JPH0474699B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is directed 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. [Prior Art] As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, 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.
Particularly 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 a-Si) is a photoconductive material that has recently attracted attention.
For example, German Publication No. 2746967
German Publication No. 2,855,718 describes its application as an image forming member for electrophotography, and German Publication No. 2,933,411 describes its application to a photoelectric conversion/reading device. [Problems to be Solved by the Invention] However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and optical properties such as dark resistance, photosensitivity, and photoresponsivity. Individual improvements have been made in terms of conductive properties, cyclic properties, use environment properties, stability over time, and durability, but the overall properties There is room for further improvement. For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use. When a photoconductive member is used repeatedly for a long period of time, fatigue due to repeated use may accumulate, 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 and chlorine atoms, and electromotive type Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms for control purposes, or other atoms for the purpose of improving other properties, but how these constituent atoms are contained is determined. As a result, problems may arise in the electrical, optical or photoconductive properties, use environment properties, and electrical voltage resistance of the formed layer. That is, for example, the lifespan of photocarriers generated in the photoconductive layer formed by light irradiation may not be sufficient, or the image transferred to the transfer paper may have localized areas commonly called "white spots". For example, during cleaning, there were image defects that were thought to be due to discharge breakdown phenomena, and so-called "white streaks" that were thought to be caused by the rubbing of the blade during cleaning. Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs. 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. [Means for Solving the Problems] 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 one of a hydrogen atom (H) and a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "hydrogenated amorphous silicon"] "a-Si(H,X)" is used as a generic notation for The photoconductive material produced by this method not only exhibits extremely excellent properties in practical use, but also exceeds conventional photoconductive materials in many respects, especially as a photoconductive material for electrophotography. This is based on the discovery that it has extremely excellent properties. 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 with excellent moisture resistance and no or almost no residual potential observed, and an image forming method using the same. Another object of the present invention is that when applied as an image forming member for electrophotography, it has sufficient charge retention ability during charging treatment for electrostatic image formation, and ordinary electrophotographic methods can be applied extremely effectively. An object of the present invention is to provide a photoconductive member having excellent electrophotographic properties and an image forming method using the same. Still another object of the present invention is to provide high density images with no image defects or blurring during long-term use.
It is an object of the present invention to provide a photoconductive member for electrophotography that can easily produce high-quality images with clear halftones and high resolution, and an image forming method using the same. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide a photoconductive member having high signal-to-noise ratio characteristics and high voltage resistance, and an image forming method using the same. A first aspect of the present invention is to provide a support for a photoconductive member, and an amorphous material provided on the support and having silicon atoms as a matrix and at least one of hydrogen atoms and halogen atoms as a constituent element. a first layer region that exhibits photoconductivity and is made of a material; a second layer region that is made of an amorphous material whose constituent elements are silicon atoms, carbon atoms, and hydrogen atoms;
an amorphous layer having in order from the support side, the first layer region has atoms belonging to group 3 of the periodic table as constituent atoms whose distribution concentration is continuous in the layer thickness direction and the support Carbon atoms are contained in a distribution state in which a portion is raised toward the body side and a portion is considerably lower on the second layer region side than on the support side, and carbon atoms are contained in the second layer region. It is a photoconductive material characterized by containing up to 60 atomic percent. Further, a second aspect of the present invention provides a support for a photoconductive member, and a non-containing material provided on the support that has a silicon atom as a matrix and at least one of a hydrogen atom and a halogen atom as a constituent element. A first layer region showing photoconductivity made of a crystalline material, and a second layer region made of an amorphous material whose constituent elements are silicon atoms, carbon atoms, and hydrogen atoms. an amorphous layer having an amorphous layer in order from the support side, and the first layer region has atoms belonging to Group Group of the Periodic Table as constituent atoms whose distribution concentration is continuous in the layer thickness direction and the first layer region has an amorphous layer having an amorphous layer in order from the support side. The carbon atoms are contained in a distribution state in which the carbon atoms have a higher portion on the side of the second layer region and a portion that is considerably lower on the second layer region side than on the support side, and the carbon atoms are contained in the second layer region. Using a photoconductive member containing up to 60 atomic percent, the photoconductive member is charged, the structure is irradiated to form a latent image, and the latent image is developed with a developer to form a developed image. In this image forming method, the developed image is transferred to a recording member to form a transferred image, and then the surface of the photoconductive member is cleaned. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic diagram showing the structure of a photoconductive member according to the present invention. A photoconductive member 100 shown in FIG. 1 has an amorphous layer 102 on a support 101 for photoconductive member.
is provided, and the amorphous layer 102 is a-Si
(H, up to atomic %, with a lower limit usually of 1×10 ^-3 atomic %, i.e. C/
It has a layer structure consisting of a second layer region 104 containing carbon atoms in an amount range such that the value of (C+Si+H) is from 1×10 ^-3 atomic % to less than 30 atomic % in %. 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. . 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, Ni, Cr,
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 above metal. , imparts conductivity to its surface. The shape of the support body is cylindrical,
The photoconductive member 100 shown in FIG. 1 may be used as an image forming member for electrophotography, for example, if the photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member. In the case of copying, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. 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. In the present invention, in order to effectively achieve the purpose, an amorphous layer 10 is formed on a support 101.
The first layer region 103 constituting a part of the semiconductor device 2 has the semiconductor properties shown below and is composed of a-Si (H, p-type a-Si(H,X)...Contains only acceptor. Alternatively, one that contains both a donor and an acceptor and has a high relative concentration of acceptor. p ^- type a-Si(H,X)... type with low acceptor concentration (Na) or low acceptor relative concentration. n-type a-Si(H,X)...Contains only a donor. Or one that contains both donor and acceptor and has a high relative concentration of donor. n ^- type a-Si(H,X)... type with low donor concentration (Na) or low relative acceptor concentration. i-type a-Si(H,X)...NaNdO,
Or NaNd ones. In the present invention, the halogen atoms (X) contained in the first layer region 103 are preferably F, Cl,
Br and I, with F and Cl being particularly desirable. In the present invention, to form the first layer region 103 composed of a-Si (H, Adopted. For example, by the glow discharge method, a
-First layer region 103 composed of Si (H, X)
Basically silicon atoms (Si) to form
A source gas for introducing hydrogen atoms (H) and/or a source gas for introducing halogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure, along with a source gas for supplying Si that can supply Si. A glow discharge is generated, and a
A layer consisting of -Si(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. As the raw material gas for supplying Si used in the present invention, silicon hydride (silanes) in a gaseous state or that can be gasified such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ is effective. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of layer preparation work and good Si supply efficiency. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Furthermore, silicon compounds containing halogen atoms, which are in a gaseous state or can be made into a gas, and which have silicon atoms and halogen atoms as constituent elements can be cited as effective in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride gas is used as a raw material gas capable of supplying Si. Even if you don't,
A layer made of a-Si containing halogen atoms as a constituent element can be formed on a predetermined support. When manufacturing a layer containing halogen atoms according to the glow discharge method, basically, silicon halide gas, which is the raw material gas for supplying Si, and gases such as Ar, H ₂ , He, etc. are mixed at a predetermined mixing ratio. These gases are introduced into the deposition chamber forming the first layer region at a flow rate of 1
However, in order to introduce hydrogen atoms, a predetermined amount of a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. To form a layer made of a-Si (H, Sputtering in a plasma atmosphere,
In the case of the ion plating method, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is subjected to resistance heating,
Alternatively, it can be carried out by heating and evaporating by an electron beam method (EB method) or the like and passing the flying evaporated material through a predetermined gas plasma atmosphere. At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to introduce the gas to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or a gas such as the above-mentioned silica, is introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gas. Just do it. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for introducing halogen atoms, but in addition, HF, HCl, HBr,
Hydrogen halides such as HI, SiH ₂ F ₂ , SiH ₂ I ₂ ,
Halogenated halogenated silicon hydrides such as SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ and the like, which are in a gaseous state or can be gasified and have a hydrogen atom as one of their constituents, are also effective as the first material. Mention may be made as starting materials for forming the layer region. These halides containing hydrogen atoms are suitable in the present invention because hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer at the same time as halogen atoms are introduced into the layer during layer formation. It is used as a raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the layer, in addition to the above, silicon hydride gas such as H ₂ or SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc. can be added to Si. This can also be carried out by causing discharge to occur by coexisting in the deposition chamber with a silicon compound for supply. For example, in the case of the reactive sputtering method, Si
Using a target, a gas for introducing halogen atoms and H ₂ gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere, and the Si target is sputtered. As a result, a layer made of a-Si(H,X) is formed on the substrate. Furthermore, a gas such as B ₂ H ₆ can also be introduced for doping with impurities. In the present invention, the first photoconductive member to be formed
The amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms contained in the layer region is usually 1 to 40 at%, preferably 5 to 30
Preferably, it is expressed as atomic percent. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the layer, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X) can be controlled. What is necessary is to control the amount of starting materials used in the deposition system introduced into the deposition system, the discharge force, etc. In the present invention, a so-called rare gas, such as He,
Suitable examples include Ne and Ar. In order to achieve the desired semiconductor properties of the first layer region 103, the amount of n-type impurity, p-type impurity, or both impurities is added to the formed layer during the formation of the layer. This is achieved by controlling and doping. Suitable examples of such impurities include atoms belonging to the periodic table group as p-type impurities, such as B, Al, Ga, In, Tl, etc., and as n-type impurities, atoms belonging to the periodic table group are listed. Atoms belonging to the group, such as N, P, As,
Preferred examples include Sb, Bi, etc., and B, Ga, P, Sb, etc. are particularly suitable. In the present invention, in order to have the desired conductivity type, the first
The amount of impurities to be doped into the layer region 103 is appropriately determined depending on the desired electrical and optical properties, but in the case of impurities belonging to Group 3 of the periodic table, the amount of impurities doped is 3×10 ⁴ atomic ppm or less. Doping may be carried out within a range of amounts, and in the case of impurities belonging to Group 3 of the periodic table, doping may be carried out within a range of 5×10 ³ atomic ppm or less. In order to dope impurities into the first layer region 103, a raw material for impurity introduction is introduced in a gaseous state into the deposition chamber together with the main raw material for forming the first layer region 103 during layer formation. good. As the raw material for introducing such impurities, 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 impurities include PH ₃ , P ₂ H ₄ , PF ₃ , PF ₅ , PCl ₃ , AsH ₃ ,
AsF ₃ , AsF ₅ , AsCl ₃ , SbH ₃ , SbF ₃ , SbF ₅ ,
_BiH3 , _{BF3 , BCl3} , _BBr3 , _B2H6 , _{B4H10 ,
B5H9 , B5H11} , _{B6H10 , B6H12 , B6H14 , AlCl3 ,}
Examples include GaCl ₃ , InCl ₃ , TlCl ₃ and the like. The layer thickness of the first layer region 103 is appropriately determined as desired so that photocarriers generated by irradiation with light having desired spectral characteristics are efficiently transported, and is usually 1 to 100 μm. , preferably,
It is said to be 2 to 50μ. In the present invention, atoms belonging to a group of the periodic table (hereinafter referred to as "group atoms") contained as impurities in the first layer region 103 in order to control the conductivity type and dark resistance value Atoms belonging to the table group (hereinafter referred to as "group atoms") are in the layer region 103.
is distributed substantially uniformly in a plane substantially perpendicular to the layer thickness direction (plane parallel to the surface of the support 101), but the distribution state is uneven in the layer thickness direction. It is considered uniform. Furthermore, in order to more effectively increase the dark resistance and improve the electric withstand voltage characteristics of the amorphous chamber layer 102 as a whole, the above-mentioned impurities are added to the support 102.
It is desirable that the material be contained in the first layer region 103 so as to form a non-uniform distribution state in which the material is distributed more toward the 01 side. Particularly when applied to electrophotography, the group atoms include boron (B) and gallium (Ga), and the group atoms include especially the neighboring atoms (P), as mentioned above. It is preferable to contain it in a uniform distribution. Further, the impurity contained in the first layer region 103 may be continuously contained in the entire region in the layer thickness direction of the layer region 103,
Further, it may be contained partially in the layer thickness direction. Next, in the present invention, a typical example in which the impurity is contained in the first layer region 104 in a non-uniform distribution state in the layer thickness direction will be explained. In order to simplify the explanation, the impurities are explained using group atoms, and the layer regions shown in the drawings are only the layer regions containing the group atoms. That is, the layer region ( ) shown in the drawing for explaining the distribution state of impurities below may be equal to the entire region of the first layer region 103 , or may be equal to the entire region of the first layer region 103 . It may be considered a part of it. , however, first layer region 1
The impurities contained in 03 are preferably contained in such a way that the layer region ( ) includes the end layer region of the first layer region 103 on the side of the support 101 . 2 to 10 show typical examples of the distribution state of group group atoms in the layer thickness direction contained in the layer region ( ) constituting the first layer region 103 of the photoconductive member in the present invention. shown. In Figures 2 to 10, the horizontal axis represents the content C of group atoms, the vertical axis represents the layer thickness of the layer region () containing group atoms, and _tB represents the interface on the support side. t _T indicates the position of the interface on the opposite side from the support side. That is, in the layer region () containing group atoms, the layer is formed from the t _B side toward the t _T side. In the present invention, the layer region ( ) containing group atoms may be made of a-Si (H, X) and occupy the entire layer region of the first layer region 103 exhibiting photoconductivity. , or may occupy a part of it. In the present invention, when the layer region () occupies a part of the layer region of the first layer region 103, as shown in the example of FIG. Preferably, it is provided in the lower layer region of region 103. FIG. 2 shows a first typical example of the distribution state of group atoms contained in the layer region ( ) in the layer thickness direction. In the example shown in FIG. 2, the content concentration of group atoms is from the interface position t _B to the position t ₁ where the surface where the layer region containing group atoms is formed and the surface of the layer region contact. While C takes a constant value of _C1 , it is contained in the layer region where group atoms are formed, and the position
From t ₁ onwards, the concentration C ₂ is gradually and continuously reduced until reaching the interface position t _T . At the interface position _tT , the concentration C of group atoms is _C3 . In the example shown in FIG. 3, the concentration C of the group atoms contained gradually and continuously decreases from the concentration C ₄ from position t _B to position t _T , and at position t _T the concentration C A distribution state of ₅ is formed. In the case of Fig. 4, the concentration C of group atoms is constant at the concentration C ₆ from position t _B to position t ₂ ;
Between the position t ₂ and the position t _T , the content concentration C is gradually and continuously decreased, and at the position t _T , the content concentration C is substantially zero. In the case of FIG. 5, the concentration of group atoms is gradually reduced from the concentration C ₈ from position t _B to position t _T , and is substantially zero at position t _T. At zero shown in FIG. 6, the concentration C of group atoms is between the position t _B and the position t ₃ , the concentration C ₉
is a constant value, and the concentration is _C10 at position _tT . Between the position t ₃ and the position t _T , the content concentration C is linearly decreased from the position t ₃ to the position t _T . At zero shown in Figure 7, from position t _B to position t ₄ , the concentration C takes a constant value of C ₁₁ , and from position t ₄ to position t _T , the concentration decreases linearly from C ₁₂ to C ₁₃ . It is said that the distribution state is as follows. In the example shown in FIG. 8, from position t _B to position t _T
Until , the concentration C of group atoms is the concentration C ₁₄
It decreases in a linear manner as it approaches zero. In FIG. 9, from position t _B to position t ₅ , the concentration C of group atoms is linearly decreased from concentration C ₁₅ to concentration C ₁₆ , and from position t ₅ to position t _T
An example is shown in which the concentration C ₁₆ is set to a constant value. In the example shown in FIG. 10, the concentration C of group atoms is C ₁₇ at position t _B ;
Until reaching position t ₆ , the concentration is first slowly decreased from this concentration C ₁₇ , and around the position t ₆ , it is rapidly decreased to the concentration C ₁₈ at position t ₆ . Between position t ₆ and position t ₇ , the concentration is decreased rapidly at first, then slowly and gradually decreased to reach C ₁₉ at position t ₇ , and then between position t ₇ and position t ₈ Then, the concentration decreases very slowly and reaches the concentration C ₂₀ at position t ₈ . Between position _t8 and position _tT , the concentration is reduced from _C20 to substantially zero according to a curve shaped as shown in the figure. As described above with reference to FIGS. 2 to 10, some typical zeros of the distribution state of group atoms contained in the layer region ( ) in the layer thickness direction, in the present invention, on the support side , a distribution state of group atoms was formed, which had a part where the content concentration C of group atoms was high, and had a part where the content concentration C was considerably lower on the interface _tT side than on the support side. Preferably, a layer region ( ) is provided in the first layer region 103 . In a more preferred embodiment of the present invention, the layer region ( ) containing group atoms constituting the amorphous layer contains group atoms at a relatively high concentration toward the support side, as described above. It has a localized region A. If the localized region A is explained using the symbols shown in FIGS. 2 to 10, it is preferable that the localized region A be provided within 5 μm from the interface position t _B. In the present invention, the localized region A may be the entire layer region L _T up to 5 μm thick from the interface position t _B , or may be a part of the layer region L _T. Whether the localized region A is a part or all of the layer region L _T is determined as appropriate depending on the characteristics required of the amorphous layer to be formed. Localized region A is a distribution state of group atoms contained therein in the layer thickness direction, and the maximum Cmax of the content distribution value (concentration distribution value) of group atoms is usually 50 atomic ppm or more with respect to silicon atoms. , preferably 80 atoms
It is desirable that the layer be formed in such a manner that a distribution state of at least ppm, optimally at least 100 atomic ppm, can be achieved. That is, in a preferred embodiment of the present invention, the layer region () containing group atoms has the maximum content distribution within 5 μm of layer thickness from the support side (layer region of 5 μm thickness from t _B ). is formed such that there is a value Cmax. In the present invention, the content of group atoms contained in the layer region () containing group atoms is appropriately determined as desired so that the object of the present invention is effectively achieved. However, the first
The amount of silicon atoms constituting the layer region 103 is usually 1 to 3×10 ⁴ atomic ppm, preferably 2 to 500 atomic ppm, and optimally 3 to 200 atomic ppm. be. In the case of group atoms, the distribution state can be such that Cmax is usually 50 atomic ppm or more, preferably 80 atomic ppm or more, and optimally 100 atomic ppm or more relative to silicon atoms. Preferably, it is layered. In addition, the content of group atoms contained in the layer region ( ) [corresponding to the layer region () described above] containing group atoms should be set such that the purpose of the present invention can be effectively achieved. It can be determined as appropriate according to your wishes, but
The amount of silicon atoms constituting the first layer region 103 is usually 1 to 5×10 ³ atoms ppm,
The content is preferably 1 to 300 atomic ppm, most preferably 1 to 200 atomic ppm. Most of the layer configuration examples of the first layer region described above have a region in which group atoms or the concentration distribution of group atoms gradually changes in the layer thickness direction. This is particularly effective in increasing the mechanical strength and repeated use characteristics of the layer. In the photoconductive member 100 shown in FIG. 1, a second layer region 104 formed on the first layer region 103 has a free surface 105 and is particularly moisture resistant.
It is provided in order to achieve the objectives of the present invention in terms of continuous repeated use characteristics, pressure resistance, usage environment characteristics, and durability. Further, in the present invention, the first layer region 103 and the second layer region 104 constituting the amorphous layer 102
Since each of the amorphous materials forming the two has a common constituent element of silicon atoms, chemical stability is sufficiently ensured at the laminated interface. The second layer region 104 is made of an amorphous material [a-
(Si _x C _1-x ) _y H _1-y , however, 0.5≦x≦0.99999, 0.6≦y
≦0.99]. The second layer region 104 composed of a-(Si _x C _1-x ) _y :H _1-y can be formed by glow discharge method, sputter rig method, ion implantation method, ion plating method, or electron beam method. This is accomplished by law, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, the level of equipment capital investment, manufacturing scale, and the desired characteristics of the photoconductive member to be produced. It is relatively easy to control the production conditions for producing a photoconductive member having a photoconductive member, and it is easy to introduce carbon atoms and hydrogen atoms together with silicon atoms into the second layer region to be produced. A discharge method or a sputtering method is preferably employed. Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same equipment system to achieve the second
The layer region 104 may be formed. To form the second layer region 104 by the glow discharge method, a source gas for forming a-(Si _x C _1-x ) _y :H _1-y is mixed with a dilution gas in a predetermined amount as necessary. The gas is mixed at a mixing ratio of 1,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000. A-(Si _x C _1-x ) _y :H _1-y may be deposited on the first layer region 103 that has been formed. 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 X as a constituent atom. Alternatively, most gasified substances can be used. When using a raw material gas containing Si as one of Si, C, and X, 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 Alternatively, an atomic gas containing Si as a constituent atom and a raw material gas containing C and X as constituent atoms may be mixed at a desired mixing ratio. or a raw material gas containing Si as a constituent atom,
It is possible to use a mixture of a raw material gas whose constituent atoms are Si, C, and X. Alternatively, a raw material gas containing Si and X as constituent atoms may be mixed with a raw material gas containing C as constituent atoms. In the present invention, gases effectively used as raw material gases for forming the second layer region 104 include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H whose constituent atoms are Si and H. Silicon hydride gas such as silanes such as No. ₁₀ , saturated hydrocarbons having 1 to 4 carbon atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and 2 to 4 carbon atoms. -3 acetylenic hydrocarbons and the like. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n _{- C4H1O} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
As propylene (C ₃ H ₆ ), 1-butene (C ₄ H ₈ ), 2-butene (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁ O), acetylenic hydrocarbons teeth,
Acetylene (C ₂ H ₂ ), Methylacetin (C ₃ H ₄ )
Examples include butyne (C ₄ H ₆ ). Examples of the source gas containing Si, C, and H as constituent atoms include alkyl silicides such as Si(CH ₃ ) 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. The second layer region 10 is formed by a sputtering method.
4, target a single crystal or polycrystalline Si wafer or 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, Si and C may be used as separate targets, or by using a single mixed target of Si and C, or by sputtering in a gas atmosphere containing at least hydrogen atoms. used. 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. are preferable as the diluent gas used when forming the second layer region 104 by the glow discharge method or the sputtering method. It can be mentioned as. The second layer region 104 in the present invention is carefully formed to provide the desired properties. That is, a substance whose constituent atoms are Si, C, and H is
Depending on the manufacturing conditions, the structure can range from crystalline to amorphous, and the electrical properties can vary from conductive to semiconductive to insulating, and from photoconductive to non-photoconductive. The properties between
Accordingly, 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. . For example, to provide the second layer region 104 with the main purpose of improving electrical thickness resistance, a-(Si _x C _1-x ) _y
H _1-y is created as an amorphous material with remarkable electrically insulating behavior in the environment of use. In addition, when the second layer region 104 is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the degree of electrical insulation is relaxed to a certain extent, and it has a certain degree of resistance to the irradiated light. A-Si _x C _1-x is created as a sensitive amorphous material. a−(Si _x C _1-x ) _y on the surface of the layer region 103 in FIG.
When forming the second layer region 104 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, and in the present invention, 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 optimum range of the support temperature when forming the second layer region 104 is selected as appropriate in accordance with the method of forming the second layer region 104. The second layer region 104 is formed at a temperature of 100°C to 300°C.
The temperature is preferably 150°C to 250°C. The second layer region 104 can be formed using the glow discharge method because it is relatively easy to finely control the composition ratio of atoms constituting the layer and control the layer thickness compared to other methods. Adoption of the sputtering method is advantageous, but when forming the second layer region 104 using these layer forming methods, the discharge power and gas pressure during layer formation as well as the support temperature described above must be adjusted. is one of the important factors that influences the characteristics of 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 are usually ,
It is desirable that the power be 10 to 300W, preferably 20 to 200W. The gas pressure inside the deposition chamber is usually 0.01 to 1 Torr,
Preferably, it is about 0.1 to 0.5 Torr. In the present invention, the values of the support temperature and discharge power for forming the second layer region 104 are preferably within the ranges described above, but these layer forming factors are independently and separately determined. The optimum value of each layer formation factor is determined based on the mutual organic relationship so that the second layer region 104 consisting of a-Si _x C _1-x with desired characteristics is formed. is desirable. Second layer region 10 in the photoconductive member of the present invention
Similar to the conditions for forming the second layer region 104, the amounts of carbon atoms and hydrogen atoms contained in the second layer region 104 are important to ensure that the second layer region 104 has the desired characteristics that achieve the object of the present invention. This is a significant factor. The amount of carbon atoms contained in the second layer region 104 in the present invention is usually the above numerical value, but
Usually 1×10 ^-5 atomic% to 30 atomic%, preferably 1
It is desirable that the content be ~30 at%, optimally 10 to 30 at%. The content of hydrogen atoms is usually 1 to 40 at%, preferably 2 to 35
It is desirable that the hydrogen content be in the range of 5 to 30 atomic %, and the photoconductive member formed when the hydrogen content is in this range is considered to be excellent in practical applications. It's something you get. That is, if expressed as a-(Si _x C _1-x ) _y :H _1-y above, x is usually 0.5 to 0.99999, preferably 0.5 to 0.99,
Optimally 0.5-0.9, y typically 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 layer region 104 in the present invention is appropriately determined according to the initial purpose so as to effectively achieve the purpose of the present invention. Furthermore, the layer thickness of the second layer region 104 is also determined based on the organic relationship according to the characteristics required for each layer region in relation to the layer thickness of the first layer region 103. It needs to be determined as appropriate according to desire. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production. In the present invention, the layer thickness of the second layer region 104 is usually 0.01 to 10μ, preferably 0.02 to 5μ, and most preferably 0.04 to 5μ. The layer thickness of the amorphous layer of the photoconductive layer member 100 in the present invention is appropriately determined according to the purpose of application to a reading device, an imaging device, an electrophotographic image forming member, etc. Ru. In the present invention, the layer thickness of the amorphous layer 102 is as follows:
The first layer region 102 and the second layer region 1 are arranged so that the characteristics imparted to the first layer region 102 and the second layer region 104 are effectively utilized and the object of the present invention is effectively achieved.
03, and is preferably determined as desired in relation to the layer thickness of the second layer region 10.
It is preferable that the layer thickness of the first layer region 102 is several hundred to several thousand times greater than the layer thickness of No. 4. The specific value of the layer thickness of the amorphous layer 102 is as follows:
Usually 3~100μ, preferably 5~70μ, optimally 5~
It is desirable that it be in the range of 50μ. Next, a method for manufacturing a photoconductive member formed by a glow discharge decomposition method will be described. FIG. 11 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method. 1102, 1103, 1104, 110 in the diagram
The raw material gas for forming each layer of the present invention is sealed in the gas cylinder No. 5,1106,
As an example, 1102 is SiH ₄ gas diluted with He (purity 99.999%, hereinafter referred to as SiH ₄ /He
It is abbreviated as ) cylinder, 1103 diluted with He
B ₂ H ₆ gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ /He) cylinder, 1104 is Si ₂ H ₆ diluted with He
Gas (purity 99.99%, hereinafter abbreviated as Si ₂ H ₆ /He) cylinder, 1105, SiF ₄ gas diluted with He (purity 99.999% or less, abbreviated as SiF ₄ /He) cylinder, 11
06 is a C ₂ H ₄ gas cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
2-1126, make sure the leak valve 1135 is closed, and also check that the inlet valve 1112
~1116, confirming that the outflow valves 1117~1121 and auxiliary valves 1132~1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and gas piping. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ⁻⁶ Torr, the auxiliary valves 1132 to 1133 and the outflow valves 1117 to 1121 are closed. To give an example of forming the first layer region on the basic cylinder 1137, the gas cylinder 110
SiH ₄ /He gas from 2, from gas cylinder 1103
B ₂ H ₆ /He gas, open valves 1122, 1123, and reduce the pressure of outlet pressure gauges 1127, 1128 to 1
Adjust to Kg/cm ² , inflow valve 1112, 1113
Gradually open the mass flow controller 110.
7,1108. Subsequently, the outflow valves 1117 and 1118 and the auxiliary valve 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. SiH ₄ /He gas flow rate at this time, B ₂ H ₆ /
Adjust the outflow valves 1117 and 1118 so that the He gas flow ratio becomes the desired value, and adjust the main valve 1134 while watching the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 becomes the desired value. Adjust the aperture. After confirming that the temperature of the substrate cylinder 1137 is set to, for example, 50 to 400°C by the heating heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. A first layer region is formed on the base cylinder 1137. When the first layer region contains halogen atoms, for example, SiF ₄ /He is further added to the above gas and the mixture is fed into the reaction chamber. Needless to say, all outflow valves for gases other than those required for forming each layer are closed, and
When forming each layer, the gas used to form the previous layer is released into the reaction chamber 1101 and through the outflow valves 1117 to 1.
121 is closed, auxiliary valves 1132 and 1133 are opened, and main valve 1134 is fully opened to temporarily evacuate the system to a high vacuum, as necessary. Also, during layer formation, the base cylinder 1137 is operated by the motor 11 in order to ensure uniform layer formation.
39 to rotate at a constant speed. Examples will be described below. Example 1 A layer was formed on a drum-shaped aluminum substrate using the manufacturing apparatus shown in FIG. 11 under the following conditions.

[Table] The substrate temperature is 250℃ and the discharge frequency is 13.56M.
Hz, the reaction chamber pressure during the formation of the first layer region is
0.5Torr, the pressure inside the reaction chamber when forming the second layer region is
Film formation was performed at 0.2 Torr. The thus obtained sensitive drum was placed in a copying machine, corona charged at 5 KV for 0.2 seconds, and a light image was irradiated. A tungsten lamp was used as the light source, and the light intensity was 1.0 lux·sec. The latent image was developed with a charged developer (containing toner and carrier) and transferred with the usual additions, but the transferred image was very good. Toner remaining on the photosensitive drum without being transferred is cleaned by a rubber blade, and the toner is moved to the next copying process. Even after repeating this process over 100,000 times, no image deterioration was observed. Example 2 When forming the second region layer, the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas was changed to change the content ratio of silicon atoms and carbon atoms in the second region layer. Layer formation was carried out in exactly the same manner as in Example 1. As a result, the following results were obtained.

[Table] ○ Very good △ Some image defects may occur Example 3 Except for changing the film thickness of the second region layer as shown below.
Layer formation was carried out in exactly the same manner as in Example 1. The results of the evaluation are shown in the table below.

【table】

[Table] [Effects of the Invention] The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the problems described above, and has extremely excellent electrical and optical properties. , photoconductive properties, durability and use environment properties. 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 and is excellent in light fatigue resistance, repeated use characteristics, moisture resistance, and pressure resistance, so it can stably produce high-quality images with high density, clear halftones, and high resolution. can be repeated.

[Brief explanation of the drawing]

FIG. 1 is a schematic layer configuration diagram for explaining one layer configuration of a preferred embodiment of the photoconductive member of the present invention, and FIGS. 2 to 10 each constitute an amorphous layer. . Explanatory diagram for explaining the distribution state of group atoms in a layer region containing group atoms, No. 11
The figure is a schematic explanatory diagram of an apparatus for manufacturing the photoconductive member of the present invention. 100...Photoconductive member, 101...Support, 1
02...Amorphous layer, 103...First layer region, 1
04...Second layer region, 105...Free surface.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member, and an amorphous material provided on the support that has silicon atoms as a matrix and at least one of hydrogen atoms and halogen atoms as a constituent element. A first layer region exhibiting photoconductivity and a second layer region composed of an amorphous material containing silicon atoms, carbon atoms, and hydrogen atoms in order from the support side. the first layer region has atoms belonging to group 3 of the periodic table as constituent atoms whose distribution concentration is continuous in the layer thickness direction and is higher toward the support side. The carbon atoms are contained in a distribution state in which the second layer region side has a considerably lower portion than the support side, and the carbon atoms are contained up to 60 atom % in the second layer region. A photoconductive member characterized by: 2 The atoms belonging to Group 3 of the periodic table are B,
The photoconductive member according to claim 1, which is made of Al, Ga, In, and Tl. 3. The photoconductive member according to claim 1, wherein the second layer region has a layer thickness of 0.01μ to 10μ. 4. A support for a photoconductive member, and a photoconductive material provided on the support and made of a non-crystalline material having a silicon atom as a matrix and at least one of a hydrogen atom and a halogen atom as a constituent element. an amorphous layer having, in order from the support side, a first layer region having a first layer region and a second layer region made of an amorphous material having silicon atoms, carbon atoms, and hydrogen atoms as constituent elements The first layer region has a portion in which the distribution concentration of atoms belonging to Group 3 of the periodic table as constituent atoms is continuous in the layer thickness direction and is higher toward the support side. A photoconductive material containing carbon atoms in a distribution state with a portion that is considerably lower on the side of the second layer region than on the side of the support, and that carbon atoms are contained up to 60 at % in the second layer region. charging the photoconductive member using a member, irradiating the structure to form a latent image, developing the latent image with a developer to form a developed image, and transferring the developed image to a recording member. An image forming method characterized in that the surface of the photoconductive member is cleaned after forming the transferred image.