JPS5811949A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photosensitive element with superior resistance in all environmental conditions, high photosensitivity and a wide range of spectral sensitivity by forming an intermediate layer of amorphous silicon (a-Si) containing N and H, an a-Si photoconductive layer and an upper layer successively on a conductive supporting member. CONSTITUTION:A non-photoconductive a-Si layer 202 containing 25-55atom% N and 2-50atom% H is formed on a conductive supporting member 201 so as to form an intermediate layer with the thickness of 30-1,000Angstrom . Subsequently, a photoconductive layer 203 obtained by adding suitable donor and acceptor to p type, n type or i type a-Si selected according to a purpose is formed with the thickness of 1-100mu on the layer 202 by a-Si:H vapor deposition. If necessary, an upper layer 205 consisting of an a-Si layer with the same composition as the intermediate layer 202, an inorganic insulating member such as Al2O3 or an organic insulating material such as polyester is formed on the layer 203. By said configuration, a picture of high quality with high resolution and clear half tone is obtained.

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. Photoconductive materials constituting photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, document reading devices, etc.
High sensitivity, SN ratio [photocurrent (Ip) / dark current (Id)]
), have the spectral characteristics of the electromagnetic waves to be irradiated, have good photoresponsiveness, have the desired dark resistance value, be non-polluting to the human body during use, and have the following characteristics: For this purpose, characteristics such as the ability to easily process afterimages within a predetermined time are required. In particular, in the case of an electrophotographic image forming member incorporated in an electrophotographic apparatus used in an office as a business machine, non-polluting during use is an important point. .

Amorphous silicon (hereinafter referred to as ff1a-8i) is a photoconductive material that has recently attracted attention based on these various points.
Publication No. 855718 describes an image forming member for electrophotography,
JP-A-55-39404 describes an application to a photoelectric conversion/reading device.

According to Heigo et al., a photoconductive member having a photoconductive layer composed of conventional a-8i has excellent electrical, optical, and photoconductive properties such as dark resistance value, photosensitivity, and photoresponsiveness, as well as weather resistance and moisture resistance. There are points that can be further improved in terms of usage environment characteristics such as The reality is that it cannot be used effectively.

For example, when applied to electrophotographic image forming members or solid-state imaging devices, it is often observed that residual potential remains during VC1 use; Accumulation of fatigue occurs due to use.
There have been many disadvantages, such as the so-called ghost phenomenon in which an afterimage occurs.

Furthermore, for example, according to many experiments conducted by the present inventors, a as a material constituting the photoconductive layer of an electrophotographic image forming member
-8i is conventional Se, CdS.

Although it has many advantages compared to OPC (organic photoconductive materials) such as ZnO or PVCz + TNF, A-8 has been given characteristics for use in conventional solar cells.
Even if the photoconductive layer of an electrophotographic image forming member having a single-layer photoconductive layer consisting of i is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast;
It is difficult to apply ordinary electrophotography methods, and the above tendency is remarkable in a humid atmosphere, and in some cases, 3J
There are cases where the charge cannot be retained at all until the image time, etc.
M[ is known for which there are possible points that can be solved.

Therefore, while efforts are being made to improve the properties of the a-8i material itself, it is necessary to take measures to obtain desired electrical, optical, and photoconductive properties when designing photoconductive members.

The present invention has been made in view of the above points, and is characterized by its applicability and applicability to A-8T 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 perspective, we have developed an amorphous material containing hydrogen atoms with silicon atoms as the base material, so-called hydrogenated amorphous silicon (hereinafter referred to as a-8t).
A photoconductive member designed and produced with a layer structure in which a specific intermediate layer is interposed between a photoconductive layer consisting of a photoconductive layer (denoted as H) and a support supporting the photoconductive layer can be used satisfactorily for practical purposes. Not only can it be used as a photoconductive member for electrophotography, but it is also superior in most respects to conventional photoconductive members, and has particularly excellent properties as a photoconductive member for electrophotography. It's based on what you found.

The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent resistance to light fatigue and does not cause deterioration even after repeated use. The main object of the present invention is to provide a photoconductive member in which no or almost no residual potential is observed.

Another object of the present invention is to provide a photoconductive member that has high photosensitivity, covers substantially the entire visible light range in its spectral sensitivity range, and has fast photoresponsiveness.

Another object of the present invention is to have charge retention properties during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member which has excellent electrophotographic properties in which the electrophotographic properties of the photoconductor are sufficiently controlled and whose properties hardly deteriorate even in a humid atmosphere.

Still another object of the present invention is to provide a photoconductive member for ``rff'' photographs that can easily produce high-quality images with high density, clear halftones, and high resolution. be.

The photoconductive member of the present invention includes a support, a photoconductive layer made of an amorphous material based on silicon atoms, and an intermediate layer made of an amorphous material based on silicon atoms and containing nitrogen atoms and hydrogen atoms. and an upper layer provided on the photoconductive layer.

A photoconductive member designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and exhibits extremely excellent electrical, optical, photoconductive properties, and use environment characteristics. .

In particular, when applied as an image forming member for electrophotography or an imaging device, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, and has good electrical properties even in a humid atmosphere. It is stable, has high sensitivity, and has a high signal-to-noise ratio, and has excellent resistance to light fatigue and repeated use. Furthermore, in the case of electrophotographic image forming members, it has high density and clear halftones. Moreover, it is possible to obtain a high-quality visible image with high resolution.

Also, when it is applied to an electrophotographic image forming member.

A-8i:H, which has a high dark resistance, has low photosensitivity, and conversely, a-8t:H, which has high photosensitivity, has a low dark resistance of around 108Ω steel. However, in the case of the present invention, it has a relatively low resistance (5X 109Ωα
Since the a-8i:H layer (above) can also constitute a photoconductive layer for electrophotography, a-8i:H, which has a relatively low resistance and high sensitivity, can also be used satisfactorily, and a-8t:H Restrictions from the characteristics aspect of can be alleviated.

Hereinafter, the photoconductive 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 a basic configuration example of a photoconductive member of the present invention.

A photoconductive member 100 shown in FIG. 1 includes a support 101 for a photoconductive member, an intermediate layer 102, and
This is the most basic example of the present invention.

The support 101 may be conductive, electrical, or electrically insulating. Examples of the conductive support include NiCr, stainless steel, and AI! , Cr.

Mo, Au, Ir, Nb, Ta,
Examples include metals such as V, Ti, Pt, and Pd, and alloys thereof.

The electrically insulating support C is polyester.

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

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, and boria, 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, its surface is NiCr.

he, Cr, Mo, Au, Ir,
Nb, Ta, V, Ti.

Pt, Pd, In, O,, SnO,, I
If conductive treatment is performed by providing a thin film such as TO (In, O, +SnO,), or if it is a synthetic resin film such as polyester film, NiCr, Ae,
Ag, Pb, Zn.

Ni, Au, Cr, Mo, Ir,
Nb, Ta, V, Ti.

The surface is treated with a metal such as PT by vacuum evaporation, electron beam evaporation, sintering, etc., or laminated with the metal to make the surface conductive. The shape of the support is
It can be of any shape such as cylindrical, belt-like, plate-like, etc., and the shape is determined depending on the need. For example, if the photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member, In the case of continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape. 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. Within this range, it will be made as thin as possible. In such cases, the thickness is usually set to 10 μ or more in view of manufacturing and handling of the support, mechanical strength, etc.

The intermediate layer 102 is made of a non-photoconductive amorphous material CB that has silicon atoms as its base material and contains nitrogen atoms and hydrogen atoms.
(SI XN, -x)y: FT+ -y Abbreviation.

However, 0<x<1, O<y<1), and effectively prevents the gear from flowing into the photoconductive layer 103 from the support 101 side, and also prevents the photoconductive layer 10 from being exposed to electromagnetic waves.
It has a function of easily allowing photocarriers generated in the photoconductive layer 103 and moving toward the support 101 to pass from the photoconductive layer 103 side to the support 101 side.

The intermediate layer 102 composed of a −(S izN+ −x)y” HI−′I is formed by a glow radiation method, a sputtering method, an ion implantation method, an ion brating method, an electron beam method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. Glow discharge layering is preferred because it is relatively easy to control the manufacturing conditions for manufacturing photoconductive members, and it is also easy to introduce nitrogen atoms and hydrogen atoms together with silicon atoms into the intermediate layer to be manufactured. A sputtering method is preferably employed.

Furthermore, in the present invention, the intermediate layer 102 may be formed by using a glow discharge method and a sputtering method in the same apparatus system.

To form the intermediate layer 102 by the glow discharge method, a
-(5iXN+ -x)y: A raw material gas for forming Hl-y is mixed with a dilution gas at a predetermined mixing ratio as needed, and then added to a deposition chamber for vacuum deposition where the support 101 is installed. A-(
SixN+-, )y: Hl-y may be deposited.

In the present invention, a-(5tXNl-x)y: )(1-
As the raw material gas for forming y, most of gaseous substances containing at least one of Si, N, and H as a constituent atom or gasified substances that can be gasified can be used.

When using a raw material gas with St as a constituent atom as one of St, N, and H, for example, a raw material gas with St as a constituent atom, a raw material gas with N as a constituent atom, and a constituent atom with ■. Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing N and II as constituent atoms may be mixed at a desired mixing ratio. Can be used by mixing.

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

In the present invention, the raw material gas for forming the intermediate layer 102 is
Starting materials usefully used to obtain Si and H
SiH, whose constituent atoms are and.

S il H6, S ls Hat S i4 Hl
Silicon hydride such as silanes such as o, N
or N and H as constituent atoms, such as nitrogen (N), ammonia (Peng), hydrazine (I).
Mention may be made of nitrogen compounds such as nitrogen, nitrides and azides which can be gasified into gaseous forms such as (tNNHx), hydrogen azide (HN, ), ammonium azide ('N'fT, N3), etc. In addition to these starting materials for forming the intermediate layer, (1) sulfur is also effectively used as the raw material gas for introduction.

To form the intermediate layer 102 by the sputtering method, single crystal or polycrystalline Si waeno-- or St, H
, or a wafer containing a mixture of Si, Si, and N may be used as a target and sputtered in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gas for introducing N and H, such as N2 or NH, is diluted with a diluting gas as necessary and placed in a deposition chamber for sputtering. The Sl wafer may be sputtered by introducing these gases into a gas plasma to form a gas plasma of these gases.

Alternatively, sputtering can be performed in a gas atmosphere containing at least H atoms by using separate targets for Si, St, and N, or by using a single target formed by mixing St, St, and NJ. It is done by ringing.

Can it be used as a raw material gas for introducing N or H? 4) The starting material gases for forming the intermediate layer shown in the above-mentioned example of glow discharge can also be used as effective gases in the case of sputtering.

In the present invention, the diluent gas used when forming the intermediate layer 102 by a glow discharge method or a sputtering method is a so-called rare gas, such as He, Ne, Ar.
etc. can be cited as effective.

The intermediate layer 102 in the present invention is carefully formed to provide the desired properties.

In other words, materials whose constituent atoms are Si, N, and H can have structural forms ranging from crystalline to amorphous depending on the preparation conditions, and electrical properties ranging from conductive to conductive to insulating. In the present invention, non-photoconductive a-(5ixN+-X)y''
The formation conditions are strictly selected so that Hl-y is formed.

a −(5txNl−
) :H, -y is the function of the intermediate layer 102 to prevent the injection of carriers from the support body y 101 side into the photoconductive layer 103, and to prevent the photocarriers generated in the photoconductive layer 103 from moving and supporting the photoconductive layer 103. Since it is intended to easily allow passage to the body 101 side, it is formed to exhibit electrically insulating behavior.

Furthermore, when the photocarriers generated in the photoconductive layer 103 pass through the intermediate layer 102, the mobility of the carriers (mobility
a-(5txN
+-X)y: H,-y is created.

a − (5txN, □)y:H with the above characteristics
An important factor in the production conditions for producing 8-7 is the temperature of the support during production.

That is, a-(5iXNl-,) is formed on the surface of the support 101.
y: When forming the intermediate layer 102 made of HJ-7, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. The temperature of the support during layer formation is strictly controlled so that a-(SixN, □)y:Hl-a having the following properties can be formed as desired.

The formation of the intermediate layer 102 is performed by appropriately selecting an optimal range according to the method of forming the intermediate layer 102, but in the normal case, the temperature range is 100° 0 to 300'O, preferably 150°C to 250°C.
℃ is desirable.

The intermediate layer 102 can be formed continuously from the intermediate layer 102 to the photoconductive layer 103 and, if necessary, a third layer formed on the photoconductive layer 103 in the same system. Glow discharge method and sputtering method are advantageous because delicate control of the composition ratio of atoms constituting each layer and control of layer thickness are relatively easy compared to other methods. When forming the intermediate layer 102 using these layer forming methods, the discharge power and gas pressure during layer formation are adjusted to 8a (Stx"+-X)y"Hl in the same manner as the support temperature described above. -It is one of the important factors that influences the characteristics of y.

a having the characteristics for achieving the object of the present invention;
-(5ixN, -x)y:H,, is normally set to 1 as the discharge power condition for effectively forming H, with good productivity.
~300W, preferably 2-100W. The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.1 to 0.5 Torr when layer formation is performed by glow discharge.
When layer formation is performed by sputtering, the temperature is usually 10-3 to 5 X 10-2 Torr.
, preferably 8X10-8 to 3 X 10-2Torr
It is desirable that it be considered as a degree.

The amounts of nitrogen atoms and hydrogen atoms contained in the intermediate layer 102 in the photoconductive member of the present invention are similar to the manufacturing conditions of the intermediate layer 102, and are determined so that the intermediate layer has the desired characteristics to achieve the object of the present invention. It is an important factor in the formation of

The amount of nitrogen atoms contained in the intermediate layer 102 in the present invention is usually 25 to 55 atomic%, preferably 35 to 55 atomic%.
A desirable value is 55 atomic%. If the hydrogen atom content is 1 to 35, it is usually 2 to 35.
It is desirable that the hydrogen content be in the atomic range, preferably 5 to 30 atomic range, and the photoconductive member formed when the hydrogen content is in this range is considered to be excellent in practice. It can be used.

That is, if expressed as above a - (St 98 to 0.65, preferably 0.95 to 0.70.

The numerical range of the thickness of the intermediate layer 1020 in the present invention is one of the important factors for effectively achieving the object of the present invention. If the layer thickness of the intermediate layer 102 is too thin, it will not be able to sufficiently prevent carriers from flowing into the photoconductive layer 103 from the support 101 side; , the probability that the photocarriers generated in the photoconductive layer 103 will pass to the support 101 side becomes extremely small, and therefore, in either case, the object of the present invention cannot be effectively achieved.

In order to effectively achieve the object of the present invention, the thickness of the intermediate layer 102 is usually 30 to 1000λ, preferably 5.
0 to 600 people.

In the present invention, in order to effectively achieve the object, the photoconductive layer 103 laminated on the intermediate layer 102 is composed of a-8i:H having the semiconductor properties shown below.

■P-type aSt: H... Contains only acceptor.

Or one that contains both a donor and an acceptor and has a high acceptor concentration (Na).

(2) P-type a-8i: H... (D type lightly doped with so-called P-type impurity having a low acceptor concentration (Na).

■n-type a-8i:H... Contains only a donor.

Or one that contains both a donor and an acceptor and has a high donor concentration (Nd).

(2) N-type a-8t:H...The donor concentration (Nd) is low in type (2). Lightly doped with so-called n-type impurities.

■ Type i a-8t: H・-Na”:: Nd:
0 or Na and Nd.

In the present invention, by providing the intermediate layer 102, the a-8i which constitutes the light guide 111 layer 103 as described above is
However, in order to obtain better results, the dark resistance of the photoconductive layer 103 to be formed is preferably 5×109Ω.
It is desirable that the photoconductive layer 103 be formed to have a resistance of at least 101 θΩm, preferably at least 101θΩm.

In particular, this numerical condition for the dark resistance value is required when the manufactured photoconductive member is used as an image forming member for electrophotography, a highly sensitive reading device or solid-state imaging device used in a low-light region, or a photoelectric conversion device. This is an important element when doing so.

The layer thickness of the photoconductive layer of the photoconductive member in the present invention is as follows:
It is suitably determined according to the purpose of the device to which it is applied, such as a reading device, a solid-state imaging device, or an electrophotographic image forming member.

In the present invention, the layer thickness of the photoconductive layer is set so that the function of the photoconductive layer and the function of the intermediate layer are effectively utilized and the object of the present invention is effectively achieved. The thickness of the layer may be determined as desired, and in normal cases, the layer thickness is preferably several hundred to several thousand times greater than the thickness of the intermediate layer.

The specific value is usually 1 to 100μ, preferably 2 to 100μ.
It is desirable that the thickness be in the range of 50μ.

In the present invention, in order to make the photoconductive layer a layer composed of asi:H, H is incorporated into the layer by the following method when forming these layers.

Here, [H is contained in the layer] means "a state in which H is bound to Sl", [a state in which H is ionized and incorporated into the layer], or [H, It means any of the following or a combination of these states:

As a method of incorporating H into the photoconductive layer, for example, when forming the layer, 5iT(, Si, I(,...) is used in the deposition system.

Silane (5i
Introduced in the form of silicon compounds such as
- Contained along with the growth of.

When a photoconductive layer is formed by this glow discharge method, the starting material for forming a-8t is decomposed by silicon hydride gas such as SiH, Si, Ru, 5inHsr, 5faao, etc. to form a layer. In this case, ■ is automatically included in the layer.

In the case of the reactive sputtering method, when performing sputtering with Si as a target in an atmosphere of an inert gas such as He or Ar or a mixed gas of these gases, or SfL s is used. st,
:u6. St, H, 1st, I(, etc.) or n, Hll which also serves as impurity doping.
It is sufficient to introduce a gas such as tPHs.

According to the knowledge of the present inventors, the H content of the photoconductive layer composed of a-8i:H determines whether the formed photoconductive member can be sufficiently applied in practice. It has been found that this is one of the major influencing factors and is extremely important.

In the present invention, in order for the photoconductive member to be formed to be sufficiently applicable to practical applications, the amount of H contained in the photoconductive layer is usually 1 to 40 atomic units, preferably 5 to 40 atomic units. 3
It is desirable to set it to 0 atomic%.

The amount of H contained in the layer can be controlled, for example, by controlling the temperature of the deposition support, the amount of starting material used to incorporate H into the deposition system, the discharge force, etc. Just do it.

To make the photoconductive layer n-type or p-type, an n-type impurity, a p-type impurity, or both impurities are added to the formed layer during layer formation using a glow discharge method, a reactive sputtering method, etc. This is achieved by controlling the amount of doping.

In order to make the photoconductive layer p-type, suitable impurities to be doped into the photoconductive layer include elements of group A of the periodic table, such as B, All', Ga, In, Te, etc. In the case of n-type, an element of group V A of the periodic table, for example, N.

Preferred examples include P, As, Sb, Bi, and the like. Since the amount of these impurities contained in the layer is on the order of pr111, it is not necessary to pay as much attention to their pollution properties as the main materials constituting the photoconductive layer, but it is important to use materials that are as non-polluting as possible. is preferred. From this point of view, B, Ga, P, Sb, etc. are optimal, taking into consideration the electrical and optical properties of the layer to be formed. In addition, it is also possible to control the n-type by, for example, interstitial doping with Li or the like by thermal diffusion or implantation.

The amount of impurity doped into the photoconductive layer is appropriately determined depending on the desired electrical and optical properties, but in the case of impurities in Group IA of the periodic table, it is usually 10' to 1.
0-" atomic%, preferably 10' to 10"a
tomicq6, usually 10 in the case of Group V A of the periodic table
-8 to 10-” atomic%, preferably 104 to 1
It is desirable to set it to 0'a tomic%.

FIG. 2 shows another embodiment of the photoconductive member of the present invention. A schematic configuration diagram for explaining the configuration of an example embodiment is shown.

The photoconductive member 200 shown in FIG.
On top of this, an upper layer 20 having a similar function to the middle layer 202
The photoconductive member 100 has the same layer structure as the photoconductive member 100 shown in FIG. 1 except that the photoconductive member 5 is provided.

That is, the photoconductive member 200 is made of a (SizN, -X)y which is the same material as the intermediate layer 102 on the support 201.
: an intermediate layer 202 formed using H,-7 to have a similar function, a photoconductive layer 203 composed of 'a-8t:H, and a free layer provided on the photoconductive layer 203 A top layer 205 having a surface 204 is provided.

When the photoconductive layer 203 is used in a manner such as when the free surface 204 is irradiated with electromagnetic waves, the free surface 204 prevents the potential charge held on the free surface 204 from flowing into the photoconductive layer 203.
It has a function of easily allowing passage of photocarriers or charged charges so as to cause a combination of the photocarriers generated inside and the charged charges of the portion irradiated with electromagnetic waves.

The upper layer 205 has the same characteristics as the middle layer 202.
(S i
-B)b" H+ -)) + (a -81(!01
-(B)d:Hl-dl (a 5tco, -c)d:
■ An amorphous material composed of silicon atoms and nitrogen atoms or oxygen atoms, which are the matrix atoms constituting the photoconductive layer such as II-d, or an amorphous material that has these atoms as the matrix and contains wood atoms, or These amorphous materials containing halogen atoms, inorganic insulating materials such as A/l', O, etc.
It can also be constructed from organic materials such as polyester, polyparaxylene, and polyurethane.

As for the material constituting the upper layer 205, productivity,
A-(
5ixN, -x')y: H, -y, or a 5iaC+ -a la (5iBC1-B
) 1) :Hl,, (), a-8tcNl-c,
a-("dC+-d)e :x,-,,a-(5i
fC+-f)g: (H+X)+-g+ a (Sih
Nt-h) 1:Xl-11a-(Si jN+-
j) k: It is desirable to configure it as (H+X)+-.

In addition to the materials listed above, suitable materials for forming the upper layer 205 include silicon atoms, C, and N.
, 0, and includes a halogen atom or a halogen atom and a hydrogen atom.

Examples of the halogen atom include F 2 , Ce 2 , Br and the like, but from the viewpoint of thermal stability, among the above amorphous materials, those containing F are effective.

The selection of the material constituting the upper layer 205 and the determination of its layer thickness are performed when the photoconductive member 200 is used in such a way that the electromagnetic waves that the photoconductive layer 203 senses are irradiated from the upper layer 205 side. This is carefully done so that a sufficient amount of electromagnetic waves can reach the photoconductive layer 203 and efficiently cause generation of photocarriers. The upper layer 205 is the middle layer 202
It can be formed using a method similar to that described above, such as a glow discharge method or a reactive sputtering method. As the starting material used in forming the upper layer 205, in addition to the above-mentioned materials used to form the intermediate layer, as a starting material for introducing carbon atoms, for example, a material having 1 to 4 carbon atoms is used. Saturated hydrocarbon, ethylene hydrocarbon having 2 to 5 carbon atoms, 2 to 4 carbon atoms
Examples include acetylene hydrocarbons and the like.

Specifically, the saturated hydrocarbon is methane (CI(,)
, ethane (ral), propane (C,H,).

n-butay (ncaii+o) I-pentane (C
JIn) t Ethylene (CtH4) is an ethylene hydrocarbon.

Propylene (CIHll), butene-1 (C,H,
), butene-2 (C,), isobutylene (C,)
), pentene (CgH+), acetylene hydrocarbons include acetylene (Cta), methylacetylene (
C3H5).

Examples include butyne (C4H11).

Examples of starting materials for containing oxygen atoms in the upper layer 205 include oxygen (01), ozone (03))-carbon oxide (CO), carbon dioxide (COt)-nitrogen oxide (N
O), nitrogen dioxide (NO2), - dinitrogen oxide (N20)
etc. can be mentioned.

In addition to these, CC/4. CHF'1. αF,.

CH,F, CH,C1, CH,Br, CH,I
, halogen-substituted paraffinic hydrocarbons such as C, H, C1, fluorinated sulfur compounds such as SF, , SF, etc.
Alkyl silicides such as 5i(CHs)t t Si (Ct&)a and 5iCI! (CHs)s p SiC/,
C (C maru.

Derivatives of silanes such as halogen-containing alkyl silicides such as Sin/, Yama, etc. can also be mentioned as effective.

These starting materials for forming the upper layer 205 are appropriately selected and used during layer formation so that predetermined atoms are included in the formed upper layer 205 as constituent atoms.

For example, if the glow discharge method is adopted, S i (
A single gas such as (CHs) or SiH.

-02(-A) system, SiH,-electrode, SiH,-
0,-N2 system.

S1ce4-Co2-H, system, 5icl! ,
-No-H, system, 5iIT4-NI(, system, 5
iCe, -NI (4 series, S 1II4-N, series,
5jH4-Ichiyu Shima + Si (CHs)4 S j
A mixed gas such as H4-based, 5ICet(CHs)z-8iH, etc. can be used as a starting material for forming the upper layer 105.

The thickness of the upper layer 2050 in the present invention is appropriately determined as desired depending on the material forming the layer, the layer forming conditions, etc. so that the above-mentioned functions are fully exhibited.

In the present invention, the thickness of the upper layer 205 is usually 30 to 100 OJ, preferably 50 to 600 OJ.

If a certain type of electrophotographic process is employed when the photoconductive member of the present invention is used as an electrophotographic imaging member, the free surface of the photoconductive member has a layer configuration as shown in FIG. 1 or FIG. It is necessary to further provide a surface coating layer on top.

In this case, the surface coating layer is, for example, Japanese Patent Publication No. 42-239
If an electrophotographic process such as the NP method described in Publication No. 10 and Publication No. 43-24748 is applied, it must be electrically insulating and have the ability to retain static charge when subjected to charging treatment. Although it is required that the thickness is sufficient and above a certain level, for example, if an electrophotographic process such as the Carlson process is applied, it is desirable that the bright and dark potentials after electrostatic image formation be very small. The surface coating layer is required to be extremely thin. In addition to satisfying its desired electrical properties, the surface coating layer must not have any adverse chemical or physical effects on the photoconductive layer or the upper layer. It is formed taking into consideration contactability and wearability, as well as moisture resistance, abrasion resistance, cleaning performance, etc.

Typical materials effectively used for forming the surface coating layer are polyethylene terephthalate,
polycarbonate, polypropylene, polyvinyl chloride,
Polyvinylidene chloride, polyhinyl alcohol, polystyrene, polyamide, polytetrafluoroethylene, polytrifluorochloride, polyvinyl fluoride, polyvinylidene fluoride, propylene hexafluoride-tetrafluoroethylene copolymer, trifluoride Ethylene-vinylidene fluoride copolymer, bolybdenum, polyvinyl butyral.

Examples include inorganic insulating materials. These synthetic resins or cellulose derivatives may be formed into a film and laminated onto the photoconductive layer or the upper layer, or a coating solution thereof may be formed and applied onto the photoconductive layer or the upper layer. However, a layer may be formed. The layer thickness of the surface coating layer is appropriately determined depending on the desired characteristics and the material used, but is usually about 0.5 to 70 μm. In particular, when the surface coating layer is required to function as the above-mentioned protection layer, it is usually 10μ or less, and conversely, when the surface coating layer is required to function as an electrical insulating layer, it is usually In this case, it is assumed to be 10μ or more. The layer thickness values that differentiate this protective layer from the electrically insulating layer vary depending on the materials used, the applied electrophotographic process, and the designed structure of the imaging member.
The above value of 10μ is not absolute.

Furthermore, if this surface coating layer also serves as an antireflection layer, its function will be further expanded and it will become more effective.

Example 1 Using the apparatus shown in FIG. 3 installed in a completely shielded clean room, an electrophotographic image forming member was produced by the following operations.

Surface cleaned Q, 51artr thickness 10crIL
A corner molybdenum plate (substrate) 309 was firmly fixed to a fixing member 303 at a predetermined position in a glow discharge deposition chamber 301 placed on a support stand 302 . The substrate 309 is heated with an accuracy of ±0.5° C. by a heater 308 within the fixing member 303. Temperature was measured directly on the backside of the substrate by a thermocouple (alumel-chromel). Next, after confirming that all the valves in the system were closed, the main pulp 310 was fully opened, and the inside of the chamber 301 was evacuated to a degree of vacuum of about 5×10' Torr.

After that, the input voltage of the heater 308 is increased by 2', and the input voltage is changed while detecting the temperature of the molybdenum substrate.
The temperature was stabilized until it reached a constant value of 00°C.

After that, the auxiliary pulp 340 and then the effluent pulp 325
, 326 , 327 and inflow pulp 320-2 , 32
1.

Fully open 322 and flow meter 316.317.

The inside of 318 was also sufficiently degassed and vacuumed. Auxiliary pulp 34
0, Pulp 325.326, 327.320-2,
After closing the 321° and 322, SiH gas (hereinafter abbreviated as smv diluted to 1% lo vo with a gas) was added.
999%) Pulp 330, N (purity 99%) in cylinder 311
．． 999%) Open the pulp 331 of the gas cylinder 312,
Adjust the pressure of the outlet pressure gauges 335 and 336 to 1 kg, gradually open the inflow pulp 320-2.321, and introduce 5iI (4/H2 gas N
2 gases were introduced. Subsequently, the outflow valve 325,
326 was gradually opened, and then the auxiliary pulp 340 was gradually opened.

At this time, the SiH, /Hz gas flow rate and N gas flow rate ratio is 1:
The inflow pulp 320-2.321 was adjusted to have a value of 10. Next, adjust the opening of the auxiliary valve 340 while paying close attention to the reading on the Villany gauge 341, and adjust the opening of the auxiliary valve 340 so that the inside of the chamber 301 is
The auxiliary valve 340 was opened until the pressure became 10"2 Torr. After the internal pressure of the chamber 301 became stable, the main pulp 310
gradually closed, and the Villany gauge 341 indicated 0.5T.
I narrowed down the aperture until it became orr. After confirming that the gas inflow is stable and the internal pressure is stable, the high frequency power supply 342 is turned on, and the induction coil 343 is connected to the
A high frequency power of 1111z was applied to generate a glow discharge in the chamber 301 of the coil section (upper part of the chamber), resulting in an input power of 3W. Maintain the above conditions for 1 minute and place 6- (5tXN
, -z)y:at-)' was formed.

Thereafter, the high frequency power supply 342 is turned off, the glow discharge is stopped, the outflow valve 326 is closed, and the 9B, H1+ (hereinafter abbreviated as BtHa/Hz) gas cylinder 313 is diluted to 50 vol. From the inlet valve 322 to 1 gas pressure (outlet pressure gauge 3
37 reading), the inflow valve 322 and the outflow valve 327
By adjusting the flowmeter 318, the reading becomes SiH4/H.
The opening of the outflow valve 327 was determined so that the flow rate of the two gases was 1150, and the flow rate was stabilized.

Subsequently, the high frequency power supply 342 was turned on again to restart the glow discharge. The input power at that time was 10W. After continuing the glow discharge for another 3 hours to form a photoconductive layer, the heater 308 is turned off, the high frequency power supply 342 is also turned off, and the substrate temperature is reduced to 1.
After waiting for the temperature to reach 00"C, the outflow valve 325, 3
27 and inlet valves 320-2, 322 are closed, the main valve 310 is fully opened, and the inside of the chamber 301 is heated to 10" Tor.
After reducing the temperature to below r, main pulp 310'& closed chamber 30
1 was brought to atmospheric pressure using a leak valve 344, and the substrate was taken out.

In this case, the total thickness of the layer formed was approximately 9μ. The image forming member obtained in this way is installed in a charging exposure experiment apparatus, and 6. Perform corona charging for 0.2 see with OKV,
A light image was immediately irradiated. The optical image was created using a tungsten lamp light source.1. , O1ux-see was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) onto the surface of the member. The toner image on the member is 5. When transferred onto transfer paper using OKV's corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Next, the above-mentioned image forming member was subjected to 05.
Corona charging is performed for 0.2 sec at 5 KV, image exposure is immediately performed at a light intensity of 0.81 ux-sec, and then a charged developer is immediately cascaded onto the surface of the member, and then transferred onto transfer paper.・When it was fixed, an extremely clear image was obtained.

From this result and the previous results, it was found that the electrophotographic image forming member obtained in this example had no dependence on charge polarity and had the characteristics of a bipolar image forming member.

Example 2 A sample was plated under the same conditions and procedures as in Example 1, except that the glow discharge holding time when forming an intermediate layer on a molybdenum substrate was varied as shown in Table 1 below. The image forming members shown in (1) to (2) were prepared, and when they were installed in the same charging exposure experimental apparatus as in Example 1 and the same image formation was performed, the results shown in Table 1 below were obtained.

As can be seen from the results shown in Table 1, in order to achieve the object of the present invention, it is necessary to form the intermediate layer with a thickness in the range of 30 λ to 1000 λ.

Table 1 ◎: Excellent ○: Good △: Practically usable The image forming members shown in Samples 9 to 15 were prepared under the same conditions and procedures as in Example 1, except that the flow rate ratios of H and N were varied as shown in Table 2. When the same image formation was carried out by installing the sample in a charging exposure experimental apparatus exactly similar to that used in 1, the results shown in Table 2 were obtained. Incidentally, Table 3 shows the results of analyzing only the intermediate layers of sample stores 11 to 15 by Auger electron spectroscopy. Second
As can be seen from the results shown in Table 3, X, which is related to the composition ratio of St and N in the intermediate layer, is necessary to achieve the object of the present invention.
must be formed within the range of 0.60 to 0.43.

Table 2: ◎: Excellent ○: Good △: Can be used in practice 5 inside room 301
After creating a vacuum of
0, then outflow pulp 325, 326, and inflow pulp 320-2. 321 fully open and flow meter 3
16 and 317 were also sufficiently degassed and vacuumed. Auxiliary pulp 340, pulps 325, 326, 320-2.
After closing 321, SiH4 gas (purity 99.990% SiH4 gas 2
) Pulp 330 of cylinder 311, gas cylinder 31
Open the pulp 331 of 2 and check the outlet pressure gauge 335°336
The pressure of the inlet valve 320-2 is adjusted to 1 m/J.

Gradually open 321 and check the flow meters 316 and 317.
S i H4/il', gas, and N2 gas were flowed into the chamber. Subsequently, the outflow valves 325 and 326 were gradually opened, and then the auxiliary pulp 340 was gradually opened. At this time, the inflow valves 320-2 and 321 were adjusted so that the ratio of gas flow rate to N was 8iH4/H and the gas flow rate ratio was 1:10.

Next, adjust the opening of the auxiliary pulp 340 while watching the reading on the Villany gauge 341, and adjust the opening of the auxiliary pulp 340 so that the inside of the chamber 301 is I
The auxiliary pulp 340 was opened until Thrr. Room 3
01 After the internal pressure stabilizes, the main pulp 310 is gradually closed until the Villany gauge 341 reads 0.5 Torr.
I narrowed my aperture until it was. After confirming that the gas inflow is stable and the internal pressure is stable, turn on the high frequency power supply 342.
Set it to the N state and apply 13.561i1 to the induction coil 343.
A glow discharge was generated in the chamber 301 of the coil section (upper part of the chamber) by applying a high frequency power of 1 f (z), and an input power of 3 W was obtained.The above conditions were maintained for 1 minute, and B (SiXN1
-X) y:H+ An intermediate layer consisting of 7 was formed.

Thereafter, the high frequency power supply 342 is turned off to stop the glow discharge, the outflow valve 326 is closed, and the high frequency power supply 342 is then turned on again to restart the glow discharge. I set it to 10W. After continuing the glow discharge for another 5 hours to form a photoconductive layer, the heater 308 is turned off.
The high frequency power supply 342 is also turned off, and the substrate temperature is 100%.
After waiting for the temperature to reach ℃, close the outflow valve 325 and the inflow valves 320-2 and 321, and then close the main pulp 31.
0 was fully opened to bring the inside of the chamber 301 to 10" Torr or less, the main pulp 310 was closed, and the inside of the chamber 3,01 was brought to atmospheric pressure by the leak pulp 344, and the substrate was taken out. In this case, the formed layer The total thickness was about 15μ.

When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, it was found that the image formed by performing zero corona discharge was better than the image formed by performing convex discharge. The image quality was superior and extremely clear. As a result, dependence on charging polarity was observed in the photoreceptor obtained in this example.

Example 5 After forming an intermediate layer for 1 minute on a molybdenum substrate under the same conditions and procedures as in Example 1, the high frequency power source 342 was turned off and glow discharge was stopped. Close the outflow valve 326 and then
vol.
By adjusting the inflow pulp 323 and the outflow valve 328, the opening of the outflow valve 328 was determined and stabilized so that the reading of the flow meter 319 was 1150° the flow rate of the SiH4/Hz gas.

Subsequently, the high frequency power source 342 was turned on again to restart the glow discharge. The input power at that time was set to IOW. After continuing the glow discharge for another 4 hours to form a photoconductive layer, the heating heater 308 is turned off, the high frequency power supply 342 is also turned off, and the substrate temperature is reduced to 1.
After waiting for the temperature to reach 00°C, the outflow valves 325 and 32
8 and inflow pulps 320-2 and 323, the main valve 310 is fully opened, and the inside of the chamber 301 is heated to 10' Torr.
After reducing the temperature to below r, the main valve 310 is closed and the chamber 301
The inside of the chamber was brought to atmospheric pressure using a leak valve 344, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 11 microns. When an image was formed on a transfer paper using the thus obtained image forming member under the same conditions and procedures as in Example 1,
The image quality formed by e-corona discharge was superior to the image formed by corona discharge (2), and it was extremely clear. From these results, it was found that the photoreceptor obtained in this example had charge polarity dependence.

Example 6 After forming an intermediate layer on a molybdenum main plate for 1 minute under the same conditions and procedures as in Example 1, a high-frequency power source 3 was applied.
42 in the off state and the glow discharge stopped, the outflow valve 326 was closed, and then 50 vol.
The inflow pulp 322 from 313 to the B2T-L+ gas bomb diluted to ppm is placed 1 m apart at a gas pressure of IKg/2J (outlet pressure gauge 337 reading), and the flow meter 318 reading is adjusted by adjusting the inflow valve 322 and outflow valve 327. The opening of the outflow valve 327 was set to be 1/10 of the flow rate of the SiH4/H2 gas, and the flow rate was stabilized.

Subsequently, the high frequency power supply 342 was turned on again to restart the glow discharge. The input power at that time was set to IOW. After continuing the glow discharge for another 3 hours to form a photoconductive layer, the heater 308 is turned off, the high frequency power supply 342 is also turned off, and the substrate temperature is reduced to 1.
After waiting for the temperature to reach 00°C, the outflow valves 325 and 32
7 and the inflow pulps 320 and 322 are closed, the main valve 310 is fully opened, and the inside of the chamber 301 is reduced to 10'6 Torr or less, and then the main valve 310 is closed and the inside of the chamber 301 is brought to atmospheric pressure by the leak pulp 344, and the substrate is removed. I put it out.

In this case, the total thickness of the layer formed was approximately 10μ. When an image was formed on a transfer paper using the image forming member obtained in this way under the same conditions and procedures as in Example 1, it was found that: (1) Image formation by corona discharge was better than image formation by θ corona discharge The image quality was also excellent and extremely clear. From this result, the photoreceptor obtained in this example had:
Dependency on charge polarity was observed. However, the charge polarity dependence was opposite to that of the image forming members obtained in Examples 4 and 5.

Example 7 After forming an intermediate layer on a molybdenum substrate for 1 minute and forming a photoconductive layer for 5 hours under the same conditions and procedures as in Example 1, the high frequency power source 342 was turned off to generate a glow discharge. In the stopped state, the outflow valve 327 was closed and the outflow valve 326 was opened again to obtain the same conditions as when forming the intermediate layer. Subsequently, the high frequency power source was turned on again to restart glow discharge.

The input power at that time was also 3 W, which is the same as when forming the intermediate layer. After the glow discharge was maintained for 2 minutes to form the upper layer on the photoconductive layer, the heating heater 308 was turned off, the high frequency power supply 342 was also turned off, and the temperature of the substrate reached 100°C. Outflow valve 325,
326 and the inflow pulps 320-2 and 321 are closed, the main valve 310 is fully opened, and the inside of the chamber 301 is heated to 10'T.
After reducing the temperature to below orr, close the main valve 310 and close the chamber 30.
The inside of the chamber 1 is brought to atmospheric pressure by the leak pulp 344, and the substrate is taken out.

The image forming member obtained in this way is installed in the charging exposure experiment apparatus similar to Example 1, and 6. Corona charging was performed for 0.2 seconds using OKV, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light amount of 1.0 lux-sec was irradiated through a transmission type test chart.

Immediately thereafter, by cascading a θ-chargeable developer (including toner and carrier) onto the surface of the member,
A good toner image was obtained on the surface of the member. The toner image on the member is 5. When transferred onto transfer paper using OKV's corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 8 During the formation of a photoconductive layer, an undiluted 5tzHa cylinder 315 was used in place of the SiH gas cylinder 311 diluted to 10 vol % with N7.

and B, except that the Ha/H2 flow rate ratio was set to 5:1.
After forming an intermediate layer and a photoconductive layer on a molybdenum substrate under the same conditions and procedures as in Example 1, the substrate was taken out of the deposition chamber 301 and placed in an electrostatic exposure experimental apparatus in the same manner as in Example 1 to form an image. When tested, corona emission of Q5.5KV'
R ■ In the case of a combination of chargeable developers, extremely high quality,
A high contrast toner image was obtained on transfer paper-1=.

Example 9 A molybdenum substrate was prepared according to the same conditions and procedures as in Example 1.
After forming an intermediate layer and a light guide 11L layer on L, the photoconductive layer 402 was fixed to a predetermined fixing member 403 in a deposition chamber 401 shown in FIG. 4 with the photoconductive layer facing down. Close the leak valve 411, open the main pulp 412, and open the room 5 x 10
Torr 4 and 17 in the sky. Then auxiliary pulp 40
9 outflow pulp old: 1-419, inflow valve 427-43
After fully opening 3 and exhausting the gas in the system, auxiliary pulp 4
09, Outflow valve 413-419 Outflow valve 427-4
Close 33. Heater 404 inside fixed member 403
After turning ON and setting the temperature to a predetermined temperature, open the outlet valves (441 to 448) of a predetermined gas cylinder among the various gas cylinders 449 to 455 according to the conditions shown in Table 4, and set the outlet pressure to I KV/ctA. Outlet pressure gauge/134~
440 reading) The flow rate of gas flowing through the flow meters 420 to 426 was controlled to a predetermined value by the inflow valve and the outflow pulp. Thereafter, the auxiliary pulp 409 was opened to allow gas to flow into the room, and the main pulp 412 controlled the room pressure. After the flow rate (reading of Pirani gauge 410) and room pressure have stabilized, the shutter 40 is closed in the case of glow discharge decomposition.
7 is closed, and in the case of sputtering, the shutter 407 is closed.
The high frequency power source 408 was turned on with the door open, and a glow discharge was generated in the room to form a layer.

After forming the layer for a predetermined time, the high frequency power source 408 and the heater 404 were turned off, the auxiliary pulp 409 was closed, and the main pulp 412 was fully opened. The substrate was taken out at base pressure.

In sputtering, polycrystalline St, polycrystalline Si with graphite partially laminated on top of polycrystalline Si, Si, and N4 were used for the target 405 as required.

Further, the types of gas in each cylinder in FIG. 4 are as follows.

Cylinder 449: 5iI(, gas (T(, 10 v
ol %), cylinder 450: SiF4 gas (
TI, ], including 0vo1%), cylinder 451:
S i (C,N3)4 (1'(=10vo1%
diluted), cylinder 4.52: C2H4 gas (1■,
(diluted to 10vo1% with H), cylinder 453: NH, gas (diluted to 10vo1% with H), cylinder 454:
Ar gas, cylinder 455: N2 gas For each of the image forming members A to H produced in this way,
Charging, exposure and transfer were carried out in the same manner as in Example 1 with regard to the polarities of 1 and O, and in all cases very clear toner images were obtained with no dependence on charging polarity.

Example 10 After changing the N2 gas cylinder to an NHs gas (denoted as NH3/H2) cylinder diluted to 10vol% with TT, Nf■,/H was added according to the same procedure as in Example 1.

An intermediate layer was formed by setting the flow rate ratio of gas to 5iTT</H2 gas to 2=1, and then a photoconductive layer was formed using the same conductivity and procedure as in Example 1. The sensitive plate formed with each layer was fixed to a predetermined fixing member in the apparatus shown in FIG.
Samples ① to Q shown in Table 5 below were prepared in the same manner as above. In the same manner as in Example 1 (G), charging, exposure and transfer were carried out three times for e-ambivalence, and all of them were highly dependent on charging polarity, resulting in extremely clear toner images (A: 1). It was done.

Table 5

[Brief explanation of the drawing]

1 and 2 are schematic configuration diagrams for explaining the configuration of preferred embodiments of the photoconductive member of the present invention, and FIG.
FIG. 4 is a schematic diagram showing an example of an apparatus for producing the photoconductive member of the present invention. Applicant: Canon Co., Ltd.

Claims (1)

[Claims] a support; an intermediate layer made of an amorphous material having silicon atoms as a base material and containing nitrogen atoms and hydrogen atoms;
1. A photoconductive member comprising a photoconductive layer made of an amorphous material containing silicon atoms as a matrix, and an upper layer provided on the photoconductive layer.