JPH0450583B2 - - 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 a photoconductive member for laser light that is 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,
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 above-mentioned non-polluting property 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 photoconductive layers composed of a-Si have poor 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, and it is necessary to improve overall characteristics. 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 was often observed that residual potential remained during use. When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes afterimages, or when used repeatedly at high speeds, the response gradually decreases. There were many cases where spots appeared. Furthermore, a-Si has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there is still room for improvement in that the light on the longer wavelength side cannot be used effectively. In addition, if the amount of irradiated light that reaches the support without being sufficiently absorbed in the photoconductive layer increases, the support itself will reflect the light that has passed through the photoconductive layer. When the ratio is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. 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 (Si) and a germanium atom (Ge) as a matrix, and an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium , or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to generically as "a-
The structure of a photoconductive member having an amorphous bath exhibiting photoconductive properties composed of "SiGe (H, Photoconductive materials not only exhibit extremely excellent properties in practical use, but also exceed conventional photoconductive materials in all respects. This is based on the discovery that it has extremely excellent properties as a photoconductive member (sometimes abbreviated as a photoconductive member), and that it has excellent absorption spectrum properties on the long wavelength side. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member that is durable, does not cause deterioration even after repeated use, and has no or almost no residual potential observed. Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponse. Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having sufficient performance. 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 to
Another object of the present invention is to provide a photoconductive member having high signal-to-noise ratio characteristics. The photoconductive member for laser light of the present invention is composed of a support for the photoconductive member and an amorphous material containing silicon atoms and germanium atoms on the support, and exhibits photoconductivity. The distribution state of germanium atoms in the amorphous layer is such that the distribution concentration is within 5μ from the support side.
It is characterized by being non-uniform in the layer thickness direction so that it has a portion with a high concentration of 1000 atomic ppm or more and a portion where the concentration is considerably lower on the surface side than on the support side. 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. Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast photoresponse. 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 is made of a-SiGe (H,
The germanium atoms contained in the amorphous layer 102 having a photoconductive amorphous layer 102 consisting of The side opposite to the side where the body 101 is provided (the surface 10 of the amorphous layer 102
4 side) to the support side (amorphous layer 10 side).
It is contained in the amorphous layer 102 so that it is more distributed toward the surface 105 side of 2. In the photoconductive member of the present invention, the distribution state of germanium atoms contained in the amorphous layer is as described above in the layer thickness direction, and in the in-plane direction parallel to the surface of the support. It is desirable to have a uniform distribution state. 2 to 10 show typical examples of the distribution state of germanium atoms contained in the amorphous layer of the photoconductive member of the present invention in the layer thickness direction. In FIGS. 2 to 10, the horizontal axis represents the germanium atom content C, the vertical axis represents the layer thickness t of the amorphous layer exhibiting photoconductivity, and t _B represents the amorphous layer on the support side. t _T indicates the position of the surface of the amorphous layer on the side opposite to the support side. That is, the amorphous layer containing germanium atoms is formed from the t _B side toward the t _T side. FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the amorphous layer in the layer thickness direction. In the example shown in FIG. 2, germanium atoms extend from the interface position t _B to the position t ₁ where the surface where the amorphous layer containing germanium atoms is formed and the surface of the amorphous layer contact each other. Germanium atoms are contained in the amorphous layer formed while the distribution concentration C takes a constant value of C ₁ , and the interface position is higher than the position t ₁ .
The distribution concentration C ₂ is gradually and continuously reduced until reaching t _T . At the interface position _tT , the distribution concentration C of germanium atoms is _C3 . In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration _C4 until it reaches the position _tT from the position _{tB .}
A distribution state is formed such that the concentration is C ₅ at . In the case of Fig. 4, the distribution concentration C of germanium atoms is constant at a concentration _C6 from position t _B to position t ₂ , and gradually and continuously between position t ₂ and position t _T. reduced, and at position t _T , the distribution concentration C
is substantially zero (substantially zero here means less than the detection limit amount). In the case of FIG. 5, the distribution concentration C of germanium atoms is gradually decreased continuously from the concentration c ₈ from position t _B to position t _T , and becomes substantially zero at position t _T. There is. In the example shown in FIG. 6, the distribution concentration C of germanium atoms between position t _B and position t ₃ is as follows:
The concentration C is a constant value of ₉ , and at the position t _T the concentration
It is said to be C ₁₀ . Between the position t ₃ and the position t _T , the distribution concentration C is linearly decreased from the position t ₃ to the position t _T . In the example shown in FIG. 7, the distribution concentration C takes a constant value of concentration C ₁₁ from position t _B to position t ₄ ,
From position _t4 to position _tT , the distribution state is such that the concentration decreases linearly from _C12 to _C13 . In the example shown in FIG. 8, from position t _B to position t _T
Up to , the distribution concentration C of germanium atoms decreases linearly from the concentration C ₁₄ to substantially zero. In FIG. 9, the distribution concentration C of germanium atoms from position t _B to position t ₅ is the concentration C ₁₅
The concentration C is linearly decreased to ₁₆ , and the position t ₅
An example is shown in which the concentration C ₁₆ is kept at a constant value between and the position t _T . In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration C ₁₇ at the position t _B , and is gradually decreased from this concentration C ₁₇ until reaching the position t ₆ , and then at t ₆ . Near the position, the concentration decreases rapidly to a concentration _C18 at position _t6 . Between position t ₆ and position T ₇ , the concentration decreases rapidly at first, then slowly decreases to C ₁₉ at position t ₇ , and then between position t ₇ and position t ₈ . Then, it is gradually decreased very slowly to reach 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 examples of the distribution state of germanium atoms contained in the amorphous layer in the layer thickness direction, in the present invention, on the support side, It has a part with a high distribution concentration C of germanium atoms, and the interface (surface) t _T
On the side, the amorphous layer is provided with a distribution of germanium atoms in which the distribution concentration C is considerably lower than on the support side. The amorphous layer constituting the photoconductive member of the present invention preferably has a localized region (A) containing germanium atoms at a relatively high concentration on the support side, as described above. . In the present invention, the localized region (A) can be explained using the symbols shown in FIGS. 2 to 10, and can be defined as the interface position.
It is desirable that it be provided within 5μ from _tB . In the present invention, the localized region (A) may be the entire layer region (L _T ) up to 5μ thick from the interface position t _B , or may be a part of the layer region (L _T ). In some cases, it may be done. 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. The localized region (A) is a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum distribution concentration Cmax of germanium atoms is usually 1000 atomic ppm or more, preferably more than 1000 atomic ppm relative to silicon atoms.
5000 atomic ppm or more, optimally 1×10 ⁴ atomic
It is desirable that the layer be formed in such a way that it can have a distribution state of ppm or more. That is, in the present invention, the amorphous layer containing germanium atoms has a layer thickness from the support side.
It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists within 5μ (layer region with a thickness of 5μ from tB). In the present invention, the content of germanium atoms contained in the amorphous layer is appropriately determined as desired so as to effectively achieve the object of the present invention, but is usually 1 to 9.5 × 10 ⁵ atomic ppm, preferably 100-8.0×10 ⁵ atomic ppm, optimally
It is desirable that the content be 500 to 7×10 ⁵ atomic ppm. 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, the amorphous layer composed of a-SiGe (H, It will be done. For example, by the claw discharge method, a
- To form an amorphous layer composed of SiGe (H, The raw material gas for supplying Ge and, if necessary, the raw material gas for introducing hydrogen atoms (H) and/or the raw material gas for introducing halogen atoms (X) are kept in a desired gas pressure state in the deposition chamber where the internal pressure can be reduced. A glow discharge is generated in the deposition chamber to control the distribution concentration of germanium atoms contained on the surface of a predetermined support grounded at a predetermined position according to a desired rate of change curve. Laa-
A layer made of SiGe(H,X) may be formed.
In addition, when forming by sputtering, a target composed of Si and a target composed of Ge are formed in an atmosphere of an inert gas such as Ar or He, or a mixed gas based on these gases. When sputtering using a Si or a mixed target of Si and Ge, hydrogen atoms (H) and/or halogen atoms (X) may be added as necessary.
The gas for introduction may be introduced into the deposition chamber for sputtering. Substances that can be used as the raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Se ₂ H ₆ are preferred. Substances that can be used as raw material gas for Ge supply include:
_{GeH4 , Ge2H6 , Ge3H8 , Ge4H10} , _{Ge5H12 , Ge6}
Germanium hydride in a gaseous state or which can be gasified, such as H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , etc., can be mentioned as one that can be effectively used. In terms of Ge supply efficiency, etc.
Preferred examples include GeH ₄ , Ge ₂ H ₆ and Ge ₃ H ₈ . 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 hydride 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 . I can do it. When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. An amorphous layer made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When manufacturing an amorphous layer containing halogen atoms according to the glow discharge method, basically, for example, silicon halide is used as a raw material gas for supplying Si, and germanium hydride is used as a raw material gas for supplying Ge. Ar,
Gases such as H ₂ and He are introduced into the deposition chamber where an amorphous layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. In particular, it is possible to form an amorphous layer on a desired support, but in order to more easily control the ratio of hydrogen atoms introduced, hydrogen gas or A desired amount of silicon compound gas containing hydrogen atoms may also be mixed 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 an amorphous layer made of a-SiGe (H, Alternatively, using a target consisting of Si and Ge, this is sputtered in the desired gas plasma atmosphere, and in the case of ion plating, for example polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal Germanium and germanium are housed in an evaporation board as evaporation sources, and the evaporation sources are heated and evaporated by a resistance heating method, an electron beam method (EB method), etc., and the flying evaporates are passed through a desired gas plasma atmosphere. You can do it with 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 gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. 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
Halogen-substituted silicon hydrides such as _I2 , _SiH2Cl , _SiHCl3 , _SiH2Br2 , _{SiHBr3 ,} and _GeHF3 , _{GeH2F2 ,
GeH3F , GeHCl3} , _GeH2Cl2 , _GeH3Cl ,
_{GeHBr3 , GeH2Br2} , _GeH3Br , _GeHI3 , _GeH2
Germanium hydrogenated halides such as I ₂ , GeH ₃ I,
Halides containing hydrogen atoms as one of their constituent elements, such as GeF ₂ , GeCl ₄ , GeBr ₄ , GeI ₄ , GeF ₂ , GeCl ₂ ,
Germanium halides such as GeBr ₂ , GeI ₂ , and other gaseous or gasifiable substances can also be mentioned as effective starting materials for forming the amorphous layer. In the case of halides containing hydrogen atoms in these substances, when forming an amorphous layer, hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time as halogen atoms are introduced into the layer. , is used as a suitable raw material for introducing halogen in the present invention. In order to structurally introduce hydrogen atoms into the amorphous layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ , Si ₃
Silicon hydride such as H ₈ , Si ₄ H ₁₀ and germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Generating a discharge by coexisting germanium hydride such as Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si in a deposition chamber. But it can be done. In a preferred example of the present invention, hydrogen atoms (H) contained in the amorphous layer of the photoconductive member to be formed
or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is normally
0.01~40atomic%, preferably 0.05~30atomic%,
The optimum range is preferably 0.1 to 25 atomic%. Hydrogen atoms (H) contained in the amorphous layer or/
and the amount of halogen atoms (X) can be controlled by, for example, the support temperature or/and the introduction of hydrogen atoms (H) or the starting materials used to contain the halogen atoms (X) into the deposition system. What is necessary is to control the amount of discharge, the discharge force, etc. The thickness of the amorphous layer in the photoconductive member of the present invention is appropriately determined as desired so that the photocarriers generated in the amorphous layer are efficiently transported, and is usually 1 to 10%. It is desirable that the thickness be 100μ, preferably 1 to 80μ, most preferably 2 to 50μ. 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, 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. . 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 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 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. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 11 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming the photoconductive member of the present invention is sealed, for example, 110
2 is SiH ₄ gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_GeH4 gas diluted with (purity 99.999% or less)
Abbreviated as GeH ₄ /He. ) cylinder, 1104 is SiF ₄ gas diluted with He (99.99% purity, hereinafter referred to as SiF ₄ /He)
It is abbreviated as ) cylinder, 1105 is He gas (purity
99.999%) cylinder, 1106 is _H2 gas (purity
99.999%) cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
2-1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112-1126 is closed.
Step 1116: After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming an amorphous layer on the cylindrical substrate 1137, the gas cylinder 11
Inject SiH ₄ /He gas from gas cylinder 1103 and GeH ₄ /He gas from gas cylinder 1103 by opening valves 1122 and 1123 and setting the pressure on outlet pressure gauges 1127 and 1128 to 1.
Adjust to Kg/cm ² , inflow valve 1112, 1113
Gradually open the mass flow controller 110.
7 and 1108, respectively. Subsequently, the outflow valves 1117, 1118 and the auxiliary valve 113
2 is gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the SiH ₄ /He gas flow rate and
Adjust the outflow valves 1117 and 1118 so that the ratio with the GeH ₄ /He gas flow rate becomes the desired value, and
While checking the reading on the vacuum gauge 1136, adjust the main valve 1 so that the pressure inside the reaction chamber 1101 reaches the desired value.
Adjust the aperture of 134. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of 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. , and at the same time GeH ₄ /H ₂ according to the pre-designed rate of change curve.
The distribution concentration of germanium atoms contained in the formed layer is controlled by gradually changing the opening of the valve 1118 by adjusting the gas flow rate manually or by using an externally driven motor. Further, during layer formation, it is desirable that the base 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Reference examples and examples will be described below. Reference Example 1 Using the manufacturing apparatus shown in FIG. 11, the following steps were carried out on a cylindrical Al substrate under the conditions shown in Table 1 and according to the rate of change curve of the gas flow rate ratio shown in FIG. 12.
An electrophotographic image forming member was obtained by forming layers while changing the gas flow rate ratio of GeH ₄ /He gas and SiH ₄ /He gas with the elapsed layer formation time. The image-forming member thus obtained was installed in a charging exposure experimental device, corona charged at 5.0 KV for 0.3 seconds, and a light image was immediately irradiated using a tungsten lamp light source, and a light intensity of 2 lux.sec was applied to a transmission type. It was irradiated through a test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
Transferred onto transfer paper with 5.0KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Reference Example 2 Using the manufacturing equipment shown in Fig. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the change rate curve of the gas flow rate ratio shown in Fig. 13 under the conditions shown in Table 2. Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Reference Example 1, an extremely clear image was obtained. Reference Example 3 Using the manufacturing equipment shown in Fig. 11, the gas flow rates of GeH ₄ /He gas and SiH 4 /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in Fig. 14 under the conditions shown in Table ₃ . Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Reference Example 1, an extremely clear image quality was obtained. Reference Example 4 Using the manufacturing equipment shown in Fig. 11, the gas flow rates of GeH ₄ /He gas and SiH _{4 /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in Fig. 15 under the conditions shown in Table 4} . Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Reference Example 1, an extremely clear image quality was obtained. Reference Example 5 Using the manufacturing equipment shown in Fig. 11, the gas flow rates of GeH ₄ /He gas and SiH 4 /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in Fig. 16 under the conditions shown in Table ₅ . Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Reference Example 1, an extremely clear image quality was obtained. Reference Example 6 Using the manufacturing equipment shown in Fig. 11, the gas flow rates of GeH ₄ /He gas and SiH _{4 /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in Fig. 17 under the conditions shown in Table 6} . Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Reference Example 1, an extremely clear image quality was obtained. Reference Example 7 Using the manufacturing equipment shown in Fig. 11, the gas flow rates of GeH ₄ /He gas and SiH _{4 /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in Fig. 18 under the conditions shown in Table 7} . Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Reference Example 1, an extremely clear image quality was obtained. Reference Example 8 In Example 1, SiH ₄ /He gas was replaced with Si ₂
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Reference Example 1, except that H ₆ /He gas was used and the conditions shown in Table 8 were used. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Reference Example 1, an extremely clear image quality was obtained. Reference example 9 In reference example 1, instead of SiH ₄ /He gas
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Reference Example 1, except that SiF ₄ /He gas was used and the conditions shown in Table 9 were used. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Reference Example 1, an extremely clear image quality was obtained. Reference Example 10 Same conditions as Reference Example 1 except that (SiH ₄ /He + SiF ₄ /He) gas was used instead of SiH ₄ /He gas and the conditions shown in Table 10 were changed. Layer formation was carried out to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Reference Example 1, an extremely clear image quality was obtained. Example 1 In Reference Example 1, the light source was an 810 nm GaAs semiconductor laser (10 mW) instead of the tungsten lamp.
Reference Example 1 was carried out under the same toner image forming conditions as in Reference Example 1, except that an electrostatic image was formed using
When the image quality of the toner-transferred image of an electrophotographic image forming member prepared under the same conditions as above was evaluated, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained.

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【table】

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[Table] The common layer forming conditions in the above examples and reference examples of the present invention are shown below. Substrate temperature: germanium atom (Ge) containing layer...
...Approx. 200℃ Germanium atom (Ge)-free layer...Approx. 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of the drawing]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are diagrams for explaining the distribution state of germanium atoms in the amorphous layer, respectively. The explanatory diagram, FIG. 11, is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS.
FIG. 8 is an explanatory diagram showing the rate of change curve of the gas flow rate ratio in each embodiment of the present invention. 100...Photoconductive member, 101...Support, 1
02...Amorphous layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member, and an amorphous layer exhibiting photoconductivity made of an amorphous material containing silicon atoms and germanium atoms as a matrix on the support. The distribution state of germanium atoms in the amorphous material is such that the distribution concentration of germanium atoms is higher on the surface side than on the support side, with a portion having a high distribution concentration of 1000 atomic ppm or more within 5μ from the support side. A photoconductive member for laser light, characterized in that the layer is non-uniform in the thickness direction so as to have a lowered portion. 2. The photoconductive member for laser light according to claim 1, wherein the amorphous layer contains hydrogen atoms. 3. The photoconductive member for laser light according to claim 1, wherein the amorphous layer contains halogen atoms. 4. The photoconductive member for laser light according to claim 1, wherein the amorphous layer contains hydrogen atoms and halogen atoms. 5 The amount of hydrogen atoms contained in the amorphous substance is
The photoconductive member for laser light according to claim 2, wherein the content is 0.01 to 40 atomic%. 6. The photoconductive member for laser light according to claim 3, wherein the amount of halogen atoms contained in the amorphous material is 0.01 to 40 atomic%. 7. The photoconductive member for laser light according to claim 4, wherein the amount of hydrogen atoms and halogen atoms contained in the amorphous material is 0.01 to 40 atomic%. 8. The photoconductive member for laser light according to claim 1, wherein the amount of germanium atoms contained in the amorphous material is 1 to 9.5×10 ⁵ atomic ppm. 9. The photoconductive member for laser light according to claim 3, wherein the halogen atom is selected from fluorine and chlorine.