JPS58150959A - Photoconductive material - Google Patents

Abstract

PURPOSE:To obtain a photoconductive material stabilized in electrical and optical properties, not causing deterioration even after repeated uses, and enhanced in durability and moisture resistance, by laminating specified layers composed mainly of amorphous silicon (a-Si). CONSTITUTION:A photoconductive material 100 is formed by laminating a first amorphous layer 102 composed mainly of a-Si and a second amorphous layer 107 composed of a-Si contg. C and H on a substrate 101. The layer 102 has a first layer region 103 composed of a-Si contg. O and a layer region 104 composed of a-Si contg. an element of group V, such as P or As, both located on the side of the substrate 101, and layer thickness tB of the region 104 and difference T between thickness of the layer 102 and tB satisfy the shown equation and inequality.

Description

Detailed Description of the Invention The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (herein, light in a broad sense refers to ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, etc.). Regarding.

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)), have absorption spectrum characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, have a desired dark resistance value, and be harmless to the human body during use. Furthermore, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages 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, the above-mentioned non-polluting property during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as --sl) is a photoconductive material that has recently attracted attention.
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

In addition, a photoconductive member having a photoconductive layer composed of conventional A-83 has excellent electrical, optical, and photoconductive characteristics such as dark resistance value, photosensitivity, and photoresponsiveness, as well as the environment in which it is used. characteristic point,
Furthermore, in terms of stability over time and durability, each individual characteristic has been improved, but the reality is that there is room for further improvement in terms of overall characteristics. .

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 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 will accumulate, resulting in a number of disadvantages such as the so-called ghost phenomenon in which an afterimage occurs.

In addition, when forming a photoconductive layer using a-stvU material, in order to improve its electrical and photoconductive properties, hydrogen atoms or halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive Whether boron atoms, phosphorus atoms, etc. are used for control purposes, or other atoms are used to improve other properties, each of which is contained in the photoconductive layer as a constituent atom, depending on how these constituent atoms are contained. However, there may be a problem with the electrical or photoconductive properties or voltage resistance of the formed layer. Ta.

! For example, the lifetime of the photocarriers generated by light irradiation in the photoconductive layer formed in 1 is not sufficient, or the injection of charge from the support side is not sufficiently prevented in the dark area. , or there may be image defects on the image transferred to the transfer paper, which are thought to be caused by localized neglect or destruction, commonly referred to as 1-white spots, or, for example, when a blade is used for cleaning, it may be caused by abrasion. Seem,
A so-called image defect commonly referred to as "one white streak" 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.

Historically, when the layer thickness exceeds 10 microns or more, the layer lifts or peels off from the surface of the support, or the layer peels off as the time passes in the air after removing it from the vacuum deposition chamber for layer formation. This results in phenomena such as cracks forming in the surface. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved 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 devise ways to solve all of the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the points set forth in ``a-8''.
As a result of comprehensive research and consideration from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc.,
An amorphous 'tA material having a silicon atom as a matrix and containing at least either a hydrogen atom (H) or a halogen atom (X), Ml hydrogenated amorphous silicon,
Halogenated amorphous silicon or halogen-containing hydrogenated amorphous silicon [hereinafter generically referred to as Table 1
A photoconductive material designed and created with the layer structure of a photoconductive member having a photoconductive layer composed of [using a-8t (H,x)J] as described below. The conductive material not only exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in all respects, especially as a photoconductive material for electrophotography. It is based on what we have found.

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

Another object of the present invention is to have excellent sealing properties between layers provided on a support and between each layer of laminated layers, and to have a dense and stable structure. The object of the present invention is to provide an optical winding part with high layer quality.

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 charging processing for forming a still image, making ordinary electrophotographic methods extremely effective. It is an object of the present invention to provide a photoconductive member having excellent electrophotographic properties that can be applied.

Yet another object of the present invention is to provide [i! I
To provide a photoconductive member for electrophotography, which can easily obtain high-quality images with no image defects or image blurring, high density, clear halftones, and high resolution. .

Yet another object of the present invention is high photosensitivity.

Another object of the present invention is to provide a photoconductive member that has high signal-to-noise ratio characteristics and high voltage resistance.

The photoconductive member of the present invention has a support using a photoconductive part and a silicon atom as a matrix, and optionally has either a hydrogen atom (T()) or a halogen atom (X) as an atom. Containing at least an amorphous material (a-s+ (H,X
) ) and a first amorphous layer having photoconductivity, the first amorphous layer having photoconductivity;
A first layer region containing oxygen atoms as constituent atoms, and a second layer region containing all atoms belonging to Group Ⅰ of the periodic table as constituent atoms and located on the support side. , these share at least a part of the force, and the layer thickness of the second layer region is tB, and the layer thickness of the first amorphous layer and the layer thickness of the second layer region are The difference from tB is T.
B/(T+tB) < The second amorphous gi layer is made of an amorphous material.

The photoconductive member of the present invention, which is formed into a film having the above-described layer structure, can solve all of the above-mentioned problems and has extremely excellent electrical and optical properties.

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

Particularly when applied as an electrophotographic imaging member, ii! ! It has no effect of residual potential on 1ffJI formation, has stable electrical characteristics, high sensitivity, and a high S/N ratio, has excellent light fatigue resistance and repeated use characteristics, has a high concentration, and has a high concentration. It is possible to stably repeat high-quality images with clear tones and high resolution.

In addition, the photoconductive member of the present invention has an amorphous layer formed on the support, which is strong and has excellent adhesion to the support, and can be continuously used at high speed for a long time. Can be used repeatedly.

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

FIG. 1 is a schematic diagram schematically showing a layer structure 1 of a photoconductive member according to a first embodiment and embodiment of the present invention.

A photoconductive member 100 shown in FIG. 1 is composed of a-s+ (:a-x) in a part of a support 101 for a photoconductive member, and a first amorphous layer (1 ) [2 and the second amorphous layer 1.07 provided on the amorphous layer (1) 1o2 and made of an amorphous material whose constituent atoms are silicon atoms, carbon atoms, and hydrogen atoms. and has.

The amorphous layer (1) 102 includes a first layer region (0) 103 containing oxygen atoms as constituent eggs, and a second layer region (0) 103 containing atoms belonging to group Ⅰ of the periodic table (group V atoms). Layer area (
v) 104, and a layer region 1 (J6) which does not contain oxygen atoms and group (I) atoms on the second layer region (V) 104.

The layer region 105 provided between the first layer region (0) 103 and the layer region 106 contains Group V atoms, but oxygen atoms are not contained therein.

The oxygen atoms 1 contained in the first layer region (0) 103 or the Group (3) atoms contained in the second layer region (V) 104 are continuous in the layer thickness direction in each layer region. It is preferable that the particles be distributed uniformly, and that they be distributed continuously and substantially uniformly in a plane substantially parallel to the surface of the support 1.

In the photoconductive member of the present invention such as the example shown in FIG. 1, the surface side portion of the amorphous layer (1) 102 has a layer region ( A layer region (corresponding to the layer region 106 shown in FIG. 1) that contains Group V atoms but does not contain oxygen atoms (layer region 105 shown in FIG. 1) is not necessarily provided. do not.

That is, for example, in FIG. 1, the first layer region (o) io
3 and the second layer region (V) 104 may be the same layer region, or the second layer region (V) 104 may be provided in the first layer region (0) 103. is also good.

In the photoconductive member of the present invention, the first layer region (0) contains oxygen atoms to provide a high dark resistance and a gap between the support and the amorphous layer (1) on which the amorphous layer (1) is directly provided. Focusing on improving the adhesion of the amorphous layer (1), the layer region on the surface side of the amorphous layer (1) does not contain oxygen atoms, further improving moisture resistance and corona ion resistance and increasing sensitivity. is being focused on.

In particular, like the photoconductive member 100 shown in FIG. 1, the amorphous layer (1) 102 has a first layer region (0
) 103, second layer region containing group ■ atoms■)
104, layer region 105 that does not contain oxygen atoms, and layer region 1 that does not contain oxygen atoms and group (Ⅰ) atoms.
Better results can be obtained in the case of a layer structure having a layer region having 06 and a layer region shared by the first layer region (0) 103 and the second layer region (V) 104.

In the photoconductive member 1 of the present invention, the first layer region (0) that constitutes a part of the amorphous layer (I) and contains oxygen atoms is, in part, the amorphous layer (I). For the purpose of improving the adhesion with the support in 1), the second layer region (G) which constitutes a part of the amorphous layer (I) and contains group (I) atoms is One purpose is to prevent charge from being injected into the amorphous layer (1) from the support side when the free surface side of the amorphous layer (It) is subjected to charging treatment. The support body and the amorphous layer (1) are each provided as a part of the amorphous layer (1) in a structure in which the support body and the amorphous layer (1) share at least a part of each other as a bonding layer region.

Alternatively, in order to more effectively improve the adhesion between the second layer regions and the layer region provided directly on the second layer region, it is possible to The first layer area (0
) is provided from the contact interface with the support to include the space between the second layer regions. It is preferable that the first layer region (0) is provided in the amorphous layer (1) so as to have a layer structure including the layer region (g).

In the present invention, P (phosphorus), S ( arsenic), sb (antimony), n+ (bismuth).

etc., and P and As are particularly preferably used.

In the present invention, v1 contained in the second layer region bacteria
The content of N atoms is appropriately determined as desired so as to effectively achieve the object of the present invention, but is usually 30
~5 X 10' atomic ppl.

Preferably 50-I x 10' atomic pp
l! , optimally 100-5 X 103 atomic
It is desirable that it be ppHl. The amount of oxygen atoms contained in the first layer region (0) is determined as desired depending on the characteristics required of the photoconductive member to be formed, but usually it is 0001 to 50 at.
omic%, preferably 0.002 to 40 atoms
It is desirable that the content be ic%, most preferably 0.003 to 30 atomle%.

In the photoconductive member 1 of the present invention, the layer thickness tB of the layer region (to) containing group (I) atoms (the layer thickness of the layer region 104 in FIG. 1), and the layer thickness tB between the layer regions. The relationship between the layer thickness T of the layer area (layer area 106 in FIG. 1) excluding the provided layer area (G) is determined so as to satisfy the relational expression shown above. However, more preferably, the value of the relational expression shown above is 0.35 or less, most preferably 0.3 or less.

In the present invention, the layer thickness tB of the layer region containing group (I) atoms is usually 30λ to 5μ, preferably 40μ.
It is desirable that A~4μ, optimally 50λ~3μ.

Further, the sum of the layer thickness T and the layer thickness tB (T + tB) is usually 1 to 100μ, preferably 1 to 80μ.

The optimum thickness is preferably 2 to 50μ.

The layer thickness t□ of the layer region (0) containing oxygen atoms is the layer region (0) that shares at least a part of the layer region (
It is desirable that the thickness be appropriately determined in accordance with the desired purpose in relation to the layer thickness tB of 2). That is, if the purpose is to strengthen the adhesion between the layer region (7) and the support that is in direct contact with the layer region (2), the layer region (0) is the layer region (to).
Since it is sufficient that at least a small amount of t and C is provided in the support side end layer region, the layer thickness t□ of the layer region (0) may be at most the layer thickness tB of the layer region (to). .

Furthermore, considering the case where the above two points are satisfied, the layer thickness t□ of the layer region (0) must be at least equal to the layer thickness tB between the layer regions; It is necessary to have a layered structure in which layer region (1) is provided in region (0).

In order to more effectively improve the adhesion between the layer region (G) and the layer region provided directly on the layer region, the layer region (0) is (opposite side of the body)
It is preferable to extend it to .

In the present invention, amorphous #(1) amorphous IN (II
) A portion containing no oxygen atoms is provided in the side end layer region,
In the case where the layer region (0) is locally unevenly distributed on the support side of the amorphous layer (1), the layer thickness t□ may be determined as desired, taking into account the above points. , normally 1
0 people to 10μ, preferably 20 people to 8μ, optimally 30 people
It is desirable that the thickness be 5 μm.

In the photoconductive member 100 shown in FIG. 1, the second amorphous layer (I) formed on the first amorphous layer (I) 102 is
1) 107 has a free surface 108 and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated usage characteristics, pressure resistance usage environment characteristics, and durability.

Further, in the present invention, the first amorphous layer (1) 102 and the second amorphous layer (II) constituting the amorphous layer (1) 102
) 107 have a common constituent element of silicon atoms, chemical stability cannot be sufficiently ensured at the laminated interface.

The second amorphous layer (n) is an amorphous material (a-(S i x'
o1-x)yH+-y+where O<x, y<1).

The second amorphous layer (n) composed of a-(Six01-1)y'H+-y can be formed by glow discharge method, sputtering method, ion implantation method, ion blating method, or electron beam method. etc. 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. It is relatively easy to control the manufacturing conditions for manufacturing the conductive member. A glow discharge method or a sputtering method is preferably employed because of the advantages of easy introduction of carbon atoms and hydrogen atoms together with silicon atoms into the second amorphous layer (It).

Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same system to form the second amorphous layer (II).
) may be formed 1.

To form the second amorphous layer (It) by the glow discharge method, z a (S I X O+ ,) y H+
The raw material gas for forming y is mixed with the diluted residue at a predetermined mixing ratio as necessary, and introduced into the deposition chamber for vacuum deposition where the support 101 is installed, and the introduced gas is subjected to glow discharge. The first amorphous p+ layer (1) which has already been formed on the support 101 by generating gas plasma
- (SixC, x) yH, , may be deposited on -H.

In the present invention, the raw material gas for forming a(SixOl,)yH, is 81. Almost any gaseous substance containing at least one of Or H as a constituent atom or a gasified substance that can be gasified can be used.

When using a raw material gas whose constituent atoms are 81 as one of Si, O, and H, for example, a raw material gas whose constituent atoms are Si, a raw material gas whose constituent atoms are C, and ■. Either the raw material gas containing atoms is mixed at a desired mixing ratio θI, or the raw material gas containing St and the raw material gas containing C and H are mixed at the desired mixing ratio. They can be mixed at a mixing ratio, or a raw material gas having constituent atoms of i:j and si and a raw material gas having three constituent atoms of Si, 0 and ■ can be mixed and used.

Alternatively, a raw material gas containing C as a constituent atom may be mixed with a raw material gas containing Si and (1) as constituent atoms.

In the present invention, the material used as the raw material waste for forming the second amorphous layer (II) is Sil. Si2H6, 5L3T4.
, 5i4I11o, etc.
Water-ice-forming silicon gases such as the above, C and 1 are @+4 atoms, for example, saturated hydrocarbons with carbon Vv1 to 4, carbon numbers 2 to 4.
4, an acetylene hydrocarbon having 2 to 3 carbon atoms, and the like.

Specifically, as the saturated hydrocarbon, methane (an4)
, ethane (02B6) + propane (OH8).

n-butane (n-0,H,.), pentane (C5■(+
2) + Ethylene hydrocarbons include ethylene (0
2H4).

Propylene (0,H,), Butene-], (0
, H8), butene-2 (0+Hs), isophthylene (04HB) + pentene ((j5H1g)
, Acetylene thread carbonization In this chapter, acetylene (02H
2), methylacetylene (0゜n, ),
Examples include butyne (C<Ha).

As a material gas whose constituent atoms are Si, C, and ■, 5
1(aTI,)4. Citing alkyl silicides such as si (a2n, ), d1 comes. In addition to these lung gases, MH2 is of course also used as a raw material gas for introduction.

To form the second amorphous layer (II) by the sputtering method, a solid or polycrystalline 8i wafer or a C wafer or a wafer containing a mixture of 81 and C is used as a target. These steps may be performed by sputtering in a yuzu gas atmosphere 7.

For example, if a Si wafer is used as a target, the i11 residue for introducing C and ■ is diluted with diluting gas as necessary and introduced into the deposition chamber for sputtering.
The St wafer may be sputtered by forming a gas plasma of these gases.

Alternatively, sputtering can be performed in a gas atmosphere containing at least hydrogen atoms, using 81 and C as separate targets or using a single mixed target of 81 and C. .

As the raw material gas for introducing 0 or H, the raw material gas shown in the glow discharge example mentioned above can be used, or it can be used as a gas also effective in the case of snot-tuttering.

In the present invention, the diluent gas used when forming the second amorphous layer (If) by a glow discharge method or a sputtering method is a so-called rare gas, such as He or Ne.
, Ar, etc. can be cited as suitable examples.

The second amorphous layer (n) in the present invention is carefully formed so as to provide the desired properties.

In other words, materials whose constituent atoms are Si, O, and H can have structural forms ranging from crystalline to amorphous depending on the conditions of their creation, and electrical properties ranging from conductive, semiconductive, and insulating. and exhibit properties ranging from photoconductive properties to non-photoconductive properties, so in the present invention, a S l xo that has desired properties depending on the purpose
In order to form 1-D, the preparation conditions are strictly selected according to the desired conditions.

For example, in order to provide the second amorphous layer (It) with the main purpose of improving pressure resistance, a-(SixO,-8)yH+
-7 is made as an amorphous material with pronounced electrically insulating behavior under conditions of use.

In addition, when the second amorphous layer (It) is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the degree of electrical insulation described above is relaxed to some extent, and the irradiation light is On the other hand, a-(Sixo, ,)aH1-a is prepared as an amorphous material that has a certain degree of sensitivity.

t-(S1xO,-x) on the surface of the first amorphous layer (I)
yH,.

When forming the second amorphous layer (II) consisting of It is desirable that the temperature of the support during layer formation be strictly controlled so that a-(SixO,-x)71i,-7 having the desired properties can be formed with a desired bend.

In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the second amorphous layer (II) should be adjusted according to the method of forming the second amorphous layer (II). The formation of the second amorphous layer (II) is carried out by selecting an optimal range as appropriate, but in normal cases, the temperature is 50°C to 350°C, preferably 100°C.
It is desirable that the temperature be ˜250°C. For the formation of the second amorphous layer (I[), delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. , glow discharge method or sputtering method is advantageous, but when forming the second amorphous layer (II) by these layer forming methods, the layer forming method should be adjusted in the same way as the above-mentioned support temperature. The discharge power and gas pressure are created during a-(81xO,-E)y: ■i which influences the characteristics of I-y! This is one of the important factors.

In order to achieve the purpose of the present invention, there is a
(St□CI-X) The discharge power conditions for AH3-1 to be produced effectively with good productivity are usually 10~
A power output of 300W, preferably 20 to 200W, is desirable. The gas pressure inside the deposition chamber is usually 0.01 to I Torr.
% is desirably about 0.1 to 0.5 Torr.

In the present invention, the values in the above-mentioned ranges are mentioned as the preferable numerical ranges of the supporting shield temperature and discharge power for creating the second amorphous layer (n), but these layer creation factors are , are not independently and separately determined, but are mutually organically related so that a second amorphous JV (It) consisting of a-(SixCI-X)7H1-a with the desired properties is formed. It is desirable that the optimum value of each layer creation factor be determined based on the following.

The amount of carbon atoms and hydrogen atoms contained in the second amorphous layer (II) in the photoconductive member of the present invention is the same as the production conditions of the second amorphous layer (n) according to the present invention. is an important factor in the formation of the second amorphous layer (n), which provides the desired properties to achieve the objective.

The amount of carbon atoms contained in the second amorphous layer (n) in the present invention is usually 1X103 to 90 atomic%, preferably 1 to 90 atomic%, and optimally 10 to 80 atomic%. It is desirable that this is the case. The content of hydrogen atoms is usually 1 to 1.
40 atomic%, preferably 2-35 atoms
ie%, preferably 5 to 30 atomic%, and the photoconductive member formed when the hydrogen content is in this range is considered to be excellent in practice. It's something you get.

That is, if we use the above expression a (81xOIx)y Hry, then X is usually 0.1 to 0.99999, suitably 01 to 099, optimally 0.15 to 0.9, and y is usually Desirably, it is between 0.6 and 0.99, preferably between 0.65 and 098, most preferably between 07 and 0.95.

The numerical range of the thickness of the second amorphous layer (b) in the present invention is one of the important factors for effectively achieving the object of the present invention.

The numerical range of the layer thickness of the second amorphous JW (I[) in the present invention is appropriately determined according to the desired purpose so as to effectively achieve the first objective of the present invention. .

Furthermore, the assignment of the second amorphous layer (II) depends on the amount of carbon atoms and hydrogen atoms contained in the layer (n), the first amorphous layer (
The relationship with the layer thickness etc. in 1) also needs to be appropriately determined as desired based on the organic relationship depending on the characteristics required for each layer region. In addition, it is desirable to take into account the cost efficiency, which takes into account productivity and mass production.

The layer thickness of the second amorphous layer (It) in the present invention is usually 0003 to 30μ, preferably ooo4 to 20μ,
The optimum value is 0005 to 10μ.

The support used in the present invention may be electrically conductive or electrically insulating. As a conductive monolithic support,
For example, Ni0r, stainless steel.

A7. Or, Mo, A, u, Nb, Ta,
V, Ti, Pt.

Examples include metal paulownia such as Pd or alloys thereof.

Polyester is used as the electrically insulating support.

Bo-11 ethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride.

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

Ceramic, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, N1or is applied to its surface.

AZ + Or + Mo + Au + 'r
+ Nb + Ta + V + T iHP t ,
Pd, In2O3, 8n02, ITO(I
Conductivity is imparted by providing a thin film consisting of n2O3+ 8nO2), etc., or if it is a synthetic resin film such as a polyester film, Ni0r, At,
Ag, Pb.

Zn, Ni, Au, Or, Mo, Ir,
Nb, Ta, V.

Conductivity is imparted to the surface by providing a thin film of metal such as TI or Pt on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. The shape of the support body is cylindrical, belt-shaped,
It can be of any shape such as a plate, and its shape is determined as desired. For example, if the photoconductive member 100 of FIG. 1 is used as an image forming member for electrophotography, in the case of continuous high speed copying The thickness of the filter support, which is preferably in the shape of an endless belt or a cylinder, is determined as appropriate so that the desired photo-bound conductive part is formed, but flexibility is required as a photoconductive member. In this case, it should be made as thin as possible within a range that allows it to function as a support. Hyakuen et al. In such cases, the thickness is usually set to 10μ or more from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.

In the present invention, the amorphous layer (I) composed of a-8i (H, done by law. For example, in order to form an amorphous layer (1) composed of a Si (H+ At the same time, a raw material gas for introducing hydrogen atoms (g) and/or for introducing halogen atoms (X) 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 to generate a predetermined amount. A layer consisting of a-S i (H,X) may be formed on the surface of a predetermined support. In addition, when forming by a sputtering method, for example, when sputtering Terkerato composed of St in an atmosphere of an inert gas such as A, R, He, etc. or a mixed gas based on these gases, hydrogen atoms are (@ or/and halogen atoms (XI introduction gas may be introduced into the deposition chamber for sputtering.

In the present invention, specific examples of the halogen atom (X) contained in the amorphous 7m(1) if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as something.

The raw material gas for Si supply used in the present invention includes 81H4, 812H6, 8i, H, 814E, o
Silicon hydride (silanes) in a gaseous state or that can be gasified, such as SiH
4, S 12B6 is preferred.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, halogen-substituted silane island conductors, etc. Preferred examples include halogen compounds that can be gasified.

Furthermore, silicon compounds containing silicon atoms and halogen atoms as m-components, which are in a gaseous state or contain gasifiable halogen atoms, can also be mentioned as effective in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, OtF, 04P3°BrF,
, BrF, , IF3 + IF7, IOl
+ Interhalogen compounds such as IBr can be mentioned.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
IF, , 5t2F, , 8IOt, , 81B
Preferred examples include silicon halides such as r4.

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 (I) consisting of a-81 containing halogen atoms can be formed on a predetermined support.

According to the glow discharge method, an amorphous layer containing halogen atoms (
When forming I), basically a silicon halide gas, which is a lees gas for supplying 81, and Ar.

Gases such as carbon dioxide, Ha, etc. are introduced into the deposition chamber in which the amorphous layer (1) is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to create a plasma atmosphere of these gases. By forming an amorphous layer (I) on a predetermined support, a silicon compound gas containing hydrogen atoms is added to these gases in order to introduce hydrogen atoms. A predetermined amount of these materials may also be mixed to form a layer.

Moreover, each gas may be used not only individually but also by mixing ah types at a predetermined mixing ratio.

In order to form the amorphous layer (1) made of a-8L (H, This is sputtered in a predetermined gas plasma atmosphere, and in the case of the ion blating method, polycrystalline silicon or single crystal silicon is housed in an evaporation boat as an evaporation source, and this silicon evaporation source is heated using a resistance heating method or an electron beam. The flying evaporated matter is heated and evaporated by a method such as the PL method (D i X
7-5 This can be done by passing it through the SM atmosphere.

At this time, in order to introduce halogen 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. It is sufficient to introduce the gas to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, y for hydrogen atom introduction
A plasma atmosphere of the gas may be formed by introducing a J, f-1 gas, for example, a gas such as (2) or the above-mentioned silanes into a deposition chamber for sputtering.

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, i(F 2 , HCt.

I (Br, hydrogen halides such as HI, SiHJ'
21 S iHz I trsiii2cz2 ,5
iHCz, , 5iH2Brz, S 1f(Br
Hydrogenated tetrahalogen-substituted silicon hydrides such as s, etc., and halides containing hydrogen atoms as one of their constituents, which are in the gaseous state or can be gasified, can also be cited as effective starting materials for forming the amorphous layer (I). I can do it.

These halides containing hydrogen atoms form an amorphous layer (1
) At the same time as halogen atoms are introduced into the layer, hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer. Ru.

To structurally introduce hydrogen atoms into the amorphous layer <I),
In addition to the above, Ru, or S iL, S iJL r
This can also be done by causing a hydrogenated deicing gas such as S 1sHs +S□4H, etc. to coexist with a silicon compound for supplying Si in the deposition chamber to generate an electric discharge.

For example, in the case of the reactive sputtering method, a Si target is used, and a gas for introducing halogen atoms, H, and gases, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to create a plasma atmosphere. to form the Si target? <By sputtering, an amorphous layer (I) consisting of a-8i(H,X) is formed on the support.

In the present invention, the amorphous layer (1
) The amount of hydrogen atoms (0) or the amount of halogen atoms (2) or the sum of the amounts of hydrogen atoms and halogen atoms (Hx) is generally 1-40 atomic%.

A preferable range is 5 to 3 Q atomic%.

In order to control the amount of hydrogen atoms and/or halogen atoms contained in the amorphous layer (1), for example, the support temperature and/or the hydrogen atoms can be adjusted to 0. Alternatively, it is sufficient to control the force of the discharge, discharge force, etc., which introduce the starting material used for containing the rogen atoms into the deposition system.

Amorphous layer (layer region ■ containing all group ■ atoms in 111)
In order to provide the layer region 0) containing oxygen atoms and oxygen atoms, the amorphous layer (1) is formed by a glow discharge method, a reactive sputtering method, etc.
), a layer formed by using a starting material for introducing a group V atom and a starting material for introducing an oxygen atom, respectively, together with the starting material for forming the amorphous layer (1) described above. This is achieved by controlling and containing the violet inside.

When a glow discharge method is used to form the layer region 0) containing oxygen atoms and the layer region 9 containing group (III) atoms, which constitute the amorphous layer (1)'e, each layer The starting materials to be the raw material gas for forming the region are those selected as desired from among the starting materials for forming the amorphous layer (1) described above, and a starting material for introducing oxygen atoms and/or Starting materials for the introduction of group atoms are added. Such starting materials for introducing oxygen atoms or starting materials for introducing Group V atoms include gaseous substances or gasified substances containing at least oxygen atoms or Group I atoms as constituent atoms. Most of them can be used.

For example, if layer region 0 is to be formed, silicon atoms (
A raw material gas containing St) as a constituent atom, a raw material gas containing an oxygen atom 0), and a raw material gas containing a hydrogen atom (■) or/and a halogen atom (■) as necessary in a desired mixing ratio. Alternatively, a raw material gas containing silicon atoms (sl) and a raw material gas containing oxygen atoms (0) and hydrogen atoms συ may be mixed at a desired mixing ratio. or by mixing silicon atoms (
The raw material gas as Si)e constituent atoms and the silicon atoms (S
i), a raw material gas having three constituent atoms: oxygen atom (0) and hydrogen atom (0) can be mixed and used.

Alternatively, a raw material gas containing oxygen atoms (0) as constituent atoms may be mixed with a raw material gas containing silicon atoms (Si) and hydrogen atoms (2) as constituent atoms.

Specifically, starting materials for introducing oxygen atoms include oxygen (02), ozone (O3), -nitrogen oxide (NO), nitrogen dioxide ('NO2), -nitrogen dioxide (N20), and Nitrogen dioxide (N203), trinitrogen tetroxide (N=04), nitrogen sesquioxide (N205), nitrogen dioxide (NOs), silicon atoms (Si), 0 oxygen atoms and 0 hydrogen atoms as constituent atoms, e.g. , disiloxane HsSiO8il(s, ) resiloxane H,
Examples include lower siloxanes such as 5iO8iH20SiH3.

When forming the layer region (V)' using a glow discharge method, the starting materials for introducing group (III) atoms that are effectively used in the present invention are PH, PH,
, hydrogen north neighbor of P2, etc., PH, I, PF, .

PFa, PCl5, PC! -5,PBrs,
PBr, , PI! etc. (7) One example is the halogen to the north. In addition, As, tfa + AsFa rAs
C41 Jinki a Muyo ASBr3r ASF5 + 5bH
s r S bl' s r S bFa rSbC4
, 5bC151Bid3, B1C4, B1Br5
＠ can also be mentioned as an effective starting material for introducing a group Ⅰ atom.

Itil region containing group (III) atoms (containing lid of group V atoms introduced into It can be arbitrarily controlled by controlling the formation power, the temperature of the support, the pressure inside the deposition chamber, etc.

To form the layer region (0) containing oxygen atoms by sputtering, a monocrystalline or polycrystalline Si wafer or 5i02 wafer -1 or Si and 5i02
This can be carried out by sputtering in a gas atmosphere of f: yuzu using Ueno-- containing a mixture of these as a target.

For example, when using Sl wafer as a target, the source gas for introducing oxygen atoms and optionally hydrogen atoms or/and Loken atoms is diluted with diluent gas as necessary. , are introduced into a deposition chamber for sputtering, and the gas plasma of these residues is completely formed to form the Si wafer/
-Sputtering is sufficient.

Alternatively, by using Si and 8102 as separate targets, or by using a single mixed target of Si and Si, in an atmosphere of dilution gas as a sputtering gas, or at least hydrogen atoms. and/or by sputtering in a gas atmosphere containing halogen atoms (2) as constituent atoms.

As the raw material waste for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases 7 shown in the glow discharge box 11 described above can be used as an effective gas also in the case of sputter link.

In the misfire ψ1, the diluent gas used to form the amorphous layer by the glow discharge method, or the sputtering gas used when forming the amorphous layer by the sputtering method, includes a so-called dilute gas, For example, He + Ne +
Ar and the like can be cited as suitable materials.

In the original publication of the Tatami Den Department of the present invention, a layer region containing group Ⅰ atoms (a layer region provided above ② and not containing group V atoms...) (layer region 106 in FIG. 1) (equivalent to) contains a substance that controls all conduction properties,
The conductive properties of the layer region (B) can be controlled as desired.

Such substances include so-called impurities in the semiconductor field, and in the present invention, for a 5i (H, X) constituting the amorphous layer (I) to be formed, P-type impurities that give P-type conductivity characteristics, specifically,
Atoms belonging to Group ■ of the periodic table (Group ■ atoms), for example,
B (boron).

Az (aluminum), Ga (gallium), In(
Indium), Tt (thallium), etc., and B and Ga are particularly preferably used.

In the present invention, the content of the substance controlling the total conduction properties contained in the layer region ('B) is determined by the amount of the substance controlling the conduction properties required for the layer region ('B) or in direct contact with the layer region (B). It can be selected as appropriate based on the organic relationship, such as the characteristics of other layer regions provided and the relationship with the characteristics at the contact interface with the other layer regions.

In the present invention, the content of the substance contained in the layer region (B) and controlling the 2nd and 4th characteristics is usually 0.0
01-1001000ato ppm, preferably 0.
05-500 atomic ppm, 0 for M
．． It is desirable that it be 1-200 atomic pprn.

In order to introduce a substance that controls conduction properties into the layer region (+3), for example, group Ⅰ atoms throughout the structure, a starting material for introducing group Ⅰ atoms is introduced in a gaseous state into the deposition chamber during layer formation. , may be introduced together with other starting materials for forming an amorphous layer. As the starting material for such introduction of Group (I) atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions.

As a starting material for introducing such Group 1 atoms, specifically for introducing boron atoms, B2H6 is used.

B4R1+1, BsHs, BsHo, BaH+
Boron hydride such as o, BaHu, B6HI4,
BF3. Examples include boron halides such as BC, BBr, and the like. In addition, AlC73, GaCLs, G
a (CHs)s.

InC4 and T94 can also be mentioned.

In the photoconductive member of the present invention, as explained in the example shown in FIGS. 1 and 2, the layer region (0) constituting the amorphous layer (1) is amorphous. In the case where gold is locally unevenly distributed toward the support side in layer <1), this is a preferred embodiment; however, the present invention is not limited thereto; for example, in layer region (0) The amorphous layer (I) may be formed by forming the entire layer region of the amorphous layer (I).

In this case, since the amorphous layer (I) needs to be formed to exhibit photoconductivity, the upper limit of the amount of oxygen atoms contained in layer region 0) is usually 3 Q ato
mic%, preferably 10 atomic%, optimally 5
It is desirable to set it to atomic%. In this case as well, the lower limit is of course set to the above value.

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

FIG. 2 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method.

202, 203, 204, 205, 20 in the figure
Gas cylinder 6 is sealed with raw material gas for forming each layer of the present invention. For example, 202 is Si:E (+ gas (purity 99.999) diluted with He). %, hereinafter abbreviated as S i H4/He) cylinder, 3 203 is PHa gas diluted with He (purity 99.99).
9%.

Hereinafter, it will be abbreviated as PH3/'He. ) cylinder 204 contains 5i2f(, gas (purity 99.99%, hereinafter 5
It is abbreviated as 12Ha/He. ) cylinder, 205 is a C2H4 gas (purity 99.999N) cylinder, and 206 is an NO gas cylinder.

When halogen atoms are formed in Fuchu, 5
For example, instead of ifL gas or 512H11 gas,
Just change the cylinder to use in4 gas.

In order to allow all of 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. 232 and 233 are opened, X4-7 is opened, and the main valve 264 is first opened to exhaust the reaction chamber 203 and gas piping. Next, when the reading on the vacuum gauge 256 reaches approximately 5 X iQ torr, the auxiliary valves 252 and 233 and the outflow valves 217 to 212 are closed.

An example of forming the first amorphous layer (1) on the base cylinder 257 will be given. Sx from gas cylinder 202
H4/He gas, gas cylinder 203 rJPHs74i
Open the harps 222, 223, and 226 for e-gas and NO gas from the gas cylinders 206, adjust the pressure on the outlet pressure gauges 227, 228, and 251 to 1 kg/co, and gradually close the inlet valves 212, 213, and 216. Open, mass flow controller 207.208.211
Let it flow inside. Subsequently the outflow valve 217.218
, auxiliary pulp 232. 233 is gradually opened to allow each gas to flow into the reaction chamber 201. StH at this time
, /He gas flow rate, PH3/Hθ gas flow rate, and NO gas flow rate are adjusted to the desired values using the outflow valve 217.21.
8°221, and while checking the reading on the vacuum gauge 256, make sure that the pressure inside the reaction chamber 201 reaches the desired value.
') Adjust the opening of the in-valve 234. Then, the temperature of the base cylinder 237 is raised to 50 to 4 by the heating heater 238.
After confirming that the temperature is set within the range of 00C, set the 240 to the desired power and turn on the workpiece 6 room 2.
First, a glow discharge is generated in the base cylinder 237 to form a layer region containing 4-3 and 4-3 wood.

At this time, after a predetermined period of time has elapsed, the introduction of PHs, 'He scum, or NO gas into the reaction chamber 201 is cut off by closing the valves of the corresponding gas introduction pipes. Alternatively, the layer thickness of the layer region containing oxygen can be arbitrarily controlled as desired.

After the layer regions each containing phosphorus and oxygen have been formed to a desired thickness as described above, each of the outflow valves 218 and 221 is closed and glow discharge is continued for a desired period of time to remove phosphorus. A layer region that does not contain phosphorus and oxygen is formed to a desired thickness on the layer region that contains phosphorus and oxygen, respectively, and the formation of the first amorphous layer (1) is completed.

When halogen atoms are contained in the first amorphous layer (1), for example, SiF4/He is further added to the above gas and fed into the reaction chamber.

By the above operation, a second amorphous layer <D> is formed on the first amorphous layer (1) formed on the base cylinder 237
To form the 'c layer, for example, 5i1 (4 gases,
This is accomplished by diluting each of the C2H4 gases with a diluent gas such as He as necessary, flowing them into the reaction chamber 201 at a desired flow rate ratio, and generating glow discharge according to desired conditions.

It goes without saying that all outflow valves other than the gas outflow valves required when forming each layer are closed;
When forming each layer, in order to prevent the gas used for forming the previous) M from remaining in the reaction chamber 201 and in the gas piping leading from the outflow valves 217 to 221 to the reaction chamber 201, the outflow valve is 217 to 221 are closed and the auxiliary valve 232
, 233 and fully open the main valve 234 to temporarily evacuate the system to high vacuum, as necessary.

Further, during layer formation, the base cylinder 237 is rotated at a constant speed by a motor 239 in order to make the layer formation uniform.3.Example 1 The manufacturing apparatus shown in FIG. A layer was formed on a drum-shaped aluminum substrate under the following conditions.

Photosensitive drum thus obtained (image forming member for electrophotography)
was installed in a copying machine, charged with a 0.2 Toyoma corona at 5 KV, and irradiated with a light image. A tungsten lamp was used as the light source, and the light intensity was 1.0 tux. The latent image was developed with a charged developer (containing toner and carrier) and transferred to ordinary paper, and the transferred image was extremely good. Toner remaining on the photosensitive drum without being transferred is cleaned by a rubber blade, and the toner is moved to the next copying process. Even after repeating this process more than 150,000 times, no deterioration of the image was observed.

//- J1 Example 2 A layer was formed on an At cylindrical substrate under the following conditions using the manufacturing apparatus shown in FIG.

Other conditions were the same as in Example 1.

The photosensitive drum obtained in this way was installed in an fc copying machine, and
Perform corona charging at 5KV between 0.2 crowns and irradiate the optical image (~
is. The light source is a tungsten lung, and the light intensity is 1. O
It was set as Lux-crown. The latent image was developed with a moderately charged developer (containing toner and gear) and transferred to regular paper, and the transferred image was very good. Toner remaining on the photosensitive drum without being transferred is cleaned by a rubber blade, and the toner is moved to the next copying process.

Even after repeating this process more than 100,000 times, no deterioration of the image was observed.

/'9:j0 Example 3 Using the apparatus shown in FIG. 2, a layer was formed on an At substrate under the following conditions.

Other conditions were the same as in Example 1.

The photosensitive drum thus obtained was installed in a copying machine, and θ5
Corona charging was performed at 0.2 KV and a light image was irradiated.

A tungsten lamp is used as the light source, and the light intensity is 1. Otu
x + See. The latent image was developed with a charged developer (containing toner and carrier) and transferred to ordinary paper, and the transferred image had extremely high density and good quality. Toner remaining on the photosensitive drum without being transferred is cleaned by a rubber blade, and the toner is moved to the next copying process. Even after repeating this process more than 150,000 times, no deterioration of the image was observed.

Example 4 When forming an amorphous layer, the content ratio of silicon atoms and carbon atoms in the amorphous layer (n) was changed by changing the flow lid ratio of gas and C2H4 gas. Other than that, Example 1
Layer formation was carried out in exactly the same manner as described above. The thus obtained photosensitive drum was subjected to the process in the transfer trench approximately 50,000 times in the manner described in Example 1, and then image evaluation was performed, and the results shown in Table 4 were obtained.

4 Example 5 Layer formation was carried out in exactly the same manner as in Example 1, except that the layer thickness of the amorphous layer (II) was changed as shown in the table below. The evaluation results are shown in the table below.

Table 5 0 Example 6 Layer formation was carried out in the same manner as in Example 1 except that the method for forming the amorphous layer (I) was changed as shown in the table below, and good results were obtained when the evaluation was 1+lIi. .

8 Practical Example 7 All layers were formed in the same manner as in Example 1 except that the method for forming the amorphous layer (1) was changed as shown in the table below, and good results were obtained when evaluated.

Flea t0 Example 8 Electronic fabrication was carried out according to the conditions and procedures shown in Example 2, except that the ~ creation conditions in the second and third layer creation stages of Example 2 were set to the conditions shown in Table 8 below. When each of the photographic image forming members was produced and evaluated in the same manner as in Example 1, good results were obtained, particularly in terms of image quality and durability.

〔;,degree

[Brief explanation of the drawing]

FIG. 1 is a schematic layer configuration diagram schematically showing the layer structure of a preferred embodiment of the photoconductive member of the present invention, and FIG. 2 is an example of an apparatus for manufacturing the photoconductive member of the present invention. FIG. 100...Photoconductive member 101...Support 102
・First amorphous layer (I) 103...first layer region 0
) (II) 104...Second layer region (V) 107...Second amorphous 1% Applicant: Canon Co., Ltd., Co. Inside Canon Co., Ltd., 3-30-2 Shimomaruko, Ota-ku, Tokyo

Claims (1)

[Claims] (1) In a photoconductive member having a support for the photoconductive member and a first amorphous layer that is composed of an amorphous material having silicon atoms as a matrix and exhibits photoconductivity, the first A first layer region in which the amorphous layer contains oxygen atoms as constituent atoms, and a second layer region containing atoms belonging to Group Ⅰ of the periodic table as constituent atoms, which are internal to the former support side. These regions share at least a part of each other, and the layer thickness of the second layer region is tB, and the layer thickness of the first amorphous layer and the second layer are If the difference from the layer thickness tB of the region is T, then the relationship tn/(T+tB)<0.4 is established, and silicon atoms, carbon atoms, and hydrogen atoms are formed on the first amorphous layer. A photoconductive member characterized by having a second amorphous layer made of an amorphous material containing as constituent atoms.