JPS6261270B2 - - 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.)
The present invention relates to photoconductive members for electrophotography that are sensitive to electromagnetic waves such as. 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,
It has a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], has absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, and has a desired dark resistance value. Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use and being able to easily dispose of afterimages within a desired time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on this point, amorphous silicon (hereinafter referred to as A-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion/reading device is described in DE 2933411. However, conventional photoconductive members made of A-Si and having photoconductive layers have excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and stability over time, which requires a comprehensive improvement in characteristics. For example, when applied to electrophotographic image forming members, when attempting to achieve high light sensitivity and high dark resistance at the same time, it has often been observed that residual potential remains during use, and such photoconductive When a member is repeatedly used for a long period of time, fatigue due to repeated use accumulates, resulting in a so-called ghost phenomenon in which an afterimage occurs. For example, according to many experiments conducted by the present inventors, A-Si as a material constituting the photoconductive layer of an electrophotographic image forming member is superior to conventional photoconductive materials such as Se, CdS, ZnO, PVCz, and TNF. The electrophotographic imaging member has a photoconductive layer with a single layer structure made of A-Si, which has many advantages over electric materials, and has properties suitable for use in conventional solar cells. Even if the conductive layer is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast, making it difficult to apply ordinary electrophotography, and the above tendency is remarkable in a humid atmosphere. It has been found that there are some problems that can be solved, such as in some cases, it is almost impossible to retain the electrostatic charges until the development time. Furthermore, A-Si materials can be impregnated with hydrogen atoms or halogen atoms such as fluorine atoms or chlorine atoms to improve their electrical and photoconductive properties, and boron atoms or phosphorus atoms to control their electrical conductivity. However, depending on how these constituent atoms are contained, problems may arise in the mechanical properties when the layer is formed. There are cases. In other words, in the case of electrophotographic image forming members, an A-Si layer is usually formed on a cylindrical support made of a metal material such as aluminum, but the extent of the layer depends on the conditions for forming the layer. However, due to the magnitude of its strain characteristics, inconveniences such as the layer cracking, floating off the support, or the entire layer peeling off occur in many cases. In addition, the normal A-Si layer itself generally does not exhibit very good adhesion properties to supports made of metal materials such as aluminum, and therefore there are problems with long-term repeated use characteristics. There is also the problem that good electrical contact between the support and the A-Si layer cannot be easily formed due to changes over time. Therefore, while efforts are being made to improve the properties of the A-Si material itself, it is also necessary to take measures to obtain the desired electrical, optical, and photoconductive properties as described above when designing photoconductive members. There is. The present invention has been made in view of the above points, and
-As a result of intensive and comprehensive research on Si from the viewpoint of its applicability and applicability as a photoconductive member used as an electrophotographic image forming member,
Amorphous materials having silicon atoms as a matrix and containing at least either hydrogen atoms (H) or halogen atoms (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon,
Or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "A-Si (H,
A photoconductive member for electrophotography designed and created to have a specific layer structure of a photoconductive member for electrophotography having a photoconductive layer composed of “ It was discovered that the material not only shows the characteristics of the photoconductive material used in electrophotography, but also that it is superior in all respects to conventional photoconductive materials, especially as a photoconductive material for electrophotography. Based on. The electrical, optical, and photoconductive properties of the present invention are always stable, and it is an all-environment type that is hardly controlled by the usage environment.It is extremely resistant to light fatigue and does not cause deterioration even when used repeatedly. Excellent durability,
The main object of the present invention is to provide a photoconductive member for electrophotography in which no or almost no residual potential is observed. 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 processing for electrostatic image formation, and ordinary electrophotographic methods can be applied extremely 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. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide a photoconductive member for electrophotography that has high adhesion and good electrical contact with a support. The photoconductive member for electrophotography of the present invention exhibits photoconductivity and is composed of a support for electrophotography and an amorphous material having silicon atoms as a matrix and containing at least one of hydrogen atoms and halogen atoms. an amorphous layer, the amorphous layer containing nitrogen atoms and atoms belonging to group 3 of the periodic table; and an upper layer region, and the nitrogen atoms are contained only in the lower layer region over the entire region, and the atoms belonging to the group of the periodic table are contained at least in the lower layer region. characterized by things. 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, and photoconductive properties and a usage environment. Show characteristics. In particular, when applied as an image forming member for electrophotography, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, has stable electrical properties, and has high sensitivity. It has a high signal-to-noise ratio and is extremely good in light fatigue resistance, repeated use characteristics, especially in a humid atmosphere, and has high density, clear halftones, and high resolution. A quality visible image can be obtained. DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic photoconductive member of the present invention will be described in detail below with reference to the drawings. FIGS. 1a to 1c are schematic structural diagrams schematically shown to explain the layer structure of a photoconductive member according to each embodiment of the present invention. The photoconductive member 100 shown in FIGS. 1a to 1c is an A-Si
Amorphous layer 1 with photoconductivity consisting of (H,X)
02, the amorphous layer 102 has a lower layer region 103 containing nitrogen atoms as constituent atoms over its entire region, and a layer containing atoms of Group Group of the Periodic Table over its entire region as constituent atoms. It has a layered structure configured to have a region 104. The lower layer region 103 is designed to have high dark resistance and improved adhesion by containing nitrogen atoms, and the upper layer region 105 is designed to have high sensitivity without containing nitrogen atoms. There is. The amount of nitrogen atoms contained in the lower layer region 103 is determined as desired depending on the characteristics required of the photoconductive member to be formed, but is usually 0.01 to 20 atomic%, preferably 0.02 to 20 atomic%. 7atomic%, optimally 0.03-3atomic
% is preferable. Similarly to the amount of nitrogen atoms, the amount of atoms of Group Group of the Periodic Table contained in the layer region 104 is determined as desired, and is usually 0.01 to 5×10 ^{4 .} atomic ppm, preferably 1
~100 atomic ppm, more preferably 3~
It is desirable that the content be 20 atomic ppm. The layer thicknesses of the lower layer region 103 and the upper layer region 105 are:
As this is one of the important factors for effectively achieving the object of the present invention, sufficient care must be taken when designing the photoconductive member so that the formed photoconductive member has sufficient desired characteristics. needs to be paid. In the present invention, the layer thickness of the lower layer region 103 is closely related to the layer thickness of the amorphous layer 102 itself. The layer thickness of the lower layer region 103 is usually 3 to 100μ,
The thickness is preferably 5 to 50μ, most preferably 7 to 30μ. In addition, the layer thickness of the upper layer region 105 is usually as follows:
0.02-10μ, preferably 0.03-5μ, optimally
It is desirable that the thickness be 0.05 to 2μ. In the photoconductive member of the present invention, as shown in FIG. Alternatively, as shown in FIG. 1B, the upper layer region 105 may not contain group atoms and the lower layer region 103 and the layer region 104 may be made into the same layer region. In a photoconductive member according to an embodiment in which the upper layer region 105 does not contain group atoms, in particular,
It exhibits remarkable characteristics when used repeatedly in a humid atmosphere, and exhibits sufficient durability for long-term use in such an atmosphere. Further, as shown in FIG. 1c, a case where a layer region 104 is formed within the lower layer region 103 can also be cited as one of the preferred embodiments. Furthermore, in the present invention, an intermediate layer made of a metal oxide such as Al ₂ O ₃ and acting as an electrical barrier may be provided between the support 101 and the lower region 103. In the present invention, atoms belonging to group of the periodic table contained in the layer region 104 include B, Al, Ga, In, and Tl, and in particular, B,
Ga may be used as preferred. The support may be electrically conductive or electrically insulating. As the conductive support, for example,
NiCr, stainless steel, Al, Cr, Mo, Au, Nb,
Examples include metals such as Ta, V, Ti, Pt, and 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, Ni on the surface,
Cr, Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti,
Conductivity is imparted by providing a thin film made of Pt, 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,
A thin film of metal such as Ni, 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. This imparts conductivity to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is to be used as an electrophotographic image forming member, 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, from the viewpoint of manufacturing and handling of the support and mechanical strength, the thickness is usually set to 10μ or more. In the present invention, specific examples of the halogen atom (X) contained in the amorphous layer as necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as such. In the present invention, for example, glow discharge method,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon, such as a sputtering method or an ion plating method. For example, A-Si
To form an amorphous layer composed of (H,X), basically silicon atoms (Si) can be supplied.
Together with the raw material gas for supplying Si, the raw material gas for introducing hydrogen atoms (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 on a predetermined support surface that has been placed in a predetermined position in advance.
A layer consisting of -Si(H,X) may be formed.
In addition, when forming by a sputtering method, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. The raw material gas for supplying Si used in the present invention includes gaseous or gasifiable silicon hydride (silanes) such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc.
are mentioned as those that can be effectively used, especially,
SiH ₄ and Si ₂ H ₆ are preferred in terms of ease of layer creation work, good Si supply efficiency, and the like. 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 Further, a silicon compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound 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 . . 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 photoconductive layer made of A-Si:X can be formed on a given support. When manufacturing an amorphous layer containing halogen atoms according to the glow discharge method, basically silicon halide gas, which is a raw material gas for supplying Si, and Ar, H ₂ ,
By introducing a gas such as He into a deposition chamber in which an amorphous layer is to be formed at a predetermined mixing ratio and gas flow rate, a glow discharge is generated to form a plasma atmosphere of these gases. Therefore, an amorphous layer can be formed on a predetermined support, but in order to introduce hydrogen atoms, a predetermined amount of silicon compound gas containing hydrogen atoms is also mixed with these gases to form a layer. It may be formed. 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 an amorphous layer made of A-Si (H, 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 heated using a resistance heating method or an electron beam method (EB method). The flying evaporated material can be passed through a predetermined gas plasma atmosphere by heating and steaming using methods such as the above method. 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, such as H ₂ or the above-mentioned silane gases, 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 raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr and HI, SiH ₂ F ₂ , SiH ₂ I ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituents are also effective amorphous materials. It can be mentioned as a starting material for layer formation. These halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming an amorphous layer. It is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the amorphous layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
This can also be done by causing a discharge by causing a silicon hydride gas such as Si ₃ H ₈ or Si ₄ H ₁₀ to coexist with a silicon compound for supplying Si in the deposition chamber. 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, an amorphous 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 amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the amorphous layer of the photoconductive member to be formed is usually 1 when the sum of the amounts of hydrogen atoms and halogen atoms is 1. It is desirable that the content be ˜40 atomic %, preferably 5 to 30 atomic %. Hydrogen atoms (H) or / contained in the photoconductive layer
and the amount of halogen atoms (X), for example by controlling the deposition support temperature or/and 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 order to introduce group atoms and nitrogen atoms into the amorphous intermediate layer to form the lower layer region 103 and the layer region 104, when forming layers by a glow discharge method, a reactive sputtering method, etc., By using the starting material, the starting material for introducing nitrogen atoms, or both starting materials together with the starting material for forming the amorphous layer described above, the amount of the starting material is controlled in the formed layer. It will be done. When the glow discharge method is used to form the lower layer region 103 constituting the amorphous layer, the starting material that becomes the raw material gas for forming the lower layer region is one of the starting materials for forming the amorphous layer described above. A starting material for introducing nitrogen atoms is added to one selected from among them as desired. As the starting material for introducing nitrogen atoms, most of the gaseous substances containing at least nitrogen atoms or gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si), a raw material gas containing nitrogen atoms (N), and hydrogen atoms (H) or halogen atoms (X) as necessary. Either a raw material gas is mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are nitrogen atoms (N) and hydrogen atoms (H) are used. , also in a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and three atoms of silicon atoms (Si), nitrogen atoms (N), and hydrogen atoms (H). It can be used in combination with a raw material gas having two constituent atoms. Alternatively, an atomic gas containing nitrogen atoms (N) may be mixed with a raw material gas containing silicon atoms (Si) and hydrogen atoms (H). Starting materials that serve as atomic gases for introducing nitrogen atoms include nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), and ammonium azide (NH ₄ N _{3 )} . ), gaseous or gasifiable nitrogen, and nitrogen compounds such as nitrides and azides. In addition to the introduction of nitrogen atoms, halogen atoms can also be introduced, so nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ), dinitrogen difluoride (N ₂ F ₂ ), fluorine azide (FN ₃ ), chlorine azide (ClN ₃ ), bromine azide (BrN ₃ ), and hydrazinium azide (N ₂ H ₅ N ₃ ). I can do it. To form the lower layer region containing nitrogen atoms by the sputtering method, single crystal or polycrystalline
Si wafer or Si ₃ N ₄ wafer or Si and
The sputtering may be carried out by targeting wafers containing a mixture of Si ₃ N ₄ and sputtering them in various gas atmospheres. For example, if a Si wafer is used as a target, nitrogen atoms and optionally hydrogen atoms or/and
The raw material gas for introducing halogen atoms is diluted with a diluent gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. All you have to do is ring it. Alternatively, Si and Si ₃ N ₄ can be used as separate targets, or by using a mixed target of Si and Si ₃ N ₄ in a diluent gas atmosphere as a sputtering gas. or by sputtering in a gas atmosphere containing at least hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing nitrogen atoms, the raw material gas for introducing nitrogen atoms among the raw material gases 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, the diluent gas used when forming the amorphous layer by the glow discharge method or the sputtering method is a so-called rare gas, such as He, Ne, Ar.
etc. can be mentioned as suitable ones. In order to form the layer region 104 constituting the amorphous layer, in addition to the raw material gas for forming the amorphous layer described above during the formation of the amorphous layer, a gas state for introducing group atoms is used. It is sufficient to introduce the starting material which can be gasified into the vacuum deposition chamber for forming the amorphous layer in a gaseous state. The content of group atoms introduced into the layer region 104 can be arbitrarily determined by controlling the gas flow rate, gas flow rate ratio, discharge power, etc. of the starting material for introducing group atoms introduced into the deposition chamber. Can be controlled. As starting materials for introducing group atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ are effectively used in the present invention for introducing boron atom. ,
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 . Other examples include AlCl ₃ , GaCl ₃ , InCl ₃ and TlCl ₃ . In the photoconductive member of the present invention, the lower layer region containing nitrogen atoms may further contain oxygen atoms. By chemically containing oxygen atoms in the lower layer region, the adhesion between the amorphous layer and the support can be further improved, and the dark resistance can be further increased. . In order to introduce nitrogen atoms into the lower layer region, a starting material for introducing nitrogen atoms may be introduced in a gaseous state into the vacuum deposition apparatus when forming the lower layer region. Alternatively, when forming the lower layer region by a reactive sputtering method, it is possible to use a SiO ₂ target or a target in which SiO ₂ is mixed with Si, Si ₃ N ₄ , etc. Oxygen atoms can thus be contained in the lower layer region formed. Specifically, starting materials that serve as raw material gases for introducing oxygen atoms include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ),
Nitrogen monoxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ),
Nitrogen tetroxide (N ₂ O ₄ ), Nitrogen pentoxide (N ₂ O ₅ ),
Nitrogen trioxide (NO ₃ ), constituent atoms of silicon atom (Si), oxygen atom (O), and hydrogen atom (H), such as disiloxane H ₃ SiOSiH ₃ , trisiloxane H ₃ SiOSiH ₂ OSiH ₃ , etc. Lower siloxanes and the like can be mentioned. Next, a method for manufacturing a photoconductive member formed by a glow discharge decomposition method will be described. FIG. 2 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method. 202, 203, 204, 205, 20 in the diagram
Gas cylinder 6 is sealed with raw material gas for forming each layer of the present invention, and as an example, 202 is SiH ₄ diluted with He.
gas (purity 99.999%, hereinafter abbreviated as SiH ₄ /He) cylinder, 203 is B ₂ H ₆ gas diluted with He (purity
99.999%, hereinafter abbreviated as B ₂ H ₆ /He. ) cylinder, 20
4 is Si ₂ H ₆ gas diluted with He (99.99% purity,
Hereinafter, it will be abbreviated as Si ₂ H ₆ /He. ) cylinder, 205 is SiF ₄ gas diluted with He (99.999% purity, hereinafter SiF ₄ /
Abbreviated as He. ) cylinder, 206 is an NH ₃ gas cylinder. In order to flow these gases into the reaction chamber 201, the valves 222 to 22 of the gas cylinders 202 to 206 are used.
6. Check that the leak valve 235 is closed, and check that the inflow valves 212 to 216, the outflow valves 217 to 221, and the auxiliary valves 232 to 233 are open. First, open the main valve 2.
34 is opened to exhaust the inside of the reaction chamber 201 and gas piping. Next, when the reading on the vacuum gauge 236 reaches approximately 5×10 ⁻⁶ torr, the auxiliary valves 232 to 233 and the outflow valves 217 to 221 are closed. To give an example of forming the lower layer region on the base cylinder 237, from the gas cylinder 202
SiH ₄ /He gas, B ₂ H ₆ /He from gas cylinder 203
Gas, NH ₃ gas from gas cylinder 211, open valves 222, 223, 226 and outlet pressure gauge 2
Adjust the pressure of 27, 228, 231 to 1Kg/cm ² ,
Gradually open the inflow valves 212, 213, 216, and the mass flow controllers 207, 208, 21
1. Subsequently, the outflow valve 21
7,218,221, auxiliary valve 232,233
are gradually opened to allow each gas to flow into the reaction chamber 201. SiH ₄ /He gas flow rate at this time, B ₂ H ₆ /
The outflow valves 217, 218, 2 are adjusted so that the ratio of He gas flow rate and NH ₃ gas flow rate is the desired value.
21 and the opening of the main valve 234 while checking the reading on the vacuum gauge 236 so that the pressure inside the reaction chamber reaches the desired value. Then, the temperature of the base cylinder 237 is controlled by the heating heater 238.
After confirming that the temperature is set at 50 to 400° C., the power source 240 is set to the desired power to generate a glow discharge in the reaction chamber 201 and form a lower layer region on the base cylinder. When halogen atoms are contained in the lower layer region, SiF ₄ /He, for example, is further added to the above gas and fed into the reaction chamber. To form the upper layer region 105, layer formation is performed without using the nitrogen atom-containing gas used in forming the lower layer region. It goes without saying that all outflow valves for gases other than those required when forming each layer are closed, and when forming each layer, the gas used to form the previous layer is inside the reaction chamber 201 and the outflow valves 217 to 217 are closed. 221
In order to avoid remaining in the piping leading from to the reaction chamber 201, the outflow valves 217 to 221 are closed, the auxiliary valves 232 and 233 are opened, and the main valve 234 is fully opened to temporarily evacuate the system to a high vacuum. Perform as necessary. During layer formation, the base cylinder 237 is rotated at a constant speed by a motor 239 in order to ensure uniform layer formation. Examples will be described below. Example 1 A layer was formed on an Al cylinder using the manufacturing apparatus shown in FIG. 2 under the following conditions. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 kV for 0.2 seconds, and a light image was immediately irradiated using a tungsten lamp light source, transmitting a light amount of 1.5 lux・sec. It was irradiated through a mold test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) over the surface of the member. When the toner image on the member was transferred onto transfer paper using 5.0kV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

[Table] Example 2 A layer was formed on an Al cylinder under the following conditions using the manufacturing apparatus shown in FIG. Enter Table 2. Other conditions were the same as in Example 1. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

[Table] Example 3 A lower region and an upper region were formed under the same conditions as in Example 1, except that the flow rate ratio of B ₂ H ₆ /SiH ₄ when forming the lower region was 1.0×10 ^-3 . An image forming member was prepared, and an image was formed on a transfer paper using the image forming member under the same conditions and procedures as in Example 1, and an extremely clear image was obtained. Example 4 A layer was formed on an Al cylinder using the manufacturing apparatus shown in FIG. 2 under the following conditions. Other conditions were the same as in Example 1. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

[Table] Example 5 A layer was formed on an Al cylinder using the production equipment shown in Figure 2 under the following conditions using a Si ₂ H ₆ He gas cylinder instead of the SiH ₄ /He gas cylinder used in Example 1. I went there. Enter Table 4. Other conditions were the same as in Example 1. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

[Table] Example 6 Oxidation treatment using anodic oxidation method to a thickness of 800 Å
An image forming member was prepared by forming a lower layer region and an upper layer region on the Al cylinder on which Al ₂ O ₃ had been formed under the same conditions and procedures as in Example 1. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 7 A layer was formed on an Al cylinder using the manufacturing apparatus shown in FIG. 2 under the following conditions. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 kV for 0.2 seconds, and a light image was immediately irradiated using a tungsten lamp light source, transmitting a light amount of 1.5 lux・sec. It was irradiated through a mold test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) over the surface of the member. When the toner image on the member was transferred onto transfer paper using 5.0kV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

【table】 [Brief explanation of the drawing]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the electrophotographic photoconductive member of the present invention, and FIG.
FIG. 2 is a schematic explanatory diagram of an apparatus used to produce the electrophotographic photoconductive member of the present invention in Examples. 100...Photoconductive member, 101...Support, 1
02...Amorphous layer, 103...Lower region, 104
. . . A region containing atoms of Group Group of the Periodic Table over its entire region, 105 . . . Upper layer region.

Claims (1)

[Claims] 1. A support for electrophotography and an amorphous layer exhibiting photoconductivity, which is composed of an amorphous material having silicon atoms as a matrix and containing at least one of hydrogen atoms and halogen atoms. In the photoconductive member for electrophotography, the amorphous layer contains a nitrogen atom and an atom belonging to Group Group of the periodic table, the amorphous layer has a lower layer region from the support side. and an upper layer region, and the nitrogen atoms are contained only in the lower layer region over the entire region, and the atoms belonging to the group of the periodic table are contained at least in the lower layer region. A photoconductive member for electrophotography, characterized by: 2. The photoconductive material for electrophotography according to claim 1, wherein the layer region containing atoms belonging to group 3 of the periodic table extends over the entire amorphous layer. Element. 3. The electrophotographic photoconductive device according to claim 1, wherein the layer region containing atoms belonging to Group 3 of the periodic table over its entire region is substantially the same as the lower layer region. Element. 4. The photoconductive member for electrophotography according to claim 1, wherein the lower layer region includes a layer region containing atoms belonging to group 3 of the periodic table over its entire region.