JPH0623857B2 - Photoconductive member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoconductive member sensitive to electromagnetic waves such as light (here, light in a broad sense, which indicates ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.). Regarding

As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an image forming member for electrophotography in an image forming field, or a document reading device, it has high sensitivity and an SN ratio (photocurrent (Ip) /
High dark current Id)], absorption spectral characteristics that match the spectral characteristics of the radiated electromagnetic waves, fast photoresponsiveness, and the desired dark resistance value, and is harmless to the human body during use. Furthermore, the solid-state imaging device is required to have characteristics such that an afterimage can be easily processed within a predetermined time. Particularly, in the case of an electrophotographic image forming member incorporated in an electrophotographic apparatus used as an office machine in an office, the pollution-free property at the time of use is an important point.

Amorphous silicon (hereinafter referred to as a-Si) is one of the photoconductive materials that has been recently receiving attention based on this point.
For example, German Laid-Open Publication Nos. 2746967 and 2855718 disclose, as an electrophotographic image forming member, German Laid-Open Publication No. 2933411.
The publication describes an application to a photoelectric conversion reading device.

In addition, the conventional photoconductive member having a photoconductive layer made of a-Si has an electrical resistance such as a dark resistance value, photosensitivity, and photoresponsiveness.
In terms of optical and photoconductive characteristics, and usage environment characteristics, as well as economic stability and durability, the characteristics have been individually improved. In reality, there is room for further improvement.

For example, when it is applied to an electrophotographic image forming member, it is often observed that residual potential remains in the conventional use when attempting to increase the photosensitivity and the dark resistance at the same time. However, when it is used repeatedly for a long time, there are many inconveniences such as accumulation of fatigue due to repeated use, which causes a so-called ghost phenomenon which causes an afterimage.

When the photoconductive layer is made of an a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type are used. A boron atom, a phosphorus atom, etc. are contained in the photoconductive layer as constituent atoms, respectively, for control purposes, or other atoms for improving other characteristics. Depending on how these constituent atoms are contained, In some cases, problems may occur in the electrical or photoconductive characteristics or pressure resistance of the formed layer.

That is, for example, the photocarriers formed by photoirradiation in the formed photoconductive layer do not have a sufficient life in the layer, or in the dark part, the injection of charges from the support side is not sufficiently blocked, or An image defect that is commonly referred to as "white blank" in an image transferred to paper, which is thought to be due to a local discharge breakdown phenomenon, and, for example, when a blade is used for cleaning, it is thought to be due to the rubbing, commonly known as "white There was a so-called image defect called "white stripe".
Further, when used in a humid atmosphere or used immediately after being left in a humid atmosphere for a long time, it is not uncommon for blurry images to occur.

Furthermore, when the layer thickness is more than 10 μm, the layer is taken out from the vacuum deposition chamber for layer formation, and then the layer floats or peels from the surface of the support, or the layer is cracked with the passage of time in the air. You will win by causing phenomena such as occurring. This phenomenon can be solved in terms of stability over time, especially when the support is usually a drum-shaped support used in the electrophotographic field. .

Therefore, while improving the characteristics of the a-Si material itself, it is necessary to devise so as to solve all of the above problems when designing the photoconductive member.

The present invention has been made in view of the above points, and is applicable to a-Si as a photoconductive member used in an electrophotographic image forming member, a solid-state imaging device, a reading device, and the like, and its applicability. As a result of continuing intensive and comprehensive research and study from the viewpoint, a silicon atom as a base material, an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X),
Light composed of so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter, "a-Si material (H, X)" is used as a generic name for these). The photoconductive member produced by designing the layer structure of the photoconductive member having the conductive layer under the specification as described below not only exhibits remarkably excellent characteristics in practical use, but also the conventional photoconductive member. It is based on the fact that it is surpassed in all respects in comparison with the above, and that it has remarkably excellent properties as a photoconductive member for electrophotography in particular.

INDUSTRIAL APPLICABILITY The present invention has electrical, optical, and photoconductive properties that are substantially stable regardless of the use environment, has a long-term resistance to light fatigue, and is durable without repeated deterioration. The main purpose of the present invention is to provide a photoconductive member which is excellent in moisture resistance and has no or almost no residual potential observed.

Another object of the present invention is to provide excellent adhesion between the layer provided on the support and the support or between the layers of the laminated layers,
It is to provide a photoconductive member that is dense and stable in terms of structural arrangement and has high layer quality.

Another object of the present invention is that when it is applied as an electrophotographic image forming member, it has a sufficient charge retention ability during a charging process for electrostatic image formation, and a normal electrophotographic method is very effectively applied. It is to provide a photoconductive member having excellent electrophotographic characteristics to be obtained.

Still another object of the present invention is to easily obtain a high-quality image having no image defect or image blurring, high density, clear halftone and high resolution in long-term use. A photoconductive member for electrophotography is provided.

Still another object of the present invention is to provide a photoconductive member having high photosensitivity, high SN ratio characteristic and high pressure resistance.

The photoconductive member of the present invention comprises a support for the photoconductive member, an auxiliary layer composed of an amorphous material containing silicon atoms (Si) as a matrix and containing nitrogen atoms (N) as constituent atoms, and silicon. A first amorphous layer having photoconductivity, which is composed of an amorphous material (a-Si) having an atom as a host, and the first amorphous layer is an oxygen atom as a constituent atom. And a second layer region containing an atom belonging to Group V of the periodic table as a constituent atom, which share at least a part of each other with the auxiliary layer. A layer thickness of the first amorphous layer and a layer thickness of the second layer region which are in contact with the layer and are present on the side of the support, where the thickness of the second layer region is t _B. If the difference from t _B is T, then t _B / (T + t _B )
A relationship of ≦ 0.4 is established, and a second amorphous layer made of an amorphous material containing silicon atoms, carbon atoms and hydrogen atoms as constituent atoms is formed on the first amorphous layer. It is characterized by having.

The photoconductive member of the present invention designed so as to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical and photoconductive characteristics and pressure resistance. And the environmental characteristics of use.

In particular, when it is applied as an electrophotographic image forming member, it has no influence of residual potential on image formation, its electrical characteristics are stable, high sensitivity, and high SN ratio. Thus, it is possible to stably and repeatedly obtain a high-quality image having light fatigue resistance, excellent repeated use characteristics, high density, clear halftone, and high resolution.

Further, in the photoconductive member of the present invention, the amorphous layer formed on the support has a tough layer itself and is excellent in adhesiveness 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 described in detail with reference to the drawings.

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

The photoconductive member 100 shown in FIG. 1 has an auxiliary layer 102 and a silicon atom as a base material on a support 101 for the photoconductive member, and if necessary, a hydrogen atom (H) or a halogen atom (H) or a halogen atom (H) as a constituent atom. X), which is composed of an amorphous material [a-Si (H, X)] containing at least one of the above, and which exhibits photoconductivity, a first amorphous layer (I) 103 and a second amorphous layer. Layer (II) 108
Have. The auxiliary layer 102 mainly includes the support 101 and the amorphous layer 10.
It is provided for the purpose of measuring the adhesion between the substrate 3 and the substrate 3, and is made of a material having the characteristics described below so that it has an affinity with both the support 101 and the amorphous layer 103.

The auxiliary layer in the photoconductive member of the present invention contains a silicon atom (Si) as a matrix, contains a nitrogen atom (N) as a constituent atom, and optionally a hydrogen atom (H) and a halogen atom (X). And an amorphous material (hereinafter referred to as “a-SiN (H, X)”).

Examples of a-SiN (H, X) include an amorphous material (hereinafter referred to as “a-SiaN _1-a ”) having a silicon atom (Si) as a matrix and a nitrogen atom (N) as a constituent atom, and a silicon atom ( Amorphous material (Si) as a matrix with nitrogen atoms (N) and hydrogen atoms (H) as constituent atoms (hereinafter referred to as "a-Si _b N _1-b ) _c H _1-c ") silicon atoms ( Si) as a host, nitrogen atom (N) and halogen atom (X)
And an amorphous material containing hydrogen atoms (H) as constituent atoms (hereinafter referred to as “a-Si _d N _1-d ) _e (H, X) _1-e ”, if necessary. I can.

In the present invention, examples of the halogen atom (X) optionally contained in the auxiliary layer include fluorine, chlorine, bromine and iodine, and particularly, fluorine and chlorine are preferable. Can be done.

When the auxiliary layer is made of the above-mentioned amorphous material, examples of the layer forming method include a glow discharge method, a sputtering method, an ion implantation method, an ion plating method, and an electron beam method. These manufacturing methods are appropriately selected and adopted depending on factors such as manufacturing conditions, load level of capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. Control of manufacturing conditions for manufacturing the conductive member is relatively easy.
The glow discharge method or the sputtering method is preferably adopted because it is easy to introduce nitrogen atoms together with silicon atoms and, if necessary, hydrogen atoms and halogen atoms into an auxiliary layer for producing them.

Further, in the present invention, the auxiliary layer may be formed by using the glow discharge method and the sputtering method together in the same apparatus system.

In order to form the auxiliary layer composed of a-SiN (H, X) by the glow discharge method, basically, a source gas for supplying Si, which can supply silicon atoms (Si), and a nitrogen atom (N). ) Introducing a raw material gas and, if necessary, introducing a hydrogen atom (H) or
And a source gas for introducing a halogen atom (X) are introduced into the deposition chamber where the inside can be decompressed to cause glow discharge in the deposition chamber, and on a predetermined support surface which is installed at a predetermined position in advance. The auxiliary layer made of a-SiN (H, X) may be formed.

In addition, when the auxiliary layer is formed by the sputtering method, for example, the following is performed.

First, for example, when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, a raw material gas for introducing nitrogen atoms (N). May be introduced into a vacuum deposition chamber in which sputtering is carried out together with a source gas for introducing hydrogen atoms (H) and / or for introducing halogen atoms (X), if necessary.

Second, Si ₃ N ₄ as a target for sputtering
Or a target composed of Si and a target composed of Si ₃ N ₄ , or S
Nitrogen atoms (N) can be introduced into the auxiliary layer formed by using a target composed of i and Si ₃ N ₄ . At this time, if the raw material gas for introducing the nitrogen atom (N) is also used, it is possible to control the flow rate, and it is easy to arbitrarily control the amount of the nitrogen atom (N) introduced into the auxiliary layer. is there.

The content of nitrogen atoms (N) introduced into the auxiliary layer controls the flow rate when the raw material gas for introducing nitrogen atoms (N) is introduced into the deposition chamber, or the nitrogen atom (N) introduction is performed. By adjusting the ratio of nitrogen atoms (N) contained in the target for use in preparing the target, or by performing both of them, the ratio can be arbitrarily controlled as desired.

As a starting material to be a raw material gas for supplying Si used in the present invention, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ etc. in a gas state or gasifiable silicon hydride (silane (S) are effectively used, and SiH ₄ and Si ₂ H ₆ are particularly preferable in view of easiness of handling layer forming work and good Si supply efficiency.

By using these starting materials, H can be introduced together with Si into the auxiliary layer formed by appropriately selecting the layer forming conditions.

As an effective starting material serving as a raw material gas for supplying Si, a silicon compound containing a halogen atom (X) in addition to the above silicon hydride, a so-called silane derivative substituted with a halogen atom, specifically, for example, SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiBr _{4 and the} like can be mentioned as a preferable halogenated silicon, and further,
Hydrogen-substituted halogenated silicon such as SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , etc., in a gas state or in a gasifiable state, one of the constituent elements is hydrogen atom. Halides can also be mentioned as a starting material for supplying Si for effective auxiliary layer formation.

Even when using a silicon compound containing these halogen atoms (X), X can be introduced together with Si into the auxiliary layer formed by suitable selection of the layer forming conditions as described above.

The halogenated silicon compound containing a hydrogen atom in the above-mentioned starting material is a hydrogen atom (H) which is extremely effective for controlling the electrical or photoelectric properties at the same time when the halogen atom (X) is introduced into the layer during the formation of the auxiliary layer. Is also introduced as a starting material for introducing a suitable halogen atom (X) in the present invention.

In the present invention, the effective starting material to be the source gas for introducing the halogen atom (X) used when forming the auxiliary layer is, for example, fluorine, chlorine, bromine,
Halogen gas of iodine, BrF, ClF, ClF ₃ ,, BrF ₅ ,, BrF ₃ ,, IF ₃ , I
Examples thereof include interhalogen compounds such as F ₇ , ICl and IBr, and hydrogen halides such as HF, HCl, HBr and HI.

A starting material effectively used as a raw material gas for introducing a nitrogen atom (N) used when forming the auxiliary layer has N as a constituent atom or N and H as a constituent atom. For example, nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂
NNH ₂ ), hydrogen azide (NH ₃ ), ammonium azide (NH ₄ N ₃ )
The nitrogenous compounds such as gaseous or gasifiable nitrogen, nitrides and azides can be mentioned. In addition to this, nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be introduced in addition to the introduction of nitrogen atom (N) and halogen atom (X).
Nitrogen halide compounds such as

In the present invention, as the dilution gas used when forming the auxiliary layer by the glow discharge method or the sputtering method,
So-called rare gases such as He, Ne and Ar can be mentioned as preferable ones.

In the amorphous material of a-SiN (H, X) constituting the auxiliary layer of the present invention, the function of the auxiliary layer is to strengthen the adhesion between the support and the amorphous layer, and in addition, Since the electrical contact between them is made uniform, the production conditions are carefully selected so that the properties required for the auxiliary layer are given as desired, and the auxiliary layer is produced carefully.

As an important factor in the layer forming conditions for forming the auxiliary layer composed of a-SiN (H, X) having the characteristics suitable for the purpose of the present invention, it is necessary to mention the support temperature at the time of forming the layer. I can.

That is, when an auxiliary layer made of a-SiN (H, X) is formed on the surface of a support, the support temperature during layer formation is an important factor that influences the structure and properties of the formed layer. In the present invention, the support temperature during layer formation is strictly controlled so that a-SiN (H, X) having the desired characteristics can be formed as desired.

In order to effectively achieve the object of the present invention, the support temperature at the time of forming the auxiliary layer is appropriately selected in accordance with the method of forming the auxiliary layer, and the formation of the auxiliary layer is performed. However, usually, 50 ℃ ~ 350 ℃, preferably 100 ℃ ~ 25
A temperature of 0 ° C is desirable. To form the auxiliary layer, the auxiliary layer, the amorphous layer (I), and the amorphous layer (I
I), and it is possible to continuously form other layers as required.It is relatively easy to finely control the composition ratio of atoms constituting each layer and control the layer thickness compared with other methods. For some reasons, it is advantageous to use the glow discharge method or the sputtering method, but when forming the auxiliary layer by these layer forming methods, it is necessary to perform the layer formation in the same manner as the above support temperature. The discharge power and the gas pressure can be mentioned as important factors that influence the characteristics of the auxiliary layer to be produced.

The discharge power condition for producing the auxiliary layer having the characteristics for achieving the object of the present invention with good productivity and efficiency is usually 1 to 300 W, preferably 2 to 150 W.
The gas pressure in the deposition chamber is usually 3 × 10 ^{−3 to 5} Torr, preferably about 8 × 10 ^{−3 to} 0.5 Torr.

The amount of nitrogen atoms contained in the auxiliary layer in the photoconductive member of the present invention, and the amount of hydrogen atoms and halogen atoms contained as necessary, achieves the object of the present invention, similarly to the preparation conditions of the auxiliary layer. Is an important factor for forming an auxiliary layer that can obtain desired characteristics.

Each of the amount of nitrogen atoms (N), the amount of hydrogen atoms (H), and the amount of halogen atoms (X) contained in the auxiliary layer is such that the object of the present invention is effectively achieved. It is arbitrarily determined according to desires in consideration of production conditions.

When the auxiliary layer is composed of a-Si _a N _1-a , the content of nitrogen atoms in the auxiliary layer is preferably 1 × 10 ^{−3 to} 60 atomic%,
It is more preferably 1 to 50 atomic%, and preferably a is displayed.
It is desirable that it is 0.4 to 0.99999, and more preferably 5 to 0.99.

When composed of a- (Si _b N _1-b ) cH _1-c , nitrogen atom (N)
The content of is preferably 1 × 10 ^{−3 to} 55 atomic
%, More preferably 1 to 55 atomic%, the content of hydrogen atoms is preferably 2 to 35 atomic%, more preferably 5 to
30 atomic%, when expressed by b and c, b is usually 0.43 to 0.99999, more preferably 0.43 to 0.99, and c is usually 0.65 to 0.98, preferably 0.7 to 0.95, and a- (Si
_When composed of _d N _1-d ) _e (H, X) _1-e , the nitrogen atom content is preferably 1 × 10 ^{−3 to} 60 atomic%, more preferably 1 to 60 atomic%, halogen. The content of atoms, or the content of halogen atoms and hydrogen atoms combined is preferably 1 to
20atomic%, more preferably 2 to 15atomic%, the content of hydrogen atoms in this case is preferably 19atomic% or less,
More preferably, it is desired to be 13 atomic% or less.

If indicated by d and e, d is preferably 0.43.
~ 0.99999, more preferably 0.43 to 0.99, and as c, preferably 0.8 to 0.99, more preferably 0.85 to 0.9.
8 is preferred.

The layer thickness of the auxiliary layer constituting the photoconductive member in the present invention is appropriately determined as desired according to the layer thickness of the amorphous layer provided on the auxiliary layer and the characteristics of the amorphous layer. .

In the present invention, the thickness of the auxiliary layer is usually 30
~ 2μ, preferably 40-1.5μ, optimally 50-1.5μ
Is desirable.

The first amorphous layer (I) 103 in the photoconductive member 100 shown in FIG. 1 comprises a first layer region (O) 104 containing oxygen atoms as constituent atoms, a group V group of the periodic table. Second layer region (V) 105 containing atoms belonging to the group (V group atom), and second layer region
(V) 105 has a layered structure including a layer region 107 containing no oxygen atom and group V atom.

The layer region 106 provided between the first layer region (O) 104 and the layer region 107 contains group V atoms but does not contain oxygen atoms.

Oxygen atoms contained in the first layer region (O) 104 or Group V atoms contained in the second layer region (V) 105 are continuous in each layer region in the layer thickness direction. Evenly distributed on the support
Preferably, it is continuously and substantially evenly distributed in a plane substantially parallel to the surface of 101.

In the photoconductive member of the present invention such as the example shown in FIG. 1, a layer region containing no oxygen atom and group V atom in the upper surface side portion of the amorphous layer (I) 103. A layer region (corresponding to the surface layer region 107 shown in FIG. 1) but containing a group V atom but not an oxygen atom (layer region 106 shown in FIG. 1) is necessarily provided. Does not need

That is, for example, in FIG. 1, the first layer region (O) 104 and the second layer region (V) 105 may be the same layer region,
Further, the second layer region (V) 105 may be provided in the first layer region (O) 104.

In the photoconductive member of the present invention, the first layer region (O) has a high dark resistance due to the inclusion of oxygen atoms, and an auxiliary layer directly provided with the first amorphous layer (I). The improvement of the adhesiveness between and is emphasized, and the enhancement of the sensitivity is emphasized without containing oxygen atoms in the layer region on the upper surface side.

In particular, like the photoconductive member 100 shown in FIG. 1, an amorphous layer (I) is used.
103 is a first layer region (O) 104 containing oxygen atoms, V-th
A second layer region (V) 105 containing a group atom, a layer region 106 containing no oxygen atom, and a layer region 107 containing no oxygen atom and group V atom, Layer area
Good results are obtained in the case of a layer structure having a layer region shared by the (O) 104 and the second layer region (V) 105.

In the photoconductive member of the present invention, the first layer region (O), which constitutes a part of the first amorphous layer (I) and contains oxygen atoms,
For one, for the purpose of improving the adhesion of the amorphous layer (I) to the auxiliary layer, and also constituting a part of the amorphous layer (I), a group V atom is contained. In the second layer region (V), for example, when a charge treatment is applied from the free surface side of the amorphous layer (II), charges are transferred from the support side to the inside of the amorphous layer (I). As a layer region where the support and the amorphous layer (I) are bonded to each other as a part of the amorphous layer (I) for the purpose of preventing injection, they share at least a part of each other. It is provided with a structure.

Further, separately, the second layer region (V) can be more effectively improved in the adhesion between the auxiliary layer and the layer region directly provided on the second layer region (V). , First layer area (O)
Is provided so as to include the second layer region (V) from the contact interface with the auxiliary layer, clogging, and extends from the contact interface with the auxiliary layer to above the second layer region (V) It is preferable to provide the first layer region (O) in the amorphous layer (I) so as to form a layer structure including the layer region (V).

In the present invention, P (phosphorus) is used as an atom belonging to Group V of the periodic table contained in the second layer region (V) constituting the first amorphous layer (I). , As (arsenic), Sb (antimony), Bi (bismuth) and the like, and P and As are particularly preferably used.

In the present invention, the V-th layer contained in the second layer region (V)
The content of the group atom is appropriately determined as desired so that the object of the present invention can be effectively achieved, but the layer region (V)
, Usually 30 to 5 × 10 ⁴ atomic ppm, preferably 5
0 to 1 × 10 ⁴ atomic ppm, optimally 100 to 5 × 10 ³ atom
It is desirable that it be ic ppm.

The amount of oxygen atoms contained in the first layer region (O) can be appropriately determined as desired according to the properties required for the photoconductive member to be formed, but usually 0.001 to 50 atomi
c%, preferably 0.002-40 atomic%, optimally 0.003
It is desirable to be set to ~ 30 atomic%.

In the photoconductive member of the present invention, the layer thickness t _B of the layer region (V) containing group V atoms (the layer thickness of the layer region 104 in FIG. 1) and the layer region (V) The layer thickness T of the layer region (layer region 106 in FIG. 1) excluding the layer region (V) provided above is such that the relation satisfies the relational expression as shown above. Although it is determined, it is more preferable that the value of the relational expression shown above is 0.35 or less, and optimally 0.3 or less.

In the present invention, the layer thickness (t _B ) of the layer region (V) containing a group V atom is usually 30 to 5 μ, preferably 40 to
It is desirable that the thickness is 4μ, and optimally 50 to 3μ.

Further, the sum (T + t _B ) of the layer thickness T and the layer thickness t _B is usually 1 to 100 μ, preferably 1 to 80 μ, and most preferably 2 to 50 μ.

As the layer thickness t _O of the layer region (O) containing oxygen atoms,
It is desirable to determine it appropriately according to the desired purpose in relation to the layer thickness t _B of the layer region (V) sharing at least a part of the layer region. That is, for the purpose of enhancing the adhesion between the layer region (V) and the auxiliary layer that is in direct contact with the layer region (V), the layer region (O) is a support for the layer region (V). Since it is sufficient that it is provided at least in the body-side end layer region, the layer thickness t _O of the layer region (O) only needs to be at most the layer thickness t _B of the layer region (V).

Further, if the adhesion between the layer region (V) and the layer region (corresponding to the layer region 107 in FIG. 1) directly provided on the layer region (V) is to be enhanced, Since the layer region (O) may be provided at least in the end layer region of the layer region (V) opposite to the side where the support is provided, the layer region (O) has a layer thickness t _O of at most. , The layer thickness (T _B ) of the layer region (V) is enough.

Furthermore, considering the case where the above two points are satisfied, the layer area
The layer thickness t _O of (O) is at least the layer thickness t of the layer region (V).
There must be only _B , and in this case, the layer area (O)
It is necessary to have a layer structure in which a layer region (V) is provided.

In order to more effectively measure the adhesion between the layer region (V) and the layer region directly provided on the layer region (V), the layer region (O) should be located above the layer region (V) (supported). It is preferable to extend it in the direction opposite to the body side).

In the present invention, a portion not containing oxygen atoms is provided in the end layer region of the amorphous layer (I) on the side of the amorphous layer (II) to form a layer region.
When (O) is locally unevenly distributed on the opposite side of the amorphous layer (II), the layer thickness t _O can be appropriately determined as desired in consideration of the above points, but usually 10 to 10 μm. It is preferably 20 to 8 μ, and most preferably 30 to 5 μ.

In the photoconductive member 100 shown in FIG. 1, the second amorphous layer (II) 108 formed on the first amorphous layer (I) 103.
Has a free surface 109, and is provided to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, pressure resistance use environment characteristics, and durability.

In the present invention, each of the amorphous materials forming the first amorphous layer (I) and the second amorphous layer (II) has a common constituent element of silicon atom. Therefore, chemical stability is sufficiently ensured at the laminated interface.

The second amorphous layer (II) is made of an amorphous material [a-Si _x C _1-x ) _y H _1-y composed of silicon atoms, carbon atoms and hydrogen atoms.
However, it is formed by 0 <x, y <1].

The second amorphous layer (II) composed of a-Si _x C _1-x ) _y H _1-y is formed by glow discharge method, sputtering method, ion implantation method, ion plating method, electron The beam method is used. These manufacturing methods are appropriately selected and adopted depending on factors such as the manufacturing conditions, the load level of capital investment, the manufacturing scale, and the desired characteristics of the photoconductive member to be manufactured. Control of manufacturing conditions for manufacturing the conductive member is relatively easy. The glow discharge method or the sputtering method is preferably adopted because it is easy to introduce carbon atoms and hydrogen atoms together with silicon atoms into the second amorphous layer (II), which can be easily introduced.

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

In order to form the second amorphous layer (II) by the glow discharge method, the raw material gas for forming a-Si _x C _1-x ) _y H _1-y is diluted with a predetermined amount of gas as necessary. It is mixed at a mixing ratio of, and is introduced into a deposition chamber for vacuum deposition in which a support is installed, and the introduced gas is turned into gas plasma by causing glow discharge to be already formed on the support. First amorphous layer (I)
It is sufficient to deposit a-Si _x C _1-x ) _y H _1-y on top.

In the present invention, the raw material gas for forming a-Si _x C _1-x ) _y H _1-y is a gaseous substance containing at least one of Si, C and H or a gasified substance. Most of the gasifications of the material obtained can be used.

When a source gas containing Si as a constituent atom is used as one of Si, C, and H, for example, a source gas containing Si as a constituent atom, a source gas containing C as a constituent atom, and H constituting atoms Or mix the raw material gas to be used in a desired mixing ratio, or
Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing C and H as a constituent atom are also mixed at a desired mixing ratio, or a raw material gas containing Si as a constituent atom, and Si ，
It is possible to mix and use raw material gases having three atoms of C and H as constituent atoms.

Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing C as constituent atoms.

In the present invention, SiH ₄ , Si ₂ H ₆ , and Si ₃ H containing Si and H as constituent atoms are effectively used as a raw material gas for forming the second amorphous layer (II). Silanes such as ₈ , Si ₄ H _{10 and the} like, silicon hydrides such as Silanes, C and H as constituent atoms, for example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene-based carbonization having 2 to 4 carbon atoms Examples thereof include hydrogen and acetylene hydrocarbons having 2 to 3 carbon atoms.

Specifically, the saturated hydrocarbons include methane (CH _4), ethane (C ₂ H _6), propane (C ₃ H _8), n- butane (nC ₄ H _10),
Pentane (C ₅ H ₁₂ ), ethylene hydrocarbons include ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ). , Isobutylene (C ₄ H ₈ ), pentene (C
₅ H ₁₀ ), acetylene-based hydrocarbons include acetylene (C ₂
H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ) and the like.

As a source gas containing Si, C and H as constituent atoms, Si (C
Alkyl silicides such as H ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ can be mentioned. In addition to these source gases, H ₂ is of course also used as an effective source gas for introducing H.

In order to form the second amorphous layer (II) by the spattering method, a single crystal or polycrystalline Si wafer or C wafer or a wafer containing Si and C mixed therein is used as a target. May be sputtered in various gas atmospheres.

For example, if you use a Si wafer as a target,
The raw material gas for introducing C and H is diluted with a diluting gas, if necessary, and then introduced into a deposition chamber for sputtering, and gas plasma of these gases is formed to sputter the Si wafer. Just do it.

Moreover, separately, Si and C are used as separate targets, or
By using a single target containing a mixture of Si and C, sputtering is performed in a gas atmosphere containing at least hydrogen atoms.

As the raw material gas for introducing C or H, the raw material gas shown in the example of the glow discharge described above can be used as an effective gas also in the case of sputtering.

In the present invention, as the diluting gas used when forming the second amorphous layer (II) by the glow discharge method or the sputtering method, a so-called rare gas, such as He, Ne, Ar or the like is suitable. It can be mentioned as something.

The second amorphous layer (I) in the present invention is carefully formed so that its required properties are provided as desired.

That is, a substance having Si, C and H as constituent atoms structurally takes a form from crystal to amorphous depending on its preparation condition, and has an electrical property ranging from conductive to semiconducting to insulating. In addition, since the properties ranging from the photoconductive property to the non-photoconductive property are respectively shown, in the present invention, a-Si _x C _1-x having desired properties according to the purpose is formed. As described above, the selection of the production conditions is strictly made according to the desire.

For example, in order to provide the second amorphous layer (II) mainly for the purpose of improving the pressure resistance, a- (SixC _1-x ) _y H _1-y is electrically insulating under the use condition. It is made as an amorphous material with remarkable behavior.

When the second amorphous layer (II) is provided mainly for the purpose of improving continuous repeated use characteristics and use environment characteristics,
The degree of electrical insulation described above is relaxed to some extent, and a- (SixC _1-x ) _y H _1-y is produced as an amorphous material having some sensitivity to irradiation light.

When the second amorphous layer (II) composed of a- (SixC _1-x ) _y H _1-y is formed on the surface of the first amorphous layer (I), the temperature of the support during the layer formation Is an important factor that influences the structure and characteristics of the formed layer, and in the present invention, a- (SixC _1-x ) _y H _1-y having the desired characteristics is desired. It is desirable that the support temperature during layer formation be strictly controlled so that it can be formed.

In order to effectively achieve the object of the present invention, the temperature of the support for forming the second amorphous layer (II) depends on the method for forming the second amorphous layer (II). The optimum range is selected appropriately and the formation of the second amorphous layer (II) is carried out, but in the usual case, it is 50 ° C to 350 ° C, preferably 100 ° C to 250 ° C. It is desirable. In the formation of the second amorphous layer (II), delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy as compared with other methods, and so on. It is advantageous to employ the glow discharge method or the sputtering method, but when forming the second amorphous layer (II) by these layer forming methods, the layer formation is performed in the same manner as the support temperature described above. It is one of the important factors that influence the characteristics of a- (SixC _1-x ) _y H _1-y , which creates the discharge power and gas pressure at that time.

A- having properties for achieving the object of the present invention
The discharge power condition for producing (SixC _1-x ) _y H _1-y with good productivity is usually 10 to 300 W, preferably 20 W.
It is desirable to be set to ~ 200W. The gas pressure in the deposition chamber is usually 0.01 to 1 Torr, preferably 0.1 to 0.5 Torr.

In the present invention, the temperature of the support for forming the second amorphous layer (II) and the desirable numerical value range of the discharge power include the values in the above-mentioned ranges. , Not mutually independently determined but mutually organic so that a second amorphous layer (II) composed of a- (SixC _1-x ) _y H _{1-y with} desired characteristics is formed. It is desirable that the optimum value for each layer formation factor be determined based on the relationship.

The amount of carbon atoms and hydrogen atoms contained in the second amorphous layer (II) in the photoconductive member of the present invention depends on the second amorphous layer (I
Similar to the production condition of I), it is an important factor for forming the second amorphous layer (II) that can obtain the desired characteristics for achieving the object of the present invention.

The amount of carbon atoms contained in the second amorphous layer (II) in the present invention is usually 1 × 10 ^{−3 to} 90 atomic%, preferably 1 to 90 atomic%, optimally 10 to 80 atomic%. It is desirable to be set to%. The content of hydrogen atom is usually 1 to 40 atomic%, preferably 2 to 35 atom
ic%, optimally 5 to 30 atomic% is desirable,
The photoconductive member formed when the hydrogen content is in these ranges is sufficiently excellent in practical use and can be sufficiently applied.

That is, x is usually 0.1 to 0.99999, preferably 0.1 to 0.99, and most preferably 0.15 to if the above a- (SixC _1-x ) _y H _1-y is displayed.
It is desirable that 0.9 and y are usually 0.6 to 0.99, preferably 0.65 to 0.98, and most preferably 0.7 to 0.95.

The numerical range of the layer thickness of the second amorphous layer (II) 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 layer (II) in the present invention is appropriately determined according to the intended purpose so as to effectively achieve the object of the present invention.

Further, the layer thickness of the second amorphous layer (II), the amount of carbon atoms and hydrogen atoms contained in the layer (II), the layer thickness of the first amorphous layer (I), etc. Also in the relation of (3), it is necessary to appropriately determine as desired under the organic relationship according to the characteristics required for each layer region. In addition, it is desirable to consider in terms of economical efficiency in consideration of productivity and mass productivity.

The thickness of the second amorphous layer (II) in the present invention is usually 0.003 to 30 μ, preferably 0.004 to 20 μ, and most preferably 0.005 to 10 μ.
It is desirable that it be μ.

The support used in the present invention may be either conductive or electrically insulating. As the conductive support, for example, NiCr, stainless steel, Al, Cr, Mo, Au, Nb, Ta, V, Ti, P
Examples thereof include metals such as t and Pd or alloys thereof.

As the electrically insulating support, a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide, glass, ceramic, paper, etc. are usually used. It It is preferable that at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is provided on the surface side subjected to the conductive treatment.

For example, if it is glass, NiCr, Al, Cr, Mo,
Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ ,, SnO ₂ ,, ITO, (In ₂ O ₃ + SnO
₂ ) is provided with conductivity by providing a thin film or the like, or a synthetic resin film such as a polyester film, NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta,
A thin film of a metal such as V, Ti, or Pt is provided on the surface by vacuum vapor deposition, electron beam vapor deposition, sputtering, or the like, or the surface is laminated with the metal to impart conductivity to the surface. The support may be formed in any shape such as a cylindrical shape, a belt shape, or a plate shape, and the shape is determined as desired. For example, the photoconductive member 100 shown in FIG. If it is used as a forming member, in the case of continuous high-speed copying, it is desirable to use an endless belt or a cylinder. The thickness of the support is appropriately determined so that a desired photoconductive member is formed, but when flexibility is required as the photoconductive member, the function as the support is sufficiently exerted. If it is within the range, it is made as thin as possible. In addition,
In such a case, in view of manufacturing and handling of the support, mechanical strength and the like, it is usually 10 μm or more.

In the present invention, in order to form the first amorphous layer (I) composed of a-Si (H, X), a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used. It is made by the vacuum deposition method used. For example, in order to form the amorphous layer (I) composed of a-Si (H, X) by the glow discharge method, it is basically possible to supply silicon atoms (Si) for supplying Si. Together with the source gas of, a source gas for introducing hydrogen atoms (H) or / and for introducing halogen atoms (X) is introduced into the deposition chamber where the inside can be depressurized to cause glow discharge in the deposition chamber, A layer made of a-Si (H, X) may be formed on the auxiliary layer which is already formed on the surface of a predetermined support which is installed in a predetermined position in advance. Further, in the case of forming by the sputtering method, for example, when sputtering the target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms (H) Alternatively, a gas for introducing a halogen atom (X) may be introduced into the deposition chamber for spattering.

In the present invention, examples of the halogen atom (X) optionally contained in the amorphous layer (I) include fluorine, chlorine, bromine and iodine, particularly fluorine and chlorine. Can be mentioned as a suitable thing.

As the raw material gas for supplying Si used in the present invention,
_{SiH 4, Si 2 H 6,} Si 3 H 8, Si 4 silicon hydride that may or gasified gas state of H _10, etc. (silanes) can be mentioned as being effectively used, in particular, the layer making work SiH ₄ and Si ₂ H ₆ are preferable as they are easy to handle and have good Si supply efficiency.

As a raw material gas for introducing a halogen atom used in the present invention, many halogen compounds can be cited, for example, halogen gas, halide, interhalogen compound, silane derivative substituted with halogen, or the like. Preferable are halogen compounds which can be gasified.

Furthermore, a silicon compound containing a halogen atom capable of gasification or gasification, which contains silicon atoms and halogen atoms as constituent elements, can be mentioned as an effective one in the present invention.

The halogen compounds that can be preferably used in the present invention, specifically, fluorine, chlorine, bromine, halogen gas _{iodine, BrF, ClF, ClF 3,} BrF 5, BrF 3, IF 3, IF 7, ICl An interhalogen compound such as IBr can be mentioned.

As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom, specifically, for example, Si
Preferable examples are silicon halides such as F ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ .

When a silicon compound containing such a halogen atom is adopted to form a characteristic photoconductive member of the present invention by a glow discharge method, a hydrogenated silicon gas is used as a source gas capable of supplying Si. Without doing so, it is possible to form the amorphous layer (I) made of a-Si containing halogen atoms on the auxiliary layer already provided on the predetermined support.

According to the glow discharge method, an amorphous layer containing halogen atoms
In the case of forming (I), basically, a silicon halide gas, which is a raw material gas for supplying Si, and a gas such as Ar, H ₂ and He are not mixed so as to have a predetermined mixing ratio and a gas flow rate. An amorphous layer can be formed on a predetermined support by introducing it into a deposition chamber that forms a crystalline layer (I) and causing a glow discharge to form a plasma atmosphere of these gases. However, in order to measure the introduction of hydrogen atoms, a predetermined amount of a gas of a silicon compound containing hydrogen atoms may be mixed with these gases to form a layer.

Further, each gas may be used not only as a single type but also as a mixture of a plurality of types at a predetermined mixing ratio.

In order to form the amorphous layer (I) made of a-Si (H, X) by the reaction sputtering method or the ion plating method, for example, in the case of the sputtering method, a target made of Si is used. This is sputtered in a predetermined gas plasma atmosphere, and in the case of the ion plating method, polycrystalline silicon or single crystal silicon is housed in the vapor deposition port as an evaporation source, and this silicon evaporation source is subjected to a resistance heating method or an electron beam method. It can be performed by heating and evaporating by a method (EB method) or the like and allowing the flying evaporate to pass through a predetermined gas plasma atmosphere.

At this time, in order to introduce a halogen atom into the layer formed by either the sputtering method or the ion plating method, the gas of the halogen compound or the silicon compound containing the halogen atom is introduced into the deposition chamber. What is necessary is just to introduce and form a plasma atmosphere of the gas.

When introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or a gas such as the above-mentioned silanes is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. You can do it.

In the present invention, the halogen compound or the halogen-containing silicon compound described above is used as an effective one as a raw material gas for introducing a halogen atom, but in addition, halogen such as HF, HCl, HBr, or HI is used. Hydrogen chloride, SiH ₂ F ₂ ,, Si
_{H 2 I 2, SiH 2 Cl} 2, SiH 2 Br 2, SiHBr 3, halogen-substituted silicon hydride etc. may or gasification of so gaseous state, halides with one of the components of the hydrogen atoms is also enabled Amorphous layer
(I) can be mentioned as a starting material for the formation.

Halides containing these hydrogen atoms form an amorphous layer (I).
At the time of formation, a hydrogen atom, which is extremely effective for controlling electrical or photoelectric properties, is introduced into the layer at the same time as the introduction of a halogen atom, so that it is used as a preferable raw material for introducing a halogen atom in the present invention.

In order to structurally introduce hydrogen atoms into the amorphous layer (I), in addition to the above, H ₂ or SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ etc. It can also be carried out by causing the above gas to coexist in the deposition chamber with a silicon compound for supplying Si to generate an electric discharge.

For example, in the case of the reaction sputtering method, a Si target is used, and a gas for introducing a halogen atom and an H ₂ gas are introduced into the deposition chamber together with an inert gas such as He and Ar as necessary, and a plasma atmosphere is obtained. Is formed and the Si target is sputtered to form a-Si (H, X) on the auxiliary layer.
An amorphous layer (I) consisting of is formed.

Further, a gas such as B ₂ H ₆ can also be introduced while also performing the impurity dopeing.

In the present invention, the amount of hydrogen atoms (H) or halogen atoms contained in the first amorphous layer (I) of the photoconductive member to be formed.
The amount of (X) or the sum of the amount of hydrogen atoms and halogen atoms (H +
X) is usually 1 to 40 atomic%, preferably 5 to 30 atomic
ic% is desirable.

To control the amount of hydrogen atoms (H) and / or halogen atoms (X) contained in the first amorphous layer (I), for example, the temperature of the support or / and hydrogen atoms (H), or The amount of the starting material used for containing the halogen atom (X) to be introduced into the deposition apparatus system, the discharge force, etc. may be controlled.

In order to provide the layer region (V) containing a group V atom and the layer region (O) containing an oxygen atom in the amorphous layer (I), the amorphous layer is formed by a glow discharge method or a reaction sputtering method. In the formation of (I), a starting material for introducing a Group V atom and a starting material for introducing an oxygen atom are used together with the above-described starting material for forming an amorphous layer (I). It is made by controlling the amount in the layer and containing it.

A glow discharge method is used to form a layer region (O) containing oxygen atoms and a layer region (V) containing group V atoms, respectively, which form the first amorphous layer (I). In this case, the starting material used as a raw material gas for forming each layer region is selected as desired from the starting materials for forming the amorphous layer (I) described above, and a starting material for introducing an oxygen atom. Alternatively, and / or starting materials for introducing the Group V atoms are added. As such a starting material for introducing an oxygen atom or a starting material for introducing a Group V atom, a gaseous substance containing at least an oxygen atom or a Group V atom as a constituent atom or a gasified substance capable of being gasified is used. Most of the can be used.

For example, if forming a layer region (O), silicon atoms
(Si) a source gas having a constituent atom, a source gas having an oxygen atom (O) as a constituent atom, and a raw material gas having a hydrogen atom (H) and / or a halogen atom (X) as a constituent atom as necessary. Or mixed with a desired mixing ratio, or a source gas containing silicon atoms (Si) as constituent atoms, and a source gas containing oxygen atoms (O) and hydrogen atoms (H) as constituent atoms. , Also mixed at the desired mixing ratio, or silicon atoms (Si)
It is possible to use a raw material gas having a constituent atom of and a raw material gas having three constituent atoms of silicon atom (Si), oxygen atom (O) and hydrogen atom (H) as a mixture.

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

Specific examples of the starting material for introducing oxygen atoms include oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), and nitrogen monoxide (N ₂ O ₂ ). ), Nitrogen dioxide (N ₂ O
₃ ), Nitrogen dioxide (N ₂ O ₄ ), Nitrogen dioxide (N ₂ O ₅ ), Nitric oxide (NO ₃ ), Silicon atom (Si) and oxygen atom (O) and hydrogen atom
(H) as a constituent atom, for example, disiloxane H ₃ SiOSi
Lower siloxanes such as H ₃ and trisiloxane H ₃ SiOSiH ₂ OSiH ₂ can be mentioned.

When the layer region (V) is formed by the glow discharge method,
As a starting material for introducing a group atom, those effectively used in the present invention include those for introducing a phosphorus atom, such as PH ₃ , P ₂ H _{4 and} other hydrogenated phosphorus, PH ₄ I, PF ₃ , PF ₅ , Examples thereof include phosphorus halides such as PCl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsCl ₃ ,
AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₂ , BiCl ₃ , B
iBr _{3 and the} like can also be mentioned as effective starting materials for introducing a Group V atom.

The content of the group V atom introduced into the layer region (V) containing the group V atom depends on the gas flow rate of the starting material for introducing the group V atom introduced into the deposition chamber, the gas flow rate ratio, and the discharge. It can be optionally controlled by controlling power, support temperature, pressure in the deposition chamber, and the like.

According to the sputtering method, in order to form a layer region (O) containing oxygen atoms, a single crystal or polycrystalline Si wafer or SiO ₂ wafer, or Si and SiO ₂ are mixed and contained. The wafer may be used as a target, and these may be sputtered in various gas atmospheres.

For example, if you use a Si wafer as a target,
A raw material gas for introducing hydrogen atoms and / or halogen atoms, if necessary, is diluted with a diluting gas, if necessary, and then introduced into a deposition chamber for spatters. It suffices to form plasma and sputter the Si wafer.

Alternatively, Si and SiO ₂ are used as separate targets, or by using a single target of Si and SiO ₂ mixed, in a diluting gas atmosphere as a gas for a sputter or at least It is formed by sputtering in a gas atmosphere containing hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the example of glow discharge described above can be used as an effective gas in the case of spattering.

In the present invention, the diluting gas used when forming the amorphous layer by the glow discharge method, or the gas for spattering used when forming the amorphous layer by the sputtering method is a so-called rare gas, for example, He. , Ne, Ar and the like can be mentioned as preferable ones.

FIG. 2 shows the layer structure of another preferred embodiment of the photoconductive member of the present invention. Photoconductive member 20 shown in FIG.
0 differs from the photoconductive member 100 shown in FIG. 1 in that the first amorphous layer (I) 203 has a lower auxiliary layer 202 in it.
-1 is to have an upper auxiliary layer 202-2 which has a similar function.

That is, the photoconductive member 200 includes a support 201, a lower auxiliary layer 202-1 and a first amorphous layer, which are sequentially stacked on the support 201.
(I) 203 and a second amorphous layer (II) 208, the amorphous layer (I) 203 is a first layer region containing oxygen atoms.
(O) 204 and a second layer region containing a Group V atom
(V) 205 and the upper auxiliary layer 20 between the layer region 206 and the layer region 207.
2-2 and.

The upper auxiliary layer 202-2 strengthens the adhesion between the layer region (V) 205 and the layer region 207 and makes the electrical contact uniform at the contact interface between them, and at the same time, the layer region (V). By providing it directly on the 205, the layer quality of the layer region (V) 205 is made strong.

Lower auxiliary layer 2 constituting the photoconductive member 200 shown in FIG.
02-1 and the upper auxiliary layer 202-2 are made of the same amorphous material as in the case of the auxiliary layer 102 constituting the photoconductive member 100 shown in FIG. It is formed according to a similar layer forming procedure and conditions.

The amorphous layer (I) 203 and the amorphous layer (II) 208 have the same characteristics and functions as the amorphous layer (I) 103 and the amorphous layer (II) 108 shown in FIG. 1, respectively. However, it is created according to the same layer creation procedure and conditions as in the case of FIG.

In the photoconductive member of the present invention, a layer region (B) provided on the layer region (V) containing a group V atom and containing no group V atom (the layer region 106 in FIG. 1). Equivalent to)
By incorporating a substance that controls the conduction characteristic, the conduction characteristic of the layer region (B) can be arbitrarily controlled as desired.

Examples of such substances include so-called impurities in the field of semiconductors. In the present invention, a-Si (H, X) forming the amorphous layer (I) to be formed is On the other hand, P-type impurities that give P-type conduction characteristics, specifically, the periodic table II.
Atoms belonging to Group I (Group III atoms) such as B (boron), Al
There are (aluminum), Ga (gallium), In (indium), Tl (thallium) and the like, and B and Ga are particularly preferably used.

In the present invention, the content of the substance that controls the conduction characteristic contained in the layer region (B) is the conduction characteristic required for the layer region (B) or the contact directly with the layer region (B). It can be appropriately selected in terms of the organic relevance such as the characteristic of the other layer region provided as described above and the characteristic at the contact interface with the other layer region.

In the present invention, the content of the substance for controlling the conductive properties contained in the layer region (B) is usually 0.001 to 1
000 atomic ppm, preferably 0.05 to 500 atomic ppm, optimally 0.1 to 200 atomic ppm is desirable.

In order to structurally introduce a substance that controls the conduction characteristics into the layer region (B), for example, a group III atom, a starting material for introducing a group III atom is introduced into the deposition chamber in a gaseous state during layer formation. , May be introduced together with other starting materials for forming the amorphous layer. As such a starting material for introducing a Group III atom, it is desirable to employ a gaseous material at room temperature and atmospheric pressure, or at least a material that can be easily gasified under the layer forming conditions. As such a starting material for introducing a Group III atom, specifically for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ .B ₅ H
₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H _14, etc., borohydrides, BF ₃ , BCl ₃ ,
Examples thereof include boron halides such as BBr ₃ . Besides this, AlCl
Other examples include ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like.

In the photoconductive member of the present invention, as described in the example shown in FIGS. 1 and 2, the layer region (O) forming the amorphous layer (I) is an amorphous layer. In the case of (I), the case of being locally contained on the side of the support is a preferred embodiment, but the present invention is not limited to this, and for example, the layer region (O)
The amorphous layer (I) may be formed by using as the whole 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 the layer region (O) is usually 30 atomic%, preferably Is preferably 10 atomic%, and optimally 5 atomic%. In this case, the lower limit is of course set to the above value.

Next, an outline of an example of the method for producing a photoconductive member of the present invention will be described.

FIG. 3 shows an example of a photoconductive member manufacturing apparatus.

In the gas cylinders 302, 303, 304, 305, 306, in the figure, raw material gases for forming the respective layer regions of the present invention are sealed, and as an example, 302 is S diluted with He.
iH ₄ gas (purity 99.999%, abbreviated as SiH ₄ / He below) cylinder, 303 is PH ₃ gas diluted with He (purity 99.999%, below P
Abbreviated as H ₃ / He. ) Cylinder, 304 is C ₂ H ₄ gas (purity 99.9
9%) is a cylinder, 305 is an NC gas cylinder, and 306 is an NH ₃ gas (purity 99.999%) cylinder.

To allow these gases to flow into the reaction chamber 301, make sure that the valves 322 to 326 and the leak valve 335 of the gas cylinders 302 to 306 are closed, and that the inflow valves 312 to 316 and the outflow valves 317 to 321, Make sure that the auxiliary valves 332 and 333 are open, and then open the main valve 334 first to open the reaction chamber 30.
1. Exhaust the inside of the gas pipe. Next, the reading of the vacuum gauge 336 is about 5
The auxiliary valves 332 and 333, the inflow valves 312 to 316, and the outflow valves 317 to 321 are closed at the time of × 10 ⁻⁶ torr. Then, the valve of the gas pipe connected to the cylinder of the gas to be introduced into the reaction chamber 301 is operated in a predetermined manner to introduce the desired gas into the reaction chamber 301.

Next, an outline of an example of producing a photoconductive member having a configuration similar to that shown in FIG. 1 will be described.

First, as an example of forming the auxiliary layer on the cylindrical support 337, SiH ₄ / He gas from the gas cylinder 302,
The NH ₃ gas is opened from the gas cylinder 306 by opening the valves 322 and 326, adjusting the pressures of the outlet pressure gauges 327 and 331 to 1 kg / cm ² , gradually opening the inflow valves 312 and 316, and the mass flow controller 30.
Inflow into 7,311. Continued outflow valves 317, 321,
Auxiliary valves 332, 323 Open gradually to allow reaction gas 301
Flow into. The outflow valves 317 and 321 are adjusted so that the ratio of the SiH ₄ / He gas flow rate and the NH ₃ gas flow rate at this time is a desired value, and a vacuum gauge is used so that the pressure in the reaction chamber 301 is a desired value. Adjust the opening of the main valve 334 while watching the reading of 336. Then, after confirming that the temperature of the support 337 is set to a temperature in the range of 50 to 400 ° C. by the heater 338, the power supply 340 is set to a desired power to cause glow discharge in the reaction chamber 301. To form an auxiliary layer on the support 337. To introduce halogen atoms into the auxiliary layer to be formed, for example, in all the description of the above-mentioned auxiliary layer preparation,
Instead of SiH ₄ gas, or using SiF ₄ gas, made Te cowpea that the addition of SiF ₄ gas to SiH ₄ gas layers formed.

The content of nitrogen atoms, hydrogen atoms, and halogen atoms contained in the auxiliary layer is adjusted by adjusting the flow rate when introducing the auxiliary layer-forming starting material containing these atoms into the reaction chamber 301. Controlled by.

For example, the nitrogen atom content is controlled by adjusting the NH ₃ gas flow rate, and the halogen atom content is controlled by adjusting the SiF ₄ gas flow rate.

Next, an example of forming the first amorphous layer (I) on the support 337 will be described. SiH ₄ / He gas from the gas cylinder 302, PH ₃ / He gas from the gas cylinder 303, and NO gas from the gas cylinder 305 are opened by opening valves 322, 323, and 325, respectively, and an outlet pressure gauge 3
Adjust the pressure of each of 27,328,330 to 1 kg / cm ² and inflow valve
Gradually open 312, 313, 315 to open the mass flow controller 30
Inflow into 7,308,310. Continued outflow valve 317,3
18, 320 and the auxiliary valve 332 are gradually opened to allow the respective gases to flow into the reaction chamber 301. SiH ₄ / He gas flow rate at this time, PH
The openings of the outflow valves 317, 318, 320 are adjusted so that the ratios of the ₃ / He gas flow rate and the NO gas flow rate become desired values,
In addition, a vacuum gauge 3 is installed so that the pressure in the reaction chamber 301 reaches a desired value.
Adjust the opening of the main valve 334 while watching the 36 reading. Then, the temperature of the support 337 becomes 50 by the heater 338.
After confirming that the desired temperature in the range of ~ 400 ° C is set, the power source 340 is set to the desired power and the reaction chamber 301 is set.
A glow discharge is generated therein to first form a layer region containing phosphorus and oxygen on the support 337.

At this time, by blocking the introduction of PH ₃ / He gas or NO gas into the reaction chamber 301 by closing the valve of the corresponding gas introduction pipe, the layer region containing phosphorus, or The layer thickness of the oxygen-containing layer region can be arbitrarily controlled as desired.

After the layer regions containing phosphorus and oxygen are formed to the desired layer thickness as described above, the outflow valves 318 and 320 are closed, and the glow discharge is continued for a desired period of time to remove phosphorus and oxygen. A layer region containing no phosphorus and oxygen is formed to a desired layer thickness on each of the layer regions containing it, and the formation of the first amorphous layer (I) is completed.

In the photoconductive member of the present invention, as described above, the amorphous layer
Since the layer region (O) and the layer region (V) constituting (I) share at least part of the layer region, the amorphous layer
When forming (I), for example, it is necessary to provide a desired length of time in which PH ₃ gas and NO gas are simultaneously introduced into the reaction chamber 301 at a desired flow rate.

For example, as described above, PH ₃ gas and NO gas are introduced into the reaction chamber 301 for a desired time from the start of formation of the amorphous layer (I), and after the elapse of the time, either gas is reacted. The layer area (O) or layer area by stopping the introduction into the chamber 301
The other layer region can be provided in one of the layer regions (V).

Alternatively, at the time of forming the amorphous layer (I), either PH ₃ gas or NO gas is introduced into the reaction chamber 301 for a desired time, and then the other is introduced into the reaction chamber 301 for a desired time. By performing the layer formation, the layer region containing both phosphorus and oxygen can be formed on the layer region containing either phosphorus or oxygen.

At this time, by stopping the introduction of either the PH ₃ gas or the NO gas into the reaction chamber 301 and continuing the introduction of the other, a layer containing both phosphorus and oxygen can be obtained. A layer region containing either phosphorus or oxygen can be formed on the region.

In the case of the photoconductive member having the upper auxiliary layer 202-2 in the first amorphous layer (I) 203 as in the case of the photoconductive member 200 shown in FIG. 2, the amorphous layer ( I) In the process of forming 203,
An upper auxiliary layer can be provided in the amorphous layer (I) by forming a layer similar to the lower auxiliary layer 202-1 formed by the above method.

By the operation as described above, to form the second amorphous layer (II) on the first amorphous layer (I) formed on the support 337, the first amorphous layer is formed. By the same valve operation as in forming the quality layer (I), for example, each of SiH ₄ gas and C ₂ H ₄ gas is diluted with a diluting gas such as He, if necessary, and the desired flow rate ratio is obtained. It is carried out in the reaction chamber 201, and the glow discharge is generated according to desired conditions.

Needless to say, all of the outflow valves other than the gas outflow valves necessary for forming each layer are closed, and when forming each layer, the gas used for forming the previous layer is the same as the reaction chamber.
In order to avoid remaining in the gas pipe from 301 to the reaction chamber 301 from the outflow valves 317 to 321, the outflow valve 317
~ 321 closed, auxiliary valves 332, 333 open and main valve 33
If necessary, perform the operation of fully opening 4 and temporarily exhausting the system to high vacuum.

Further, during the layer formation, the cylindrical support 337 is constantly rotated by the motor 339 at a desired speed in order to make the layer formation uniform.

Example 1 A layer was formed on a drum-shaped aluminum substrate under the following conditions by the manufacturing apparatus shown in FIG.

The image-forming member thus obtained was placed in a charging exposure phenomenon apparatus, _{subjected to} corona charging at 5 V for 0.2 _sec , and immediately irradiated with a light image. The light source is a tungsten lamp, 1.0lux
A light amount of _sec was applied using a transmission type test chart.

Immediately thereafter, a chargeable developer (including toner and carrier) was cascaded on the surface of the member to obtain a good toner image on the surface of the member.

The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No degradation of the image was observed even after repeating 150,000 times or more.

Example 2 A layer was formed on a drum-shaped Al substrate under the conditions shown in Table 2 below by the manufacturing apparatus shown in FIG.

Other conditions were the same as in Example 1.

The image-forming member thus obtained was placed in a charging exposure developing device, subjected to corona charging for 0.2 _{sec at} KV, and immediately irradiated with a light image. A tungsten lamp is used as the light source, and 1.0 lux ・_sec
Was irradiated with a transmission type test chart.

Immediately thereafter, a chargeable developer (including toner and carrier) was cascaded on the surface of the member to obtain a good toner image on the surface of the member.

The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No deterioration of the image was observed even after repeating 100,000 times or more.

Example 3 A layer was formed on the drum-shaped Al substrate under the conditions shown in Table 3 below by the apparatus shown in FIG. Other conditions are
The same procedure as in Example 1 was carried out.

The image-forming member thus obtained was placed in a charging exposure developing device, subjected to corona charging for 0.2 _{sec at} KV, and immediately irradiated with a light image. A tungsten lamp is used as the light source, and 1.0 lux ・_sec
Was irradiated with a transmission type test chart.

Immediately thereafter, a chargeable developer (including toner and carrier) was cascaded on the surface of the member to obtain a good toner image having extremely high density on the surface of the member.

The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No degradation of the image was observed even after repeating 150,000 times or more.

Example 4 When forming the second amorphous layer (II) and changing the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas, silicon atoms in the amorphous layer (II) were changed. An image forming member was prepared in the same manner as in Example 3 except that the content ratio of carbon atoms was changed.

The image forming member thus obtained was subjected to image evaluation after repeating the image forming, developing and cleaning steps as described in Example 1 about 50,000 times, and the results shown in Table 4 were obtained.

Example 5 An image forming member was prepared in the same manner as in Example 1 except that the layer thickness of the second amorphous layer (II) was changed. The steps of image formation, development and cleaning as described in Example 1 were repeated and the following results were obtained.

Example 6 An image forming member was prepared in the same manner as in Example 1 except that the method for forming the auxiliary layer and the amorphous layer (I) was changed as follows, and evaluation was performed in the same manner as in Example 1. Good results were obtained on the vine.

Example 7 An image forming member was prepared in the same manner as in Example 1 except that the method for forming the auxiliary layer and the amorphous layer (I) was changed as follows, and evaluation was performed in the same manner as in Example 1. As a result, good results were obtained.

Example 8 A layer was formed on the drum Al substrate in the same manner as in Example 1 except that the conditions shown in Table 8 below were applied by the manufacturing apparatus shown in FIG.

Example 2 was applied to the electrophotographic image-forming member thus obtained.
When the same evaluation as in (1) was performed, good results were obtained.

Example 9 Layers were formed on an Al substrate under the conditions shown in Table 9 below by the manufacturing apparatus shown in FIG.

Other conditions were the same as in Example 1.

The image forming member thus obtained was evaluated in the same manner as in Example 3, and it was found that a high quality image was obtained and the durability was excellent.

Example 10 Example 3.4 of Example 8. Each of the electrophotographic image forming members was prepared and carried out in accordance with the conditions and procedures shown in Example 8 except that the layer forming conditions at the layer forming stage were changed to those shown in Table 10 below. When evaluated in the same manner as in Example 1,
Good results were obtained for each of them, especially in terms of image quality durability.

[Brief description of drawings]

1 and 2 are schematic layer configuration diagrams schematically showing the layer structure of a preferred embodiment of the photoconductive member of the present invention,
FIG. 3 is a schematic explanatory view showing an example of an apparatus for producing the photoconductive member of the present invention. 100, 200 ... Photoconductive member 101, 201 ... Support 102, 202-1, 202-2 ... Auxiliary layer 103, 203 ... First amorphous layer (I) 104, 204 ... First layer region (O) 105, 205 ... Second layer region (V ) 108,208… Second amorphous layer (II) 109,209… Free surface

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Megumi Saito 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yoichi Osato 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Incorporated (72) Inventor Teruo Triangle 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-57-58159 (JP, A) JP-A-56-142680 (JP) , A) JP 58-88753 (JP, A)

Claims (1)

[Claims] 1. A support for a photoconductive member, an auxiliary layer composed of an amorphous material containing silicon atoms as a matrix and containing nitrogen atoms as constituent atoms, and an amorphous material containing silicon atoms as a matrix. And having a first amorphous layer exhibiting photoconductivity, wherein the first amorphous layer has a first layer region containing oxygen atoms as constituent atoms, and a periodic structure as constituent atoms. A second layer region containing atoms belonging to Group V of the table,
These are at least partially shared with each other and are in contact with the auxiliary layer and are internally present on the side of the support, and the layer thickness of the second layer region is t _B. Assuming that the difference between the layer thickness of the quality layer and the layer thickness t _B of the second layer region is T, the relationship of t _B / (T + t _B ) ≦ 0.4 holds, and the first amorphous A photoconductive member having thereon a second amorphous layer composed of an amorphous material containing silicon atoms, carbon atoms and hydrogen atoms as constituent atoms.