JPS58111045A - Photoconductive member - Google Patents

Abstract

PURPOSE:To improve the high sensitivity and high S/N ratio by forming an amorphous Si layer contg. H and halogen on a support so that the 1st layer region contg. O uniformly in the thickness direction and the 2nd layer region cong. B are laminated. CONSTITUTION:A cylindrical support 101 of Al or the like is set in the evacuated reaction chamber of a glow discharge decomposition apparatus. By operating valves, gaseous SiH4 diluted with He(SiH4/He), B2H2/He, Si2H6/He, NO and SiF/ He are fed onto the surface 104 of the support 101 to form an armophous Si layer 102 contg. H and F or other halogen by a glow discharge decomposition method. At this time, by laminating the 1st layer region contg. O in an uniformly distributed state in the thickness direction and the 2nd layer region contg. B so that they have a common region partly, a photoconductive member 100 with high sensitivity and a high S/N ratio is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to the use of light guides that are sensitive to electromagnetic waves such as light (here, light in a broad sense, ultraviolet light, 10T visible light, infrared light, X-rays, gamma rays, etc.). Regarding parts.

As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic forming member in the field of corporate formation, or a document reading device, it is highly sensitive and has a photocurrent (Ip) of 8N ratio.
/dark current (Id)), has nine absorption spectrum characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has the desired dark resistance value, and is harmless to the human body during use. Furthermore, solid-state imaging devices are required to have characteristics such as being able to easily treat residual health within a predetermined time. Particularly, in the case of an electrophotographic component to be incorporated into a Seiko photographic device used in an office as an office machine, the above-mentioned non-pollution during use is an important point.

Based on these points, amorphous silicon (hereinafter referred to as 1k a-8i) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion/reading device is described in Japanese Publication No. 2933411.

In addition, photoconductive members having a photoconductive layer composed of conventional a-8i have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and use environment characteristics. In terms of stability, stability over time, and durability, improvements have been made to improve the Fi characteristics individually, but the reality is that there is still room for further improvement in order to improve the overall characteristics. It is.

For example, when applied to electrophotographic image forming members, it has often been observed that in the past, residual potential remains during use when attempting to simultaneously achieve high photosensitivity and high dark resistance. When used repeatedly for a long period of time, fatigue accumulates due to repeated use, and there are many disadvantages such as the phenomenon of ghosting.

In addition, when forming a photoconductive layer using a-8i material, in order to improve its electrical and photoconductive properties, halogen atoms such as hydrogen atoms, fluorine atoms, basic atoms, etc. Ninthly, other atoms such as finely wired atoms, phosphorus atoms, or other atoms are contained as constituent atoms in the photoconductive layer for the purpose of improving properties. Depending on the method used, problems may arise in the electrical or photoconductive properties or voltage resistance of the formed layer.

That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer may not be sufficient, or the injection of charge from the support side may not be sufficiently prevented in dark areas. There was a case.

Therefore, while efforts are being made to improve the properties of the a-8i material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the above points, and its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive research and consideration from this point of view, we have discovered an amorphous RX material, hydrogenated amorphous silicon, which has a silicon atom as its base material and contains at least either a hydrogen atom () () or a halogen atom (X).

Halogenated amorphous silicon or halogen-containing hydrogenated amorphous silicon (hereinafter referred to as "a-8j (H, It not only exhibits excellent characteristics, but also exceeds conventional photoconductive materials in all respects, especially as a photoconductive material for electrophotography, and has nine characteristics. It is based on the point that was found.

The electrical, optical, and photoconductive properties of the present invention are almost unaffected by the usage environment, are always stable, and are extremely resistant to light fatigue.
Excellent durability with no deterioration even after repeated use.
The main objective is to provide a photoconductive member in which no or almost no residual potential is 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 photoconductive member having excellent electrophotographic properties.

Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily obtain high-quality #i images with high density, clear halftones, and high resolution. It is.

Yet another object of the present invention is photosensitivity.

Another object of the present invention is to provide a photoconductive member having high 8N ratio characteristics and high voltage resistance.

The photoconductive member of the present invention includes a support for the photoconductive member, a silicon atom as a base material, and a hydrogen atom (H) as a constituent atom.
or a photoconductive member having a photoconductive amorphous layer made of an amorphous material [a-8i(H,X)) containing at least one of halogen atoms (X), a, wherein the amorphous layer contains oxygen atoms as constituent atoms in a continuous and substantially uniform distribution state in the layer thickness direction;
A layer region of ll and a layer region of t It is characterized by having.

The photoconductive member of the present invention, which is designed to have a similar layer structure, can solve all of the above-mentioned problems and has extremely excellent mechanical and optical properties.

Indicates photoconductive properties, pressure resistance, and usage environment characteristics.

In particular, when applied as a self-forming member for electrophotography, there is no influence of residual potential on image formation, its electrical characteristics are stable, it is highly sensitive, and it has a high 8N ratio. Therefore, high-quality images with good light fatigue resistance and repeated use characteristics, high density, clear halftones, and high resolution can be repeatedly obtained at low cost.

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

FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention.

84! The photoconductive member 100 shown in FIG. The amorphous layer 102 has a layer region (0) containing oxygen atoms as constituent atoms and a layer region (III) containing atoms belonging to Group 1 of the periodic table. The oxygen atoms contained in the layer region (0) are distributed in a continuous and substantially uniform manner in the layer thickness direction, and in a region parallel to the interface 104 between the support 101 and the amorphous layer 102. and is contained in the layer region (0) in a substantially uniform distribution state. Atoms belonging to group P of the periodic table contained in the layer region (1) are in the amorphous layer 1.
02 is continuous in the layer thickness direction and the support 10
1 (the free surface 103 side of the amorphous layer 102) and the support side (the interface 104 side between the support 101 and the amorphous layer 102). is contained in the layer region (1) in such a manner that it is distributed in a large amount.

In the present invention, the layer region (1
), the atoms belonging to Group Ⅰ of the periodic table include B (boron), 9M (aluminum), Ga (gallium), and In (indium).

T/ (thallium), etc., and particularly preferably used are ijB and Ga.

In the present invention, the distribution state of the group atoms contained in the layer region (Fl) is as described above in the layer thickness direction, and the distribution state is parallel to the surface 104 of the support 101. The distribution is substantially uniform in the direction.

In the present invention, the layer region (0
) and layer region (1) are taken into consideration when forming the amorphous layer 102 so as to share at least a part of the layer region in order to effectively achieve the object of the present invention.

2 to 10 show the 4[1
A typical example of the distribution state of group atoms in the layer thickness direction is shown.

In the examples shown in FIGS. 2 to 10, the layer region (0)Fi containing oxygen atoms may be the same layer region as layer region (1) or may include layer region (1). , or layer region (1
) may be books that share some layer areas. Therefore, in the explanation of sweeping temperature, the layer region (0) containing f11 elementary atoms will not be mentioned unless a particular explanation is required.

In Figure gg2 to Figure 1θ, the horizontal axis represents the content C of C group atoms, and the vertical axis represents the amorphous layer exhibiting photoconductivity.
Indicates the layer thickness of the layer region (1) containing the m-group atoms, t
B indicates the position of the interface on the support side, and tT indicates the position of the interface on the opposite side to the support side (i.e., the layer region (1) where carbonate group atoms are contained) At8
Layer formation is performed toward the 6 tT side.

In the present invention, layer regions containing group atoms (■
) is a-8i (H.

X) and may occupy the entire layer area of the amorphous layer exhibiting photoconductivity, or may occupy a portion thereof.

In the present invention, when the layer region (1) occupies a part of the layer region of the amorphous layer, the example shown in FIG. 1 is used.

FIG. 2 shows a first typical example of the distribution state of group III atoms contained in the amorphous layer in the layer thickness direction.

In the example shown in FIG. 2, from the interface position t8, where the surface where the layer region (II) containing the group atom is formed and the surface of the layer region (1) are in contact, to the position tl, While the concentration C of the group A atoms takes a constant value C1, they are contained in the layer region (II) where the group III atoms are formed, and from the position t to the interface position IT from the concentration C1. It has been gradually and continuously reduced. At the interface position IT, the concentration C of ill group atoms is C1.

In the example shown in FIG. 3, the concentration C of the group III atoms contained is from the position tB to the position tTK.
4, the concentration C gradually decreases at position 1T.
A distribution state is formed in which the number is 1.

In the case of FIG. 4, at position 1B and position ti, the concentration of group (III) atoms is set to a constant value cFi concentration C0, and at position t,
and position 1T, it is gradually and continuously decreased,
At position tT, the contained chain fC is substantially zero.

In the case of FIG. 5, the group Ⅰ atoms are from position t8 to position tT
Until K is reached, the contained chain fC1 is gradually decreased continuously, and becomes substantially zero at the position tT.

In the example shown in FIG. 6, the chain containing the Group C0 is included. Between the position - and the position 1T, the content concentration C decreases linearly until it reaches the position t and then the position 1T.

In the example shown in FIG. 7, the position t4 is lower than the position t8.
At t, a constant value of concentration C1 is taken, and from position t4 to position t
At T1, the concentration c1. It is said that the distribution state decreases in a linear function until .

In the example shown in FIG. 8, from position 1B to position C, the concentration C of the group atoms decreases in a linear manner from the concentration CI4 to zero.

In Fig. 9, until position - is reached,
Concentration C5et from concentration CFi and concentration C1l of group atoms
An example is shown in which the concentration C1 is decreased linearly at a constant value between positions t1 and tT.

In the example shown in FIG.
tC is once c1 at position -, and until it reaches position -, it is initially slowly decreased from this concentration C□, and near the position of electric, it is rapidly decreased and becomes the concentration C1l at position t. be done.

Between position t6 and position t, the concentration is first rapidly decreased, and then gradually decreased to reach C1 at position t, and between position fly and position t.

is gradually decreased very slowly to the position t
, the density C3 is reached. Position 1. and the position tT, the fete is reduced to substantially zero according to a curve shaped as shown in the figure.

As described above with reference to FIG. 2 to FIG. In the group Im
On the ~ side, the amorphous layer is provided with a layer region (Wl) in which the distribution state of the C-group atoms is formed, and the torsion content C is lower than that on the support side. .

In the present invention, the layer region (circle) containing the carbonate group atoms constituting the amorphous layer is the area where the carbonate group atoms are contained at a relatively high concentration on the support side as described above. It has a large area.

If explained using the symbols shown in FIGS. 2 to 1O, the localized region is provided within 5 μm from the interface position IB.

In the present invention, the above-mentioned localized area size is the interface position indicator.
It may be for every layer region up to 5# thickness, or it may be for a part of a layer region →.

Whether the localized region size is a part or all of the layer region → is determined as appropriate depending on the characteristics required of the amorphous layer to be formed.

The localized area size is defined as the distribution state of group III atoms contained therein in the layer thickness direction, and is determined by the maximum concentration distribution value (concentration distribution value) of group III atoms (jnax is usually 50 atomic for silicon atoms). ppm or more, preferably 80 at
omic ppm or more, optimally 100100ato
It is desirable that the layers be formed in such a way that a distribution state of at least ppm can be achieved.

That is, in the present invention, the layer region containing group (I) atoms is such that the maximum value Qnax of the content distribution exists within 5 μm in layer thickness from the support side (layer region 5 μ thick from IB). It is formed.

In the present invention, the content of the group (III) atoms contained in the layer region (III) containing the dXI group 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 amorphous layer is usually 1 to 3 x 10"ato
mic ppm, preferably 2-500 atoms
c ppm, optimally 3 to 209 atoms@ppm.

The amount of oxygen atoms contained in the layer region (01) is determined as appropriate depending on the characteristics required of the photoconductive member formed according to the purpose of the present invention, but is usually 0.001 to 0.01. 3
0 atomic %, better 0.002~20
Atomic K, optimally 0.003 to 10 atoms
icX is preferable.

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

A/, Cr, Mo, Au, Nb,
Examples include metals such as Ta, V, Ti, Pi, Pd, and alloys thereof.

Polyester is used as an electrically insulating support.

Polyethylene/, polycarbonate, cellulose acetate, polypropylene/, polyvinyl chloride.

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

Ceramics, paper, etc. are usually used. Preferably, at least one surface of such an electrically insulating support is subjected to a conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, NiCr is applied to its surface.

A/, Cr, Mo, Au, Ir, Nb, Ta, V, T
j, Pt, Pd.

In, 0. ,8nO,,ITO(In,O,+5n0
- Conductivity can be imparted by providing a thin film consisting of NiCr, U, Ag, Pb, etc., or if a synthetic resin film such as a polyester film is provided.
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, m-beam evaporation, snobbing, etc., or the surface is laminated with the metal. , conductivity is imparted 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, it is desirable to use an endless belt or cylindrical shape for continuous high-speed copying. 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 this range.

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

In the present invention, the amorphous layer composed of M-8i (H, be done. For example, in order to form an amorphous layer composed of a-8i (H, Hydrogen atom (H
) A source gas for introduction of Fi/and halogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber, and is set in a predetermined position in advance. A dove consisting of a-8i(H,X) may be formed on the surface of a predetermined support. In addition, when forming by sputtering method, S
When sputtering a target composed of T, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) may be introduced into the deposition chamber for sputtering.

In the present invention, specific examples of the halogen atom (X) contained in the amorphous layer as necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can list them.

The raw material gas for supplying 81 used in the present invention includes 5it-14,8il1%, 8i,l(,,8
Silicon hydride (silanes) in a gaseous state or capable of being gasified, such as i, H, etc., are listed as being effectively used.
In particular, 5il-(, 8i, H) are preferred in terms of ease of layer preparation work, good Si supply efficiency, etc.

Many halogen compounds are effective as the raw material residue for introducing halogen atoms used in the present invention, such as gaseous halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into gas or gasified.

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

Specifically, halogen compounds that can be suitably used in the present invention include halogens of fluorine, chlorine, bromine, and iodine, BrF, C/F, and C2F.

BrF, , BrF@, IF, , IP, ,
Intergen compounds such as ICI and IBr (Q/% 0) can be mentioned.

Examples of silicon compounds containing halogen atoms, Shinkai, and silane derivatives substituted with halogen atoms include, for example, 8
i1i'4.8i, 1%, 8iC/4.5iBr,
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 is not used as a raw material gas capable of supplying Si. In either case, an amorphous layer made of a-8i containing halogen atoms can be formed on a predetermined support.

When forming an amorphous layer containing halogen atoms according to the glow discharge method, basically silicon halide gas, which is a raw material gas for supplying 8i, and Ar are used.

)1. , He, etc. are introduced into a deposition chamber in which an amorphous layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a non-crystalline material on the support in the gas plasma atmosphere. Although a crystalline layer can be formed, a layer may also be formed by mixing a predetermined amount of a silicon compound gas containing hydrogen atoms with these gases in order to introduce hydrogen atoms.

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

In order to form an amorphous layer made of a-8i (H, Sputtering is carried out in a gas plasma atmosphere of This can be carried out by heating and evaporating the flying evaporated material using a method such as the gB method) and passing the flying evaporated material through a predetermined gas plasma atmosphere.

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

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as Tsuru or the above-mentioned nine silanes, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Just do it.

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

Permanent halides such as HBr, Hl, 8iH, F,...
Si 搗4゜8iH, Cz, , 8iHCz, ,
8..., Br, , 8iHBr, isohalogen-substituted silicon hydride, and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituent elements are also cited as effective starting materials for forming an amorphous layer. I can do things.

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

In order to structurally introduce hydrogen atoms into the amorphous layer, in addition to the above, Hl, or
-8.

This can also be achieved by causing a discharge to occur by causing a silicon hydride gas such as 8 i4H to coexist with a silicon compound for supplying Si 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 carbon dioxide gas, including inert gases such as He and λr as necessary, into the deposition chamber. A-8i on the substrate by forming and sputtering the 8i target.
An amorphous layer consisting of 1(H,X) is formed.

Furthermore, B! also serves as doping with impurities! It is also possible to introduce a gas such as H@.

In the present invention, the amount of hydrogen atoms (H) or halogen atoms (X) contained in the amorphous layer of the photoconductive member to be formed
or the sum of the amounts of hydrogen atoms and halogen atoms is usually 1 to 40 atomicX, preferably 5 to 30 atomicX.
It is desirable to set it to mic%.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the amorphous layer, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X )
This can be achieved by controlling the amount of starting material used to contain the material introduced into the deposition system, the discharge force, etc.

In order to provide the layer region Gl) containing Group 1 atoms and the layer region Gl) containing oxygen atoms in the amorphous layer, when forming the amorphous layer by a glow discharge method, a reactive sputtering method, etc. In this method, a starting material for introducing a group group atom and a starting material for introducing an oxygen atom are used together with the above-mentioned starting material for forming an amorphous layer, and the amounts thereof are controlled in the formed layer. It is achieved by containing.

The layer region containing oxygen atoms (0
) and the layer region (II) containing group (III) atoms, respectively, when the glow discharge method is used to form the layer region (II) containing group (II) atoms, the starting material serving as the raw material gas for forming each layer region is the above-mentioned amorphous layer forming material. A starting material for introducing an oxygen atom and/or a starting material for introducing an atom of the sulfur group is added to the starting material selected from among the starting materials as desired. The starting materials for introducing oxygen atoms or the starting materials for introducing atoms of the fifth group are as follows:
Most of the gaseous substances or gasified substances having at least tunic oxygen atoms or Group Ⅰ atoms as constituent atoms can be used.

For example, if layer region (0) is to be formed, a raw material gas containing silicon atoms (SS) and oxygen atoms (0
) and, if necessary, a raw material gas containing waterfowl atoms (H) or halogen atoms (X) as constituent atoms at a desired mixing ratio, or ,
A raw material gas containing silicon atoms (old) as constituent atoms and a raw material gas containing oxygen atoms (0) and hydrogen atoms (H) in a desired mixing ratio, or
A source gas containing silicon atoms (Sl), silicon atoms (84), oxygen atoms (0), and hydrogen atoms (H
) can be used in combination with a raw material gas having three constituent atoms.

Alternatively, it is also possible to use a mixture of a raw material gas containing silicon atoms (8i) and hydrogen atoms (H) and a raw material gas containing oxygen atoms (0) as constituent atoms.

Specifically, starting materials for introducing oxygen atoms include, for example, oxygen (Ol>, ozone (0,), -nitrogen oxide (NO), nitrogen dioxide (NO,), -nitrogen dioxide (N
IO), mini nitric oxide (N, 0.), nitrogen tetroxide (N
O1), mini nitric oxide (r%0s) - nitrogen trioxide (N
O,>, silicon atom (8i) and oxygen atom (0)
and a bulky water atom (H) as constituent atoms, for example, disiloxane H,8i0SiH,,)disiloxane H,8i0
8iH, 08i&4. Examples include lower siloxanes such as

When layer region (I) is formed using a glow discharge method, the starting materials for introducing group (I) atoms that are effectively used in the present invention are:
B4H,. , Nipo, B, H, , Akira - BaHs * -
Boron hydride such as BsHt4, BFa, BC/,
BBr.

Examples include boron halides such as. In addition to this, Ice
,, GaC1,, Ga(CHs),, InC/,
, TlCl5, etc. can also be mentioned.

Layer region (II) containing Group 1 atoms (II)
The content of group atoms can be arbitrarily determined by controlling the gas flow rate of the starting material for introducing group 11M atoms into the deposition chamber, gas flow rate ratio, discharge power, support temperature, pressure in the deposition mold, etc. can be controlled.

To form the layer region (0) containing oxygen atoms by sputtering, a single crystal or polycrystalline Si wafer or 8i0. This can be carried out by sputtering a wafer or a wafer containing a mixture of Si and StO in various gas atmospheres.

For example, if an 81 wafer is used as a target, the raw material gas for introducing oxygen atoms and, if necessary, hydrogen atoms and/or halogen atoms, is diluted with a diluent gas as necessary, and the material gas for sputtering is deposited. The Si wafer may be sputtered by introducing these gases into a chamber and forming a gas plasma of these gases.

Also, separately, Si and 8i0. or as separate targets from 81 and 80. By using a single target in which a mixture of This is accomplished by sputtering with K. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the example of glow discharge described above can be used as an effective gas also in the case of sputtering.

In the present invention, as the diluting gas used when forming the amorphous layer by a glow discharge method or the sputtering gas used when forming the amorphous layer by a sputtering method, a rare gas such as He , Ne, Ar
etc. can be mentioned as suitable ones.

The thickness of the amorphous layer is appropriately determined as desired so that photocarriers generated in the amorphous layer are efficiently transported, and is usually 1 to 100 μm, preferably 3 to 80 μm.
, it is desirable that Fi% be optimally set to 5071.

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

Fig. 811 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method.

# to the gas cylinder 1102.1103.1104 in the diagram.
i. The raw material gas for forming each layer region of the present invention is sealed, and as an example, 1102 is a diluted Su''i4 gas (purity 99.999N).
, hereinafter abbreviated as S old and /ru. ) cylinder, interpreted 8i,
H, gas (purity 99.99 mushrooms, hereinafter 8i, H.

Gas (purity 99.999k, hereinafter 8tFa/') is abbreviated as Ie. ) It is a cylinder.

These gases are introduced into the reaction chamber 1101.K is the pulp of gas cylinders 1102-1105, 1122-112
5. Check that the leak pulp 1135 is closed, and also check that the inflow pulps 1112 to 1115 and the outflow pulp 1
117-112G, after confirming that the auxiliary pulp 1132 is opened, the main pulp 1134 is first opened for reaction @ 1101, and the inside of the gas pipe is exhausted. Next, vacuum gauge 1
The reading of 136 is about 5 X 10' torr K At the time of running, the auxiliary pulp is 1132, the outflow pulp is 1117~1
Close 120.

To give an example of forming the layer region (1) constituting the amorphous layer on the base cylinder 1137, the gas cylinder 1
From 102 8 iH4/He gas, gas cylinder 1103
Yoshi B, 11. /He gas to pulp 1122°1123
Open the outlet pressure gauge 1127.1128 and check the pressure on the 1st floor/
cd and gradually open the inflow pulp 111λ1113 to allow it to flow into the mass flow controllers 1107 and 1108. Subsequently, the effluent pulp 1117.1118,
The auxiliary pulp 1132 is gradually opened to allow each gas to flow into the reaction chamber 1101. Adjust the outflow pulp 1117° and 1118 so that the ratio of the 8iH, /He gas flow rate to the 8iH, /He gas flow rate becomes the desired value, and the pressure inside the reaction chamber becomes the desired value. Adjust the opening of the main pulp 1134 while checking the reading on the vacuum gauge 1136.

Then, the temperature of the base cylinder 1137 becomes higher than that of the heating heater 1.
After confirming that the temperature is set at 50 to 400 °C by 138, the power supply 114G is set to the desired power to generate a glow discharge in the reaction chamber 1101,
At the same time, B, H according to the pre-designed rate of change curve.
The concentration of group (I) atoms such as B contained in the formed layer is controlled by gradually changing the flow rate of the L/He gas in the pulp 1118 manually or by using an externally driven motor.

To form the layer region (0), the layer is formed using NO gas in addition to the 9B, H@/Ha gas used in the formation of the layer region (1), or in addition to the Maki gas.

Needless to say, all the outflowing pulp other than the gas required when forming each layer is closed, and when forming each layer, the gas used to form the previous layer is inside the reaction chamber 1101 and the outflowing pulp 1117 is closed. In order to avoid remaining in the piping leading from ~1120 into the reaction chamber 1101, the outflow pulps 1117~1120 are closed, the auxiliary valve 1132 is opened, and the main pulp 1134 is fully opened to evacuate the system to high vacuum. Perform operations as necessary.

During layer formation, the base cylinder 1137 is rotated by a motor 1139 at a constant speed in order to ensure uniform layer formation.

Example 1 A layer was formed on the M cylinder using the manufacturing apparatus shown in FIG. 11, using the boron content in the layer as a parameter. In this case, the common manufacturing conditions are shown in Table 1.・The concentration distribution of B in the layer thickness direction in the amorphous layer is 1ilZ
As shown in Figures 1 to 14, respectively.

Table 2 shows the boron (B) content at each position in the layer thickness direction and the evaluation results of the obtained sample (All-413). The numbers in the left column of the table indicate sample numbers.

The produced electrophotographic image forming member undergoes a series of electrophotographic processes including charging, exposure, development, and transfer to achieve the [density], [resolution], and [gradation reproducibility] of the image visualized on the transfer paper.
Comprehensive evaluation was made based on the merits and demerits.

The values in Table 2 are boron content (atomic ppm)
shows.

◎; Excellent O; Good Δ; Fully usable for actual river use Example 2 Same as Example 1 except that the content of B in the amorphous layer was changed as shown in Figures a115 to 17. Under the following manufacturing conditions, a good result was obtained for the amorphous layer.

Example 3 As shown in FIGS. 18 to 20, an amorphous layer was prepared under the same manufacturing conditions as in Example 1 except that the content of B in the amorphous layer was changed. We obtained various results.

Example 4 As shown in FIGS. 21 to 23, an amorphous layer was prepared under the same manufacturing conditions as Example 1 except that the content of B in the amorphous layer was changed. We obtained results that showed that M.

Example 5 As shown in FIGS. 24 to 26, an amorphous layer was prepared under the same manufacturing conditions as in Example 1 except that the content of B in the amorphous layer was changed. We obtained results that showed that M.

Example 6 8 iH4/He Using 51gH,/He gas as a gas substitute, B equivalent to the samples (411-A53) shown in Examples 1 to 5 was prepared according to the conditions shown in Table 1.
Electrophotographic imaging acid No. 1 having a content distribution state of
Table No. 1 Flea Table □ Cow In Table 3, for example, sample/% 611 means a sample having the same B content distribution state as sample All in Table 2.

Example 7 Sample 41 of the samples in Examples 1 to 5
3 gates 421. M23. rot 33. Electron I having a layered structure having a content distribution state of 8 similar to that of 52; A secondary photographic imaging member was heated to 8 iF with an 84 temperature gas.

Each sample was prepared under the same conditions except that /He gas was added. At this time, 8iF for S-gas,
Gas heating ratio (8iF, /8iF (4+ 81F4)
The pressure was set to 30 mOl, and the other differences in production conditions and operating procedures were the same as in Example 1. The thus obtained electrophotographic plate forming members were formed on transfer paper using a series of electrophotographic processes and evaluated in the same manner as in Example 1. It was also found that the gradation reproducibility was excellent.

[Brief explanation of the drawing]

FIG. 1 shows one of the preferred embodiments of the photoconductive member of the present invention.
2 to 1O and 12 to 26 are schematic layer configuration diagrams for explaining the two layer configurations, respectively. FIG. 11, which is an explanatory diagram for explaining the distribution state of So group atoms, is a schematic explanatory diagram of nine devices used in the present invention. Applicant: Canon Co., Ltd. “I”;-, 15th grade Ll 10.0 Layer thickness dψ
) 200 Procedures Amendment (self-effect 1. Indication of the case 1982 Patent Application No. 215486 2, Name of the invention Photoconductive member 3, Person making the amendment Relationship with the case 0 Patent applicant address Ota-ku, Tokyo Shimomaruko 3-30-2 name (100
) Canon Co., Ltd. Representative: Ryu Kaku, Department 4, Agent address: 3-30-25 Shimomaruko, Ota-ku, Tokyo 148, Column 6 of “Detailed Description of the Invention” of the specification to be amended, Details of the contents of the amendment 16th page, line 12 of "-111 usually 1---preferably" is r----1 usually 0.01 to 5
104atoa+ic ppm, preferably 1-3
X 10' atomic ppm, more preferably.

Claims (3)

[Claims] (1) A photoconductive amorphous material made of a support for a photoconductive member and an amorphous material based on silicon atoms and containing at least either a hydrogen atom or a halogen atom as a constituent atom. a first layer region containing oxygen atoms as constituent atoms in a continuous and substantially uniform distribution state in the layer thickness direction; and a second layer region containing atoms belonging to group (I) of the periodic table as constituent atoms in a distribution state that is continuous and distributed more toward the support side. (2) The photoconductive member according to claim 1, wherein the first layer region and the second layer region share at least a portion thereof. (3) The photoconductive member according to claim 1, wherein the second layer region occupies substantially the entire layer region of the amorphous layer.