that can be effectively used, and in particular, from the viewpoint of ease of handling in layer creation work and good Si supply efficiency, etc.
S-H is preferred.

Effective raw material gases for introducing halogen atoms used in the present invention include many 710-gen compounds, such as halogen gases, halides, interhalogen compounds, and halogen-substituted sila/derivatives. Preferable mention may be made of halogen compounds in the state or which can be gasified.

Furthermore, silicon atoms and norogen atoms constitute 1
In the present invention, silicon compounds containing a halogen atom, which are in a gaseous state or can be gasified as shown in Table 1, are also effective.

Examples of halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, Brl', crt', and CtF.

BrP, , BrF@ , IP, , IP, ,
IC/, IBr, etc. (D 7% C177 intercompounds can be mentioned.

Specifically, silicon compounds containing halogen atoms, new products, and silane derivatives substituted with halogen atoms include, for example, 8
iF4.84. F, , 8iCz, , 8iBr4
Preferred examples include silicon halides such as the following.

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 as a raw material gas capable of supplying 8i is not used. In either case, a layer consisting of a-8i 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, a silicon halide gas, which is a raw material gas for supplying Si, and a gas such as Ar, H, He, etc. are mixed at a predetermined mixing ratio. Make sure the flow rate is #! A tenth layer region can be formed on a predetermined support by introducing the gas into a deposition chamber forming a layer region No. 1 and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to introduce hydrogen atoms, a layer may be formed by mixing a predetermined amount of a silicon compound gas containing hydrogen atoms with these gases.

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 consisting of a-84 (H, Sputtering is performed in a plasma 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 or an electron beam method (EB method). This can be carried out by heating and evaporating the flying evaporated material by, for example, passing through a predetermined gas plasma atmosphere.

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

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as Tsuru 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 raw material gases for introducing halogen atoms, but in addition, IF, HC/.

HBr, HI, etc...Hydrogen chloride, 8J? , ,
8 iH,I,.

SiH,C/, , 8iHC/s, SiH,Br,
, 8iHBr, etc., and gaseous or gasifiable halides containing hydrogen atoms as one of their constituent elements can also be mentioned as effective starting materials for forming the first layer region. .

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, it is also possible to use 錉, 8iH4,Si, crosspiece, Si, H,, 84,H
l.

This can also be done by causing a discharge by causing a silicon hydride gas such as 8i to coexist with a silicon compound for supplying 8i in the deposition chamber.

For example, in the case of the reactive sputtering method, an 8i target is used, and a plasma atmosphere is created by introducing a gas for introducing halogen atoms and a stirring gas, including inert gases such as He and Ar as necessary, into the deposition chamber. A-8i on the substrate by forming and sputtering the 8i target.
A layer consisting of i(H,X) is formed.

l! Alternatively, a gas such as BtHs may be introduced to also serve as impurity doping.

In the present invention, the amount of hydrogen atoms (H) or halogen atoms (
The sum of the amounts of noble or hydrogen atoms and halogen atoms in X) is usually 1 to 403 tomt c%, preferably 5 to 36 at.
What is considered omicX! ! ! Delicious.

K, which controls the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the layer, is determined by, 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 to form the first layer region by a glow discharge method or a sputtering method may be a rare gas, for example, ie.

Suitable examples include Ne, Ar, and the like.

K, which makes the semiconductor properties of the first layer region 1030 desirable among those from ■ to
This is achieved by doping a type impurity or both impurities into the layer to be formed while controlling the amount thereof. Such impurities are listed in the periodic table al. as p-type impurities.
Atoms belonging to group I, such as B, A/, Ga, In,
Examples of suitable n-type impurities include atoms belonging to Group V of the periodic table, such as N and P.
, As, 8b, Bi, and the like are preferred, with B, Ga, P, 8b, and the like being particularly optimal.

In the present invention, the amount of impurity doped into the first layer region 103 in order to have a desired conductivity type is appropriately determined depending on the desired electrical and optical characteristics, but it is determined according to the periodic table. kjh total of impurities of carbonate group u 3 x 10”at
It is sufficient to dope in one range below omic %, and in the case of impurities in group Ⅰ of the periodic table, 5 X I Q
``It is sufficient to dope the amount within the range of atomic X or less.

To dope impurities into the first layer region 103,
During layer formation, a 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 first layer region 103.

As the raw material for introducing such impurities, it is desirable to employ a material that is in a gaseous state at room temperature and normal pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such impurities include PHa, P
IH4, PFs, PFs, PCIs-B, H,
, ,B,Il,4. MC/1. GaC/, , I
nC/, 'r/c/, etc. can be mentioned.

The column thickness of the first layer region 103 is determined as desired so that photocarriers generated by irradiation with light having desired spectral characteristics are efficiently transported, and is usually 1 to 100 μm, preferably. is 2 to 50μ.

In the present invention, atoms belonging to Group Ⅰ of the periodic table (group ① atoms) contained in the first layer region 103 as impurities in order to control the conductivity type and dark resistance value, The atoms belonging to the group V (group V atoms) are substantially in the plane substantially parallel to the layer thickness direction of the layer region 1030 (the plane parallel to the surface of the support 101). Although it is uniformly distributed, the distribution state may be uniform or unrestricted in the layer thickness direction.

Both years et al., the first 1-
Preferably, it is contained in region 103. Also, the first
The impurity contained in the layer region 103 may be continuously contained in the entire region in the layer thickness direction of the layer region 103, or may be contained partially in the layer thickness direction. Also good.

Next, in the present invention, a typical example of the distribution state where the impurity is contained in the first layer region 104 in a non-uniform distribution state in the layer thickness direction will be explained.

In order to simplify the explanation, impurities will be explained in terms of group atoms, and the illustrated layer regions will only show the layer regions containing group group atoms. I made it. That is, the layer region (1) shown in the drawing for explaining the impurity distribution state below may be equal to the entire region of the first layer region 103, or may be equal to the entire region of the first layer region 103. Even if it is considered a part of the ``Hikimono''. According to both years, the impurities contained in the first layer region 103 are preferably contained so that the layer region (1) includes the end layer region of the first layer region 103 on the side of the support 101. .

2 to 10 show typical distribution states of group (III) atoms in the layer thickness direction contained in the layer region (III) constituting the first layer region 103 of the photoconductive member of the present invention. An example is shown.

In FIGS. 2 to 1θ, the horizontal axis represents the content C of group 4 atoms, and the vertical axis represents the layer region containing carbonate group atoms (C).
III) indicates the layer thickness, tB indicates the position of the interface on the support side, and D indicates the position of the interface on the opposite side to the support side. That is, the layer region (III) containing group (III) atoms =
"222ni v'ld', a toward the tT side from the tB side
ll*j1. . . 'i, a-gi, b layer region (1) is
a-8i (H,

In the case where the layer region (III) occupies a part of the layer region of the first layer region 103, as shown in the example of FIG. Preferably, it is provided in the lower layer region.

FIG. 2 shows a first typical example of the distribution state of the WCM group atoms contained in the layer region (1) in the layer thickness direction.

From the interface position tB where the surface contacts the surface to the position t, JI
While the concentration C of the EI group atoms takes a constant value CI, they are contained in the layer region where the m group atoms are formed, and the concentration C2 is gradually continuous from the position tl until reaching the cutting surface position 1fly. has been reduced to At the interface position @T, the concentration of group m atoms is cF! c.

In the example shown in FIG. 3, the concentration C of the m-group atoms contained is # from position 1litB to position tT.
A distribution state is formed in which the concentration gradually and continuously decreases from fC4 to reach C1 at position 1 and fllflr.

In the case of Fig. 4, the concentration C of group m atoms from position tB to position t1 is a constant value of concentration C, and gradually and continuously at intervals of 0 between position - and position tT. The content concentration C is reduced to substantially zero at the position IT.

In the case of FIG. 5, the m-th group atoms are from position t8 to position tT.
The content concentration C8 is continuously and gradually decreased until the content reaches C8, and becomes substantially zero at the position IT.

In the example shown in FIG. 6, the concentration C of the m-th group is concentrated #tC between position tJ1 and position t.

is a constant value, and the concentration C1o is lowered at position 1T. Between position t and position IT, the content concentration C is linearly decreased from position - to position tT.

In the example shown in FIG. 7, from position t to position t4
Until then, a constant value of the concentration qI is observed, from position t to position 1T.
Up to this point, the distribution state is such that the concentration Cent is linearly decreased from the concentration C4.

In the example shown in FIG. 8, from the position tB to the position 1T, the concentration C of group (I) atoms decreases linearly from the concentration C14 to zero.

In FIG. 9, from position t8 to position t, the content concentration FIILC of group 1 atoms is reduced numerically from the concentration C11 to the concentration C1, and between position fit's and position tT. An example is shown in which the concentration CI# is set to a constant value between .

In the example shown in FIG. 10, the content concentration of gI group atoms [C is the concentration C1 at position t8, and this concentration C1? At first, it decreases slowly, and near the - position, it decreases rapidly, and at the - position, it becomes dark J[Ct@.

Between positions t and t, the concentration is first rapidly decreased, and then slowly decreased to a concentration C1 at position t, and between positions t and tQ, the concentration is decreased rapidly. , is gradually reduced very slowly to reach the concentration C3· at position t. Between position t and position 1T,
The concentration is reduced from C2° to substantially zero according to a curve shaped as shown in the figure.

Above is the 8g2 diagram! According to Figure 10, the layer area (Iff)
Some typical examples of the distribution state of group m atoms contained in the f-thickness direction will be explained. At the interface 1T@, the layer region (Iff) in which the distribution state of group m atoms is formed has a portion where the content concentration C is considerably lower than that on the support side.
03 is preferable.

In the present invention, the layer region (II) containing Group I atoms constituting the amorphous layer is a layer region (II) containing Group M atoms at a relatively high concentration on the support side, as described above. Has people living in the territory.

The localized region is provided within 5 μm from the interface position t8, if explained using the symbols shown in FIGS. 2 to 10.

In the present invention, the localized region AFi, the interface position tB
In some cases, the entire layer region up to a thickness of 5 μm →, or in other cases, it is a part of the layer region ξ.

Whether the localized region A is made into a part or all of the layer region LT is determined as appropriate according to the characteristics required of the amorphous layer to be formed.

The localized area size is defined as the distribution state of the group 1 atoms contained therein in the layer thickness direction, and the maximum Qnax of the content distribution value (concentration distribution value) of the group Ⅰ atoms is normally 50
Atomic ppm or more, preferably 80 atoms
ic ppn or later, optimally 1001004to p
It seems that the distribution state can be such that it is more than pm
1 is preferably formed.

That is, in a preferred embodiment of the present invention, faI
The layer region (lit) containing the group atoms is formed such that the maximum value Cmax of the content distribution exists within five thicknesses from the support side (layer region from 18 to 5 μm thick).

In the present invention, the content of group (III) atoms contained in the layer region (1) containing group (III) atoms may be adjusted as desired so as to effectively achieve the object of the present invention. However, the amount of silicon atoms constituting the first layer region 103 is usually l-5-X10' a
t, omlo PP11. Preferably 2 to 500 at
omia ppwh, optimally 6~'l Q Q at
Preferably, it is oxia ppwm.

In the case of Group V atoms, C11l&x should have a distribution state that is usually 5 Q atomio ppm or more, preferably 8 Q atomia ppm or more, and optimally 10100 atom ppm or more, relative to silicon atoms. It is desirable that the layers be formed in such a way that the following can be achieved.

Further, the content of group (III) atoms contained in the layer region (V) containing group V atoms may be determined as desired so as to effectively achieve the object of the present invention. , the amount of silicon atoms constituting the first layer region 103 is usually 1 to 5×10”, preferably 1 to 300 atoms, optimally 1
~200 ato■1.I)- is desirable.

Many of the layer configuration examples of the first layer region explained above are tlN
It has a region in which the concentration distribution of group I atoms or group V atoms changes gradually in the layer thickness direction. This is particularly effective in increasing the mechanical strength and repeated use properties of the layer.

In the photoconductive member 100 shown in FIG. It is provided to achieve the purpose of the invention.

In addition, in the present invention, each of the amorphous materials forming the i@10 layer region 103 and the second layer region 104 constituting the amorphous 141102 has a common constituent element of silicon atoms. Therefore, the 1m-area interface is sufficiently acidified to ensure chemical stability.

The second layer region 104 is made of an amorphous material (a-8'XC1-X%, where O<X
<1).

The second layer region 104 composed of a-8'xCs-x
is formed by a sputtering method, an ion plantation method, an ion blating method, an electron beam method, or the like. 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 photoconductive member to be manufactured. The sputtering method or the electron beam method has the advantages that it is relatively easy to control the manufacturing conditions for manufacturing the conductive member, and that it is easy to introduce carbon atoms together with silicon atoms into the intermediate layer to be manufactured. Ion blating method is preferably employed.

In order to form the second layer region 104 by the sputtering method, a single crystal or polycrystalline 81 wafer and a C wafer, or a wafer containing a mixture of 1j8i and C are used as targets, and these are subjected to various treatments. This can be done by sputtering in a gas atmosphere.

For example, when using 81 wafers and C wafers as targets, sputtering gases such as He, Ne, and Ar are introduced into a deposition chamber for sputtering to form a gas plasma, and the Si wafer and C wafer are used as targets. C
Just sputter the wafer.

Another method is to use 91 targets made of a mixture of Si and C, introduce a sputtering gas into the apparatus system, and perform sputtering in the gas atmosphere. When using the electron beam method, single-crystal or polycrystal high-purity silicon and high-purity graphite are placed in two evaporation boats, and each is independently co-deposited using an electron beam, or
Alternatively, silicon and graphite placed in a desired mixing ratio in the same deposition port may be deposited using a single electron beam. In the former case, the content ratio of silicon and carbon contained in the second layer region 104 is controlled by changing the acceleration voltage of the electron beam with respect to silicon and graphite, and in the latter case, the content ratio of silicon and carbon is controlled in advance by changing the acceleration voltage of the electron beam with respect to silicon and graphite. It is controlled by determining the amount of graphite mixed. When using the ion blating method, various gases are introduced into the vapor deposition tank, and a high-frequency electric field is applied to a coil placed around the cypress tree to produce a glow, which is then ejected using the electron beam method. and C may be deposited.

The second layer region 104 in the present invention is carefully formed to provide the desired properties.

In other words, substances whose constituent atoms are 8i, C, 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,
a-s t zC1 that has desired characteristics depending on the purpose
-X is formed, the conditions for its formation are strictly selected according to desire.

For example, in order to provide the second layer region 104 primarily for the purpose of improving voltage resistance, a-8ixC1z is made as an amorphous material with significant dielectric behavior in the environment of use.

In the case where the AG20 layer region 104 is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of fainting property is alleviated to some extent, and the degree of irradiation light is reduced to some extent. A-8g zCl-z is created as an amorphous material with a texture.

When forming the second layer region 104 made of a-8I In the present invention, the temperature of the support during layer formation is strictly controlled so that a-8i) (C1-x) having the desired properties can be formed as desired. is desirable.

In order to effectively achieve the purpose of the present invention, the optimum range of the support temperature when forming the second layer region 104 is selected as appropriate in accordance with the method of forming the second layer region 104. The layer region 104 of s2 is formed at a temperature of preferably 20 to 100°C, most preferably 20 to 50°C.

The second layer region 104 can be formed using a sputtering method because fine control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. Adoption of the electron beam method is advantageous, but when forming the second layer region 104 using these layer forming methods, the discharge power during layer formation is created in the same manner as the support temperature described above. It can be cited as one of the important factors that influence the characteristics of a-8izC1-1.

a- having the characteristics for achieving the object of the present invention;
The discharge power conditions for effectively creating 8izC1-3 with good productivity are preferably SOW ~ 250w,
For moths, it is desirable to set the power to 80W to 150W.

In the present invention, the above-mentioned ranges are listed as the preferable numerical ranges for the support temperature and discharge power for creating the second layer region 104, but these layer creation factors are independent of each other. Rather than being determined separately, the optimum value of each layer creation factor is determined based on the mutual organic relationship so that the second layer region 104 made of H-8ize1-x with desired characteristics is formed. desirable.

The amount of carbon atoms contained in the second layer region 104 in the photoconductive member of the present invention is the same as the manufacturing conditions of the second layer region 104, so that the layer can obtain the desired characteristics to achieve the object of the present invention. is an important factor in the formation of

preferably /rutataatomic%, optimally /θ
~ Ta θ atomic It can be decided.

Further, the layer thickness of the second layer region 104 is the same as that of the first layer region 103.
The relationship with the layer thickness also needs to be appropriately determined as desired based on organic relationships depending on the characteristics required for each layer region.

In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production.

In the present invention, the 1-region 1040 layer thickness of M2 is as follows:
It is usually desirable that ρ be 07~lθμ, preferably /, t)2~riμ, and optimally ρ, ρ4~taμ.

The thickness of the amorphous layer of the photoconductive layer member 100 in the present invention is appropriately determined according to the purpose of the application, such as a reading device, a photographing device, or an electrophotographic preforming member. .

In the present invention, the thickness of the amorphous layer is as follows:
The layer region 102 of the body and the second
The layer thickness of the first layer region 1020 is determined as desired depending on the layer thickness relationship with the layer region 103 of 11g2, and preferably the layer thickness of the first layer region 1020 is several 6
It is preferable that it be made to be several thousand times or more.

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

FIG. 11 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method.

Gas cylinders 1111 to 1115 in the figure are sealed with raw material gas for forming each layer of the present invention,
As an example, SiH gas (purity 99.999-, hereinafter 8iH) diluted with 1111 it.
, /He. ), Bo/Pe, 1112 has a dilution degree of 99.991G with He, hereinafter abbreviated as 8i, H, /He0)
cylinder, 1114. To make these gases flow into the reaction chamber 201, pulps 1131 to 1135 of gas cylinders 1111 to 1115. Confirm that the leak pulp 1106 is closed, and
Inflow pulp 221-225. Outflow pulp 1126-11
After confirming that the 30° auxiliary pulp 1141 is opened, first open the main pulp 111G and open the reaction chamber 1101.
When the reading of the zero-order vacuum needle 1142 that exhausts the gas piping reaches approximately 5 x 10 torr, the auxiliary pulp 1
141° Close the outflow pulp 112 and 113G.

If the IHt is increased when forming the III region layer on the base cylinder 1137, the shutter 1105 is closed 8iH,
/He gas, B from gas cylinder 1112, Hs/Hez
Open the gas and pulp 1131 and 1132 and adjust the outlet pressure gauge 1136゜1137F) pressure to 1/cdK g,
Inflow pulp 1121.

The mass flow controller 11 opens every 1t22tlk.
Then, the outflow pulp o26.1127 and the auxiliary pulp 1141 are gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the flow rate of the outflow pulp is 1126°1 so that the ratio of the e gas flow rate and the B*Hs/He gas flow rate becomes the desired value.
127, and while checking the reading on the vacuum gauge 1142 so that the pressure in the reaction chamber 1 reaches the desired value,
Adjust the aperture of the substrate 11090 and ensure that the temperature of the substrate 11090 is set to a temperature of 50-400°C by the heater 1108.

The power supply 1143 is set to a desired power to generate glow discharge in the reaction chamber 1101 to form a first region layer on the substrate.

When the first region layer contains halogen atoms, 9, for example, SiF, /He is further added to the above gas and sent into the reaction chamber.To form the second layer region, first, the shutter 110
Open 5. All the gas supply pulps are once closed, and are exhausted by fully opening the reaction tank 1101 Fib main pulp 111G.

A high purity silicon wafer 1104-1 is placed on the electrode 1102 to which high voltage power is applied. and high purity graphite 1104
-2 are installed at a desired area ratio. gas cylinder 1
115, Ar gas is introduced into the reaction tank 1101, and the internal pressure of the cypress becomes 0.0! The main 11 pulp 1110 is articulated so that r (torr) is achieved. By turning on the high voltage power supply and sputtering Si and 0 at the same time.

A 20th layer region can be formed on the first layer region.

Examples will now be described.

Example 1) A layer was formed on an aluminum substrate under the following conditions using the FTL1L manufacturing apparatus shown in FIG.

Table 1 The warp-forming member thus obtained was placed in a charging/exposure developing device, corona charged at θ50 for 0.2 seconds, and immediately irradiated with light. Light dl uses evening/Gesten lamp,
Immediately thereafter, a charged developer (including toner and carrier) was applied to the surface of the component by cascading the surface of the component. Get a good toner image.

The toner image thus obtained was once cleaned with a rubber blade, and the above-described preparation and cleaning process was repeated again. No deterioration of 1 image was observed even after repeating 10,000 times or more.1 Formation was carried out on the M substrate under the following conditions using the manufacturing equipment shown in Figure 11.Other conditions were Example 1. Do the same thing as 9.

Immediately irradiate the circle with a light image. A tungsten lamp was used as a light source, and a light amount of 5LOjux-s@e was irradiated using a test chart of a transparent part.

A good toner image was then obtained on the surface of one member by immediately cascading the Ke-charged lJLgII agent (containing toner and carrier) over the surface of the member.

The nine toner images thus obtained are once cleaned with a rubber blade, and the above image forming and cleaning steps are repeated again. No deterioration of the image was observed even after repeating the same number of times over 100,000 times.

Example S) Using the apparatus shown in FIG. 11, a layer was formed on the AJ substrate under the following conditions.

3rd I! For other conditions, carry out the same procedure as in Example 1).

The image-forming member thus obtained was placed in a charging, exposing and developing device, and a light image was immediately irradiated by discharging the image forming member between agaec and esxv. The light source uses a tungsten 2 lamp.
LOIx-C light intensity was irradiated using a transparent test chart.9.

Immediately thereafter, a Ke-chargeable developer (containing toner and carrier) was cascaded over the surface of the member to obtain a good toner III image with extremely high concentration on the surface of one member.

The toner plate thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. Even if it is repeated more than 100,000 times, ii
No deterioration was observed on my part.

Example 4) Completely the same as Example 3 except that when forming the second region layer, the area ratio of the silicon wafer and graphite was changed and the content ratio of silicon atoms and carbon atoms in the second region layer was changed. An image forming member is made and circled by a similar method. As a result, the results shown in Table 4 were obtained.

○: Very good Δ: Easy to cause image defects Example 5) An image forming member was prepared in exactly the same manner as in Example 3) except that the thickness of the second layer was curved fc-A. Example 1
), the steps of image formation, development, and cleaning were repeated nine times to obtain the following results. An image forming member was prepared in the same manner as in Example 1) and evaluated in the same manner as in Example 1), and good results were obtained.

Table 6 Example 7) A layer forming member was created using the same method as Example 1) except that the method for forming the first region layer was changed as shown in the table below.
When the evaluation was carried out in the same manner as in 1), good results were obtained.

Table 7

[Brief explanation of drawings]

FIG. 1 is an explanation and diagram for explaining the distribution of Group 1 atoms in a layer region containing Group 1 atoms, which constitutes a preferred front implementation layer of a photoconductive member of the present invention; The figure is a schematic explanatory diagram of an apparatus for producing photoconductive material dyeing according to the present invention. Zoo... Photoconductive member 101... Support / 102... Amorphous layer 103... Fth layer region 104... Jth layer region 105... Free surface Applicant Canon Co., Ltd. Company □C □C □C Procedural amendment (voluntary) Last day of November 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1, Indication of the case 1983 Patent Application No. 208493 2, Name of the invention Photoconductive member 3. Relationship with the case of the person making the amendment Patent applicant address 3-30-2 Shimomaruko, Ota-ku, Tokyo Name (100
)Representative of Canon Co., Ltd. Kaku Yoshimi 3-30-25 Shimomaruko, Ota-ku, Tokyo 148 3-30-25 Shimomaruko, Ota-ku, Tokyo 148 Kusunoki 6 of ``Detailed explanation of the invention in the specification subject to the amendment'' Contents of the amendment ■Details On page 11, line 18 of the book, the text ``1...amorphous layer'' is corrected to ``1...first layer region 106''. ■ On page 19, line 5, [' ”・3 X 10' at
omic%...” is [...3 X i O
' atomic ppm...]. ■Page 19, line 7 of the same page says “...5 X 103 atoms
ic chip..." there is l-"" 5 X 1Q3a
Correct as tomic ppm++ss J. ■Page 20, line 14 to line 15 [...The φ distribution state is...good. " is corrected to "...the distribution state is assumed to be non-uniform." ■Page 24, line 9 of the same page: “...-1 of Group 1II”
Correct the statement to read, ``...of Group ■ atoms...''. ■Page 38, line 5 [Base cylinder 1137...
.'' is corrected to ``Base 1109...''. ■ Item 1 “Used gas” and “Flow rate ratio (or area ratio)” in Table 1 on page 40 of the same page, husband k in the first column.
, [B2Ha/He = 1 0-3 J
, [SiH4:B2H6:1: 10-5-
1: Add each OJ. ■ In the 18th line of page 40, "...θ5KV..." is corrected to "...e5KV...". ■ In the second line of page 41, the text "... ■ Cargo..." has been corrected to "...O cargo...". 0 The first row of [flow rate ratio (or area ratio)] in Table 2 on page 41 of the same page is r SiH4:B2H6=1:10-5
~ItC)J. ■ In the first row of the item 1 "Used gas" in Table 6 on page 45, r' 82H6/He = 10-3J, r R
[Si2H6
:B2H621:10-'-COJ are added respectively.

Claims (1)

[Claims] A support for a photoconductive member, and an amorphous material provided on the support and having silicon atoms as a matrix and at least one of hydrogen atoms or halogen atoms as a constituent element, and having photoconductivity. An electrically conductive member comprising an amorphous layer including a first layer region as shown in FIG.