JPH1184698A - Light receiving member for electrophotography - Google Patents

Abstract

PROBLEM TO BE SOLVED: To significantly improve temperature characteristics and linearity of sensitivity, improve chargeability, reduce temperature characteristics and reduce optical memory at a high level, and to achieve excellent potential characteristics suitable for red-visible laser light. Provided is a light receiving member having image characteristics. The photoconductive member has at least a conductive support, and a photoreceptive layer having, on the surface of the support, a photoconductive layer containing silicon atoms as a host and containing hydrogen atoms and / or halogen atoms. The layer has a layer region having different characteristic energies of the hydrogen content, the optical band gap, and the exponential function tail obtained from the light absorption spectrum, and the hydrogen content of each of the first photoconductive region / second photoconductive region. The amount is 15 to 30/5 to 25 at%, the optical band gap is 1.75 to 1.85 / 1.55 to 1.70 eV, and the characteristic energy at the exponential function tail obtained from the light absorption spectrum is 55.
６５65 / 50〜65 meV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light receiving member which is sensitive to electromagnetic waves such as light (in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, .gamma.-rays, etc.).

[0002]

2. Description of the Related Art In the field of image formation, a photoconductive material for forming a light receiving layer in a light receiving member has high sensitivity.
S / N ratio "Photocurrent (Ip) / Dark current (Id)" is high, it has an absorption spectrum suitable for the spectral characteristics of the radiated electromagnetic wave, photoresponse is fast, it has a desired dark resistance value, Harmless to the human body,
And other characteristics are required. In particular, in the case of a light receiving member to be incorporated in an electrophotographic apparatus used in an office as an office machine, the above-mentioned non-pollutability at the time of use is important.

A photoconductive material exhibiting such excellent properties is hydrogenated amorphous silicon (hereinafter referred to as a-Si: H). For example, Japanese Patent Publication No. 60-35059 discloses an electrophotographic material. Application as a light receiving member is described.

In general, such a light receiving member is prepared by heating a conductive support to 50 to 350 ° C. and depositing the conductive support on the support by a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, or the like. A photoconductive layer made of a-Si is formed by a film forming method such as a photo CVD method or a plasma CVD method. Among them, a plasma CVD method, that is, a method in which a raw material gas is decomposed by high-frequency or microwave glow discharge to form an a-Si deposited film on a support has been put into practical use as a suitable method.

Japanese Patent Application Laid-Open No. 58-1983 discloses the use of an amorphous material containing silicon atoms and germanium atoms for a photoconductive member.
-171039. Japanese Patent Application Laid-Open (JP-A) No. 58-171054 proposes a photoreceptor using an amorphous silicon-germanium photoconductive layer having sensitivity to near-infrared light.

Japanese Patent Application Laid-Open No. 56-83746 discloses an electronic device comprising a conductive support and an a-Si (hereinafter a-Si: X) photoconductive layer containing a halogen atom as a constituent element. Photographic light receiving members have been proposed. In this publication, a-Si contains 1 to 40 atomic% of halogen atoms.
It is disclosed that by containing the compound, high heat resistance is obtained, and good electrical and optical characteristics can be obtained as a photoconductive layer of a light receiving member for electrophotography.

Japanese Patent Application Laid-Open No. 57-115556 discloses that a photoconductive member having a photoconductive layer composed of an a-Si deposited film has an electrical property such as dark resistance, photosensitivity, and photoresponsiveness. In order to improve the use environment characteristics such as optical and photoconductive properties and moisture resistance, and the stability over time, silicon atoms and carbon atoms are formed on a photoconductive layer composed of an amorphous material containing silicon atoms as a base material. A technique for providing a surface barrier layer made of a non-photoconductive amorphous material containing is described. Further, Japanese Patent Application Laid-Open No. 60-67951 describes a technique for a photoconductor in which a light-transmitting insulating overcoat layer containing amorphous silicon, carbon, oxygen and fluorine is laminated. 16
No. 8161 describes a technique in which an amorphous material containing silicon atoms, carbon atoms, and 41 to 70 atomic% of hydrogen atoms as constituent elements is used as a surface layer.

Further, Japanese Patent Application Laid-Open No. 62-83470 discloses a photoconductive layer of an electrophotographic photoreceptor in which the characteristic energy at the exponential function tail of the light absorption spectrum is set to 0.09 eV or less so that the afterimage phenomenon can be prevented. Techniques for obtaining quality images have been disclosed.

Japanese Patent Application Laid-Open No. 58-21257 discloses that the bandgap width in the photoconductive layer is changed by changing the temperature of the support during the formation of the photoconductive layer, and the photoconductive layer has a high resistance. A technique for obtaining a photoreceptor having a wide sensitivity region is disclosed. Japanese Patent Application Laid-Open No. 58-121042 discloses that the energy gap state density of the surface layer is changed from 10 ¹⁷ to 10 ¹⁷ by changing the energy gap state density in the thickness direction of the photoconductive layer. A technique for preventing the surface potential from lowering due to humidity by setting the pressure to 10 ¹⁹ cm ^-3 is disclosed. JP-A-59-143379 and JP-A-61-201481 disclose techniques for obtaining a photosensitive member having high dark resistance and high sensitivity by laminating a-Si: H having different hydrogen contents. ing.

On the other hand, Japanese Patent Application Laid-Open No. Sho 60-95551 discloses that in order to improve the image quality of an amorphous silicon photoreceptor, charging, exposure, development and transfer are performed while maintaining the temperature near the photoreceptor surface at 30 to 40 ° C. By performing such an image forming process, there is disclosed a technique for preventing a reduction in surface resistance due to the adsorption of moisture on the surface of a photoreceptor and an image deletion caused thereby.

[0011] These techniques have improved the electrical, optical, photoconductive properties and operating environment properties of the electrophotographic light-receiving member, and accordingly the image quality.

[0012]

However, the conventional electrophotographic light-receiving member having a photoconductive layer made of an a-Si-based material has a low electric resistance such as dark resistance, light sensitivity, and photoresponsiveness. In terms of optical, photoconductive, and use environment characteristics, and in terms of aging stability and durability, individual characteristics have been individually improved, but in order to improve overall characteristics, The fact is that there is still room for further improvement.

In particular, the electrophotographic apparatus has been rapidly improving in image quality, speed, and durability. In the electrophotographic light-receiving member, the electric characteristics and photoconductive characteristics have been further improved.
It is required to greatly extend the performance under any environment while maintaining the charging ability and sensitivity.

As a result of the improvement of the optical exposure device, the developing device, the transfer device and the like in the electrophotographic apparatus in order to improve the image characteristics of the electrophotographic apparatus, the image characteristics of the electrophotographic light-receiving member have been improved. Has been required to be improved.

Further, with the spread of computers in offices and general homes in recent years and the digitization of texts and images, the electrophotographic apparatus plays a role of not only a conventional copying machine but also a facsimile and a printer for the multimedia age. Therefore, digitalization has been required. Semiconductor lasers and LEDs used for digitization have long wavelengths from infrared to red visible light from the viewpoint of emission intensity and price. For this reason, there has been a demand for improvements in characteristics that have not been seen in conventional analog copying machines using halogen light.

Under these circumstances, the above-mentioned prior art has made it possible to improve the characteristics to some extent on the above-mentioned problems, but it cannot be said that further improvement in charging performance and image quality is still sufficient. In particular, as a challenge for further improving the image quality of amorphous silicon-based light-receiving members, it has become even more demanded to reduce fluctuations in electrophotographic characteristics due to changes in ambient temperature, light fatigue, and optical memories such as blank memories and ghosts. Have been. In addition, with the digitalization, red-visible wavelength lasers and LEDs
By using, the slope of the linear portion of the light quantity / charging ability curve changes with temperature (temperature characteristics of sensitivity), and the linear portion decreases, and the overall becomes dull and hyperbolic (sensitivity characteristics). (Linearity) has been attracting attention as a new problem (see FIG. 11).

Under such circumstances, silicon germanium films having sensitivity to long wavelengths have been studied. However, germanium-added films used in conventional light receiving members for electrophotography are employed on the support side. Therefore, it is intended to prevent interference due to transmission of a long-wavelength laser.

Conventionally, a drum heater is installed in a copying machine to reduce the surface temperature of the photoconductor to 40, as described in Japanese Patent Application Laid-Open No. 60-95551 to prevent image deletion on the photoconductor. ℃ was maintained. However,
In conventional photoconductors, the temperature dependence of the charging ability due to the generation of pre-exposure carriers and thermally excited carriers, the so-called temperature characteristics, is large, and in the actual use environment in a copying machine, the charging is more than the photoconductor originally has I had to use it with low performance. For example, in a state where the drum heater is used to heat the temperature to about 40 ° C. when used at room temperature, the charging ability is 100%.
About V.

Also, conventionally, even when the copying machine is not used at night, the drum heater is energized, and the ozone product generated by the corona discharge of the charger is adsorbed on the surface of the photoconductor at night to prevent image flow. I was trying to prevent it. However, at present, the power supply to the copying machine at night is not performed as much as possible in order to save resources and power. When continuous copying is performed in such a state, the ambient temperature of the photoreceptor in the copying machine gradually increases, and accordingly, the charging ability decreases, causing a problem that the image density changes during copying.

If the temperature of the photosensitive member is not controlled to be constant by a drum heater or the like in a digital machine using a laser beam or an LED as described above, the photosensitive member may not be used due to the temperature characteristic of sensitivity and the linearity of sensitivity. There has been a problem that the sensitivity changes and the image density changes when the body temperature changes.

On the other hand, when the same original is continuously and repeatedly copied, the image density may decrease or fog may occur due to light fatigue of the photosensitive member due to image exposure. In addition, a so-called ghost or the like, which is generated on an image at the next copying operation due to an afterimage of image exposure in a previous copying process, has been a problem in improving image quality.

Therefore, when designing the light receiving member for electrophotography, the layer structure of the light receiving member for electrophotography, the chemical composition of each layer, and the like are taken into consideration so as to solve the above-mentioned problems. Along with the improvement, it is necessary to further improve the characteristics of the a-Si material itself.

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems in the conventional electrophotographic light-receiving member having a light-receiving layer composed of a-Si.
In other words, the main object of the present invention is to improve the chargeability, reduce the temperature characteristics and reduce the optical memory at a high level, and dramatically improve the image quality. An object of the present invention is to provide a light receiving member having a light receiving layer made of a material.

In particular, the electrical, optical, and photoconductive properties are substantially always stable almost without depending on the use environment, are excellent in light fatigue resistance, do not cause deterioration when repeatedly used, and have durability. An object of the present invention is to provide a light-receiving member having a light-receiving layer composed of a non-single-crystal material containing silicon atoms as a base and having excellent moisture resistance, little residual potential, and good image quality.

[0025]

Means for Solving the Problems To solve the above problems, the present inventors have focused on the distribution and behavior of carriers due to exposure of a photoconductive layer, and have investigated the local state density within the band gap of a-Si. As a result of intensive studies on the relationship between distribution and temperature characteristics and optical memory, we control the distribution of hydrogen content, optical band gap and localized state density in the band gap in the thickness direction of the photoconductive layer. It has been found that the above object can be achieved. That is, in a photoreceptor member having a photoconductive layer composed of a non-single-crystal material containing silicon atoms as a base and containing hydrogen atoms and / or halogen atoms, the photoreceptor member is designed and manufactured so as to specify the layer structure. The light receiving member has not only excellent properties in practical use, but also superior in all respects as compared with the conventional light receiving member, and particularly excellent properties as a light receiving member for electrophotography. Have been found.

In addition, the present invention relates to a method for optimizing a red-visible laser or an LED compatible with digitalization, and in particular, for a light incident portion related to photoelectric conversion, in order to efficiently absorb red-visible light, hydrogenated amorphous silicon is used. The knowledge that adding germanium and controlling the optical band gap, the hydrogen content, and the distribution of localized states within the band gap can achieve the objective of improving the temperature characteristics of sensitivity and the linearity of sensitivity can be achieved. Was. By making the light absorption region thinner, it is possible to achieve an improvement in optical memory and an improvement in charging ability.

Conventional germanium-doped films for the purpose of preventing interference have not taken into account the traveling properties of carriers. Therefore, when such a photoconductor is used at a high speed, the residual potential increases and the linearity of sensitivity increases. A drop has occurred. In the prior art, in a hydrogenated amorphous silicon film to which germanium for a photoconductive layer is added, dangling bonds, which are defects in the film, are eliminated by containing hydrogen and oxygen atoms. However, the inclusion of oxygen atoms inevitably reduces the mobility of carriers due to the increased resistance of the film. Therefore, in the present invention, it is possible to substantially reduce the defects in the film such as dangling bonds without containing oxygen atoms by examining the film forming conditions in detail, thereby making it possible to reduce the conventional germanium-added film. As a result, the present invention has been completed by employing a film having good carrier running properties.

From the above, the above objects and objects are solved and achieved by the present invention described below. That is, the present invention discloses a light receiving member having the following features.

First, in a photoreceptor member having a photoconductive layer composed of a non-single-crystal material containing silicon atoms as a base and containing hydrogen atoms and / or halogen atoms, an optical band gap is formed in the photoconductive layer. The hydrogen content, the hydrogen content and the characteristic energy of the exponential tail obtained from the light absorption spectrum are within a specific range in the first photoconductive region and the second photoconductive region, and the hydrogen content in the first photoconductive region The amount is in the range of 15 to 30 atomic%, the optical band gap is in the range of 1.75 to 1.85 ev, and the characteristic energy of the exponential function tail obtained from the light absorption spectrum is 55 to 6
5 meV, the hydrogen content in the second photoconductive region is in the range of 5 to 25 atomic%, the optical band gap is in the range of 1.55 to 1.70 eV, and the exponential function tail obtained from the light absorption spectrum is Characteristic energy 50-65me
By setting the range of V, it is possible to solve the temperature characteristics of sensitivity and the linearity of sensitivity caused when a red-visible laser is used, and to improve the charging ability and the temperature characteristics so that no optical memory is generated. It is characterized by exhibiting various characteristics.

Second, the photoconductive layer comprises a second photoconductive region laminated on the first photoconductive region on the surface of the conductive support, and the second photoconductive region comprises: The film thickness is required so that the light absorption rate of image exposure is in the range of 70 to 95%. Third, the second photoconductive region comprises:
It is characterized in that it contains germanium atoms in the range of 3 to 35% based on the sum of silicon atoms and germanium atoms.

Fourth, the photoconductive layer is characterized in that the photoconductive layer contains at least one element belonging to Group IIIb of the periodic table. Fifth, the content of the element belonging to Group IIIb of the periodic table on the light incident side of the second photoconductive region is smaller than the content of the first photoconductive region on the support side. I have.

Sixth, the amount of the element belonging to Group IIIb of the periodic table contained in the first photoconductive region is in the range of 0.2 to 30 ppm with respect to silicon atoms. Seventh, the amount of the element belonging to Group IIIb of the periodic table contained in the second photoconductive region is in the range of 0.005 to 10 ppm based on silicon atoms. Eighth, the photoconductive layer is characterized in that a surface layer made of a silicon-based non-single-crystal material containing at least one of carbon, oxygen and nitrogen is provided on the surface of the photoconductive layer.

Ninth, the photoconductive layer is made of a non-single-crystal material containing silicon atoms as a base material and containing at least one of carbon, oxygen and nitrogen and at least one element selected from Group IIIb of the periodic table. A surface layer made of a silicon-based non-single-crystal material containing at least one of carbon, oxygen and nitrogen is provided on the surface of the charge injection blocking layer, and further on the surface of the photoconductive layer. I have. Tenth, the surface layer is characterized in that its layer thickness is in the range of 0.01 to 3 μm.

Eleventh, the thickness of the charge injection blocking layer is
It is characterized by a range of 0.1 to 5 μm. Twelfth, the thickness of the photoconductive layer is in the range of 20 to 50 μm.

The exponential function tail used in the present invention refers to an absorption spectrum obtained by subtracting the tail toward the low energy side from the absorption of the light absorption spectrum. It means the slope of the function tail.

This will be described in detail with reference to FIG.
FIG. 1 shows the photon energy hν on the horizontal axis and the absorption coefficient α on the vertical axis.
1 is an example of a sub-gap light absorption spectrum of a-Si in which is shown as a logarithmic axis. This spectrum is roughly divided into two parts. That is, a portion B (exponential function tail or Urbach tail) in which the absorption coefficient α changes exponentially, that is, linearly, with respect to the photon energy hν, and a portion A in which α has a more gradual dependence on hν.

The B region corresponds to light absorption due to optical transition from the tail level on the valence band side to the conduction band in a-Si, and the exponential dependence of the absorption coefficient α on hν in the B region is Is represented by

Α = α. exp (hν / Eu) If the logarithm of both sides is taken, lnα = (1 / Eu) · hν10α ₁ (I) (where α ₁ = lnα), and the characteristic energy E
The reciprocal of u (1 / Eu) represents the slope of the B portion. Since Eu corresponds to the characteristic energy of the exponential energy distribution of the tail level on the valence band side, a smaller Eu means that the tail level on the valence band side is smaller.

[0039]

The present inventors have proposed an optical band gap (hereinafter, referred to as an optical band gap).
Eg) and the characteristic energy of the exponential tail (Urbuck tail) obtained from the sub-bandgap optical absorption spectrum measured by CPM (hereinafter, referred to as “Eg”).
As a result of examining the correlation between Eu and the characteristics of the photoreceptor over various conditions, it was found that the charging ability, temperature characteristics and optical memory of Eg, Eu and the a-Si photoreceptor were closely related. Further, they have found that the lamination of these different films exhibits good photoreceptor characteristics, and have completed the present invention.

In particular, in order to optimize a red visible light laser or an LED, Eg, Eu at the light incident portion and the laser or the LED are used.
As a result of a detailed study of the photoreceptor characteristics when
It was found that Eg, Eu and the temperature characteristics of sensitivity and the linearity of sensitivity were closely related, and germanium was added to the light incident portion to make the Eg, Eu, and hydrogen contents within specific ranges, so that the red color was obtained. The inventors have found that good photoreceptor characteristics suitable for visible light lasers and LEDs can be obtained, and have completed the present invention.

That is, the layer region in which germanium is contained in a-Si: H to reduce the optical band gap and the trapping rate of the carrier to the localized level is reduced is defined as the interface region between the photoconductive layer and the surface layer. The present inventors' tests have revealed that the temperature characteristics of sensitivity and the linearity of sensitivity can be significantly improved and substantially eliminated by intervening in the. Then, by increasing the light absorptance due to the inclusion of germanium, it becomes possible to make the layer region interposed at the interface region between the photoconductive layer and the surface layer thinner, and the traveling distance of carriers, particularly electrons, becomes smaller, It has been found that the photoreceptor characteristics such as charging ability and optical memory can be further improved because the capture to the localized level is reduced by the amount.

This will be described in more detail. In general, the tail (tail) level based on the structural disorder of the Si-Si bond and the dangling bond of Si are present in the band gap of a-Si: H. (Dangling bonds) and other deep defects due to structural defects. It is known that these levels act as trapping and recombination centers for electrons and holes, and cause deterioration of device characteristics. In the a-SiGe: H system, similarly, the tail (tail) level based on the structural disorder of the Si-Ge bond and the Ge-Ge bond, and structural defects such as dangling bonds, etc. There is a deep level attributable. As a method of measuring the state of the localized level in such a band gap, generally, deep level spectroscopy, isothermal capacity transient spectroscopy, photothermal deflection spectroscopy, photoacoustic spectroscopy, constant photocurrent method, etc. are used. ing. Above all, constant photocurrent method (Constant
Photocurrent Method: hereinafter abbreviated as CPM)
This is useful as a method for easily measuring the subgap light absorption spectrum based on the localized level of a-Si: H.

The reason why the charging ability is reduced when the photosensitive member is heated by a drum heater or the like is that the thermally excited carrier is attracted by the electric field at the time of charging, and the localized level at the band base or the deep level within the band gap. It travels to the surface while repeating capture and emission to the level, and cancels the surface charge. At this time, the carrier that has reached the surface while passing through the charger has little effect on the reduction of the charging ability, but the carrier captured at a deep level reaches the surface after passing through the charger. It is observed as a temperature characteristic to cancel the surface charge. Carriers that are thermally excited after passing through the charger also cancel the surface charge and cause a reduction in charging ability. Therefore, it is necessary to increase the optical band gap of the main photoconductive layer to suppress the generation of thermally excited carriers, and to improve the mobility of the carriers by reducing the deep localized levels. Necessary for improvement.

Further, in the optical memory, the optical carriers generated by the exposure are trapped at the localized levels in the band gap,
It is caused by carriers remaining in the photoconductive layer.
That is, of the photocarriers generated in a certain copying process, the carriers remaining in the photoconductive layer are swept out by the electric field due to the surface charge at the next charging or thereafter, and the potential of the light-irradiated portion is changed to the other. Lower than the area, resulting in shading on the image. Therefore, it is necessary to improve the traveling property of the carrier so that the optical carrier travels in one copying process without remaining as much as possible in the photoconductive layer.

Further, the temperature characteristic of the sensitivity occurs because the difference in the traveling properties of holes and electrons in the photoconductive layer is large, and the traveling properties change with temperature. In the light incident part, hole electrons are generated as a pair, and the holes travel to the support side, and the electrons travel to the surface layer side. Increase the rate of recombination before reaching. Since the recombination ratio changes due to thermal excitation from the recapture center, the exposure dose, that is, the number of photogenerated carriers and the number of carriers that cancel the surface potential, change with temperature, and as a result, the sensitivity changes with temperature. Will be. Therefore, the rate of recombination at the light incident part is reduced, that is, the deep level serving as the recapture center is reduced, and the light absorption rate of long-wavelength light is reduced so that the mixed region of holes and electrons is reduced. It has to be bigger, and the runnability of the carrier must be improved.

Further, as the linearity of sensitivity increases, the number of photo-generated carriers relatively deep from the surface increases as the exposure amount of the long-wavelength laser increases, and the carrier having a long running distance (in the case of positive charging, Electrons) increase. Therefore, the light absorptance of the light incident part must be increased, and the traveling property of electrons in the light incident part and the traveling property of holes on the support side must be improved and balanced.

Therefore, by providing a layer region in which Eu is controlled (reduced) while reducing Ch and narrowing Eg as a light incident portion, the rate at which thermally excited carriers and photocarriers are trapped in localized levels can be reduced. The ability to reduce the size of the carrier dramatically improves the traveling performance of the carrier. By reducing Eg, absorption of long-wavelength light is increased and the light incident portion can be reduced, so that the hole-electron mixed region can be reduced. Further, as a further effect, the support-side photoconductive layer can be designed as a layer in which the main carrier is holes to improve its running property.
That is, by using a layer in which Eu is controlled (reduced) while enlarging Ch and enlarging Eg as the main photoconductive layer, generation of thermally excited carriers is suppressed, and the thermally excited carriers and photocarriers are localized. Since the ratio of being trapped by the level can be reduced, the traveling property of the carrier is dramatically improved.

That is, the second photoconductive region is provided on the outermost surface side of the light receiving member, and the region that substantially absorbs light is used as the second photoconductive region.
The temperature characteristics of sensitivity and the linearity of sensitivity when using are greatly improved, and remarkable effects are seen in terms of charging ability, temperature characteristics and memory.

Therefore, according to the present invention,
The temperature characteristics of sensitivity when using laser light or LED, the linearity of sensitivity and the improvement of charging performance and the reduction of temperature characteristics and the reduction of optical memory are compatible at a high level, and all of the above-mentioned problems in the prior art are solved. It is possible to obtain a light-receiving member exhibiting excellent electrical, optical, and photoconductive properties, image quality, durability, and environment for use.

[0050]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a light receiving member of the present invention will be described in detail with reference to the drawings. FIG. 2 is a schematic configuration diagram for explaining a layer configuration of the light receiving member of the present invention. In the light receiving member 200 shown in FIG. 2A, a light receiving layer 202 is provided on a support 201 for a light receiving member. The light receiving layer 202 is made of a non-single-crystal material having silicon atoms as a base material and has a photoconductive property.
The photoconductive layer 203 includes a first photoconductive region 211 and a second photoconductive region 212 in order from the support 201 side.
It consists of

The light receiving member 200 shown in FIG. 2B has a light receiving layer 20 on a support 201 for the light receiving member.
2 are provided. The photoreceptive layer 202 is made of a non-single product material containing silicon atoms as a base material, and has a photoconductive layer 203 having a photoconductive property, and an amorphous silicon based surface layer 204.
It is composed of The photoconductive layer 203 includes a first photoconductive region 211 and a second photoconductive region 212 in order from the support 201 side.

The light receiving member 200 shown in FIG. 2C has a light receiving layer 20 on a support 201 for the light receiving member.
2 are provided. The light receiving layer 202 comprises a support 201
Amorphous silicon charge injection blocking layer 20 in order from the side
5, a photoconductive layer 203 made of a non-single-crystal material having silicon atoms as a base material and having photoconductivity, and an amorphous silicon-based surface layer 204. The photoconductive layer 203 includes a first photoconductive region 211 and a second photoconductive region 212 in order from the charge injection blocking layer 205 side.

(Support) The support used in the present invention may be either conductive or electrically insulating. As the conductive support, Al, Cr, Mo, Au, In, Nb,
Examples include metals such as Te, V, Ti, Pt, Pd, and Fe, and alloys thereof, such as stainless steel. Also, at least the surface of the electrically insulating support such as a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, etc., at least on the side on which the light-receiving layer is formed, such as a glass or ceramic. Can be used.

The shape of the support 201 used in the present invention may be a cylindrical surface or an endless belt having a smooth surface or an uneven surface, and the thickness thereof may form the light receiving member 200 as desired. As described above, if the light receiving member 200 is required to have flexibility, the light receiving member 200 can be made as thin as possible within a range where the function as the support 201 can be sufficiently exhibited. However, the support 2
01 is usually 10 μm or more in terms of production, handling, mechanical strength and the like.

In particular, when image recording is performed using coherent light such as a laser beam, the surface of the support 201 is effectively removed in order to more effectively eliminate image defects due to so-called interference fringe patterns appearing in a visible image. May be provided with irregularities. The irregularities provided on the surface of the support 201 are described in JP-A-60-1
No. 68156, No. 60-178457, No. 60-225
It is prepared by a known method described in each publication of No. 854.

As another method for more effectively eliminating image defects due to interference fringe patterns when coherent light such as laser light is used, an uneven shape formed by a plurality of spherical trace depressions on the surface of the support 201 is provided. It may be provided. That is, the surface of the support 201 has irregularities smaller than the resolving power required for the light receiving member 200, and the irregularities are caused by a plurality of spherical trace depressions. The unevenness due to the plurality of spherical trace dents provided on the surface of the support 201 is described in JP-A-61-2.
It is prepared by a known method described in Japanese Patent No. 31561.

(Photoconductive Layer) In the present invention, the photoconductive layer 203 formed on the support 201 and constituting a part of the light receiving layer 202 is formed by a vacuum deposition film forming method in order to effectively achieve the object. Thus, the film is formed by appropriately setting the numerical conditions of the film forming parameters so as to obtain desired characteristics.
Specifically, for example, an AC discharge C such as a glow discharge method (a low-frequency CVD method, a high-frequency CVD method, or a microwave CVD method) is used.
VD method, DC discharge CVD method, etc.), sputtering method, vacuum deposition method, ion plating method, optical CVD
And a thin film deposition method such as a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the light-receiving member to be produced. The glow discharge method, particularly the high-frequency glow discharge method using a power frequency in the RF band, is suitable because the conditions for manufacturing the light receiving member are relatively easy to control.

In order to form the photoconductive layer 203 by the glow discharge method, basically, a source gas for supplying Si that can supply silicon atoms (Si) and a source gas for supplying H that can supply hydrogen atoms (H) are used. And / or a source gas for X supply capable of supplying a halogen atom (X) and a source gas for Ge supply capable of supplying a germanium atom (Ge),
It is introduced in a desired gas state into a reaction vessel in which the inside can be decompressed to generate a glow discharge in the reaction vessel, and a-Si: H is placed on a predetermined support 201 previously set at a predetermined position. , X may be formed.

In the present invention, it is necessary that the photoconductive layer 203 contains a hydrogen atom and / or a halogen atom, which compensates for dangling bonds of silicon atoms and improves the layer quality. It is indispensable for improving photoconductivity and charge retention characteristics. Therefore, in the case of the first photoconductive region, the content of the hydrogen atom or the barogen atom or the amount of the sum of the hydrogen atom and the halogen atom is 15 to 30 atoms with respect to the sum of the silicon atom and the hydrogen atom or / and the halogen atom. %, And in the case of the second photoconductive region, it is preferably in the range of 5 to 25 atomic% with respect to the sum of silicon atoms and hydrogen atoms and / or halogen atoms.

In the present invention, it is necessary to contain germanium atoms in the second photoconductive region of the photoconductive layer 203, but this does not increase the local density of states.
It is indispensable to adjust the optical band gap and absorb the image exposure efficiently. Therefore, it is desirable that the content of germanium atoms be in the range of 3 to 35% based on the sum of silicon atoms and germanium atoms.

The substances that can serve as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si.
₄ gaseous state of H _10, etc., or silicon hydride can be gasified (silanes) can be mentioned as being effectively used, and further, the layer created readiness in handling, points and Si-feeding efficiency And SiH ₄ and Si ₂ H ₆ are preferred.

Then, hydrogen atoms are structurally introduced into the formed photoconductive layer 203 so that the introduction ratio of hydrogen atoms can be more easily controlled, and the film characteristics that achieve the object of the present invention can be obtained. Therefore, it is necessary to form a layer by mixing a desired amount of a gas of a silicon compound containing H ₂ and / or He or a hydrogen atom with these gases. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

A substance that can be a Ge supply gas used when forming the second photoconductive region is GeH
_4, the _{Ge 2 H 6, Ge 3 H} 8, GeHF 3, GeHCl 3 such gaseous state, or germanium hydride (germane compound) which can be gasified are exemplified as being effectively used, further layers when creating Ge in terms of ease of handling and good Ge supply efficiency
H ₄ is preferred.

The raw material gas for supplying a halogen atom used in the present invention may be, for example, a gaseous or gaseous gas such as a halogen gas, a halide, an interhalogen compound containing halogen, or a silane derivative substituted with halogen. The obtained halogen compounds are preferred. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound. Specific examples of the halogen compound that can be suitably used in the present invention include fluorine gas (F ₂ ), BrF,
Inter-halogen compounds such as ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ can be mentioned. As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, specifically, for example, silicon fluoride such as SiF ₄ or Si ₂ F ₆ is preferable.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 203, for example, the temperature of the support 201, a raw material used for containing hydrogen atoms and / or halogen atoms, etc. What is necessary is just to control the amount of the substance introduced into the reaction vessel, the discharge power and the like.

In the present invention, it is preferable that the photoconductive layer 203 contains atoms for controlling conductivity as necessary. In order to remarkably obtain the effect of the present invention, the content of the atom controlling the conductivity of the light incident side of the second photoconductive region is smaller than the content of the first photoconductive region on the support side. Desirably, it is contained.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors.
An atom belonging to Group IIIb of the Periodic Table that gives p-type conduction characteristics (hereinafter abbreviated as Group IIIb atom) can be used. Specific examples of Group IIIb atoms include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl).
l and Ga are preferred.

The content of atoms controlling the conductivity contained in the photoconductive layer 203 is preferably 2 × 10 ⁻³ to 1
× 10 ² atomic ppm, more preferably 1 × 10 ^-2 to 50
It is desirable that the content be in the range of atomic ppm, most preferably 5 × 10 ^{-2 to} 20 atomic ppm. Further, it is preferable to reduce the content of atoms for controlling the conductivity in the second photoconductive region as compared with the first photoconductive region.

Atoms controlling conductivity, for example, IIIb
In order to introduce the group-atom structurally, the III
A raw material for introducing a group b atom in a gaseous state into a reaction vessel,
It may be introduced together with another gas for forming the photoconductive layer 203. It is preferable that a material that can be used as a raw material for introducing a Group IIIb atom be a gaseous material at normal temperature and pressure or a material that can be easily gasified at least under layer forming conditions.

As such a raw material for introducing a Group IIIb atom, specifically, B is used for introducing a boron atom.
_{2 H 6, B 4 H 10} , B 5 H 9, B 5 H 11, B 6 H 10, B 6 H 12, B 6 H
_And borohydrides such as BF ₃ , BCl ₃ , and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , G
a (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like can also be mentioned. Further, these raw materials for introducing atoms for controlling the conductivity may be diluted with H ₂ and / or He as necessary.

Further, in the present invention, the photoconductive layer 203
It is also effective to include a carbon atom and / or an oxygen atom and / or a nitrogen atom. Carbon atoms and / or
Alternatively, the content of oxygen atoms and / or nitrogen atoms is preferably 1 × 10 ⁻⁵ to 10 atomic%, more preferably 1 × 10 ⁻⁴ to 8%, based on the sum of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms. Atomic%, optimally 1 × 10 ^{-3 to} 5 atomic%
Is desirable. The carbon atoms and / or oxygen atoms and / or nitrogen atoms may be uniformly contained in the photoconductive layer, or may have an uneven distribution such that the content changes in the thickness direction of the photoconductive layer. May be provided.

In the present invention, the layer thickness of the photoconductive layer 203 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics, economic effects, and the like.
It is desirable that the thickness be in the range of 0 to 50 μm, more preferably 23 to 45 μm, and most preferably 25 to 40 μm. When the thickness is less than 20 μm, electrophotographic characteristics such as charging ability and sensitivity become practically insufficient, and when the thickness is more than 50 μm, the production time of the photoconductive layer becomes longer and the production cost becomes higher.

In the present invention, in particular, it is necessary to determine the film thickness of the second photoconductive region so that the light absorption of the laser used is in the range of 70 to 95%, and the absorption is 70% or less. With this thickness, light reaches a considerably deep portion of the first photoconductive region, which is designed to be a layer that is advantageous for hole transportability. In that part, the effect of improving the temperature characteristics of sensitivity and the linearity of sensitivity cannot be sufficiently exhibited because the traveling property of electrons is small. When the thickness of the second photoconductive region becomes 95% or more of light absorption, a large number of holes must travel a considerable distance in the second photoconductive region. Usually, the second photoconductive region on the side of the surface layer is hardly doped with Group IIIb atoms, with emphasis on electron traveling properties.
Therefore, the mobility of holes in the second photoconductive region is small, causing an increase in sensitivity and residual potential, and it is difficult to obtain the effects of the present invention. In addition, when doping is also performed on this portion in order to increase the hole mobility, the electron mobility decreases, the sensitivity increases, and the effects of the present invention, such as a decrease in charging ability and an increase in dark decay, are exhibited. Not done. Therefore,
The SiGe film that can be satisfied as the second photoconductive region needs to be of good quality with few defects.

However, even if a high-quality film is used, the film thickness is 95%.
With the above, the factors that hinder the effects of the present invention increase, and sufficient effects cannot be exhibited.

Further, even if the second photoconductive region on the surface layer side is coherent light such as laser light, it absorbs 70 to 95% of the light, so that special interference occurs in the support and the lower layer. There is no need to take measures against stripes, and a good image can be obtained.

In order to achieve the object of the present invention and to form the photoconductive layer 203 having desired film characteristics, the mixing ratio of the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power, It is necessary to appropriately set the temperature of the support.

[0077] The flow rate of H ₂ and / or He used as a dilution gas is properly selected within an optimum range in accordance with the layer design, to Si-feeding gas H ₂ and / or H
e is usually 3 to 2 in the first photoconductive region.
0 times, preferably 4 to 15 times, and optimally 5 to 10 times. In the second photoconductive region, usually 2 to 12 times, preferably 3 to 10 times,
Optimally, it is desirable to control it in the range of 4 to 8 times.

The optimum range of the gas pressure in the reaction vessel is also appropriately selected in accordance with the layer design, but both the first photoconductive region and the second photoconductive region are usually 1.0 × 10 4
^{-2 ~2. 0 × 10 3 Pa} , preferably ^5. 0 × 10 ^{-2 ~5.}
0 × 10 ² Pa, optimally ^{1. 0 × 10 1 ~2.} 0 × 10 2
It is preferable to set the range of Pa. And it is important that the gas pressure does not change abruptly in the change region from the first photoconductive region to the second photoconductive region.

Similarly, the optimum range of the discharge power is appropriately selected according to the layer design. The ratio of the discharge power to the flow rate of the gas for supplying Si is set to 2 to 8 in the first photoconductive region, preferably to 8 to 8. It is desirable to set in the range of 1-6. Further, the ratio of the discharge power to the flow rate of the Si supply gas in the second photoconductive region is smaller than that of the first photoconductive region, and is preferably formed in the range of 0.5 to 4.

Further, an optimum range of the temperature of the support 201 is appropriately selected according to the layer design.
Preferably from 200 to 350 ° C, more preferably from 230 to
It is desirable to set the temperature to 330 ° C., optimally in the range of 250 to 300 ° C.

In the present invention, the preferable ranges of the temperature of the support and the gas pressure for forming the photoconductive layer include the above-mentioned ranges. However, the conditions are not usually determined separately and independently. It is desirable to determine the optimum value based on mutual and organic relevance to form a light receiving member having desired properties.

(Surface Layer) In the present invention, it is preferable to further form an amorphous silicon-based surface layer 204 on the photoconductive layer 203 formed on the support 201 as described above. This surface layer 204 is a free surface 2
06, and is provided in order to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electric pressure resistance, use environment characteristics, and durability.

In the present invention, the light receiving layer 202
Since each of the amorphous materials forming the photoconductive layer 203 and the surface layer 204 has a common component of silicon atoms, chemical stability is sufficiently ensured at the lamination interface. I have.

The surface layer 204 can be made of any material as long as it is an amorphous silicon material. For example, a hydrogen atom (H) and / or a halogen atom (X) can be used.
And further contains carbon atom-containing amorphous silicon (hereinafter a-SiC: H, X), hydrogen atom (H) and / or halogen atom (X), and further contains oxygen atom Amorphous silicon (hereinafter
a-SiO: H, X), a hydrogen atom (H) and / or
Alternatively, amorphous silicon containing a halogen atom (X) and further containing a nitrogen atom (hereinafter a-SiN: H, X
Amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing at least one of a carbon atom, an oxygen atom, and a nitrogen atom (hereinafter, a-SiCON: H, X And the like are preferably used.

In the present invention, in order to effectively achieve the object, the surface layer 204 is formed by a vacuum deposition film forming method by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics. You. Specifically, for example, a glow discharge method (an AC discharge CVD method such as a low-frequency CVD method, a high-frequency CVD method, or a microwave CVD method, or a DC discharge CVD method), a sputtering method, a vacuum deposition method, an ion plating method , A photo-CVD method, a thermal CVD method and the like.
These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the light receiving member to be produced. It is preferable to use a deposition method equivalent to that of the photoconductive layer from the viewpoint of properties.

For example, a-SiC:
In order to form the surface layer 204 made of H and X, a source gas for supplying Si that can supply silicon atoms (Si) and a source gas for supplying C that can supply carbon atoms (C) are basically used. And a source gas for H supply capable of supplying hydrogen atoms (H) and / or a source gas for X supply capable of supplying halogen atoms (X) are placed in a reaction vessel capable of reducing the pressure inside the reactor to a desired gas state. To generate a glow discharge in the reaction vessel, and a photoconductive layer 20 previously set at a predetermined position.
A layer made of a-SiC: H, X may be formed on the support 201 on which the substrate 3 is formed.

The material of the surface layer used in the present invention may be any amorphous material containing silicon, but is preferably a compound with a silicon atom containing at least one element selected from carbon, nitrogen and oxygen. Those containing -SiC as a main component are preferable. A-
When SiC is the main component, the carbon content is preferably in the range of 30 to 90% based on the sum of silicon atoms and carbon atoms.

Further, in the present invention, it is necessary that the surface layer 204 contains hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves the quality of the layer, especially the optical quality. It is indispensable to improve the conductivity characteristics and the charge retention characteristics. The hydrogen content is usually 30 to 70 atoms based on the total amount of the constituent atoms.
%, Preferably 35-65 atom%, optimally 40-60 atom
% Is desirable. In addition, the content of fluorine atoms is usually in the range of 0.01 to 15 atomic%, preferably 0.1 to 10 atomic%, and most preferably 0.6 to 4 atomic%. .

The light receiving member formed within the range of the hydrogen and / or fluorine content has a practically
It can be applied sufficiently as an unprecedentedly excellent one. That is, it is known that defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer adversely affect the characteristics as a light receiving member for electrophotography. For example, deterioration of charging characteristics due to injection of electric charge from the free surface, fluctuation of charging characteristics due to changes in the surface structure under the use environment, for example, high humidity, and furthermore, from the photoconductive layer to the surface layer at the time of corona charging or light irradiation. The adverse effect is that the charge is injected and the charge is trapped in the defect in the surface layer, thereby causing an afterimage phenomenon at the time of repeated use.

However, when the hydrogen content in the surface layer is 30
By controlling the atomic percentage or more, defects in the surface layer are significantly reduced, and as a result, the electrical characteristics and the high-speed continuous usability can be dramatically improved as compared with the related art.

On the other hand, if the hydrogen content in the surface layer exceeds 70 atomic%, the hardness of the surface layer is reduced, so that the surface layer cannot withstand repeated use. Therefore, controlling the hydrogen content in the surface layer within the above-mentioned range is one of the very important factors in obtaining a very excellent desired electrophotographic property. The hydrogen content in the surface layer can be controlled by the flow rate (ratio) of the raw material gas, the temperature of the support, the discharge power, the gas pressure, and the like.

Further, the fluorine content in the surface layer is 0.01
By controlling the content to the range of at least atomic%, it becomes possible to more effectively achieve the generation of the bond between silicon atoms and carbon atoms in the surface layer. Further, as a function of the fluorine atoms in the surface layer, it is possible to effectively prevent the bond between the silicon atom and the carbon atom from being broken due to damage such as corona.

On the other hand, when the fluorine content in the surface layer is 15 atoms
If it exceeds 0.1%, the effect of generating the bond between the silicon atom and the carbon atom in the surface layer and the effect of preventing the breaking of the bond between the silicon atom and the carbon atom due to damage such as corona are hardly recognized. Furthermore, since excess fluorine atoms hinder the mobility of carriers in the surface layer, residual potential and image memory are remarkably observed. Therefore, controlling the fluorine content in the surface layer within the above range is one of the important factors for obtaining desired electrophotographic characteristics. Like the hydrogen content, the fluorine content in the surface layer can be controlled by the flow rate (ratio) of the raw material gas, the temperature of the support, the discharge power, the gas pressure, and the like.

The substance which can be a gas for supplying silicon (Si) used in forming the surface layer of the present invention includes:
Silicon hydrides (silanes) in a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ or the like which can be gasified are used effectively. ease of handling, SiH _4, Si ₂ H ₆ in terms of and Si-feeding efficiency can be mentioned as preferred. Further, these raw material gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

Examples of the substance that can serve as a carbon supply gas include:
CH_Four, C_TwoH_Two, C_TwoH₆, C_ThreeH₈, C_FourH _TenEtc. in the gas state,
Or that gaseous hydrocarbons are used effectively
In addition, ease of handling when creating layers, Si
CH in terms of good supply efficiency, etc._Four, C_TwoH_Two, C_TwoH₆Is preferred
It is mentioned as a new thing. In addition, these C
Feed gas as needed_Two, He, Ar, Ne, etc.
May be used after dilution.

Substances that can serve as nitrogen or oxygen supply gas include NH ₃ , NO, N ₂ O, NO ₂ , O ₂ , CO, CO ₂ , N
Compounds in a gaseous state or capable of being gasified, such as ₂ , are effectively used. If necessary, these nitrogen and oxygen supply source gases may be replaced with H ₂ , He, Ar,
It may be used after diluted with a gas such as Ne.

In order to make it easier to control the introduction ratio of hydrogen atoms introduced into the surface layer 204 to be formed, these gases may be further mixed with hydrogen gas or silicon compound gas containing hydrogen atoms. Also, it is preferable to form a layer by mixing desired amounts. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

Examples of the effective source gas for supplying halogen atoms include gaseous or gasizable halogen compounds such as halogen gas, halides, interhalogen compounds containing halogen, and silane derivatives substituted with halogen. . Further, a silicon hydride compound containing a silicon atom and a halogen atom as a component and containing a gaseous or gasifiable halogen atom can also be mentioned as an effective compound. Specific examples of the halogen compound that can be suitably used in the present invention include fluorine gas (F ₂ ), BrF, ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ ,
And a halogen compound between IF ₇ or the like. As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, specifically, for example, silicon fluoride such as SiF ₄ or Si ₂ F ₆ is preferable.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer 204, for example, the temperature of the support 201, a raw material used to contain hydrogen atoms and / or halogen atoms The amount to be introduced into the reaction vessel and the discharge power may be controlled.

Carbon atoms and / or oxygen atoms and / or
Alternatively, the nitrogen atoms may be uniformly contained in the surface layer, or there may be a portion having a non-uniform distribution such that the content changes in the thickness direction of the surface layer.

Further, in the present invention, it is preferable that the surface layer 204 contains atoms for controlling conductivity as necessary. The atoms for controlling the conductivity may be contained in the surface layer 204 in a state of being uniformly distributed without unevenness,
Alternatively, there may be portions contained in a non-uniform distribution state in the layer thickness direction.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors. An atom belonging to Group IIIb of the Periodic Table giving p-type conduction characteristics (hereinafter abbreviated as Group IIIb atom). ) Can be used.

Specific examples of Group IIIb atoms include zirconium (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl).
Al and Ga are preferred.

The content of atoms for controlling conductivity contained in the surface layer 204 is preferably 1 × 10 ⁻³ to 1 ×.
10 ³ atomic ppm, more preferably 1 × 10 ^{-2 to} 5 × 1
0 ² atomic ppm, optimally 1 × 10 ^-1 to 1 × 10 ² atomic p
pm. To structurally introduce conductivity controlling atoms, for example, Group IIIb atoms,
In forming the layer, a raw material for introducing Group IIIb atoms may be introduced in a gaseous state into the reaction vessel together with another gas for forming the surface layer 204.

As a raw material that can be used as a source material for introducing a Group IIIb atom, it is preferable to employ a material that is gaseous at normal temperature and normal pressure or that can be easily gasified at least under layer forming conditions. As a raw material for introducing a Group IIIb atom, specifically, for introducing a boron atom,
_{2 H 6, B 4 H 10} , B 5 H 9, B 5 H 11, B 6 H 10, B 6 H 12, B 6 H
_And borohydrides such as BF ₃ , BCl ₃ , and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ ,
Ga (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like can also be mentioned. Further, these raw materials for introducing atoms for controlling the conductivity may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

The thickness of the surface layer 204 in the present invention is usually 0.01 to 3 μm, preferably 0.05 to 2 μm,
Most preferably, it is in the range of 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to abrasion or the like during use of the light-receiving member, and if it exceeds 3 μm, the electrophotographic characteristics such as an increase in residual potential are reduced. The surface layer 204 according to the present invention is carefully formed so as to give its required properties as desired. That is, a substance containing Si, C and / or N and / or O, H and / or X as a constituent element takes a form from crystalline to amorphous depending on its forming condition, and has electrical conductivity as conductive. In the present invention, a compound having desired properties according to the purpose is shown, since the properties between the properties from a semiconductive property to an insulating property, and properties from a photoconductive property to a non-photoconductive property are respectively shown. The formation conditions are strictly selected as desired so that is formed. For example, in order to provide the surface layer 204 mainly for the purpose of improving the pressure resistance, the surface layer 204 is formed as a non-single-crystal material having a remarkable electrical insulating behavior in a use environment.

When the surface layer 204 is provided mainly for the purpose of improving the continuous repetitive use characteristics and the use environment characteristics, the above-described degree of electrical insulation is alleviated to some extent, and the applied light is irradiated to a certain degree. Formed as a sensitive non-single crystal material.

In order to form the surface layer 204 having characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the temperature of the support 201 and the gas pressure in the reaction vessel as desired.

The optimum range of the temperature (Ts) of the support 201 is appropriately selected according to the layer design.
Preferably from 200 to 350 ° C, more preferably from 230 to
It is desirable to set the temperature to 330 ° C., optimally in the range of 250 to 300 ° C.

The gas pressure in the reaction vessel is also appropriately selected in the same manner according to the layer design, but is usually 1.0 × 10 ^{−2 to} 2.0 × 10 ³ Pa, more preferably. Is from 5.0 × 10 ^{−1 to} 5.0 × 10 ² Pa, optimally 1.
It is preferable to set the range of 0 × 10 ^{−1 to} 2.0 × 10 ² Pa.

In the present invention, the preferable ranges of the temperature and the gas pressure of the support for forming the surface layer include the above-mentioned ranges. However, the conditions are not usually determined separately and independently. It is desirable to determine the optimum value based on mutual and organic relevance to form a light receiving member having the following characteristics.

Further, in the present invention, it is also possible to provide a blocking layer (lower surface layer) in which the content of carbon atoms, oxygen atoms and nitrogen atoms is smaller than that of the surface layer between the photoconductive layer and the surface layer. It is effective to further improve the characteristics of.

Further, a region where the content of carbon atoms and / or oxygen atoms and / or nitrogen atoms changes so as to decrease toward photoconductive layer 203 may be provided between surface layer 204 and photoconductive layer 203. Good. This improves the adhesion between the surface layer and the photoconductive layer, smoothes the movement of the photocarrier to the surface, and reduces the influence of interference due to light reflection at the interface between the photoconductive layer and the surface layer. it can.

(Charge Injection Blocking Layer) In the photoreceptor member of the present invention, a charge injection blocking layer having a function of blocking charge injection from the conductive support side between the conductive support and the photoconductive layer. Is more effective. That is,
The charge injection blocking layer has a function of preventing charges from being injected from the support side to the photoconductive layer side when the photoreceptive layer receives a charge treatment of a fixed polarity on its free surface. Such a function is not exhibited when it is subjected to processing, that is, it has a so-called polarity dependency. In order to provide such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared to the photoconductive layer.

The atoms for controlling the conductivity contained in the layer may be uniformly distributed in the layer uniformly, or may be uniformly distributed in the layer thickness direction but not uniformly. May be present in a state of being distributed in the form. When the distribution concentration is non-uniform, it is preferable that the compound be contained so as to be distributed more on the support side.

However, in any case, it is necessary to uniformly contain the particles in the in-plane direction parallel to the surface of the support from the viewpoint of making the characteristics uniform in the in-plane direction. .

Examples of the atoms for controlling conductivity contained in the charge injection blocking layer include so-called impurities in the field of semiconductors, and atoms belonging to Group IIIb of the periodic table giving p-type conduction characteristics (hereinafter referred to as atoms). IIIb group atom).

As the Group IIIb atom, specifically, B
(Boron), Al (aluminum), Ga (gallium),
There are In (indium) and Tl (thallium), and B, Al, and Ga are particularly preferable.

In the present invention, the content of atoms for controlling conductivity contained in the charge injection blocking layer is appropriately determined as desired so that the object of the present invention can be effectively achieved. 10-1 × 10 ⁴ atom pp
m, more preferably 50 to 5 × 10 ³ atomic ppm, and most preferably 1 × 10 ^{2 to} 3 × 10 ³ atomic ppm.

Further, the charge injection blocking layer contains carbon atoms,
By containing at least one of a nitrogen atom and an oxygen atom, the adhesion to another layer provided in direct contact with the charge injection blocking layer can be further improved.

The carbon atoms, nitrogen atoms or oxygen atoms contained in the layer may be uniformly distributed throughout the layer, or may be evenly distributed in the layer thickness direction. May be present in a non-uniformly distributed state. However, in any case, it is necessary to uniformly contain the particles in the in-plane direction parallel to the surface of the support in order to make the characteristics uniform in the in-plane direction.

In the present invention, carbon atoms and / or nitrogen atoms contained in the entire region of the charge injection blocking layer and / or
Alternatively, the content of the oxygen atom is appropriately determined so that the object of the present invention can be effectively achieved. In the case of one kind, the content is two times or more. ^-3 to 30 atomic%, more preferably 5 × 10 ^-3 to 2
It is desirable that the content be in the range of 0 atomic% and, for an optimal person, 1 × 10 ⁻² to 10 atomic%.

Further, the hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer in the present invention compensate for dangling bonds existing in the layer and are effective in improving the film quality.
The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the charge injection blocking layer is preferably 1
~ 50 atomic%, more preferably 5-40 atomic%, optimally 1
It is desirable to set it in the range of 0 to 30 atomic%.

In the present invention, the thickness of the charge injection blocking layer is preferably from 0.1 to 5 μm, more preferably from 0.3 to 5 μm, from the viewpoints of obtaining desired electrophotographic characteristics and economic effects. It is desirable that the thickness be 4 μm, most preferably 0.5 to 3 μm. When the layer thickness is less than 0.1 μm, the ability to prevent charge injection from the support is insufficient, and sufficient charging ability cannot be obtained. Even if the layer thickness is more than 5 μm, improvement in electrophotographic properties cannot be expected, Only the production cost is increased due to the extension of the production time.

In the present invention, to form the charge injection blocking layer, a vacuum deposition method similar to the above-described method of forming the photoconductive layer is employed.

In order to form the charge injection blocking layer 205 having characteristics capable of achieving the object of the present invention, similarly to the photoconductive layer 203, the mixing ratio between the gas for supplying Si and the diluent gas, It is necessary to appropriately set the gas pressure, the discharge power, and the temperature of the support 201.

The flow rate of the diluent gas H ₂ and / or He is appropriately selected in accordance with the layer design. The flow rate of H ₂ and / or He to the Si supply gas is usually 0.3. It is desirable to control the pressure within a range of from 20 to 20 times, preferably from 0.5 to 15 times, and most preferably from 1 to 10 times.

Similarly, the optimum range of the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design.
0 × 10 ^{-2 to} 2.0 × 10 ³ Pa, preferably 5.0 × 1
0 ^{-1 to} 5.0 × 10 ² Pa, optimally 1.0 to 2.0 × 10
^It is preferred to be in the range of ² Pa.

Similarly, the optimum range of the discharge power is appropriately selected according to the layer design. The ratio of the discharge power to the flow rate of the gas for supplying Si is usually 0.5 to 8, preferably 0.5. It is desirable to set it in the range of 8-7, optimally 1-6.

Further, the optimum temperature of the support 201 is appropriately selected according to the layer design.
Preferably from 200 to 350 ° C, more preferably from 230 to
It is desirable to set the temperature to 330 ° C., optimally in the range of 250 to 300 ° C.

In the present invention, the desirable ranges of the mixing ratio of the diluent gas, the gas pressure, the discharge power, and the temperature of the support for forming the charge injection blocking layer include the above-mentioned ranges. Is usually not independently determined separately, but it is desirable to determine the optimum value of each layer forming factor based on mutual and organic relevance in order to form a surface layer having desired properties.

In addition, in the light receiving member of the present invention, at least an aluminum atom, a silicon atom, a hydrogen atom and / or
It is desirable to have a layer region in which halogen atoms are contained in a non-uniform distribution state in the layer thickness direction.

In the light receiving member of the present invention, the support 201 and the photoconductive layer 203 or the charge injection blocking layer 2
For the purpose of further improving the adhesiveness between Si and N.05, for example, Si ₃ N ₄ , SiO ₂ , SiO ₂ or a silicon atom as a base, a hydrogen atom and / or a halogen atom, a carbon atom and / or an oxygen atom And / or an adhesion layer formed of an amorphous material containing nitrogen atoms or the like may be provided.
Further, a light absorbing layer for preventing an interference pattern from being generated by light reflected from the support may be provided.

(Forming Method) Next, an apparatus and a film forming method for forming a light receiving layer will be described in detail. FIG. 3 is a schematic diagram showing an example of an apparatus for manufacturing a light receiving member by a high-frequency plasma CVD method (hereinafter abbreviated as RF-PCVD) using an RF band as a power supply frequency. The configuration of the manufacturing apparatus shown in FIG. 3 is as follows.

This apparatus is roughly classified into a deposition apparatus 310
0, source gas supply device 3200, and reaction vessel 31
It is composed of a haiku device (not shown) for reducing the pressure inside the chamber 11. Reaction vessel 3111 in deposition apparatus 3100
Inside the cylindrical support 3112, the heater 3 for heating the support
113, a source gas introduction pipe 3114 is installed, and a high frequency matching box 3115 is further connected.

The source gas supply device 3200 is composed of SiH ₄ , Ge
Cylinder 32 for source gas such as H ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH ₃
21 to 226 and valves 3231 to 236, 3241
3246, 3251 to 3256, and mass flow controllers 3211 to 3216, and the cylinders for each raw material gas are supplied via a valve 3260 to the reaction vessel 3111.
Connected to a gas introduction pipe 3114 in the inside.

The formation of a deposited film using this apparatus can be performed, for example, as follows. First, the reaction vessel 31
A cylindrical support 3112 is set in the chamber 11, and the inside of the reaction vessel 3111 is evacuated by an exhaust device (not shown) (for example, a vacuum pump). Subsequently, the temperature of the cylindrical support 3112 is controlled to a predetermined temperature of 200 to 350 ° C. by the support heating heater 3113.

The raw material gas for forming the deposited film is supplied to the reaction vessel 311.
In order to make the gas flow into the valve 1, the valves 3231 to 331 of the gas cylinder are used.
236, confirming that the leak valve 3117 of the reaction vessel is closed, and checking the inflow valves 3241 to 324
6. Outflow valves 3251 to 256, auxiliary valve 326
Make sure that the main valve 3 is open.
Open 118 to open reaction vessel 3111 and gas pipe 31
Exhaust 16.

Next, the reading of the vacuum gauge 3119 was about 6.5 × 1.
When the pressure becomes 0 ^-4 Pa, the auxiliary valve 3260 and the outflow valves 3251 to 256 are closed. After that, gas cylinder 3
From 221 to 226, each gas is supplied to a valve 3231 to 32.
36 is opened and introduced, and each gas pressure is adjusted to ² kg / cm ² by the pressure adjusters 3261 to 3266. Next, the inflow valves 3241 to 246 are gradually opened to introduce each gas into the mass flow controllers 3211 to 216.

After the preparation for film formation is completed as described above, each layer is formed in the following procedure. Cylindrical support 31
When 12 reaches a predetermined temperature, the outflow valve 3251
Required of ５６3256 and auxiliary valve 326
0 is gradually opened, and a predetermined gas is supplied from the gas cylinders 3221 to 226 through the gas introduction pipe 3114 to the reaction vessel 311.
Introduce into 1. Next, the mass flow controller 321
Adjustment is made so that each source gas has a predetermined flow rate according to 1-316. At this time, the opening of the main valve 3118 is adjusted while watching the vacuum gauge 3119 so that the pressure in the reaction vessel 3111 becomes a predetermined pressure of 1.0 × 10 ² Pa or less. When the internal pressure stabilizes, the frequency is 13.56 MH
z RF power supply (not shown) is set to a desired power, and the reaction vessel 311 is passed through the high-frequency matching box 3115.
RF power is introduced into 1 to cause glow discharge. The raw material gas introduced into the reaction vessel is decomposed by the discharge energy, and a deposited film mainly containing predetermined silicon is formed on the cylindrical support 3112.
After the formation of the desired film thickness, the supply of the RF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed. By repeating the same operation a plurality of times, a light receiving layer having a desired multilayer structure is formed.

When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed, and each gas is supplied to the reaction vessel 3111.
, Outflow valves 3251-256 to reaction vessel 311
In order to avoid remaining in the piping leading to 1, the operation of closing the outflow valves 3251 to 256, opening the auxiliary valve 3260, and further fully opening the main valve 3118 to once evacuate the system to a high vacuum is performed as necessary. Do it.

In order to make the film formation uniform, it is also effective to rotate the support 3112 at a predetermined speed by a driving device (not shown) during the layer formation. Further, it goes without saying that the above-mentioned gas types and valve operations are changed according to the conditions for forming each layer.

[Test Examples] The effects of the present invention will be specifically described below by test examples. (Test Example 1) A charge injection blocking layer was formed on a mirror-finished aluminum cylinder (support) having a diameter of 80 mm under the conditions shown in Table 1 using an apparatus for manufacturing a light receiving member by the RF-PCVD method shown in FIG. A light receiving member comprising a photoconductive layer and a surface layer was prepared. At this time, the photoconductive layer was formed in the order of the first photoconductive region and the second photoconductive region from the charge injection blocking layer side.

On the other hand, instead of the aluminum cylinder,
A glass substrate (Corning Co., Ltd. 7) was used by using a grooved cylindrical sample holder for installing the sample substrate.
059) and an a-Si film having a thickness of about 1 μm was deposited on the Si wafer under the conditions for forming the first photoconductive region and the second photoconductive region. After measuring the optical band gap (Eg), the deposited film on the glass substrate
A skewer electrode of Cr was deposited, and characteristic energy (Eu) of the exponential function tail was measured by CPM. The hydrogen content (Ch) of the deposited film on the Si wafer was measured by FTIR.

In the example of Table 1, the first photoconductive region is Ch, E
g and Eu are 23 atom%, 1.77 eV and 60 me, respectively.
V, and in the second photoconductive region, Ch, Eg, and Eu were 18 atom%, 1.60 eV, and 57 meV, respectively.

Next, in the second photoconductive region, the mixing ratio of the SiH ₄ gas and the H ₂ gas, the ratio of the SiH ₄ gas and the discharge power, and the gas flow ratio of the SiH ₄ and GeH ₄ are variously changed. Various light receiving members having different photoconductive regions of Eg (Ch) and Eu were prepared.

The film thickness of the second photoconductive region on the surface layer side was adjusted to about 60, 70, 80, 90, 95 and 9 by image exposure.
A light receiving member was prepared with a film thickness capable of absorbing 8%. However, the total photoconductive layer including the first photoconductive layer and the second photoconductive region was adjusted to have a thickness of 30 μm. The produced light receiving member was set in an electrophotographic apparatus (NP-6750 manufactured by Canon Inc. modified for testing), and the potential characteristics were evaluated.

At this time, first, the process speed was 380 mm
/ Sec, pre-exposure (700nm wavelength LED) 4lux ・ s
ec, set in a test electrophotographic apparatus for image exposure (LED of 680 nm), and evaluated the potential characteristics. The temperature characteristics of sensitivity, the linearity of sensitivity, and the charging ability) were measured. Under these conditions, the surface potential of the light-receiving member was measured by a potential sensor of a surface electrometer (Model 344, TREK) set at the developing device position of the electrophotographic apparatus, and the measured potential was used as the charging ability.

The charging ability was measured under the above conditions by changing the temperature from room temperature (about 25 ° C.) to 50 ° C. using a drum heater built in the light receiving member.
The change in chargeability per ° C was taken as a temperature characteristic. The memory potential was measured by measuring the potential difference between the surface potential in the non-exposure state and the potential after the exposure and then the recharging under the above-described conditions using the same potential sensor.

The temperature characteristics of sensitivity are room temperature and 50 ° C., and the exposure amount of {350, the set voltage (exposure amount = 0), and the
It was obtained by extrapolating a straight line connecting two points of 200 exposures.
Evaluation was made based on the absolute value of the difference from the exposure amount of 350. The linearity of sensitivity is as follows: surface potential is set potential (exposure amount = 0) and
The inclination of the straight line connecting the two exposure amounts at the time of was compared and evaluated. Thereafter, the temperature characteristics of sensitivity, the linearity of sensitivity, and the image check (interference fringe pattern) were set in an electrophotographic apparatus using a visible laser of 680 nm and evaluated.

FIGS. 4 to 8 show the relationship between Eu and Eg of this example and temperature characteristics of sensitivity, linearity of sensitivity, charging ability, temperature characteristics, and memory, respectively. 9 to 10 show the relationship between the temperature characteristic of sensitivity and the linearity of sensitivity. With respect to the respective characteristics, the improvement direction is shown to be 1 or less as a relative value when the photoconductive layer (total film thickness 30 μm) is constituted by only the first photoconductive region is set to 1. As is clear from FIGS. 4 to 10, Eg is 1.55 to 1.70 eV and Eu is in the second photoconductive region.
Is 55 to 65 meV, and the hydrogen content is in a range of 5 to 25 atomic% to a film thickness capable of absorbing 70 to 95% of the image exposure, particularly in an electrophotographic apparatus using an infrared visible laser, It was found that the linearity of the sensitivity was good, and good characteristics were obtained in all of the charging ability, temperature characteristics and memory.

Further, the film of the second photoconductive region from which good characteristics were obtained was examined for the content of silicon atoms and germanium atoms. As a result, the content of germanium atoms was 3 to 3 times the sum of silicon atoms and germanium atoms. It was found to be in the range of 35%.

[0153]

[Table 1] * Content of B with respect to Si. ** The second photoconductive region has a film thickness capable of absorbing about 90% of 680 nm light (absorbance of 680 nm light is measured with a sample).

(Test Example 2) On a mirror-finished aluminum cylinder (support) having a diameter of 80 mm under the same conditions as in Test Example 1, using the apparatus for manufacturing a light receiving member by the RF-PCVD method shown in FIG. Then, a light receiving member including a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared. At this time, the first photoconductive region and the second photoconductive region were stacked in this order from the charge injection blocking layer side. The layer thickness of the first photoconductive region on the support side was fixed at 27 μm, and the film thickness of the second photoconductive region on the surface layer side was set to a thickness capable of absorbing about 90%.

On the other hand, instead of the aluminum cylinder,
A glass substrate (Corning Co., Ltd. 7) was used by using a grooved cylindrical sample holder for installing the sample substrate.
059) and an a-Si film having a thickness of about 1 μm was deposited on the Si wafer under the conditions for forming the first photoconductive region and the second photoconductive region. After measuring the optical band gap (Eg), the deposited film on the glass substrate
A skewer electrode of Cr was deposited, and characteristic energy (Eu) of the exponential function tail was measured by CPM. The hydrogen content (Ch) of the deposited film on the Si wafer was measured by FTIR.

In the example of Table 2, the first photoconductive region is Ch, E
g and Eu are 28 atom%, 1.80 eV and 62 me, respectively.
V, Ch, Eg, and Eu in the second photoconductive region were 10 atomic%, 1.58 eV, 60 meV, and the content of Ge atoms was 7 atomic%, respectively.

Next, by changing the mixing ratio of the SiH ₄ gas and the H ₂ gas and the ratio of the SiH ₄ gas to the discharge power in the first photoconductive region, the Eg of the first photoconductive region was changed.
(Ch), various light receiving members having different Eu were produced.

The potential characteristics of each of the produced light receiving members were evaluated in the same manner as in Test Example 1. As a result, in the first photoconductive region, Eg was 1.75 to 1.85 eV, Eu was 55 to 65 meV, and Ch was 75%. Is in the range of 15 to 30 atomic%, compared with the case where the photoconductive layer is composed of only the first photoconductive region, the temperature characteristic of sensitivity, the linearity of sensitivity, the charging ability, the temperature characteristic, the optical memory and It was found that all of the adhesiveness was improved, and the temperature characteristics of sensitivity and the linearity of sensitivity were significantly improved in laser and LED light. Also, no interference fringe pattern was observed in the image even when a red-visible laser was used.

[0159]

[Table 2] * Content of B with respect to Si. ** The second photoconductive region has a film thickness capable of absorbing about 90% of 680 nm light (absorbance of 680 nm light is measured with a sample).

(Test Example 3) On a mirror-finished aluminum cylinder (support) having a diameter of 80 mm under the same conditions as in Test Example 1, using the apparatus for manufacturing a light receiving member by the RF-PCVD method shown in FIG. Then, a light receiving member including a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared. At this time, the first photoconductive region and the second photoconductive region were stacked in this order from the charge injection blocking layer side. The layer thickness of the first photoconductive region on the support side is fixed at 27 μm, and the thickness of the second photoconductive region on the surface layer side is about 70% and two types of photoreceptor members having a film thickness capable of absorbing 90%. Was prepared. The deposition conditions for each layer were the same as in Table 2, and
The content of the group Ib element was as described below. Then, a light receiving member having only the first photoconductive layer was prepared for reference.

Here, regarding the inclusion of the Group IIIb element in the photoconductive layer, image exposure was performed at 50, 60, 70, 80 and 9
Photoreceptor members having different content distributions of Group IIIb elements, with the content in the layer region from the surface side required to absorb 0% being 0.2 ppm and the content in other layer regions being uniformly 1.0 ppm. Were produced in various ways.

Each of the produced light receiving members was evaluated for potential characteristics in the same manner as in Test Example 1. FIGS. 12 to 16 show the relationship between the above-described content distribution and the layer thickness of the second photoconductive region and the charging ability, the temperature characteristic of the charging ability, the optical memory, the temperature characteristic of the sensitivity, and the linearity of the sensitivity, respectively.

As is clear from FIGS. 12 to 16, the content of the Group IIIb element in the layer region from the surface side required for absorbing 70% or more of the image exposure in the second photoconductive region is equal to the first content of the support. The light receiving member having less than the photoconductive region of No. III
It was found that all the characteristic levels of the charging ability, the temperature characteristic of the charging ability, the optical memory, the temperature characteristic of the sensitivity, and the linearity of the sensitivity were improved as compared with those containing the group b element uniformly.

[0164]

The present invention will be described more specifically with reference to the following examples. Example 1 A charge injection blocking layer, a photoconductive layer, and a surface were formed on a mirror-finished aluminum cylinder (support) having a diameter of 80 mm using the apparatus for manufacturing a light receiving member by the RF-PCVD method shown in FIG. A light receiving member composed of a layer was produced. At this time, the photoconductive layer was arranged in the order of the first photoconductive region and the second photoconductive region from the charge injection blocking layer side. Table 3 shows the conditions for manufacturing the light receiving member at this time.

In this example, Ch, Eg, and Eu of the first photoconductive region of the photoconductive layer are 20 atomic% and 1.77 eV, respectively.
The results were 60 meV, Ch, Eg, and Eu of the second photoconductive region were 10 atomic%, 1.58 eV, and 52 meV, respectively, and the Ge atom content was 9 atomic%.

The light receiving member thus manufactured was modified with an electrophotographic apparatus (NP-6550 manufactured by Canon Inc. for testing purposes).
(nm LED), and the potential characteristics were evaluated. As a result, good characteristics were obtained in all of the temperature characteristics of sensitivity, the linearity of sensitivity, the charging ability, the temperature characteristics, and the memory.

When the produced photoreceptor member was positively charged and evaluated for an image, no optical memory was observed on the image, and good electrophotographic characteristics were obtained with respect to other image characteristics (pockets, image deletion). Was.

That is, even when the photoconductive layer is arranged in the order of the first photoconductive region and the second photoconductive region from the charge injection blocking layer side, the first photoconductive region of the photoconductive layer has C
h, Eg, and Eu are respectively 15 to 30 atomic%, 1.75 to
It is preferable that the range is 1.85 eV, 55 to 65 meV, and the second photoconductive region has Eg of 1.55 to 1.70 eV, Eu of 55 to 65 meV, and Ch of 5 to 25 atom%. It is understood that it is necessary to obtain electrophotographic characteristics.

[0169]

[Table 3] * Content of B with respect to Si. ** The second photoconductive region has a film thickness capable of absorbing 90% of 680 nm light (the absorbance of 680 nm light is measured with a sample).

[Embodiment 2] In this embodiment, the photoconductive layer is arranged in the order of the first photoconductive region and the second photoconductive region from the charge injection blocking layer side. A surface layer was provided in which the content of silicon atoms and carbon atoms in the layer was unevenly distributed in the thickness direction. Table 4 shows the conditions for manufacturing the light receiving member at this time.

In this example, Ch, Eg, and Eu of the first photoconductive region of the photoconductive layer are 22 atomic% and 1.78 eV, respectively.
As a result, 61 meV, Ch, Eg, and Eu of the second photoconductive region were 6 atom%, 1.59 eV, and 58 meV, respectively, and the Ge atom content was 22 atom%. When the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, the photoconductive layer is arranged in the order of the first photoconductive region and the second photoconductive region from the charge injection blocking layer side, and the content of silicon atoms and carbon atoms in the surface layer is uneven in the thickness direction. Even in the case where the surface layer in a distributed state is provided, even when the photoconductive layer is arranged in the order of the first photoconductive region and the second photoconductive region from the charge injection blocking layer side, In one photoconductive region, Ch, Eg, and Eu are respectively 15 to 30 atomic%, 1.75 to 1.85 eV, 55 to 55 atomic%.
65 meV, and C in the second photoconductive region.
h, Eg, and Eu are each 5 to 25 atomic%, 1.55-1.
It is understood that the ranges of 70 eV and 50 to 65 meV are necessary for obtaining good electrophotographic characteristics.

[0173]

[Table 4] * Content of B with respect to Si. ** The second photoconductive region has a film thickness capable of absorbing 75% of light of 680 nm (absorbance of 680 nm light is measured with a sample).

[Embodiment 3] In this embodiment, the photoconductive layer is arranged in the order of the first photoconductive region and the second photoconductive region from the charge injection blocking layer side. A surface layer was provided in which the contents of silicon and carbon atoms in the layers were non-uniformly distributed in the layer thickness direction, and all the layers contained fluorine, boron, carbon, oxygen, and nitrogen atoms. Table 5 shows the conditions for manufacturing the light receiving member at this time.

In this example, Ch, Eg, and Eu of the first photoconductive region of the photoconductive layer are 26 atomic%, 1.83 eV, respectively.
The results were as follows: 62 meV, Ch, Eg, and Eu of the second photoconductive region were 11 atom%, 1.57 eV, and 64 meV, respectively, and the Ge atom content was 29 atom%.

Further, the content of the element belonging to Group IIIb of the Periodic Table is adjusted from 2.5 ppm on the support side of the first photoconductive region to 0.05 ppm on the outermost surface side of the second photoconductive region. Was changed to. The shape of the change was linearly distributed and contained as shown in FIG. When the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, the periodic table IIIb in the photoconductive layer
Even if the content of the element belonging to the group is linearly distributed and contained as shown in FIG. 17A, the photoconductive layer is formed from the first photoconductive region and the second photoconductive region from the charge injection blocking layer side. In addition to the above, a surface layer in which the content of silicon atoms and carbon atoms in the surface layer is non-uniformly distributed in the thickness direction is provided, and fluorine, boron, carbon, oxygen, and nitrogen atoms are provided in all the layers. Even in the case of containing, even when the photoconductive layer is in the order of the first photoconductive region and the second photoconductive region from the charge injection blocking layer side, in the first photoconductive region of the photoconductive layer, Ch, Eg, Eu each 15-30
Atomic%, 1.75 to 1.85 eV, 55 to 65 meV, Ch, Eg, and Eu in the second photoconductive region are 5 to 25 atoms, respectively,% 1.55 to 1.70 ev, 50 to
It is understood that the range of 65 mev is necessary for obtaining good electrophotographic characteristics.

[0178]

[Table 5] * Content of B with respect to Si. ** The second photoconductive region has a film thickness capable of absorbing 85% of 680 nm light (the absorbance of 680 nm light is measured with a sample).

[Embodiment 4] In this embodiment, the photoconductive layer is arranged in the order of the first photoconductive region and the second photoconductive region from the charge injection blocking layer side. A surface layer was provided in which the contents of silicon and carbon atoms in the layers were non-uniformly distributed in the layer thickness direction, and all the layers contained fluorine, boron, carbon, oxygen, and nitrogen atoms. Table 6 shows the manufacturing conditions of the light receiving member at this time.

In this example, Ch, Eg, and Eu of the first photoconductive region of the photoconductive layer are 20 atomic% and 1.80 eV, respectively.
The results were as follows: 59 meV, Ch, Eg, and Eu of the second photoconductive region were 7 atom%, 1.61 ev, and 55 mev, respectively. The Ge atom content was 9 atom%.

The content of the element belonging to Group IIIb of the periodic table is 5.0 ppm on the support side of the first photoconductive region.
70% of the exposure wavelength from the outermost surface of the second photoconductive region
Was changed so as to be 0.1 ppm on the outermost surface side of the region required to absorb the nitrogen. As shown in FIG. 17 (f), the shape of the change was such that the film thickness was equally divided and distributed in a stepwise manner. When the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, the periodic table IIIb in the photoconductive layer
As shown in FIG. 17 (f), even when the content of the element belonging to the group is equally distributed in the film thickness and distributed stepwise, the first photoconductive region of the photoconductive layer is exposed to Ch, Eg, Each of Eu is 15 to 30 atomic%, 1.75 to 1.85 eV, 55 to 65
meV, and Ch, E in the second photoconductive region.
g and Eu are respectively 5 to 25 atomic%, and 1.55 to 1.70e.
V, in the range of 50 to 65 meV, and at least 70% of the exposure wavelength from the outermost surface of the second photoconductive region.
By setting the content of the element belonging to Group IIIb of the periodic table in the region required to absorb the above to be smaller than the content of the first photoconductive region on the support side, good electrophotographic characteristics are obtained. It is necessary to understand.

[0183]

[Table 6] * Content of B with respect to Si. ** The second photoconductive region has a film thickness capable of absorbing 90% of 680 nm light (the absorbance of 680 nm light is measured with a sample).

[Embodiment 5] In this embodiment, the photoconductive layer is a first photoconductive region and a second photoconductive region from the charge injection blocking layer side, and the contents of silicon atoms and carbon atoms are set in the thickness direction. A surface layer with a non-uniform distribution was provided. Table 7 shows the conditions for manufacturing the light receiving member at this time.

In this example, Ch, Eg, and Eu of the first photoconductive region of the photoconductive layer are 21 atomic%, 1.81 eV, respectively.
As a result, 61 mev, Ch, Eg, and Eu of the second photoconductive region were 9 atom%, 1.57 eV and 58 meV, respectively, and the Ge atom content was 16 atom%.

When the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained. Further, the content of the element belonging to Group IIIb of the periodic table is from 6.0 ppm on the support side of the first photoconductive region,
It was changed to 0.3 ppm in a region required to absorb 60% of the exposure wavelength from the outermost surface of the second photoconductive region. As shown in FIG. 17B, the shape of the change was abruptly changed in the first photoconductive region, and then was changed gently and smoothly up to the outermost surface. When the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, as shown in FIG. 17 (b), even when the first photoconductive region changes abruptly and then gradually changes to the outermost surface, the first photoconductive layer of the photoconductive layer has the same effect. 15-30 atoms each of Ch, Eg, Eu in the region
%, 1.75 to 1.85 eV, 55 to 65 meV, and in the second photoconductive region, Ch, Eg, and Eu are each 5 to 25 atomic%, 1.55 to 1.70 eV, 50 to 65 at%.
and the content of the element belonging to Group IIIb of the Periodic Table in the region required to absorb at least 70% or more of the exposure wavelength from the outermost surface of the second photoconductive region. It can be seen that it is necessary to make the content less than the content of the photoconductive region on the support side in order to obtain good electrophotographic properties.

[0188]

[Table 7] * Content of B with respect to Si. ** The second photoconductive region has a film thickness capable of absorbing 80% of 680 nm light (the absorbance of 680 nm light is measured with a sample).

Example 6 In this example, the photoconductive layer was made into a first photoconductive region and a second photoconductive region from the charge injection blocking layer side, and all layers contained carbon atoms. Table 8 shows the conditions for producing the light receiving member at this time. Other points were the same as in Example 1.

In this example, Ch, Eg, and Eu of the first photoconductive region of the photoconductive layer are 27 atomic%, 1.83 eV, respectively.
The results of 56 meV, Ch, Eg, and Eu of the second photoconductive region were 18 atomic%, 1.55 eV, and 60 meV, respectively, and the Ge atom content was 19 atomic%.

The light receiving member thus produced was evaluated in the same manner as in Example 1. As a result, similarly good electrophotographic characteristics were obtained. Further, the content of the element belonging to Group IIIb of the periodic table is from 3.0 ppm on the support side of the first photoconductive region,
The concentration was changed to 1 ppm in the second photoconductive region and further to 0.008 ppm on the outermost surface side of the second photoconductive layer. As shown in FIG. 17 (e), the shape of the change was a gradual change in the first photoconductive region, and then a steep and smooth change to the outermost surface in a region required to absorb 70% of the exposure wavelength. When the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, as shown in FIG. 17 (e), after a gradual change in the first photoconductive region, a steep and smooth change is made to the outermost surface in a region required to absorb 70% of the exposure wavelength. In addition, even in the case where carbon atoms are contained in all layers, Ch, E
g and Eu are respectively 15 to 30 atomic%, 1.75 to 1.85
eV, in the range of 55 to 65 meV, and in the second photoconductive region, Ch, Eg, and Eu are 5 to 25 atomic%, respectively.
It is in the range of 55 to 1.70 eV and 50 to 65 meV, and belongs to Group IIIb of the periodic table in the territory required for absorbing at least 70% of the exposure wavelength from the outermost surface of the second photoconductive region. It is understood that it is necessary to make the content of the element smaller than the content of the first photoconductive region on the support side in order to obtain good electrophotographic properties.

[0193]

[Table 8] * Content of B with respect to Si. ** The second photoconductive region has a film thickness capable of absorbing 90% of 680 nm light (the absorbance of 680 nm light is measured with a sample).

Example 7 In this example, He was used for the photoconductive layer instead of H ₂ , the first photoconductive region and the second photoconductive region were arranged in this order from the charge injection blocking layer side. As the atoms constituting the layer, nitrogen atoms were included in the surface layer instead of carbon atoms. Table 9 shows the manufacturing conditions of the light receiving member at this time. Other points were the same as in Example 1.

In this example, Ch, Eg, and Eu of the first photoconductive region of the photoconductive layer are 23 atomic%, 1.81 eV, respectively.
The results were 60 mev, Ch, Eg, and Eu of the second photoconductive region were 21 atom%, 1.55 eV, and 64 mev, respectively, and the Ge atom content was 32 atom%.

The content of the element belonging to Group IIIb of the periodic table is 10.0 ppm on the support side of the first photoconductive region.
From, 50% of the exposure wavelength from the outermost surface of the second photoconductive region
Was changed so as to be 0.2 ppm in a region required to absorb the chromium. The shape of the change has a certain portion on the support side of the first photoconductive region as shown in FIG. 17 (c), and then changes linearly, and then becomes constant in the region required to absorb 90% of the exposure wavelength. Was changed to become Further, when the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, as shown in FIG. 17 (c), the first photoconductive region has a certain portion on the support side, and after changing linearly, the region required to absorb 90% of the exposure wavelength is used. Even when the surface layer is changed to be constant, and He is used for the photoconductive layer instead of H ₂ , and a surface layer containing nitrogen atoms instead of carbon atoms is provided as an atom constituting the surface layer, In the first photoconductive region of the photoconductive layer, Ch, Eg, and Eu are respectively 15 to 30 atomic%, and 1.
75 to 1.85 eV, 55 to 65 meV, and Ch, Eg, Eu in the second photoconductive region are 5 to 5, respectively.
25 atomic%, 1.55-1.70 eV, 50m-65me
V and the content of the element belonging to Group IIIb of the periodic table in a region required to absorb at least 70% or more of the exposure wavelength from the outermost surface of the second photoconductive region. It can be seen that it is necessary to make the content less than the content of the photoconductive region on the support side in order to obtain good electrophotographic properties.

[0198]

[Table 9] * Content of B with respect to Si. ** The second photoconductive region has a film thickness capable of absorbing 70% of 680 nm light (the absorbance of 680 nm light is measured with a sample).

[Embodiment 8] In this embodiment, the photoconductive layer is arranged in the order of the first photoconductive region and the second photoconductive region from the charge injection blocking layer side, and the surface layer contains nitrogen atoms and oxygen atoms. Was. Table 10 shows the conditions for manufacturing the light receiving member at this time. Other points were the same as in Example 1.

In this example, Ch, Eg, and Eu of the first photoconductive region of the photoconductive layer are 24 atom%, 1.83 eV, respectively.
The results were 60 mev, Ch, Eg, and Eu of the second photoconductive region were respectively 12 atomic%, 1.68 eV, and 52 meV, and the Ge atom content was 4 atomic%.

Further, the content of the element belonging to Group IIIb of the Periodic Table is 5.0-1.0 p on the side of the support in the first photoconductive region.
pm, from the support side 1.0 of the second photoconductive region to 0.01 ppm on the outermost surface side. The shape of the change was a two-step linear change from the support side of the first photoconductive region as shown in FIG. Further, when the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, as shown in FIG. 17 (g), a two-step linear change from the support side of the first photoconductive region and a surface layer containing nitrogen atoms and oxygen atoms are provided on the surface layer. Also, in the first photoconductive region of the photoconductive layer, Ch, Eg, and Eu are each in the range of 15 to 30 atomic%, 1.75 to 1.85 eV, and 55 to 65 meV, and the second photoconductive region In the above, each of Ch, Eg, and Eu was 5 to 25 atomic%, 1.55 to 1.70 eV, and 50 to 6 atomic%.
The range of 5 meV and the content of the element belonging to Group IIIb of the Periodic Table in the region required to absorb at least 70% of the exposure wavelength from the outermost surface of the second photoconductive region, It can be seen that it is necessary to make the content less than the content of the photoconductive region on the support side in order to obtain good electrophotographic properties.

[0203]

[Table 10] * Content of B with respect to Si. ** The second photoconductive region has a film thickness capable of absorbing 90% of 680 nm light (the absorbance of 680 nm light is measured with a sample).

[Embodiment 9] In this embodiment, He is used for the photoconductive layer instead of H ₂ , and the first photoconductive region and the second photoconductive region are arranged in this order from the charge injection blocking layer side. A surface layer was provided in which the contents of atoms and carbon atoms were unevenly distributed in the layer thickness direction. Table 11 shows the conditions for manufacturing the light receiving member at this time. Other points were the same as in Example 1.

In this example, Ch, Eg, and Eu of the first photoconductive region of the photoconductive layer are 29 atomic% and 1.85 eV, respectively.
The results were as follows: 64 mev, Ch, Eg, and Eu of the second photoconductive region were 22 atom%, 1.55 eV, and 63 mev, respectively, and the Ge atom content was 34 atom%.

Further, the content of the element belonging to Group IIIb of the periodic table linearly decreases from 8.0 ppm on the support side of the first photoconductive stop region, and 0.3 ppm in the second photoconductive region. It was changed to be constant. Figure 17 shows the shape of the change
As shown in (d), the change was made so as to have a change area and a constant area. Further, when the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, as shown in FIG. 17D, the first photoconductive region is changed from the support side in a straight line so as to be constant in the second photoconductive region, and the photoconductive layer is replaced with H ₂ . Also, when He is used and an intermediate layer (upper blocking layer) containing atoms for controlling conductivity is provided, in the first photoconductive region of the photoconductive layer, Ch, Eg, and Eu are respectively 15 to 30 atomic%, 1.75 to 1.85 eV, 55 to 65
meV, and Ch, E in the second photoconductive region.
g and Eu are respectively 5 to 25 atomic%, and 1.55 to 1.70e.
V, in the range of 50 to 65 meV, and at least 70% of the exposure wavelength from the outermost surface of the second photoconductive region.
By setting the content of the element belonging to Group IIIb of the periodic table in the region required to absorb the above to be smaller than the content of the first photoconductive region on the support side, good electrophotographic characteristics are obtained. It is necessary to understand.

[0208]

[Table 11] * Content of B with respect to Si. ** The second photoconductive region has a film thickness capable of absorbing 95% of 680 nm light (the absorbance of 680 nm light is measured with a sample).

[0209]

According to the present invention, the temperature characteristic of sensitivity, the linearity of sensitivity, the temperature characteristic, and the like are remarkably improved in the operating temperature range of the light receiving member, and the occurrence of optical memory is substantially eliminated. In addition, since the charging ability is also improved, the stability of the light receiving member with respect to the use environment is improved, and a high quality image with a clear halftone and high resolution is obtained. Thus, a light receiving member for electrophotography can be obtained.

Therefore, the a-Si light receiving member of the present invention has a specific configuration as described above,
Can solve all the problems in the conventional electrophotographic light-receiving member composed of, and exhibit extremely excellent electrical characteristics, optical characteristics, photoconductive characteristics, image characteristics, durability and use environment characteristics. .

In particular, in the present invention, the photoconductive layer is divided into layer regions having different optical band gaps and levels within the gap, and the exposure wavelength of 70 nm is applied from the outermost surface of the second photoconductive region.
By controlling the content of the element belonging to Group IIIb of the Periodic Table in the region required to absorb at least% to be smaller than the content on the support side of the first photoconductive region, the chargeability is high, In addition, it is characterized in that a change in surface potential due to a change in the surrounding environment is suppressed, and that the device has extremely excellent potential characteristics and image characteristics. By focusing attention on the light incident part, long wavelength lasers and LEDs for digitization
In contrast, the temperature dependence (slope and curve) of the sensitivity line is kept small, the charging ability is high, and the change of the surface potential due to the fluctuation of the surrounding environment is suppressed, so that it has extremely excellent potential characteristics and image characteristics. It has the feature of.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing an example of an a-Si subgap light absorption spectrum for explaining characteristic energy of an exponential function tail according to the present invention.

FIG. 2 is a schematic explanatory view showing a layer configuration of a preferred embodiment of the light receiving member of the present invention.

FIG. 3 is a schematic explanatory view showing an example of an apparatus for forming a light receiving layer of the light receiving member of the present invention, which is an apparatus for manufacturing a light receiving member by a glow discharge method using an RF band high frequency power supply.

FIG. 4 shows the characteristic energy (E) of the Urbach tail of the second photoconductive region of the photoconductive layer in the light receiving member of the present invention.
FIG. 7 is a graph showing the relationship between u) and temperature characteristics of sensitivity.

FIG. 5 shows the characteristic energy (E) of the Urbach tail of the second photoconductive region of the photoconductive layer in the light receiving member of the present invention.
FIG. 6 is a graph showing the relationship between u) and linearity of sensitivity.

FIG. 6 shows the characteristic energy (E) of the Urbach tail of the second photoconductive region of the photoconductive layer in the light receiving member of the present invention.
FIG. 4 is a graph showing the relationship between u) and charging ability.

FIG. 7 shows the characteristic energy (E) of the Urbach tail of the second photoconductive region of the photoconductive layer in the light receiving member of the present invention.
FIG. 7 is a graph showing the relationship between u) and temperature characteristics.

FIG. 8 shows the characteristic energy (E) of the Urbach tail of the second photoconductive region of the photoconductive layer in the light receiving member of the present invention.
FIG. 7 is a graph showing the relationship between u) and an optical memory.

FIG. 9 is a graph showing the relationship between the film thickness and the temperature characteristic of sensitivity of the second photoconductive region of the photoconductive layer in the light receiving member of the present invention, which is determined based on the light absorptance of the exposure amount.

FIG. 10 is a graph showing the relationship between the film thickness and the linearity of sensitivity determined for the second photoconductive region of the photoconductive layer in the photoreceptor member of the present invention based on the light absorptance of the exposure amount.

FIG. 11 is an explanatory view showing an example of an exposure dose-surface potential curve of an amorphous silicon photoconductor for explaining the temperature characteristic of sensitivity and the linearity of sensitivity in the present invention.

FIG. 12 is a periodic table IIIb determined by the thickness and light absorption of the second photoconductive region of the photoconductive layer in the light receiving member of the present invention.
FIG. 3 is a graph showing the relationship between the control range of elements belonging to group III and the temperature characteristics of sensitivity.

FIG. 13 shows the relationship between the control range of elements belonging to Group IIIb of the periodic table and the sensitivity linearity determined by the thickness and light absorption of the second photoconductive region of the photoconductive layer in the photoreceptor member of the present invention. FIG.

FIG. 14 is a table Шb of the periodic table determined by the thickness and light absorption of the second photoconductive region of the photoconductive layer in the photoreceptor member of the present invention.
FIG. 4 is a graph showing a relationship between a control range of elements belonging to the group and charging ability.

FIG. 15 is a periodic table No. III determined by the film thickness and light absorption of the second photoconductive region of the photoconductive layer in the light receiving member of the present invention.
FIG. 5 is a graph showing a relationship between a control range of an element belonging to group b and temperature characteristics.

FIG. 16 is a periodic table III determined by the film thickness and light absorption of the second photoconductive region of the photoconductive layer in the light receiving member of the present invention.
FIG. 4 is a graph showing a relationship between a control range of an element belonging to group b and an optical memory.

FIG. 17 is a schematic diagram for explaining the distribution of elements belonging to Group IIIb of the periodic table in a preferred embodiment of the light receiving member of the present invention.

[Explanation of symbols]

 Reference Signs List 200 light receiving member 201 conductive support 202 light receiving layer 203 photoconductive layer 204 surface layer 205 charge injection blocking layer 210 free surface 211 first photoconductive region 212 second photoconductive region 3100 deposition device 3111 reaction vessel 3112 cylinder Support 3113 Heater for heating the support 3114 Source gas introduction pipe 3115,4116 Matching box 3116 Source gas pipe 3117 Reaction vessel leak valve 3118 Main exhaust valve 3119 Vacuum gauge 3200 Source gas supply device 3211-316 Mass flow controller 3221-226 Source gas cylinder 3231-236 Source gas cylinder valve 3241-246 Gas inflow valve 3251-256 Gas outflow valve 3261-266 Pressure regulator

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03G 5/08 360 G03G 5/08 360 C23C 16/00 C23C 16/00 // C23C 16/42 16/42 16/50 16 / 50 (72) Inventor Daisuke Tazawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc.

Claims (12)

[Claims] At least a conductive support and, on a surface of the support, a hydrogen atom and / or a halogen atom and at least one element belonging to Group IIIb of the periodic table, and a silicon atom serving as a matrix A photoreceptive layer having at least a photoconductive layer comprising a non-single-crystal material, and a photoreceptive layer having a photoreceptive layer. Wherein the optical band gap (Eg) of the second photoconductive region is narrower than the optical band gap (Eg) of the first photoconductive region, and the hydrogen content and the photon energy are smaller. linear relationship portion of the function represented by independent (hv) variable and to the absorption coefficient of the light absorption spectrum (alpha) the following expression for the dependent variable (I) lnα = (1 / Eu) · hν tens alpha ₁ (I) (Exponential function tail) The obtained characteristic energy (Eu) is within a specific range for the first photoconductive region and the second photoconductive region, and the characteristic energy (Eu) is 55 to 65 in the first photoconductive region.
and the hydrogen content is between 15 and 30 atoms.
%, The optical band gap (Eg) is in the range of 1.75 to 1.85 eV, and in the second photoconductive region, the characteristic energy (Eu) is in the range of 50 to 65 meV.
A light-receiving member for electrophotography, wherein the hydrogen content is in the range of 5 to 25 at% and the optical band gap (Eg) is in the range of 1.55 to 1.70 eV. 2. The second photoconductive region laminated on the surface side of the first photoconductive region has a film thickness necessary for the light absorptance of image exposure to be in the range of 70 to 95%. The light receiving member for electrophotography according to claim 1, wherein: 3. The second photoconductive region laminated on the surface side of the first photoconductive region contains 3 to 35% of germanium atoms with respect to the sum of silicon atoms and germanium atoms. The light receiving member for electrophotography according to claim 1, wherein: 4. The photoconductive layer according to claim 1, wherein said photoconductive layer is provided in said layer.
The light receiving member for electrophotography according to any one of claims 1 to 3, further comprising at least one element belonging to Group Ib. 5. The photoconductive layer, wherein the content of an element belonging to Group IIIb of the periodic table on the light incident side of the second photoconductive region is the content of the element on the support side of the first photoconductive region. The light receiving member for electrophotography according to claim 4, wherein the number is less. 6. The method according to claim 1, wherein an amount of an element belonging to Group IIIb of the periodic table contained in the first photoconductive region is in a range of 0.2 to 30 ppm based on silicon atoms. 6. The light receiving member for electrophotography according to 5. 7. The amount of an element belonging to Group IIIb of the Periodic Table contained in the second photoconductive region is in the range of 0.005 to 10 ppm based on silicon atoms. 6. The light receiving member for electrophotography according to 5. 8. The photoconductive layer according to claim 1, wherein the photoconductive layer has carbon, oxygen,
The light receiving member for electrophotography according to any one of claims 1 to 4, further comprising a surface layer made of a silicon-based non-single-crystal material containing at least one kind of nitrogen. 9. The charge injection blocking of the photoconductive layer is made of a non-single-crystal material containing silicon atoms as a base material and containing at least one of carbon, oxygen, and nitrogen and at least one element selected from Group IIIb of the periodic table. A surface layer made of a silicon-based non-single-crystal material containing at least one of carbon, oxygen and nitrogen on the surface of the photoconductive layer. Item 5. An electrophotographic light-receiving member according to any one of Items 1 to 4. 10. The light-receiving member for electrophotography according to claim 8, wherein the thickness of the surface layer is in the range of 0.01 to 3 μm. 11. The charge injection blocking layer has a thickness of 0.1.
10 to 5 μm.
The light receiving member for electrophotography according to the above. 12. The photoconductive layer having a thickness of 20 to 5
The light receiving member for electrophotography according to claim 1, wherein the thickness is in a range of 0 μm.