JPH1172938A - Electrophotographic light receiving member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve electrifying ability, to decrease a temp. characteristic, to decrease a photomemory and to improve an image quality by controlling a hydrogen content and the distribution of the density of a locally existing state in an optical band gap or an a-Si band gap in the thickness direction of a photoconductive layer. SOLUTION: A light receiving member 200 is provided with a light receiving layer 202 on a supporting body 201. The light receiving layer 202 consists of a photoconductive layer 203 comprising a nonsingle crystal material of silicon atoms as a main component. The photoconductive layer 203 consists of, in order from the supporting body 201 side, a first photoconductive region 211 and a second photoconductive region 212. In the first photoconductive region 211, a hydrogen content is 10 to 25 atom.%, an optical band gap is 1.70 to 1.80 eV and characteristic energy is in the range of 50 to 55 meV. In the second photoconductive region 212, the hydrogen content is 5 to 25 at.%, the optical band gap is 1.55 to 1.70 eV and the characteristic energy is in the range of 50 to 65 meV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to light (light in a broad sense,
(Including ultraviolet light, visible light, infrared light, X-rays, γ-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, Characteristics such as harmlessness to the human body 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-SiH). For example, Japanese Patent Publication No. 60-35059 discloses an electrophotographic photoreceptor. Application as a component 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. Same 58-
Japanese Patent No. 171054 proposes a photoconductor using an amorphous silicon-germanium photoconductive layer having sensitivity to near infrared light.

JP-A-56-83746 discloses an electrophotography comprising an a-Si (hereinafter referred to as a-Si: X) photoconductive layer containing a conductive support and a halogen atom as a constituent element. A light receiving member is disclosed. According to the publication, by including a halogen atom in a-Si of 1 to 40 atomic%, good electrical and optical characteristics can be obtained as a photoconductive layer of a light receiving member for electrophotography having high heat resistance. And

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. Sho 60-67951 describes a technique relating to a photoconductor in which a light-transmitting insulating overcoat layer containing amorphous silicon, carbon, oxygen and fluorine is laminated.
No. 1 describes a technique using, as a surface layer, an amorphous material containing silicon atoms, carbon atoms, and 41 to 70 atomic% of hydrogen atoms as constituent elements.

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 preparation of the photoconductive layer, and the light- A technique for obtaining a photoreceptor having a wide sensitivity region is disclosed, and JP-A-58-121042 discloses that the energy gap state density is changed in the thickness direction of the photoconductive layer so that the energy gap state density on the surface layer side is 10 ^17. A technique for preventing the surface potential from lowering due to temperature by setting the surface pressure to 10 ¹⁹ cm ^-3 is disclosed. Also, Japanese Unexamined Patent Publication No. 59-14337
No. 9 and No. 61-201481 disclose a technique of obtaining a photosensitive member having high dark resistance and high sensitivity by laminating a-SiH having different hydrogen contents.

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, high image quality, high speed, and high durability of an electrophotographic apparatus are rapidly progressing, and in a photoreceptor for electrophotography, the electric properties and photoconductive properties are further improved, and the charging ability and sensitivity are improved. It is required to greatly extend the performance in all environments while maintaining the above.

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, in recent years, the spread of computers in offices and general homes and the digitization of texts and images have progressed, and in the multimedia era, electrophotographic apparatuses will play the role of not only conventional copiers but also facsimile machines and printers. Digitalization has been required. Semiconductor lasers and LEDs used for digitization are mainly of a long wavelength 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 found in conventional analog copying machines using halogen light.

Under such circumstances, the above-mentioned prior art has made it possible to improve the above-mentioned problems to some extent, but it is still not enough to further improve the charging ability and image quality. In particular, as a challenge for further improving the image quality of amorphous silicon light receiving members,
There has been an increasing demand for reducing optical memory such as variations in electrophotographic characteristics due to changes in ambient temperature, optical fatigue, blank memory and ghost.
In addition, along with the digitalization, lasers with visible-red wavelengths and LE
By using D, the relationship between the exposure amount (E) and the surface potential (V), that is, the so-called EV curve changes with temperature (temperature characteristic of sensitivity), and the linearity of the EV curve (linearity of sensitivity) ) Has become noticeable as a new issue.

[0017] That is, a red-visible wavelength laser or LE
In digital machines using D as an exposure light source, there is a new problem that the sensitivity changes depending on the ambient temperature and the image density changes due to an increase in sensitivity temperature characteristics and a decrease in sensitivity linearity. Was. Under such circumstances, a silicon germanium film having sensitivity to a long wavelength has been studied. However, the hydrogenated amorphous silicon film to which germanium is added, which has been used for the conventional light receiving member for electrophotography, has been employed on the support side to prevent interference due to transmission of a long-wavelength laser. In addition, the hydrogenated amorphous silicon film to which germanium is added for the photoconductive layer is formed by containing hydrogen and oxygen atoms to eliminate dangling bonds which are defects in the film. However, the inclusion of oxygen atoms inevitably reduces the mobility of carriers due to the increased resistance of the film.

Further, conventionally, as described in JP-A-60-95551, a drum heater is installed in a copying machine to reduce the surface temperature of the photoreceptor in order to prevent image deletion on the photoreceptor. It was kept at about 40 ° C. However, in the conventional photoconductor, the temperature dependence of the charging ability due to the generation of the pre-exposure carrier and the thermally excited carrier, that is, the so-called temperature characteristic is large, and under the actual use environment in the copying machine, the photoconductor originally has. It had to be used with a low charging ability. For example, when the drum heater is heated to about 40 ° C. as compared with the use at room temperature, the charging ability becomes 1
It had dropped by about 00V.

Conventionally, even when the copying machine is not used, the drum heater is energized even at night to prevent the ozone product generated by the corona discharge of the charger from adsorbing on the surface of the photoconductor at night to prevent image flow. I was trying to do 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.

When the temperature of the photosensitive member is not controlled to a constant value by a drum heater or the like in a digital machine using laser light as described above, the temperature around the photosensitive member may be reduced due to the temperature characteristic of sensitivity and the linearity of sensitivity. When the temperature changes, the sensitivity changes and the image density changes.

On the other hand, when the same original is continuously and repeatedly copied, the image density may be reduced or fogging may occur due to light fatigue of the photosensitive member due to image exposure. In addition, in order to save toner, a blank memory in which the density difference occurs on the copy image due to the so-called blank exposure, which is applied to the photoreceptor between sheets during continuous copying, and an afterimage of the image exposure in the previous copy process are performed. A so-called ghost or the like generated on an image at the next copy has been a problem in improving image quality.

Therefore, when designing a light receiving member for electrophotography, the layer structure of the light receiving member for electrophotography, the chemical composition of each layer, and the like from the comprehensive viewpoint 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.

Therefore, the present invention provides the above-described conventional a-Si
An object of the present invention is to solve various problems in a light receiving member for electrophotography having a light receiving layer composed of
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]

In order to solve the above-mentioned problems, the present inventors have focused on the distribution and behavior of carriers due to exposure of a photoconductive layer, and have studied the distribution of localized state densities within the band gap of a-Si. As a result of intensive studies on the relationship between temperature, temperature, and optical memory, the above results were obtained by controlling the hydrogen content, the optical band gap, and the distribution of localized states in the band gap in the thickness direction of the photoconductive layer. The knowledge that the purpose can be achieved was obtained. 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 groove structure. The obtained light receiving member not only shows remarkably excellent properties in practical use, but also surpasses in all respects compared with the conventional light receiving member, and in particular, has excellent characteristics 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 absorbing region thinner, it was also possible to achieve an improvement in optical memory and an improvement in charging ability.

The conventional germanium-added film for the purpose of preventing interference has not taken into consideration the carrier running property. Therefore, when such a photoconductor is used, the residual potential increases and the sensitivity linearity decreases. Occurred. In the prior art, a hydrogenated amorphous silicon film to which germanium is added for a photoconductive layer has been used to eliminate dangling bonds, which are defects in the film, 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 and thereby, compared with the conventional germanium-added film. The present invention has been completed by using 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 10 to 25 atomic%, the optical band gap is 1.70 to 1.80 eV, the characteristic energy of the exponential function tail obtained from the light absorption spectrum is in the range of 50 to 55 meV, and hydrogen in the second photoconductive region is The content is 5
25 atomic%, optical band gap of 1.55-1.70
By setting the characteristic energy of the tail of the exponential function obtained from the eV and the light absorption spectrum in the range of 50 to 65 meV, the problems of the temperature characteristic of sensitivity and the linearity of sensitivity that occur when using a red-visible laser or LED are solved. In addition, the present invention is characterized in that the charging ability and the temperature characteristics are improved, and good characteristics without generation of optical memory are exhibited.

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 3 to 35% of germanium atoms with respect to the sum of silicon atoms and germanium atoms (the amount of germanium atoms when the sum of silicon atoms and germanium atoms is 100).

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. And Ninth, the photoconductive layer is a charge injection blocking layer made of a non-single-crystal material containing a silicon atom 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. Provided on the surface, and further on the surface of the photoconductive layer, carbon,
A surface layer made of a silicon-based non-single-crystal material containing at least one of oxygen and nitrogen is provided.

Tenth, the surface layer has a layer thickness of 0.5.
It is characterized by being in the range of 01 to 3 μm. First
1, the charge injection blocking layer has a thickness of 0.1 to 5 μm.
m. 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.
Is an example of an a-Si sub-gap light absorption spectroscopy which shows a logarithmic axis. This spectrum is roughly divided into two parts. That is, the absorption coefficient α is the photon energy h
A part B (exponential function tail or Urbach tail) which changes exponentially, that is, linearly with respect to ν, and a part 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 It is represented by

Α = α. exp (hν / Eu) When the logarithm of both sides is taken, lnα = (1 / Eu) · hν + α ₁ (I) (where α ₁ = 1nα), and characteristic energy Eu
(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 characteristic energy of an exponential tail (Urbuck tail) determined from a sub-bandgap optical absorption spectrum measured by CPM (hereinafter, referred to as “Eg”).
As a result of examining the correlation between Eu and the photoreceptor characteristics under various conditions, it was found that Eg, Eu and the chargeability, temperature characteristics and optical memory of 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, Eg and Eu at the light incident portion and the photoreceptor characteristics when a laser light source was used were examined in detail. Is found to be closely related to the linearity of Eg, Eg, E
It has been found that by setting the contents of u and hydrogen within specific ranges, it is possible to obtain good photoreceptor characteristics suitable for red-visible light lasers and LEDs, and completed the present invention.

That is, a layer region in which germanium is contained in a-SiH to reduce the optical band gap and reduce the capture ratio of carriers to localized levels is interposed in the interface region between the photoconductive layer and the surface layer. As a result, the temperature characteristics of the sensitivity and the linearity of the sensitivity can be greatly improved and substantially eliminated by the tests of the present inventors. 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 and improved because the capture to the localized level is reduced by the amount.

To explain this in more detail, generally, in the band gap of a-SiH, the tail (tail) level based on the structural disorder of the Si-Si bond, and the dangling bond of Si (dangling). There is a deep level due to a structural defect such as a ring bond. It is known that these levels function as trapping and recombination centers for electrons and holes, and cause deterioration of device characteristics. This is also due to structural defects such as tail (tail) levels and dangling bonds (dangling bonds) due to structural disorder of Si-Ge bonds and Ge-Ge bonds in the a-SiGe: H system. Deep levels exist.

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. Is used. In particular, the constant photocurrent method (Co
The nstant photocurrent method (hereinafter abbreviated as CPM) is useful as a method for simply measuring the subgap light absorption spectrum based on the localized level of a-SiH.

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 station 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, the optical memory is generated by capturing photocarriers generated by blank exposure or image exposure at a localized level in a band gap and remaining carriers in the photoconductive layer. That is, the carriers remaining in the photoconductive layer among the optical carriers generated in a certain copying process are:
At the time of the next charging or thereafter, the electric field is swept out by the electric field due to the surface charge, and the potential of the portion irradiated with light becomes lower than that of the other portions. 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, but during the movement, if the holes and electrons are mixed at the light incident part, they reach the support and the surface The rate of recombination before that time increases. 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 change. 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, the linearity of the sensitivity is such that as the exposure amount of the long-wavelength laser increases, the number of photogenerated carriers relatively deep from the surface increases and the number of carriers (electrons) having a long running distance increases. Occurs. Therefore, the light absorptance of the light incident portion must be increased, and the mobility of the electrons on the light incident portion and the mobility of the holes on the support side must be improved and balanced.

Accordingly, by providing a layer region in which Eu is controlled (reduced) while adding Ch while decreasing Ge and narrowing Eg while providing light as the light incident portion, the thermally excited carriers and the photocarriers become localized levels. Since the trapped ratio can be reduced, the traveling property of the carrier is dramatically improved. 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 a hole and the traveling property is improved. Further, by using a layer in which Eu is controlled (reduced) while Eg is larger than that of the light incident part side photoconductive layer, generation of the thermally excited carriers is suppressed. Since the rate at which the optical carriers are captured by the localized levels can be reduced, the traveling properties of the carriers are dramatically improved.

That is, by providing the second photoconductive region on the outermost surface side of the light receiving member and making the region that substantially absorbs light the second photoconductive region, especially when laser light is used. The temperature characteristics of sensitivity and the linearity of sensitivity have been greatly improved.
In addition, a remarkable effect can be seen in charging ability, temperature characteristics and memory point.

Therefore, the present invention has
Solves all of the above-mentioned problems in the prior art by improving the temperature characteristics of sensitivity when using laser light, improving the linearity of sensitivity, and improving the charging performance and reducing the temperature characteristics and reducing the optical memory at a high level. Thus, it is possible to obtain a light receiving member exhibiting extremely excellent electrical, optical and photoconductive properties, image quality, durability and use environment.

[0051]

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 containing silicon atoms as a base material and has a photoconductive property.
3, the photoconductive layer 203 includes a first photoconductive region 211 and a second photoconductive region 212 in this order from the support 201 side.

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 light receiving layer 202 is made of a non-single-crystal material containing silicon atoms as a base material and has photoconductivity, 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, I
Metals such as n, Nb, 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 shape or an endless belt shape having a smooth surface or an uneven surface, and the thickness thereof is appropriately determined so that the desired light receiving member 200 can be formed. However, when 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 thickness of the support 201 is usually 10 μm or more in terms of production, handling, mechanical strength, and the like.

In particular, in the case of performing image recording using coherent light such as laser light, 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
168156, 60-178457, 60-2258
It is prepared by a known method described in, for example, Japanese Patent Application Publication No. 54-54.

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 used. 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 depressions provided on the surface of the support 201 is disclosed in
It is prepared by a known method described in JP-A-231561.

(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 manufactured 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 manufactured. 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. Source gas and / or germanium atom for supplying a raw material gas or / and a halogen atom (X)
A source gas for supplying Ge capable of supplying (Ge) is introduced in a desired gas state into a reaction vessel in which the inside can be reduced in pressure, and a glow discharge is generated in the reaction vessel, and is previously set at a predetermined position. A-Si: H, on a predetermined support 201
What is necessary is just to form the layer which consists of X.

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 hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms is 10 to 25 atoms with respect to the sum of silicon atoms and hydrogen atoms and / or halogen atoms. %, And in the case of the second photoconductive region, the content is preferably 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 that germanium atoms be contained in the second photoconductive region of the photoconductive layer 203. This is necessary in order to adjust the optical band gap and efficiently absorb image exposure. Indispensable. Therefore, the content of germanium atoms is desirably 3 to 35 atomic% (however, the sum of Si atoms and Ge atoms is 10 atomic%).
Ge atom amount when 0).

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.
The gaseous state, such as ₄ H _10, or silicon hydride can be gasified (silanes) can be mentioned as being effectively used. SiH ₄ and Si ₂ H ₆ are preferred from the viewpoints of easy handling at the time of producing the exposed layer and good Si supply efficiency.

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, when further layers produced 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 preferably used in the present invention include fluorine gas (F ₂ ), BrF, and Cl.
Examples thereof include interhalogen compounds such as F, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ . As a silicide compound containing a halogen atom, that is, a silashi derivative substituted with a so-called halogen atom, specifically, silicon fluoride such as SiF ₄ or Si ₂ F ₆ can be mentioned as a preferable example.

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). In particular, B, Al, and Ga include It is suitable. As the group Vb atom, specifically, phosphorus (P),
There are arsenic (As), antimony (Sb), bismuth (Bi) and the like, and P and As are particularly preferable.

The content of the atoms for 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 to set the atomic ppm, optimally 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, 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
₁₄ borohydride; and boron halide 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 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
The content of oxygen atoms and / or nitrogen atoms is preferably from 1 × 10 ⁻⁵ to 10 at%, more preferably from 1 × 10 ⁻⁴ to 8 at%, based on the sum of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms. Atomic%, optimally 1 × 10 ^{-3 to} 5 atomic%
Is desirable. Carbon atom and / or oxygen atom and / or
Alternatively, the nitrogen atoms may be uniformly contained in the photoconductive layer, or there may be a portion having a non-uniform distribution such that the content changes in the thickness direction of the photoconductive layer. .

In the present invention, the thickness of the photoconductive layer 203 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, and is preferably 2 or more.
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 70 to 95%.
When the film thickness is less than the above range, light reaches a considerably deep portion of the first photoconductive region, which is designed to be a layer which is advantageous for the traveling property of holes.
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. Further, the thickness of the second photoconductive region is equal to the light absorption 95.
%, A large number of holes must travel a considerable distance in the second photoconductive region. Usually, in the second photoconductive region on the surface layer side, importance is placed on the traveling property of electrons, and
Almost no doping of group b atoms is performed. Therefore, the traveling property of holes in the second photoconductive region is low, which causes a decrease in sensitivity and an increase in residual potential, and it is difficult to obtain the effects of the present invention. Also, if this portion is doped in order to enhance the hole traveling property, the electron traveling property is lowered, the sensitivity is lowered, and the charging ability is reduced, resulting in an increase in dark decay.
Therefore, SiGe satisfactory as the second photoconductive region
The film must be of good quality with few defects. Also,
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,
A good image can be obtained without requiring any special measures against interference fringes in the support and the lower layer.

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.

[0076] 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
In the first photoconductive region, e is usually 0.5 to
It is desirable to control the ratio to 10 times, preferably 1 to 8 times, optimally 2 to 6 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 similarly according to the layer design. However, both the first photoconductive region and the second photoconductive region are usually 1 × 10 ⁻² to
2 × 10 ³ Pa, preferably 5 × 10 ^{-2 to} 5 × 10 ² P
a, optimally, preferably in the range of 1 × 10 ⁻¹ to 2 × 10 ² Pa, and the gas pressure does not change abruptly in the changing region from the first photoconductive region to the second photoconductive region. is important.

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 0.3 to 5 in the first photoconductive region. It is desirable to set the value in the range of 0.5 to 4. Preferably, the ratio of the discharge power to the flow rate of the Si supply gas in the second photoconductive region is 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 temperature range of the support for forming the photoconductive layer and the desirable numerical range of the gas pressure include the above-mentioned ranges, but the conditions are usually not independently determined separately but have desired characteristics. It is desirable to determine the optimum value based on mutual and organic relationships to form the light receiving member.

(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, the chemical stability is sufficiently ensured at the lamination interface. ing.

The surface layer 204 can be made of any material as long as it is an amorphous silicon material. For example, the surface layer 204 contains a hydrogen atom (H) and / or a halogen atom (X) and further contains a carbon atom. Amorphous silicon (hereinafter referred to as a-SiC: H, X), amorphous silicon containing hydrogen atoms (H) and / or halogen atoms (X) and further containing oxygen atoms (hereinafter a-SiO: H, X)
Amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing a nitrogen atom (hereinafter a-SiN: H, X), a hydrogen atom (H) and Amorphous silicon containing 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 suitably used.

In the present invention, in order to effectively achieve the object, the surface layer 204 is manufactured by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics by a vacuum deposited film forming method. Is done. 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,
It can be formed by various thin film deposition methods such as an ion plating method, a photo CVD method, and 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 manufactured. 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 preferred. A-Si for surface layer
When C is a main component, the amount of carbon is preferably in the range of 30 to 90% based on the sum of silicon atoms and carbon atoms.

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 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 above range of the content of hydrogen and / or fluorine can be sufficiently applied in practical terms 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. As an adverse effect, the charge is injected and the charge is trapped in the defect in the surface layer to cause 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, the number of defects in the surface layer is greatly reduced, and as a result, the electrical characteristics and the high-speed continuous usability can be significantly improved as compared with the related art.

On the other hand, when 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, by controlling the fluorine content in the surface layer to 0.01 atomic% or more, it is possible to more effectively achieve the generation of the bond between silicon atoms and carbon atoms in the surface layer. Become. Further, as a function of fluorine atoms in the surface layer, it is possible to effectively prevent the bond between silicon atoms and carbon atoms from being broken due to damage such as corona.

On the other hand, the fluorine content in the surface layer is 15 atomic%.
If it exceeds 300, the effect of generating the bond between the silicon atom and the carbon atom in the surface layer and the effect of preventing the break of the bond between the silicon atom and the carbon atom due to damage such as corona can hardly be recognized. Furthermore, since excess fluorine atoms hinder the mobility of carriers in the surface layer, remnant 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. 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, similarly to the hydrogen content.

The substance that can be a silicon (Si) supply gas used in the formation of the surface layer of the present invention includes Si (Si).
Silicon hydrides (silanes) in a gaseous state such as H ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , or the like, which are capable of being gasified, are used effectively. SiH ₄ and Si ₂ H ₆ are preferred in terms of ease of handling and good Si supply efficiency. 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 ₄ , C ₂ H ₂ , C ₂ H ₆ , C ₃ H ₈ , C ₄ H _10, etc.
Alternatively, hydrocarbons that can be gasified are effectively used, and CH ₄ , C ₂ H ₂ , and C ₂ H ₆ are preferable in terms of ease of handling at the time of forming a layer, high Si supply efficiency, and the like. It is listed as. Further, if necessary, the raw material gas for supplying C may be diluted with a gas such as H ₂ , He, Ar, or Ne before use.

Substances that can be nitrogen or oxygen supply gases 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 further facilitate the control of the introduction ratio of hydrogen atoms introduced into the surface layer 204 to be formed, hydrogen gas or a silicon compound containing hydrogen atoms is added to these gases. It is preferable to form a layer by mixing a desired amount of gas. 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 gasifiable halogen compounds such as halogen gas, halides, interhalogen compounds containing halogen, and silane derivatives substituted with halogen. . 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 which can be preferably used in the present invention include fluorine gas (F ₂ ), BrF, ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ , I ₃
It can be exemplified interhalogen compounds such as F _7. Specific examples of the silicon compound containing a halogen atom, ie, a silane derivative substituted with a halogen atom, include, for example, S
Silicon fluoride such as iF ₄ and Si ₂ F ₆ can be mentioned as preferred.

In order to control the amount of hydrogen atoms and / or parogen 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 above-mentioned atoms for controlling 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 shelf (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). In particular, B, Al, Ga Is preferred.

The content of atoms 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 × l
0 ² atom ppm, optimally 1 × 10 ^-1 to 1 × 10 ² atom 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. 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, 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
₁₄ borohydride; and boron halide 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 conductivity may be diluted with a gas such as H ₂ , He, Ar, or Ne as necessary.

The layer 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 that its required properties are provided as desired. That is, Si, C and / or N, and / or
Alternatively, a substance containing O, H and / or X as a constituent element takes a form structurally from crystalline to amorphous depending on its forming condition, and has a property between electrical conductivity, semiconductivity and insulating property in terms of electrical properties. And the properties between photoconductive properties and non-photoconductive properties, respectively, so that in the present invention, a compound having desired properties according to the purpose is formed, The selection of the forming conditions is strictly made.

For example, in order to provide the surface layer 204 mainly for the purpose of improving the pressure resistance, the surface layer 204 is made of a non-single-crystal material having a remarkable electric insulating behavior in a use environment. Also,
When the surface layer 204 is provided mainly for the purpose of improving the characteristics of continuous repetitive use and the characteristics of the use environment, the degree of the above-described electrical insulation is alleviated to some extent, and the non-uniformity having a certain sensitivity to irradiated light is provided. Formed as a crystalline 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 temperature (Ts) of the support 201 is appropriately selected in an optimum range according to the layer design, but is usually 200 to 350 ° C., more preferably 230 to 3 ° C.
It is desirable that the temperature is 30 ° 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 × 10 ^-2 to 2 × 10 ³ Pa, more preferably 5 × 10 ³ Pa. ^{-2 to} 5 × 10 ² Pa, optimally 1 × 10 ⁻¹ to 2
It is preferable to be in the range of × 10 ² Pa.

In the present invention, the preferable ranges of the temperature of the support and the gas pressure for forming the surface layer include the above-mentioned ranges. However, the conditions are not usually independently determined separately, but are preferably determined separately. It is desirable to determine the optimum value based on mutual and organic relevance to form a light receiving member having properties. Further, in the present invention, the provision of a blocking layer (lower surface layer) in which the content of carbon atoms, oxygen atoms, and nitrogen atoms is lower than that of the surface layer between the photoconductive layer and the surface layer may also provide characteristics such as charging ability. It is effective for further improvement.

A region where the content of carbon atoms and / or oxygen atoms and / or nitrogen atoms changes so as to decrease toward the photoconductive layer 203 may be provided between the surface layer 204 and the 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 with the photoconductive layer.

The atoms controlling the conductivity contained in the layer may be uniformly distributed throughout the layer, or may be uniformly distributed in the thickness direction of the layer, but may not be uniformly distributed. Some portions may be contained in a state of being uniformly distributed. 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 that the metal is uniformly distributed and uniformly distributed in the in-plane direction parallel to the surface of the support from the viewpoint of making the characteristics in the in-plane direction uniform. .

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),
Examples include In (indium) and Tl (thallium), and B, Al, and Ga are particularly preferable. Specific examples of group Vb atoms include P (phosphorus), As (arsenic), Sb (antimony),
Bi (bismuth) and the like, and P and As are particularly preferable.
In the present invention, the content of the atom controlling the 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 ⁴ atomic ppm, more preferably 50 to 5 × 10 ³ atomic ppm, and most preferably 1 × 10 ² to
It is desirable that the concentration be in the range of 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. Some portions may be contained 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 0 atomic%, optimally 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 4 μm, from the viewpoint of obtaining desired electrophotographic characteristics and economic effects. Most preferably, it is in the range of 0.5 to 3 μm. If the layer thickness is less than 0.1 μm, the ability to stop injection of electric charge from the support becomes 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 an increase in manufacturing time due to the extension of time is caused. 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 according to the layer design.
10 ^{−2 to} 2 × 10 ³ Pa, preferably 5 × 10 ^{−2 to} 5 ×
It is preferable that the pressure be in the range of 10 ² Pa, most preferably 1 × 10 ⁻¹ to 2 × 10 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 0.8. It is desirable to set it in the range of 7, most preferably 1１〜6.

Further, the temperature of the support 201 is appropriately selected in an optimum range 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 relationships in order to form a surface layer having desired properties.

In addition, in the light receiving member of the present invention, at least aluminum atom, silicon atom, 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 example, Si ₃ N ₄ , SiO ₂ , SiO ₂ or a silicon atom is used as a base, and a hydrogen atom and / or a halogen atom and 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, a source gas supply device 3200, and an exhaust device (not shown) for reducing the pressure inside the reaction vessel 3111. A cylindrical support 3112 and a heater 311 for heating the support are provided in a reaction vessel 3111 in the deposition apparatus 3100.
3. A source gas introduction pipe 3114 is installed, and a high frequency matching box 3115 is 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 source 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.
237, 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 is about 6 × 10 ^−4.
When the pressure becomes Pa, the auxiliary valve 3260 and the outflow valve 3
Close 251 to 256.

Thereafter, each gas is introduced from the gas cylinders 3221 to 226 by opening the valves 3231 to 236.
Each gas pressure is adjusted to 2 kg by pressure regulators 3261 to 3266
/ Cm ² . Next, the inflow valves 3241-32
46 is gradually opened to introduce each gas into the mass flow controllers 3211 to 3216.

After the preparation for film formation is completed as described above, each layer is formed by 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 pressure in the reaction vessel 3111 becomes 1
The opening of the main valve 3118 is adjusted while watching the vacuum gauge 3119 so that the pressure becomes a predetermined pressure of Torr or less. When the internal pressure is stabilized, an RF power source (not shown) having a frequency of 13.56 MHz is set to a desired power, and RF power is introduced into the reaction vessel 3111 through the high frequency matching box 3115 to generate 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 several 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.
, 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 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 production conditions of 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 using a cylindrical sample holder with a groove for mounting the sample substrate.
059) and an a-Si film having a film 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 15 atom%, 1.72 eV and 52 me, respectively.
V, and in the second photoconductive region, Ch, Eg, and Eu were 19 atom%, 1.61 eV, and 58 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 to obtain the second photoconductive region. Various light receiving members having different photoconductive regions of Eg (Ch) and Eu were prepared.

In addition, several kinds of film thicknesses of the second photoconductive region on the surface layer side in a range capable of absorbing about 60% or more of image exposure were prepared. However, the total photoconductive layer including the first photoconductive layer and the second photoconductive region was adjusted to have a thickness of 30 μm. An electrophotographic device (Canon N
P-6750 was modified for testing) and the potential characteristics were evaluated.

At this time, the process speed was 380 mm / se.
c) The electrophotographic apparatus was set in a pre-exposure (700 nm wavelength LED) 4 lux.sec, image exposure (680 nm LED and laser can be exchanged), and the potential characteristics were evaluated. At this time, a surface voltmeter (TREK Co., Ltd.) was set at the developing device position of the electrophotographic apparatus under the condition of a charger current value of 1000 μA.
The surface potential of the light receiving member was measured by a potential sensor of Model 344), and the measured value was used as the charging ability. In addition, the temperature was set to room temperature (about 25
° C) to 50 ° C, and the chargeability was measured under the above conditions, and the change in chargeability per 1 ° C of the temperature at that time was defined as a temperature characteristic.

[0146] The memory potential is set to the LE for the image exposure light source.
Using D, the potential difference between the surface potential in the non-exposed state and the potential after being exposed and then charged again was measured using the same potential sensor under the above conditions. The temperature characteristics of sensitivity
Charged to a surface potential of 400 V as a dark potential,
Next, the exposure is performed, and the absolute value of the difference between the value at room temperature and the value at about 45 ° C. of the exposure amount (half reduction exposure amount) when the difference between the dark potential and the bright potential becomes 200 V (△ 200 V). Was evaluated. The sensitivity linearity connects the exposure amount (actually measured value) when the difference between the dark potential and the bright potential becomes 350 V (Ｖ350 V), the point without exposure (dark state), and the point when the half-exposure exposure amount is irradiated. The straight line was extrapolated and evaluated by the absolute value of the difference from the exposure amount (calculated value) of △ 350 V (see FIG. 11).

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.
The relationship between Eu and Eg of this example and the temperature characteristics of sensitivity, sensitivity linearity, charging ability, temperature characteristics, and optical memory are shown in FIGS. 4 to 8, respectively. 9 to 10 show the relationship between the temperature characteristic and the linearity of the sensitivity. Regarding each characteristic, the photoconductive layer (total film thickness 30μ)
m) is shown as a relative value when the case where only the first photoconductive region is formed is set to 1, and a value smaller than 1 indicates that the characteristic is improved.

As is clear from FIGS. 4 to 10, the second photoconductive region has a thickness of 1.55 to 1.70 eV, a Eu of 50 to 65.meV, and a film thickness capable of absorbing 70 to 95% of image exposure. Under these conditions, in an electrophotographic apparatus using an LED or a visible laser as an exposure light source, it is understood that the temperature characteristics of sensitivity and the linearity of sensitivity are good, and good characteristics are obtained in all of the charging ability, temperature characteristics and memory. It was also found that the second photoconductive region having an Eg of 1.55 to 1.70 eV contained 3 to 35% of germanium atoms with respect to the sum of silicon atoms and germanium atoms.

[0149]

[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). *** The thickness of the first photoconductive region was 30 μm minus the thickness of the second photoconductive region.

(Test Example 2) Using an apparatus for manufacturing a light-receiving member by the RF-PCVD method shown in FIG. 3, under the same conditions as in Test Example 1, on an 80 mm-diameter mirror-finished aluminum cylinder (support). 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 film 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 10 atom%, 1.70 eV and 50 me, respectively.
V, and in the second photoconductive region, Ch, Eg, and Eu were 16 atom%, 1.58 eV, and 60 meV, 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 the individual photoreceptor members produced were evaluated in the same manner as in Test Example 1. As a result, Eg was 1.70 to 1.80 eV, Eu was 50 to 55 meV, and hydrogen was hydrogen in the first photoconductive region. Under the condition of a content of 10 to 25 atomic%, both the laser light and the LED light have sensitivity temperature characteristics, sensitivity linearity, charging ability, and temperature as compared with the case where the photoconductive layer is composed of only the first photoconductive region. It can be seen that the characteristics and the optical memory are all improved, and the temperature characteristics of sensitivity and the linearity of sensitivity are greatly improved in laser and LED light. In addition, even when a visible laser was used, a good image without interference fringe patterns was obtained.

[0155]

[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) An aluminum cylinder having a mirror-finished surface with a diameter of 80 mm applied under the conditions shown in Table 1 in the same manner as in Test Example 1 using the apparatus for manufacturing a light receiving member by the RF-PCVD method shown in FIG. On the (support), 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. Then, a light receiving member having only the first photoconductive region was prepared for reference.

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 film 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 regions are Ch, E
g and Eu are 15 atom%, 1.72 eV and 52 me, respectively.
V, and in the second photoconductive region, Ch, Eg, and Eu were 19 atom%, 1.61 eV, and 58 meV, respectively.

Here, regarding the inclusion of the group IIIb element in the photoconductive layer, the image exposure was carried out at 50, 60, 70 and 8 respectively.
The content in the layer region from the surface side required for absorption of 0 and 90% is set to 0.2 ppm, and the content in the other layer regions is uniformly set to 1.0 ppm. Various receiving members were produced.

The individual light-receiving members produced were evaluated for potential characteristics in the same manner as in Test Example 1. FIGS. 12 to 16 show the relationship between the above-mentioned 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.

As apparent 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 can be seen 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 are improved as compared with those containing the group b element uniformly.

(Test Example 4) Using the apparatus for manufacturing a photoreceptor member by the RF-PCVD method shown in FIG. 3, under the conditions shown in Table 1 of Test Example 1, the content of B with respect to Si in the photoconductive layer was made second. Are fixed at 0.05 ppm, and the first photoconductive regions are respectively 0.1, 0.2, 5, 10, 20,
A light receiving member comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared on a mirror-finished aluminum cylinder (support) having a diameter of 80 mm under the same conditions except that the amounts were changed to 30 and 35 ppm. .

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, those produced with the content of B relative to Si in the first photoconductive region being 0.2 to 30 ppm were obtained. Good results were obtained as in Test Example 1.

(Test Example 5) Using the apparatus for manufacturing a photoreceptor member by the RF-PCVD method shown in FIG. 3, under the conditions shown in Table 1 of Test Example 1, the content of B with respect to Si in the photoconductive layer was first determined. Are fixed at 12 ppm, and the second photoconductive regions are respectively 0.003, 0.005, 0.1, and 0.1.
A light receiving member comprising a charge injection blocking layer, a photoconductive layer, and a surface layer on an 80 mm diameter mirror-finished aluminum cylinder (support) under the same conditions except that the amounts were changed to 2, 5, 10 and 11 ppm. Was prepared.

The potential characteristics of the individual photoreceptor members produced were evaluated in the same manner as in Test Example 1. When the content of B with respect to Si in the second photoconductive region was 0.005 to 10 ppm, the produced photoreceptor members were tested. Good results were obtained as in Example 1.

(Test Example 6) The content of B with respect to Si in the photoconductive layer was determined under the conditions shown in Table 1 of Test Example 1 using the apparatus for manufacturing a photoreceptor member by the RF-PCVD method shown in FIG. I did it. (1) The first photoconductive region is 11 → 2
ppm, and as shown in FIGS. 17A to 17G, the second photoconductive region is changed from 1.5 to 0.1 for each.
ppm was changed as shown in FIGS. 17 (a) to 17 (g). (2) The first photoconductive region is changed from 11 to 2 ppm as shown in FIG.
(A) to (g), and the second photoconductive region was kept constant at 1.2 ppm for each. (3) The first photoconductive region was fixed at 11 ppm, and the second photoconductive region was changed from 1.5 to 0.1 ppm for each, as shown in FIGS. 17 (a) to (g). When the potential characteristics of the light receiving members (1) to (3) were evaluated in the same manner as in Test Example 1, good results were obtained as in Test Example 1.

[0167]

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 mirror-finished aluminum cylinder (support) having a diameter of 80 mm were formed using an apparatus for manufacturing a photoreceptor member by the RF-PCVD method shown in FIG. A light receiving member composed of a surface 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 10 atomic% and 1.70 e, respectively.
V, 50 meV, Ch, Eg, Eu of the second photoconductive region
Obtained 19 atomic%, 1.58 eV and 52 meV, respectively.

The produced light receiving member was modified with an electrophotographic apparatus (NP-6750, manufactured by Canon Inc.) for testing.
(LED and laser are interchangeable), and the potential characteristics were evaluated in the same manner as in Test Example 1. Both the LED light and the laser light had sensitivity temperature characteristics, sensitivity linearity, charging ability, and temperature characteristics. And good memory characteristics were obtained.

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 side of the charge injection blocking layer, even if the first photoconductive region of the photoconductive layer is C
h, Eg, and Eu are each 10-25 atomic%, 1.70-
1.80 eV, 50 to 55 meV, and each of Ch, Eg, and Eu in the second photoconductive region is 5 to 25 atoms.
%, It is understood that it is necessary to set them to 1.55 to 1.75 eV and 50 to 65 meV in order to obtain good electrophotographic characteristics.

[0172]

[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). *** The thickness of the first photoconductive region was 30 μm minus the thickness of the second photoconductive region.

[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. The operation was performed under the same conditions as in Example 1 except that a surface layer was provided in which the content of silicon atoms and carbon atoms in the layer was unevenly distributed in the layer thickness direction.

Table 4 shows the conditions for manufacturing the light receiving member at this time. The produced light receiving member was evaluated in the same manner as in Example 1. As a result, good electrophotographic characteristics were obtained for both the LED light and the laser light.

That is, the photoconductive layer is arranged in the order of the second photoconductive region and the first 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. In the case of providing a surface layer in a distributed state, Ch, Eg, and the like in the first photoconductive region of the photoconductive layer.
Each of Eu is 10 to 25 atomic%, 1.70 to 1.80 e
V, 50 to 55 meV, and Ch, Eg, and Eu in the second photoconductive region were 5 to 25 atomic% and 1.55 to 1.5 atomic%, respectively.
It is understood that it is necessary to set 1.70 eV and 50 to 65 meV to obtain good electrophotographic characteristics.

[0176]

[Table 4] * 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). *** The thickness of the first photoconductive region was 30 μm minus the thickness of the second photoconductive region.

[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 content of silicon atoms and carbon atoms in the layer was unevenly distributed in the 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 25 atomic% and 1.80 e, respectively.
V, 54 meV, Ch, Eg, Eu of the second photoconductive region
Obtained 5 atomic%, 1.55 eV and 50 meV, respectively. When the produced light receiving member was evaluated in the same manner as in Example 1, good electrophotographic characteristics were obtained for both the LED light and the laser light.

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. In the case where a surface layer having a proper distribution state is provided and all the layers contain fluorine atoms, boron atoms, carbon atoms, oxygen atoms, and nitrogen atoms, Ch, Eg in the first photoconductive region of the photoconductive layer. , Eu are respectively 10 to 25.
Atomic%, 1.70 to 1.80 eV, 50 to 55 meV, and in the second photoconductive region, Ch, Eg, and Eu were 5 to 25 atomic%, 1.55 to 1.70 eV, 50 to 6 respectively.
It is understood that 5 meV is necessary to obtain good electrophotographic characteristics.

[0180]

[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). *** The thickness of the first photoconductive region was 30 μm minus the thickness of the second photoconductive region.

[0181] [Example 4] In this example, the first photoconductive region photoconductive layer from the charge injection blocking layer side, and the order of the second photoconductive region, the He instead of H ₂ of Example 1 used. Table 6
The production conditions of the light receiving member at this time are shown below.

In this example, Ch, Eg, and Eu in the second photoconductive region of the photoconductive layer are 25 atomic% and 1.78 e, respectively.
V, 53 meV, Ch, Eg, Eu of the second photoconductive region
Obtained 15 atomic%, 1.58 eV and 55 meV, respectively. When the produced light receiving member was evaluated in the same manner as in Test Example 1, good electrophotographic characteristics were obtained for both the LED light and the laser light.

That is, even when He is used instead of H ₂ and 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, Ch, Eg, and Eu are each set to 10 in the first photoconductive region.
-25 atomic%, 1.70-1.80 eV, 50-55me
V, Ch, Eg, and Eu in the second photoconductive region are each 5 to 25 atomic%, 1.55 to 1.70 eV, 50
It is understood that it is necessary to set the pressure to 65 meV in order to obtain good electrophotographic characteristics.

[0184]

[Table 6] * 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). *** The thickness of the first photoconductive region was 30 μm minus the thickness of the second photoconductive region.

[Embodiment 5] This embodiment is the same as the embodiment 4 except that a surface layer is provided in which the contents of silicon atoms and carbon atoms are unevenly distributed in the layer thickness direction.
The procedure was performed under the same conditions as described above.

Table 7 shows the conditions for producing the light receiving member at this time. When the produced light-receiving member was evaluated in the same manner as in Test Example 1, good electrophotographic characteristics were obtained for both the LED light and the laser light.

That is, using He instead of H ₂ to form the photoconductive layer 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 Is provided in the first photoconductive region of the photoconductive layer, Ch, Eg, and Eu are respectively 10 to 25 atoms and% 1.7 in the first photoconductive region of the photoconductive layer.
Electrophotography in which 0 to 1.80 eV, 50 to 55 meV, and Ch, Eg, and Eu in the second photoconductive region are preferably 5 to 25 atomic%, 1.55 to 1.70 eV, and 50 to 65 meV, respectively. It turns out that it is necessary to obtain the characteristics.

[0188]

[Table 7] * 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). *** The thickness of the first photoconductive region was 30 μm minus the thickness of the second photoconductive region.

[Embodiment 6] 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 carbon atoms are used as atoms constituting the surface layer. Instead, nitrogen atoms were included in the surface layer. Table 8 shows the manufacturing conditions of the light receiving member at this time.

In this example, Ch, Eg, and Eu in the first photoconductive region of the photoconductive layer are 28 atomic% and 1.78 e, respectively.
V, 55 meV, Ch, Eg, Eu of the second photoconductive region
Obtained 20 atomic%, 1.70 eV and 65 meV, respectively. When the produced light-receiving member was evaluated in the same manner as in Example 1, good electrophotographic characteristics were obtained for both the LED light and the laser light.

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 contains nitrogen atoms instead of carbon atoms as atoms constituting the surface layer. In the case where a surface layer is provided, Ch, Eg, and Eu are respectively 10 to 25 atomic%, 1.70 to 1.80 eV, and 50 to 5 in the first photoconductive region of the photoconductive layer.
5 meV, and in the second photoconductive region, Ch, Eg,
Eu is 5 to 25 atomic% respectively, and 1.55 to 1.70 e.
It is understood that V and 50 to 65 meV are necessary for obtaining good electrophotographic characteristics.

[0192]

[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). *** The thickness of the first photoconductive region was 30 μm minus the thickness of the second photoconductive region.

[Embodiment 7] 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 atoms and carbon atoms were unevenly distributed in the layer thickness direction. Table 9 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 1.78 e, respectively.
V, 52 meV, Ch, Eg, Eu of the second photoconductive region
Obtained 25 atomic%, 1.70 eV and 58 meV, respectively. When the produced light-receiving member was evaluated in the same manner as in Example 1, good electrophotographic characteristics were obtained for both the LED light and the laser light.

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 contains nitrogen atoms instead of carbon atoms as atoms constituting the surface layer. In the case where a surface layer is provided, Ch, Eg, and Eu are respectively 10 to 25 atomic%, 1.70 to 1.80 eV, and 50 to 5 in the first photoconductive region of the photoconductive layer.
5 meV, and in the second photoconductive region, Ch, Eg,
Eu is 5 to 25 atomic% respectively, and 1.55 to 1.70 e.
It is understood that V and 50 to 65 meV are necessary for obtaining good electrophotographic characteristics.

[0196]

[Table 9] * 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). *** The thickness of the first photoconductive region was 30 μm minus the thickness of the second photoconductive region.

[0197]

According to the present invention, the temperature characteristic of sensitivity, the linearity of sensitivity, the temperature characteristic, and the temperature characteristic are remarkably improved in the operating temperature range of the light receiving member, and the occurrence of optical memory is substantially reduced. In addition, the light receiving member for electrophotography can improve the stability of the light receiving member in the use environment, and can stably obtain a high-quality image with a clear halftone and high resolution. can get.

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

In particular, in the present invention, by dividing the photoconductive layer into layer regions having different optical band gaps and levels in the gap, and particularly focusing on the light incident portion, a long wavelength laser for digitization can be obtained. For LEDs and LEDs, the temperature dependence (slope and curve) of the sensitivity line is kept small, the charging ability is high, and the change in surface potential due to the fluctuation of the surrounding environment is suppressed. It has the feature of having.

[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 in 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 memory.

FIG. 9 is a graph showing the relationship between the light absorptance of the second photoconductive region of the photoconductive layer and the temperature characteristic of sensitivity in the photoreceptor member of the present invention.

FIG. 10 is a graph showing the relationship between the light absorptivity of the second photoconductive region of the photoconductive layer and the linearity of sensitivity in the light receiving member of the present invention.

FIG. 11 is a schematic diagram showing an example of an exposure dose-surface potential curve for explaining the temperature characteristic of sensitivity and the linearity of sensitivity according to the present invention.

FIG. 12 is a graph showing the relationship between the light absorptance of the second photoconductive region of the photoconductive layer and the temperature characteristic of sensitivity in the light receiving member of the present invention.

FIG. 13 is a graph showing the relationship between the light absorptance of the second photoconductive region of the photoconductive layer and the linearity of sensitivity in the photoreceptor member of the present invention.

FIG. 14 is a graph showing the relationship between the light absorptivity of the second photoconductive region of the photoconductive layer and the charging ability in the photoreceptor member of the present invention.

FIG. 15 is a graph showing the relationship between the light absorptance of the second photoconductive region of the photoconductive layer and the temperature characteristics in the light receiving member of the present invention.

FIG. 16 is a graph showing the relationship between the optical absorptance of the second photoconductive region of the photoconductive layer and the optical memory in the light receiving member of the present invention.

FIG. 17 is a schematic view showing a distribution state of an element belonging to Group IIIb of the periodic table contained in the photoconductive layer in 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 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- 3236 Raw material gas cylinder valve 3241-3246 Gas inflow valve 3251-3256 Gas outflow valve 3261-3266 Pressure regulator

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Daisuke Tazawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc.

Claims (12)

[Claims] At least one conductive support, and a hydrogen atom and / or a halogen atom and at least one element belonging to Group IIIb of the periodic table are contained on the surface of the conductive support. An electrophotographic light-receiving member having at least a light-receiving layer having a photoconductive layer comprising a non-single-crystal material as a base material and having a photoconductive layer, wherein the photoconductive layer has a first photoconductive region and a An optical bandgap (Eg) of the second photoconductive region is smaller than an optical bandgap (Eg) of the first photoconductive region, and a hydrogen content and Linear relationship part of the function represented by the formula (I) lnα = (1 / Eu) · hν + α ₁ (I) where photon energy (hν) is an independent variable and absorption coefficient (α) of the light absorption spectrum is a dependent variable ( Exponential tail) The characteristic energy (Eu) of the first photoconductive region and the second photoconductive region is within a specific range, and the characteristic energy (Eu) of the first photoconductive region is 50 to 55.
meV range and the hydrogen content is 10-25 atoms
%, An optical band gap (Eg) of 1.70 to 1.80 eV, a characteristic energy (Eu) of 50 to 65 meV in the second photoconductive region,
A light-receiving member for electrophotography, wherein the hydrogen content is in the range of 5 to 25 atomic% 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 germanium atoms in the range of 3 to 35% with respect to the sum of silicon atoms and germanium atoms. The light receiving member for electrophotography according to claim 1 or 2, wherein 4. The electron according to claim 1, wherein the photoconductive layer contains at least one element belonging to Group IIIb of the periodic table in the photoconductive layer. Light receiving member for photography. 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 higher than the content of the first photoconductive region on the support side. The light receiving member for electrophotography according to claim 4, wherein the number is small. 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. Item 6. An electrophotographic light-receiving member according to item 5. 7. An amount of an element belonging to Group IIIb of the periodic table contained in the second photoconductive region is in a range of 0.005 to 10 ppm with respect to silicon atoms. Item 6. An electrophotographic light-receiving member according to item 5. 8. The photoconductive layer is provided with a surface layer made of a silicon-based non-single-crystal material containing at least one of carbon, oxygen and nitrogen on a surface thereof.
The electrophotographic light-receiving member according to claim 1. 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 0.01 to 3 μm. 11. The charge injection blocking layer has a thickness of 0.1.
The light receiving member for electrophotography according to claim 10, wherein the thickness is from 5 to 5 µm. 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 0 μm.