JPH0368380B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. Highly sensitive, SN
It has a high ratio [photocurrent (Ip)/dark current (Id)], has absorption spectral characteristics that match the spectral characteristics of the electromagnetic wave to be irradiated, has fast photoresponsiveness, has the desired dark resistance value, and when used Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body, and being able to easily process afterimages within a predetermined time.
On the other hand, in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the pollution-free nature during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and use environment characteristics. Although individual improvements have been made in terms of stability, stability over time, and durability, the reality is that there is still room for further improvement in terms of improving overall properties. be. For example, when applied to electrophotographic image forming members, when trying to achieve high photosensitivity and high dark resistance at the same time, it has often been observed in the past that residual potential remains during use, and this type of photoconductive member When used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in a so-called ghost phenomenon in which an afterimage occurs. In addition, when the photoconductive layer is composed of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms to control the properties of the photoconductive layer, and other atoms are included in the photoconductive layer to improve properties. In some cases, problems may arise in the electrical or photoconductive properties, pressure resistance, durability, etc. of the formed layer. For example, when used as an electrophotographic image forming member, photocarriers generated in the formed photoconductive layer due to light irradiation may not have a sufficient lifespan in the layer, or charges may accumulate from the support side in dark areas. Insufficient prevention of the injection of
For example, when a blade is used for cleaning, so-called image defects commonly referred to as "white streaks" may occur, which is thought to be caused by the rubbing of the blade. or,
When used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs. Furthermore, when the layer thickness exceeds 10-odd microns, the layer may lift or peel from the surface of the support, or it may crack as the time passes after it is left in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it caused phenomena such as . This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. . Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms 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(H,X)" will be used as a general notation for these). A photoconductive member designed and produced by specifying the layer structure of a photoconductive member having a conductive layer as explained below not only exhibits extremely superior properties in practical use, but also has superior properties to conventional photoconductive members. This is based on the fact that it has been found to be superior in all respects when compared with other materials, and has particularly excellent properties as a photoconductive member for electrophotography. The electrical, optical, and photoconductive properties of the present invention are virtually always stable regardless of the environment in which it is used, and it is extremely resistant to light fatigue and does not deteriorate even after repeated use, making it durable. The main object of the present invention is to provide a photoconductive member that has excellent moisture resistance and has no or almost no residual potential observed. Another object of the present invention is to provide excellent adhesion between a layer provided on a support and the support and between each laminated layer, to provide a dense and stable structural arrangement, and to provide layer quality. It is an object of the present invention to provide a photoconductive member with high quality. Another object of the present invention is that, when applied as an electrophotographic image forming member, the present invention has sufficient charge retention ability during charging processing for electrostatic image formation, and ordinary electrophotographic methods can be applied very effectively. It is an object of the present invention to provide a photoconductive member having excellent electrophotographic properties that can be used. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. The photoconductive member of the present invention includes a support for the photoconductive member, a silicon atom as a base material, and 1 as a constituent atom.
×10 ^-3 atomic% or more and up to 25 atomic% of nitrogen atoms and hydrogen atoms. An auxiliary layer made of an amorphous material containing nitrogen atoms and hydrogen atoms, and a silicon atom as the base material and constituent atoms that belong to Group Group of the Periodic Table. A charge injection prevention layer composed of an amorphous material containing silicon atoms as a matrix and an amorphous material containing at least one of hydrogen atoms or halogen atoms as a constituent atom, and photoconductive. a first amorphous layer exhibiting; a second amorphous layer provided on the amorphous layer and made of an amorphous material containing silicon atoms, carbon atoms, and hydrogen atoms as constituent atoms; It is characterized by having the following. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, photoconductive properties, and pressure resistance. and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it is highly sensitive and has high
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. In addition, the photoconductive member of the present invention has a strong amorphous layer formed on the support, and has excellent adhesion to the support, so that it can be repeatedly used continuously at high speed for a long time. can do. 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 the layer configuration of a photoconductive member according to a first embodiment of the present invention. The photoconductive member 100 shown in FIG. 1 has an auxiliary layer 102,
A charge injection prevention layer 103, a first amorphous layer (I) 104 having photoconductivity, an amorphous material whose constituent atoms are silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as "a-Si _X C _{1 -X} )yH _1-y "), the amorphous layer ( ) 105 has a free surface 106. The auxiliary layer 102 is provided mainly for the purpose of measuring the adhesion between the support 101 and the charge injection prevention layer 103, and has affinity with both the support 101 and the charge injection prevention layer 103. It is constructed from the materials described below. The charge injection prevention layer 103 mainly has a function of effectively preventing charges from being injected into the amorphous layer 104 from the support 101 side. The amorphous layer ( ) 104 generates photocarriers in the layer 104 upon irradiation with sensitive light;
Its main function is to transport the photo carrier in a predetermined direction. The amorphous layer ( ) 105 is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, pressure resistance, use environment characteristics, and durability. The auxiliary layer in the present invention is made of silicon atoms (Si).
contains nitrogen atoms and hydrogen atoms as constituent atoms, and the nitrogen atom content C _co1 is 25 atomic
% (hereinafter a-(SiaN ₁ -a))
It is written as bH ₁ −b. However, it is composed of 0.6<a, 0.65≦b). The auxiliary layer composed of a-(SiaN ₁ -a)bH ₁ -b can be formed by glow discharge method, sputtering method,
This is done by ion implantation method, ion blating method, 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 produced. The glow discharge method is preferred because it is relatively easy to control the manufacturing conditions for manufacturing the photoconductive member, and it is also easy to introduce nitrogen atoms and hydrogen atoms together with silicon atoms into the auxiliary layer to be manufactured. Alternatively, 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. To form the auxiliary layer by glow discharge method,
The raw material gas for forming a-(SiaN ₁ -a)bH ₁ -b,
If necessary, it is mixed with a dilution gas at a predetermined mixing ratio and introduced into a deposition chamber for vacuum deposition where a support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge. a- on the support
(SiaN ₁ -a)bH ₁ -b may be deposited. In the present invention, the raw material gas for forming a-(SiaN ₁ -a)bH ₁ -b is a gaseous substance or a gasified substance containing at least one of Si, N, and H as a constituent atom. Most gasified vertebrae can be used. When using a raw material gas containing Si as one of Si, N, and H, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing N as a constituent atom, and a raw material gas containing H as a constituent atom. Alternatively, a raw material gas containing Si and a raw material gas containing N and H may be mixed at a desired mixing ratio. Can be mixed and used. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing N as constituent atoms. In the present invention, the starting materials that can be effectively used as raw material gas for forming the auxiliary layer are:
SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ whose constituent atoms are Si and H,
Silicon hydrides such as silanes such as Si ₄ H ₁₀ ,
Examples of nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (NH ₃ ), ammonium azide ( Mention may be made of gaseous or gasifiable nitrogen such as NH ₄ N ₃ ), nitrogen compounds such as nitrides and azides. In addition to these starting materials for forming the auxiliary layer, H ₂ is of course also used as an effective raw material gas for introducing H. To form the auxiliary layer by the sputtering method, a monocrystalline or polycrystalline Si wafer or
This can be carried out by sputtering a Si ₃ N ₄ wafer or a wafer containing a mixture of Si and Si ₃ N ₄ in various gas atmospheres. For example, if a Si wafer is used as a target, the raw material gas for introducing N and H, e.g.
H ₂ and N ₂ or NH ₃ are diluted with a diluting gas as necessary and introduced into a deposition chamber for sputtering to form a gas plasma of these gases to sputter the Si wafer. Just do it. Alternatively, a gas atmosphere containing at least H atoms can be created by using separate targets for Si and Si ₃ N, or by using a single target formed by mixing Si and Si ₃ N ₄ . This is done by sputtering inside. As a raw material gas for introducing N or H, the starting material gas for forming the auxiliary layer shown in the glow discharge example described above can also be used as an effective gas in the case of sputtering. In the present invention, the diluting gas used when forming the auxiliary layer by the glow discharge method or sputtering method includes so-called rare gases such as He, Ne,
Ar and the like can be cited as suitable examples. a-(SiaN ₁ -a) constituting the auxiliary layer of the present invention
bH ₁ -b is an auxiliary layer because the function of the auxiliary layer is to strengthen the adhesion between the support and the charge injection prevention layer, and also to make the electrical contact between them uniform. The manufacturing conditions are strictly selected and carefully formed so as to provide the desired characteristics. a- having characteristics suitable for the purpose of the present invention;
(SiaN ₁ -a)bH ₁ -b can be produced by the temperature of the support at the time of production as an important element in the production conditions. That is, on the surface of the support a-(SiaN ₁ -a)bH ₁
When forming the auxiliary layer consisting of -b, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. has a−(SiaN ₁ −a)bH ₁ −
The temperature of the support during layer formation is strictly controlled so that b can be formed as desired. In order to effectively achieve the purpose of the present invention, the optimal range of the support temperature when forming the auxiliary layer is selected as appropriate in accordance with the method of forming the auxiliary layer, and the formation of the auxiliary layer is carried out. However, in normal cases, the temperature is 50℃~
A temperature of 350°C, preferably 100°C to 250°C is desirable. To form the auxiliary layer, it is possible to continuously form the auxiliary layer, the charge injection prevention layer, the amorphous layer, and even other layers formed on the amorphous layer as necessary in the same system. The glow discharge method and sputtering method are advantageous because it is relatively easy to finely control the composition ratio of atoms constituting each layer and control the layer thickness compared to other methods. However, when forming an auxiliary layer using these layer forming methods, the discharge power and gas pressure during layer formation are created in the same way as the support _temperature described above _. It is cited as an important factor that influences the characteristics of -b. The discharge power conditions for effectively forming a-(SiaN ₁ -a)bH ₁ -b with good productivity, which have the characteristics to achieve the object of the present invention, are as follows:
Usually 1 to 300W, preferably 2 to 100W. The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.1 to 5 Torr when layer formation is performed by glow discharge.
When forming a layer by sputtering, the temperature is usually 10 ^-3 to 5 x 10 ^-2 Torr, about 0.5 Torr.
It is preferably about 8×10 ⁻³ to 3×10 ⁻² Torr. The amounts of nitrogen atoms (N) and hydrogen atoms (H) contained in the auxiliary layer in the photoconductive member of the present invention are determined to provide the desired characteristics to achieve the object of the present invention, as well as the conditions for producing the auxiliary layer. This is an important factor in the formation of an auxiliary layer. The amount C _{(N) of nitrogen atoms (N)} contained in the auxiliary layer in the present invention is usually within the above-mentioned value range, but preferably 1×
It is desirable that 10 ^-3 ≦C _(N) <25, more preferably 1≦C _(N) <25, optimally 10≦C _(N) <25. or,
The amount of hydrogen atoms (H) is preferably 2 to 2.
It is desirable that it be 35 atomic%, optimally 5 to 30 atomic%. When expressed as a and b in a-(SiaN ₁ -a)bH ₁ -b, the value of a is preferably 0.6<a≦0.9999, more preferably 0.6<a
≦0.99, optimally 0.6<a≦0.9, the value of b is
Preferably 0.65≦b≦0.98, more preferably 0.7≦b≦
A value of 0.95 is desirable. The numerical range of the layer thickness of the auxiliary layer in the present invention is appropriately determined as desired so as to effectively achieve the object of the present invention. In order to effectively achieve the purpose of the present invention, the thickness of the auxiliary layer is usually 30 Å to 2 μ, preferably
It is desirable that the thickness be 40 Å to 1.5 μ, most preferably 50 Å to 1.5 μ. The charge injection prevention layer constituting the photoconductive member of the present invention has a silicon atom (Si) as its base material, and preferably contains an atom belonging to a group of the periodic table (a group atom) and a hydrogen atom (H) or a halogen atom. (X), or both of these as constituent atoms (hereinafter referred to as "a-Si(,H,X)"), the layer thickness t and the content of group atoms in the layer The quantity C ₍ 〓 ₎ is
It can be appropriately determined as desired so that the object of the present invention can be effectively achieved. The layer thickness t of the charge injection prevention layer in the present invention is preferably 0.3 to 5μ, more preferably 0.5 to 2μ.
It is preferable that the content of group atoms C ₍ 〓 ₎
preferably 1×10 ² to 1×10 ⁵ atomic
ppm, more preferably 5×10 ² to 1×10 ⁵ atomic
Preferably in ppm. In the present invention, the atoms belonging to group of the periodic table contained in the charge injection prevention layer are B (boron), Al (aluminum), Ga (gallium), In (idium), Tl ( thallium) etc.
Particularly preferably used are B and Ga. In the present invention, specific examples of the halogen atom (X) contained in the charge injection prevention layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as such. To form the charge injection prevention layer composed of a-Si(,H,X), as in the case of forming the auxiliary layer,
For example, a vacuum deposition method using a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is employed. 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. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having silicon atoms, and if necessary, hydrogen atoms (H) and halogen atoms (X) are created in the charge injection prevention layer. The glow discharge method or the sputtering method is preferably employed because of the advantages that it can be easily introduced. Furthermore, in the present invention, the charge injection prevention layer may be formed by using both the glow discharge method and the sputtering method in the same apparatus system. For example, a-Si (,
In order to form a charge injection prevention layer composed of H, A raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) as needed is introduced into a deposition chamber whose interior is made to have a reduced pressure, and a glow is generated in the deposition chamber. A discharge is generated, and a
A layer consisting of -Si(,H,X) may be formed. In addition, when forming by sputtering method,
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, the raw material gas for introducing group atoms may be replaced with hydrogen as necessary. atom
(H) and/or halogen atoms (X) may be introduced into a deposition chamber for sputtering together with a gas for introducing halogen atoms (X). The following are effective starting materials for the raw material gas used to form the charge injection prevention layer in the present invention. First, silicon hydride (silanes) in a gaseous state or capable of being gasified, such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc., is effective as the starting material that becomes the raw material gas for supplying Si. It is cited as a material used in the production of silicon, especially in terms of ease of layer creation work and good Si supply efficiency.
Preferred examples include SiH ₄ and Si ₂ H ₆ . If these starting materials are used, the auxiliary layer formed by appropriately selecting the layer forming conditions will contain
H may also be introduced together with Si. In addition to the above-mentioned silicon hydride, effective starting materials that serve as raw material gas for supplying Si include silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, specifically, for example,
Preferred examples include silicon halides such as SiF ₄ , Si ₂ H ₆ , SiCl ₄ , SiBr, and more preferably SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
Halogen-substituted silicon hydrides such as SiH ₂ Br ₂ and SiHBr ₃ ,
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituents can also be cited as starting materials for supplying Si for forming an effective charge injection prevention layer. Even when these silicon compounds containing halogen atoms (X) are used, as mentioned above, it is possible to introduce X together with Si into the charge injection prevention layer formed by appropriately selecting the layer formation conditions. I can do it. Among the above-mentioned starting materials, silicon halide compounds containing hydrogen atoms are hydrogen atoms ( Since H) is also introduced, it is used as a suitable starting material for introducing a halogen atom (X) in the present invention. In addition to the above-mentioned materials, examples of effective starting materials as raw material gases for introducing halogen atoms (X) used in forming the auxiliary layer in the present invention include halogen atoms such as fluorine, chlorine, bromine, and iodine. Gas, BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ , IF ₇ ,
Interhalogen compounds such as ICl, IBr, HF, HCl, HBr,
Examples include hydrogen halides such as HI. In order to structurally introduce group atoms into the charge injection prevention layer, during layer formation, a starting material for introducing group atoms is placed in a gaseous state in a deposition chamber in addition to other materials for forming the charge injection prevention layer. It may be introduced together with the starting material. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group group atoms include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ ,
Boron hydride such as B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ ,
Examples include boron halides such as BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ ,
TlCl ₃ etc. can also be mentioned. In the present invention, the group atoms contained in the charge injection prevention layer to provide charge injection prevention properties are
It is preferable that it is distributed substantially uniformly in a plane substantially parallel to the layer thickness direction of the electricity injection prevention layer (a plane parallel to the surface of the support) and in the layer thickness direction. In addition, when forming a charge injection prevention layer by a sputtering method, for example, when sputtering a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, The raw material gas for introducing group atoms may be introduced into the vacuum deposition chamber in which sputtering is performed together with the raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as necessary. In the present invention, the content of group atoms introduced into the charge injection prevention layer is determined by the gas flow rate of the starting material for introducing group atoms introduced into the deposition chamber, the gas flow rate ratio, the discharge power, and the support. It can be arbitrarily controlled by controlling body temperature, pressure inside the deposition chamber, etc. In the present invention, examples of the halogen atom (X) that may be contained in the charge injection prevention layer as necessary include the same halogen atoms (X) as described in the description of the auxiliary layer. In the present invention, the diluent gas used when forming the charge injection prevention layer by a glow discharge method or a sputtering method is a so-called rare gas, for example.
Preferred examples include He, Ne, Ar, and the like. In the present invention, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used to form the first amorphous layer (I) composed of a-Si(H,X). It is made by a vacuum deposition method. For example, to form an amorphous layer composed of a-Si (H, together with hydrogen atom
A raw material gas for introducing (H) and/or for introducing halogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. a-Si on the charge injection prevention layer already formed on the surface of a certain support.
A layer consisting of (H,X) may be formed. or,
For example, when forming by sputtering method,
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, it is necessary to introduce hydrogen atoms (H) and/or halogen atoms (X). The gas may be introduced into a deposition chamber for sputtering. In the present invention, if necessary, an amorphous layer ()
As the halogen atom (X) contained therein, the same ones as mentioned in the case of the auxiliary layer can be mentioned. In the present invention, the raw material gas for supplying Si used to form the amorphous layer () is the same as those mentioned when explaining the auxiliary layer and the charge injection prevention layer.
Gaseous or gasifiable hydrogen silanes (silanes) such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ can be used effectively, especially in layer forming operations. In terms of ease of handling, good Si supply efficiency, etc.
SiH ₄ Si ₂ H ₆ is preferred. As in the case of the auxiliary layer, many halogen compounds are effective as the raw material gas for introducing halogen atoms used when forming the amorphous layer () in the present invention, such as halogen gas, halogen compounds, Preferred examples include halogen compounds in a gaseous state or which can be gasified, such as interhalogen compounds and halogen-substituted silane derivatives. Furthermore, silicon compounds containing silicon atoms (Si) and halogen atoms (X) in a gaseous state or containing gasified halogen atoms can also be mentioned as effective in the present invention. . In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or hydrogen atoms contained in the charge injection prevention layer and the amorphous layer () of the photoconductive member to be formed is (H). The sum of the amounts of halogen atoms (X) (H+
X) is usually 1 to 40 atomic%, preferably 5
It is desirable that it be ~30 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the charge injection prevention layer or the amorphous layer (), for example, the support temperature or/and the hydrogen atoms (H), Alternatively, the amount of the starting material used to contain the halogen atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, the diluting gas used when forming the amorphous layer () by the glow discharge method or the sputtering gas used when forming the amorphous layer by the sputtering method is a so-called rare gas. gas,
For example, He, Ne, Ar, etc. can be cited as suitable examples. In the present invention, the thickness of the amorphous layer (2) is determined as appropriate depending on the characteristics required of the photoconductive member to be produced, but is usually 1 to 1.
It is desirable that the thickness be 100μ, preferably 1 to 80μ, optimally 2 to 50μ. In the photoconductive member of the present invention, a second amorphous layer () provided on the first amorphous layer () is provided.
is an amorphous material [a-(Si _x C _1-x ) _y H _1-y where 0<
x, y<1], so each of the amorphous materials forming the first amorphous layer () and the second amorphous layer () constituting the amorphous layer () is Since they have a common constituent element of silicon atoms, chemical stability is sufficiently ensured at the laminated interface. The second amorphous layer ( ) 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. method, 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 produced. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having silicon atoms, and it is easy to introduce carbon atoms and hydrogen atoms together with silicon atoms into the second amorphous layer (2). Due to their advantages, the glow discharge method or the sputtering method is preferably employed. Furthermore, in the present invention, the second amorphous layer ( ) may be formed by using a glow discharge method and a sputtering method in the same apparatus system. In order to form the second amorphous layer () by the glow discharge method, the raw material gas for forming a-(Si _x C _1-x ) _y H _1-y is mixed with a diluting gas as necessary. The mixture is mixed at a predetermined mixing ratio and introduced into a deposition chamber for vacuum deposition in which a support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge, and the gas is already deposited on the support 101. What is necessary is to deposit a-(Si _x C _1-x ) _y H _1-y on the formed first amorphous layer ( ). In the present invention, at least one of Si, C, and H is used as the raw material gas for forming a-(Si _x C _1-x ) _y H _1-y.
Most gaseous substances or gasified substances having two constituent atoms can be used. When using a raw material gas containing Si as one of Si, C, and H, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing C as a constituent atom, and a raw material gas containing H as a constituent atom. Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing C and H as constituent atoms may be mixed at a desired mixing ratio. Mix, but
Alternatively, a raw material gas containing Si as a constituent atom and Si, C
It is possible to use a mixture of a raw material gas having three constituent atoms: and H. 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, Si and H are effectively used as raw material gases for forming the second amorphous layer ().
Si ₂ H ₆ , Si ₃ H ₈ , SiH ₄ ,
Silicon hydride gas such as silanes such as Si ₄ H ₁₀ , whose constituent atoms are C and H, for example, carbon number 1
-4 saturated hydrocarbons, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (CH ₈ ), n
-Butane (n _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
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 ), acetylenic hydrocarbons ,
Examples include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like. Examples of the source gas containing Si, C, and H as constituent atoms include alkyl silicides such as Si(CH ₃ ) ₄ and Si(C ₂ H ₅ ) ₄ . In addition to these raw material gases, H
Of course, H ₂ is also effectively used as the raw material gas for introduction. To form the second amorphous layer () by the sputtering method, target a single crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C.
These may be performed by sputtering in various gas atmospheres. For example, if a Si wafer is used as a target, the raw material gases for introducing C and H are diluted with diluting gas as necessary and introduced into a deposition chamber for sputtering. The Si wafer may be sputtered by forming plasma. Alternatively, sputtering can be carried out in a gas atmosphere containing at least hydrogen atoms by using separate targets for Si and C or by using a single target in which Si and C are mixed. It is accomplished by doing so. As the raw material gas for introducing C or H, the raw material gas shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, so-called rare gases such as He, Ne, Ar, etc. can be used as the diluting gas when forming the second amorphous layer () by a glow discharge method or a sputtering method. It can be mentioned as a suitable one. The second amorphous layer ( ) in the present invention is carefully formed so as to provide the desired properties. In other words, materials whose constituent atoms are Si, O, and H can have structural forms ranging from crystalline to amorphous, depending on the conditions for their creation, and electrical properties ranging from conductive to semiconductive to insulating. and the properties between photoconductive and non-photoconductive properties,
In the present invention, the preparation conditions are strictly selected according to the needs so that a-Si _x C _1-x having the desired characteristics depending on the purpose is formed. Ru. For example, in order to provide the second amorphous layer () with the main purpose of improving pressure resistance, a-(Si _x C _1-x ) _y
H _1-y is produced as an amorphous material with pronounced electrically insulating behavior under conditions of use. In addition, if a second amorphous layer () is provided for the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation will be relaxed to some extent, and it will be more effective against the irradiated light. As an amorphous material with a certain degree of sensitivity, a-(Si _x C _1-x ) _y
H _1-y is created. a−(Si _x C _1-x ) _y on the surface of the first amorphous layer ()
When forming the second amorphous layer ( ) consisting of H _1-y , the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. In this case, a-(Si _x
It is desirable that the temperature of the support during layer formation be strictly controlled so that C _1-x ) _y H _1-y can be formed as desired. In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the second amorphous layer () is determined as appropriate in accordance with the method of forming the second amorphous layer (). An optimal range is selected to perform the formation of the second amorphous layer (), typically at 50°C.
The temperature is preferably 100°C to 250°C, preferably 100°C to 250°C. In order to form the second amorphous layer (2018), we use a glow method, as it is relatively easy to finely control the composition ratio of the atoms that make up the layer and control the layer thickness compared to other methods. It is advantageous to adopt the discharge method or the sputtering method, but when forming the second amorphous layer () using these layer formation methods, the temperature during layer formation as well as the support temperature described above must be adjusted. The discharge power and gas pressure are one of the important factors that influence the characteristics of the a-(Si _x C _1-x ) _y H _1-y that is created. The discharge power conditions for effectively producing a-(Si _x C _1-x ) _y H _1-y with good productivity, which have the characteristics to achieve the purpose of the present invention, are usually as follows: Ten
~300W, preferably 20~200W. It is desirable that the gas pressure in the deposition chamber is usually about 0.01 to 1 Torr, preferably about 0.1 to 0.5 Torr. In the present invention, the preferable numerical ranges of the support temperature and discharge power for forming the second amorphous layer ( ) include the values in the above ranges, but these layer forming factors are , the desired characteristics a−(Si _x C _1-x ) _y are not determined independently and separately.
It is desirable that the optimum values of each layer formation factor be determined based on the mutual organic relationship so that a second amorphous layer ( ) consisting of H _1-y is formed. The amounts of carbon atoms and hydrogen atoms contained in the second amorphous layer () in the photoconductive member of the present invention are as follows:
The conditions for forming the second amorphous layer ( ) are also important factors in forming the second amorphous layer ( ) that provides the desired properties to achieve the objects of the present invention. The amount of carbon atoms contained in the second amorphous layer () in the present invention is usually 1×10 ^-3 to 90 atomic
%, preferably 1 to 90 atomic %, most preferably 10 to 80 atomic %. The content of hydrogen atoms is usually 1
~40 atomic%, preferably 2-35 atomic%, optimally 5-30 atomic%,
Photoconductive members formed with hydrogen contents within these ranges are of excellent practical application. That is, if expressed as a-(Si _x C _1-x ) _y H _1-y , x is usually 0.1 to 0.99999, preferably 0.1 to 0.99, optimally 0.15 to 0.9, and y is usually 0.6. ~0.99, preferably
It is desirable that it be between 0.65 and 0.98, most preferably between 0.7 and 0.95. The numerical range of the layer thickness of the second amorphous layer ( ) 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 ( ) in the present invention is appropriately determined according to the desired purpose so as to effectively achieve the purpose of the present invention. In addition, the layer thickness of the second amorphous layer () is determined by the amount of carbon atoms and hydrogen atoms contained in the layer (),
The relationship with the layer thickness of the first amorphous layer () also needs to be appropriately determined as desired based on the organic relationship depending on the characteristics required for each layer region. There is. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production. The layer thickness of the second amorphous layer ( ) in the present invention is usually 0.003 to 30μ, preferably 0.004 to 20μ,
The optimum value is 0.005 to 10μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. 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, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al , Ag, Pb, Zn, Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The support may have any shape such as a cylinder, a belt, or a plate, and the shape may be determined as desired. For example, the photoconductive member 100 shown in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. FIG. 2 shows the layer structure of another preferred embodiment of the photoconductive member of the present invention. The photoconductive member 200 shown in FIG. 2 differs from the photoconductive member 100 shown in FIG.
An upper auxiliary layer 204 is provided between the charge injection prevention layer 203 and the amorphous layer 205 exhibiting photoconductivity. That is, the photoconductive member 200 includes a support 201 and a lower auxiliary layer 2 laminated in this order on the support 201.
02, charge injection prevention layer 203, upper auxiliary layer 20
4. Comprising a first amorphous layer ( ) 205 and a second amorphous layer ( ) 206, the amorphous layer ( ) 2
06 has a free surface 207. Upper auxiliary layer 20
4 is a charge injection prevention layer 203 and an amorphous layer () 2
05 and uniform electrical contact at the contact interface between both layers, and at the same time, by providing the charge injection prevention layer 203 directly on the charge injection prevention layer 203. The layer quality is strong. The lower auxiliary layer 202 and the upper auxiliary layer 204 constituting the photoconductive member 200 shown in FIG.
Auxiliary layer 1 constituting the photoconductive member 100 shown in the figure
Using the same amorphous material as in the case of 02, it is formed under similar layer formation procedures and conditions so as to provide similar properties. The charge injection prevention layer 203, the amorphous layer () 205, and the amorphous layer () 206 are also the charge injection prevention layer 103, the amorphous layer () 104, and the amorphous layer () 105 shown in FIG. It has the same characteristics and functions as those shown in FIG. Next, a method for manufacturing a photoconductive member formed by a glow discharge decomposition method will be described. FIG. 3 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method. 302, 303, 304, 305, 30 in the diagram
Gas cylinder 6 is sealed with raw material gas for forming each layer of the present invention, and as an example, 302 is SiH ₄ diluted with He.
Gas (purity 99.999%, hereinafter abbreviated as SiH ₄ /He) cylinder, 303 is B ₂ H ₆ gas diluted with He (purity
99.999%, hereinafter abbreviated as B ₂ H ₆ /He. ) cylinder, 3
04 is NH ₃ gas (99.9% purity), cylinder, 305
306 is a cylinder of SiF ₄ gas (purity 99.999%, hereinafter abbreviated as SiF ₄ /He) diluted with He, and 306 is a cylinder of C ₂ H ₄ gas (purity 99.999%). The type of gas filled in these cylinders is
Needless to say, it can be changed as appropriate depending on the type of layer to be formed. In order to flow these gases into the reaction chamber 301, valves 322 to 32 of gas cylinders 302 to 306 are used.
6. Check that the leak valve 335 is closed, and check that the inflow valves 312 to 316, the outflow valves 317 to 321, and the auxiliary valves 332 and 333 are open.
34 is opened to exhaust the reaction chamber 301 and gas piping. Next, the reading on the vacuum gauge 336 is approximately 5×
When the temperature reaches 10 ^-6 torr, the auxiliary valve 332,3
33. Close the outflow valves 317-321. Thereafter, a desired gas is introduced into the reaction chamber 301 by operating the valve of the gas pipe connected to the cylinder of the gas to be introduced into the reaction chamber 301 as prescribed. Next, an outline of an example of producing a photoconductive member having the configuration shown in FIG. 1 will be described. The valve 32 supplies SiH ₄ /He gas from the gas cylinder 302 and NH ₃ gas from the gas cylinder 304.
2,324 open and outlet pressure gauge 327,329
The pressure is adjusted to 1 Kg/cm ² , respectively, and then the inflow valves 312 and 314 are gradually opened to allow the flow into the mass flow controllers 307 and 309, respectively. Subsequently, the outflow valve 317,
319, the auxiliary valve 332 is gradually opened to allow each gas to flow into the reaction chamber 301. At this time
The openings of the outflow valves 326 and 329 are adjusted so that the ratio of the SiH ₄ /He gas flow rate to the NH ₃ gas flow rate becomes the desired value, and the vacuum gauge 336 is adjusted so that the pressure inside the reaction chamber becomes the desired value. Adjust the opening of the main valve 334 while checking the reading. Then, the temperature of the support body 337 becomes higher than that of the heater 33.
After confirming that the temperature is set in the range of 50 to 400°C by step 8, the power source 340 is set to the desired power to generate glow discharge in the reaction chamber 301 and maintain the glow discharge for the desired time. An auxiliary layer of a desired thickness is created on the support. The charge injection prevention layer can be formed on the auxiliary layer in the following manner, for example. After the formation of the auxiliary layer is completed, the power supply 340 is turned off to stop the discharge, and once the valves of the entire system of gas introduction piping of the apparatus are closed, the gas remaining in the reaction chamber 301 is discharged to the outside of the reaction chamber 301. Achieve the specified degree of vacuum. Thereafter, the valves 322 and 323 are opened to adjust the pressures of the outlet pressure gauges 327 and 328 to 1 Kg/cm ² , respectively, and the SiH ₄ /He gas is supplied from the gas cylinder 302 and the B ₂ H ₆ /He gas is supplied from the gas cylinder 303. The valves 312 and 313 are gradually opened to allow the water to flow into the mass flow controllers 307 and 308, respectively. Subsequently, the outflow valves 317, 318 and the auxiliary valve 332 are gradually opened to allow the respective gases to flow into the reaction chamber 301. Adjust the outflow valves 327 and 328 so that the ratio of the SiH ₄ /He gas flow rate and the B ₂ H ₆ /He gas flow rate at this time becomes a desired value,
Further, the opening of the main valve 334 is adjusted while checking the reading of the vacuum gauge 336 so that the pressure in the reaction chamber reaches a desired value. After confirming that the temperature of the support body 337 is set to a temperature in the range of 50 to 400°C by the heating heater 338, the power source 337
0 to a desired power to generate a glow discharge in the reaction chamber 301, and maintain the glow discharge for a predetermined time to form a charge injection prevention layer with a desired thickness on the auxiliary layer. The first amorphous layer ( ) is formed by using, for example, SiH ₄ /He gas filled in the cylinder 302 and by the same procedure as in the case of the auxiliary layer and the charge injection prevention layer described above. I can do it. In addition to SiH ₄ /He gas, Si ₂ H ₆ /He gas is also used as the raw material gas for forming the first amorphous layer (2) to improve the layer formation rate. It is valid. To form the second amorphous layer ( ) on the first amorphous layer ( ), for example, SiH ₄ /He gas filled in the cylinder 302 and
This can be carried out using the C ₂ H ₄ gas filled in 6 and following the same procedure as in the case of the auxiliary layer and the charge injection prevention layer described above. When containing halogen atoms (X) in the auxiliary layer, the charge injection prevention layer, and the first amorphous layer, the gas used to form each of the above layers may contain, for example, SiF ₄ /He. This is accomplished by further adding and feeding into the reaction chamber 301. Example 1 A layer was formed on a drum-shaped aluminum substrate under the following conditions using the manufacturing apparatus shown in FIG.

[Table] 〓

Claims (1)

[Claims] 1. A support for a photoconductive member, with silicon atoms as a matrix, and 1×10 ^-3 atomic% or more as constituent atoms,
An auxiliary layer made of an amorphous material containing up to 25 atomic% of nitrogen atoms and hydrogen atoms, and an amorphous material whose base material is silicon atoms and which contains atoms belonging to group of the periodic table as constituent atoms. A charge injection prevention layer composed of and silicon atoms as a matrix,
a first amorphous layer that is made of an amorphous material that contains at least either hydrogen atoms or halogen atoms as constituent atoms and exhibits photoconductivity; A photoconductive member comprising: a second amorphous layer made of an amorphous material containing carbon atoms and hydrogen atoms as constituent atoms.