JPH11202515A - Electrophotographic photoreceptive member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoreceptive member with which the improvement in electrostatic chargeability and temp. characteristics as well as the decrease of optical memories are compatible with higher order and which has an excellent potential characteristic and image characteristic. SOLUTION: The layer regions varying in hydrogen contents, optical band gaps and the characteristic energy of exponential functions obtd. from light absorption spectra are composed in the photoconductive layer of the phoreceptive member 200. The first layer region 211 and second layer region 212 having specific characteristics are constituted. The contents of the elements of the group 111b of the Periodic Table are so determined as to be greater in the respective layer regions and the substrate sides. In addition, the respective min. contents and max. contents of the first layer region 211 and the second layer region 212 are regulated within specific ranges. The content of the elements belonging to the group 111b of the Periodic Table in the region down to >=0.5 to <=1.5 μm from the front surface side of the second layer region 212 is so determined as to attain >=0 to <=0.1 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[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 irradiating electromagnetic wave, it has fast photoresponse, it has a desired dark resistance value, and it is used. Are required to be harmless to the human body. In particular, in the case of a light receiving member to be incorporated in an electrophotographic apparatus used in an office as an office machine, the above-mentioned non-pollutability at the time of use is important.

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

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

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

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

Furthermore, in JP-A-57-158650, hydrogen containing 10 to 40 atomic%, 0.2 absorption coefficient ratio of the absorption peak of ^2100cm-1 and 2000 cm ^-1 in the infrared absorption spectrum It is described that by using a-Si: H of 1.7 for the photoconductive layer, a high-sensitivity and high-resistance electrophotographic photoconductor can be obtained. In the photoconductive layer of the photoconductor, the characteristic energy at the exponential function tail of the light absorption spectrum is 0.09e.
A technique for obtaining a high-quality image free from an afterimage phenomenon by setting the voltage to V or less is disclosed.

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

Japanese Patent Application Laid-Open No. 58-88115 discloses that a group IIIb element of the periodic table is distributed in the photoconductive layer of an amorphous silicon photoreceptor so as to increase toward the support, so that the charge retention ability is improved. There is disclosed a technique for obtaining a photoconductor which is improved and has no residual potential.

On the other hand, Japanese Patent Application Laid-Open No. 60-95551 discloses that in order to improve the image quality of an amorphous silicon photoreceptor, the temperature near the photoreceptor surface is maintained at 30 to 40.degree. 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, In fact, there is room for further improvement.

In particular, the electrophotographic apparatus has been rapidly developing high image quality, high speed, and high durability. In the electrophotographic light-receiving member, the electric properties and photoconductive properties have been further improved, and the charging ability and sensitivity have been improved. There is a need to significantly extend performance in all environments while maintaining. As a result of the improvement of the optical exposure device, the developing device, and the transfer device in the electrophotographic device for improving the image characteristics of the electrophotographic device, the image characteristics of the electrophotographic light-receiving member have been improved more than before. It has become required.

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 performance and image quality. In particular, as a challenge to further improve the image quality of amorphous silicon light receiving members,
There has been an increasing demand for reduction of variations in electrophotographic characteristics due to changes in ambient temperature and optical memories such as blank memories and ghosts.

For example, conventionally, as described in the above-mentioned Japanese Patent Application Laid-Open No. 60-95551, a drum heater is installed in a copying machine to reduce the surface temperature of the photoconductor to 40 to prevent image deletion on the photoconductor. ℃ was maintained. However, the conventional photoconductor has a large temperature dependence of the charging ability due to the generation of the pre-exposure carrier and the thermally excited carrier, that is, a so-called temperature characteristic. However, 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.

Further, conventionally, even at night when a copying machine is not used, the drum heater is energized 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 the image flow from occurring. 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.

On the other hand, when the same original is continuously and repeatedly copied, the image density may decrease or fog may occur due to light fatigue of the photosensitive member due to image exposure. In addition, a blank memory in which a difference in density occurs on a copy image due to the effect of a so-called blank exposure, which is applied to a photoconductor between sheets during intermittent copying in order to save toner, or an afterimage of an image exposure in a previous copying process Appears on the image at the next copy,
So-called ghosts have become 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 and the chemical composition of each layer are improved from a comprehensive viewpoint so as to solve the above-mentioned problems. At the same time, it is necessary to further improve the characteristics of the a-Si material itself.

An object of the present invention is to solve various problems in the conventional electrophotographic light receiving member having a light receiving layer composed of a-Si. That is,
The main object of the present invention is a non-single-crystal material based on silicon atoms, which has improved chargeability, reduced temperature characteristics and reduced optical memory at a high level to dramatically improve image quality. An object of the present invention is to provide a light receiving member having a light receiving layer configured.

In particular, the electrical, optical, and photoconductive properties are substantially always stable without being substantially dependent on the use environment, are excellent in light fatigue resistance, and do not cause deterioration when repeatedly used. 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.

[0020]

Means for Solving the Problems In order to solve the above problems, the present inventors focused on the behavior of carriers in the photoconductive layer,
As a result of intensive studies on the relationship between the distribution of localized state density in the band gap of a-Si and the distribution of group IIIb elements in the periodic table that controls electric conductivity, temperature characteristics and optical memory, the thickness of the photoconductive layer was found. In the direction, the knowledge that the above object can be achieved by controlling the hydrogen content, the distribution of the optical band gap and the localized state density in the band gap, and specifying the distribution state of the group IIIb element of the periodic table. Obtained. That is, 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 is designed and manufactured to specify the layer structure. The light receiving member not only exhibits remarkably excellent properties in practical use, but also surpasses in all respects as compared with the conventional light receiving member, and particularly has excellent characteristics as a light receiving member for electrophotography. I have what I have.

Accordingly, the present invention provides an electrophotographic light-receiving member having the following features. That is, the photoreceptor member of the present invention is 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. Hydrogen content in the layer,
Optical memory having an optical band gap and a layer region having different characteristic energies of exponential function tails obtained from an optical absorption spectrum, and distributing elements belonging to Group IIIb of the periodic table to improve chargeability and temperature characteristics, and to improve optical memory. This is characterized in that good characteristics are exhibited by eliminating the occurrence of blemishes.

The photoconductive layer is formed by laminating a first layer region and a second layer region. The first layer region has a hydrogen content of 10 to 25 at% and an optical band gap of at least 25 at%. 1.65 eV or more and less than 1.75 eV, the characteristic energy of the exponential function tail obtained from the light absorption spectrum is 50 me.
V to 55 meV, the hydrogen content in the second layer region is 15 to 30 atomic%, the optical band gap is 1.75 eV to 1.85 eV, and the characteristic energy of the exponential function obtained from the light absorption spectrum. Is 55m
It is characterized in that it is not less than eV and not more than 65 meV.

Furthermore, the photoconductive layer is characterized in that the photoconductive layer contains at least one element belonging to Group IIIb of the periodic table and is increased on the substrate side in each layer region. Further, the photoconductive layer is characterized in that a second layer region is laminated on the first layer region on the surface of the conductive support.

Second, the photoconductive layer is characterized in that the ratio of the thickness of the first layer region to the entire photoconductive layer is in the range of 0.01 to 0.3. Third, in the region from the surface side of the second layer region to 0.5 μm or more and 1.5 μm or less, the content of the element belonging to Group IIIb of the periodic table is reduced to 0%.
To 0.1 ppm or less.

Fourth, Periodic Table IIIb of the first layer region
It is characterized in that the minimum content of elements belonging to the group is in the range of 0.1 to 15 pm with respect to silicon atoms.
Fifth, the maximum content of the element belonging to Group IIIb of the periodic table in the first layer region is set to 0.5 to 50 with respect to silicon atoms.
pm range.

Sixth, Periodic Table IIIb of the second layer region
It is characterized in that the maximum content of elements belonging to the group is in the range of 0.01 to 20 pm with respect to silicon atoms. Seventh, the photoconductive layer includes at least one of carbon, oxygen, and nitrogen in the photoconductive layer.

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. I have. Ninth, the photoconductive layer is a charge injection blocking layer made of a 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. The photoconductive layer is provided on the surface, and the 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. １０Tenth, the surface layer has a thickness of 0.0
It is characterized by a range of 1 to 3 μm. Eleventh
The charge injection blocking layer has a thickness of 0.1 to 5 μm.
It is characterized by being within the range. Twelfth, the photoconductive layer is characterized in that its layer thickness 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 from the absorption of the light absorption spectrum to the lower energy side.
The “characteristic energy” means the slope of the exponential function tail. This will be described in detail with reference to FIG. FIG. 1 is an example of an a-Si subgap light absorption spectrum in which the horizontal axis represents the photon energy hν and the vertical axis represents the absorption coefficient α as a logarithmic axis. This spectrum is roughly divided into two parts. That is, a portion B in which the absorption coefficient α changes exponentially, that is, linearly with the photon energy hν (exponential function tail or Urbach tail).
And α are portions A showing 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

[0030] _{α = α o exp (hν /} Eu) and taking the logarithm of the both sides 1nα = (1 / Eu) · hν ± α1 ( However, α1 = 1nα _o), and the inverse of the characteristic energy Eu (1 / Eu ) Is B
It represents the inclination of the part. 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.

(Effects) The present inventors have determined the characteristic energy of the optical bandgap (hereinafter abbreviated as Eg) and the exponential function tail (urbuck tail) obtained from the sub-bandgap light absorption spectrum measured by CPM. As a result of examining the correlation between (hereinafter abbreviated as Eu) and the characteristics of the photoreceptor under various conditions, it was found that the charging ability, temperature characteristics and optical memory of Eg, Eu and the a-Si photoreceptor were closely related. It was found that by laminating these different films, good or good photoreceptor characteristics were exhibited.

Further, as a result of a detailed study of the movement of holes and electrons, which are photogenerated carriers, in the layer, it was found that the movement of holes was deeply related to temperature characteristics and memory.
Then, the movement of the hole and the characteristics of the photoconductor are described in the Periodic Table II.
The control by the distribution of the elements belonging to the group Ib in the photoconductive layer is examined in more detail, and the different layers of Eg and Eu are stacked, and the electric field that changes as the main charge travels in each layer, The present inventors have found that the runnability changes at each time, and found that the distribution of elements belonging to Group IIIb of the periodic table can be controlled so as to compensate for the runnability, and have completed the present invention.

That is, by providing a layer region having a large optical band gap and a small trapping ratio of carriers to localized levels on the photoconductive layer and the surface side, the charging performance is greatly improved while the charging performance is greatly improved. And the portion where the main charge is a hole on the substrate side of the photoconductive layer has fewer defects than the layer region on the surface side, that is, a layer region in which carriers, particularly holes, are less trapped in the localization order and have high mobility. By disposing them, it is possible to substantially eliminate the memory and improve the adhesion with a dense layer having few defects. To explain this in more detail, generally, in the band gap of a-Si: H, the tail (tail) level based on the structural disorder of the Si-Si bond and the dangling hand of Si (dangling). There are deep levels due to structural defects such as bonds. It is known that these levels function as trapping and recombination centers for electrons and holes, and cause deterioration of device characteristics.

As a method for measuring the state of the localized level in the band gap, generally, deep level spectroscopy, isothermal capacity transient spectroscopy, photothermal deflection spectroscopy, photoacoustic spectroscopy, constant photocurrent method, etc. Is used. Above all, constant photocurrent method (C
instant PhotoCurrent Metho
d: hereinafter abbreviated as CPM) is useful as a simple method for measuring the subgap light absorption spectrum based on the localized level of a-Si: H.

The reason why the charging ability is reduced when the photosensitive member is heated by a drum heater or the like is that a thermally excited carrier is attracted by an electric field at the time of charging and a localized level at a band base or a deep station within a band gap. It travels to the surface while repeating capture and emission to a state, 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 suppress the generation of thermally excited carriers by increasing the optical band gap, and to improve the traveling properties of the carriers in order to improve the temperature characteristics.

Further, the optical memory is generated by the photo carriers generated by the blank exposure or the image exposure being captured by the localized levels in the band gap and remaining 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.

Therefore, by providing a layer region in which Eu is controlled (reduced) while increasing Ch and increasing Eg on the surface side, generation of thermally excited carriers is suppressed, and the thermally excited carriers and optical carriers are reduced. By improving the mobility of carriers because the ratio of trapped by the localized level can be reduced, and providing a dense and Eu-reduced layer region on the support side by further reducing Ch, particularly in the case of holes, Drivability is dramatically improved.

Further, the distribution and the amount of the element of Group IIIb of the periodic table for controlling the electric conductivity are adjusted in each layer so that the carriers travel in the photoconductive layer in one copying process. The characteristics required for each layer can be effectively derived.

At this time, the region of the photoconductive layer which substantially absorbs the light of the analog light source (halogen lamp) whose long wavelength has been cut (light having a wavelength distribution with the longest wavelength around 600 nm), that is, the second region In the region from 0.5 to 1.5 μm from the surface side of the layer region, the periodic table III
By adjusting the content of the element of the group b to an extremely small value so that the mobility of electrons is emphasized, the mobility of carriers in the entire photoconductive layer can be improved in a well-balanced manner.

That is, the second layer region is provided on the outermost surface side of the light receiving member, the region that substantially absorbs light is set as the second layer region, and the first layer region is provided on the substrate side. Ritsuyo III
In the region from 0.5 to 1.5 μm from the surface side of the second layer region where the distribution of group b elements is large on the substrate side, the content of elements belonging to group IIIb of the periodic table is 0 to 0. .1p
By setting it to not more than pm, a remarkable effect can be obtained particularly with respect to charging ability, temperature characteristics and memory.

Therefore, according to the present invention,
Improving the charging ability and reducing the temperature characteristics and optical memory at a high level, it is possible to solve all of the above-mentioned problems in the prior art, extremely excellent electrical, optical, photoconductive properties, A light receiving member exhibiting image quality, durability and use environment can be obtained.

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. The 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 composed of a photoconductive layer 203 made of a-Si: H, X and having photoconductivity.
01 layer region 211 and second layer region 21 in order from the 01 side.
It consists of two.

The light receiving member 200 shown in FIG. 2 (b) 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-Si: H, X
It comprises a photoconductive layer 203 of photoconductive property and an amorphous silicon-based surface layer 204. The photoconductive layer 203 is composed of a first layer region 211 and a second layer 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, an a-Si: H, X photoconductive layer 203 having photoconductivity, and an amorphous silicon-based surface layer 204. The photoconductive layer 203 includes a first layer region 211 and a second layer region 212 in order from the charge injection blocking layer 205 side.

(Support) The support used in the present invention may be either conductive or electrically insulating. As the conductive support, Al, Cr, Mo, Au, In, Nb, Te,
Metals such as V, Ti, Pt, Pd, and Fe and alloys thereof, for example, stainless steel. In addition, polyester, polyethylene, polycarbonate cellulose acetate,
Polypropylene, polyvinyl chloride, polystyrene, polyamide or other synthetic resin film or sheet, glass,
A support in which at least the surface on the side on which a light receiving layer is formed of an electrically insulating support such as a ceramic is subjected to a conductive treatment can also be used.

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

(Photoconductive Layer) In the present invention, the photoconductive layer 203 which is formed on the support 201 and effectively constitutes a part of the light receiving layer 202 for achieving the object is formed by a vacuum deposition film forming method. 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, 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 basically used. And / or a source gas for X supply capable of supplying a halogen atom X 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 a predetermined position is previously determined. A layer made of a-Si: H, X may be formed on a predetermined support 201 provided on the substrate.

Further, in the present invention, it is necessary that the photoconductive layer 203 contains hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves the quality of the layer. This is because it is indispensable to improve photoconductivity and charge retention characteristics. Therefore, in the case of the first layer region, the content of the hydrogen atom or the halogen atom or the sum of the hydrogen atom and the halogen atom is 10 to 25 atom% with respect to the sum of the silicon atom and the hydrogen atom and / or the halogen atom. In the case of the second layer region, the content is desirably 15 to 30 atomic% based on the sum of silicon atoms and hydrogen atoms and / or halogen atoms.

The substances that can serve as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si.
The gaseous state, such as ₄ H _10, or the like as silicon hydride can be gasified (silanes) can be effectively used, and further, the layer during production of the easy handling, the point of and Si-feeding efficiency And SiH ₄ and Si ₂ H ₆ are preferred.

Then, hydrogen atoms are structurally introduced into the formed photoconductive layer 203 so that the control of the introduction ratio of hydrogen atoms is further facilitated to obtain film characteristics which achieve the object of the present invention. 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.

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

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 203, for example, the temperature of the support 201, a raw material used to contain hydrogen atoms and / or halogen atoms, 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 necessary to distribute atoms for controlling conductivity in the photoconductive layer 203. If the atoms for controlling the conductivity are distributed in the photoconductive layer 203 so that the first layer region and the second layer region are increased on the side of the support in the layer thickness direction, a non-uniform distribution state is formed in the layer region. In the region from 0.5 to 1.5 μm from the surface side of the second layer region, it is necessary to distribute so that the content of atoms controlling conductivity is very small. It is.

Examples of the atoms for controlling the conductivity include so-called impurities in the semiconductor field.
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.

Examples of Group IIIb atoms include boron B, aluminum Al, gallium Ga, and indium I.
n, thallium Tl, etc., and B, Al, Ga are particularly preferable.

The content of atoms for controlling conductivity contained in the photoconductive layer 203 is preferably 5 × 10 ⁻³ to 5 × 10 ⁻³ .
The distribution is changed by appropriately selecting the maximum content and the minimum content from 50 atomic ppm, more preferably from 1 × 10 ⁻² to 40 atomic ppm, and most preferably from 1 × 10 ⁻¹ to 1 × 25 atomic ppm. It is desirable to be contained. At that time, it is necessary to increase the content of atoms controlling conductivity on the substrate side of each layer region. Further, regarding the distribution in the first layer region 211, the maximum content of the atoms controlling the conductivity in the first layer region is 0.5 ppm or more and 50 ppm or more with respect to silicon atoms.
ppm or less, the minimum content is 0.1 with respect to silicon atoms.
It is desirable that the concentration be not less than 15 ppm and not more than 15 ppm. With respect to the distribution in the second layer region 212, the maximum content of atoms for controlling conductivity in the second layer region is 0.01 ppm or more and 20 ppm or more with respect to silicon atoms.
0.5 to 1.5 μm from the surface side of the second layer region
In the region up to m or less, it is desirable that the content of atoms for controlling conductivity be 0 to 0.1 ppm or less with respect to silicon atoms.

In each layer region, it is desirable that atoms for controlling the conductivity be changed from the maximum content to the minimum content. When the maximum content of the atom for controlling the conductivity is 0.5 ppm or less in the first layer region and / or 0.01 ppm or less in the second layer region, the mobility of holes is small, and the characteristics are improved. Unshown, a rise in the residual potential and the memory potential occurs. In addition, the minimum content of atoms for controlling conductivity is 15 ppm or more in the first layer region and / or 0.1 ppm or more in the second layer region, particularly the content of atoms for controlling conductivity in the second layer region. If the average of the amount in the layer is 10 ppm or more, the content is excessive and the level of free carriers becomes too large, so that the chargeability and temperature characteristics are not improved.

In order to structurally introduce an atom for controlling conductivity, for example, an atom of group IIIb, it is necessary to form a layer of IIIb
The raw material for introducing group atoms may be introduced in a gaseous state into the reaction vessel 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
Alternatively, the content of oxygen atoms and / or nitrogen atoms is preferably 1 × 10 ⁻⁵ to 10 at%, more preferably 1 × 10 ⁻⁴ to 8 at%, based on the sum of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms. atomic%, 1 × 10 ^over 3-5 atomic% and most desirably. The carbon atoms and / or oxygen atoms and / or nitrogen atoms may be uniformly contained in the photoconductive layer, or may have an uneven distribution such that the content changes in the thickness direction of the photoconductive layer. May be provided.

In the present invention, the layer thickness of the photoconductive layer 203 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
It is desirable that the thickness be 0 to 50 μm, more preferably 23 to 45 μm, and most preferably 25 to 40 μm. 20μ layer thickness
When the thickness is less than m, 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, the ratio of the thickness of the first layer region to the entire photoconductive layer 203 (the first layer region + the second layer region) is from 0.01 to 0.3. It is desirable to do. If the film thickness ratio is smaller than 0.1, the portion of the second layer region in the section where the hole travels increases, and the role of the first layer region optimized for the hole traveling property cannot be exhibited. In addition, the effect of improving the charging ability and reducing the memory cannot be sufficiently exhibited. Further, the effect of improving the adhesion cannot be sufficiently exhibited.

When the first layer region is larger than 0.3, the region having a small optical band gap is increased, so that the generation of thermally excited carriers is increased and the effect of reducing the temperature characteristics is reduced. Further, since it is necessary to reduce the deposition rate in order to obtain the first layer region having the desired characteristics, increasing the thickness of the first layer region increases the production time and increases the cost.

In order to achieve the object of the present invention and to form the photoconductive layer 203 having desired film properties, the mixing ratio of the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power and the supporting power It is necessary to set the body temperature appropriately. The flow rate of H ₂ and / or He used as the dilution gas is
The optimum range is appropriately selected according to the layer design.
The H ₂ and / or He is usually 3-20 times, preferably 4-15 times, optimally 5-10 times the feed gas.
It is desirable to control in the double range.

Similarly, the optimum range of the gas pressure in the reaction vessel is appropriately selected according to the layer design.
0 × 10 ^over 2 ~1.0 × 10 ³ Pa, preferably 5.0 × 1
0 ^{over 2} ~5.0 × 10 2 Pa, and optimally 1.0 × 10 ^over 1 to 1.
It is preferably set to 0 × 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 0.5 to 4 for the first layer region.
Preferably, it is set in the range of 1-3, and the second layer region is set in the range of 3-8, preferably 4-6. In addition, it is preferable that the ratio of the discharge power to the flow rate of the Si supply gas in the second layer region is made larger than that in the first layer region, and that the second layer region is manufactured in a so-called flow limit region. Furthermore, the temperature of the support 201 is appropriately selected in an optimum range according to the layer design. In a normal case, the temperature is preferably 200 to 350 ° C., more preferably 23 ° C.
Desirably, the temperature is 0 to 330 ° C, most preferably 250 to 310 ° C.

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

(Surface Layer) In the present invention, it is preferable to further form an amorphous silicon-based surface layer 204 on the photoconductive layer 203 formed on the support 201 as described above. This surface layer 204 is a free surface 2
06, and is provided in order to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electric pressure resistance, use environment characteristics, and durability. Further, in the present invention, since each of the amorphous materials forming the photoconductive layer 203 and the surface layer 204 constituting the light receiving layer 202 has a common component of silicon atoms, Ensuring chemical stability has been sufficient.

The surface layer 204 may be made of any material as long as it is an amorphous silicon material. For example, amorphous silicon containing a hydrogen atom H and / or a halogen atom X and further containing a carbon atom (hereinafter referred to as amorphous silicon) may be used. , A-SiC: H, X), amorphous silicon containing a hydrogen atom H and / or a halogen atom X, and further containing an oxygen atom (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 / or a halogen atom X In addition, a material such as amorphous silicon (hereinafter, a-SiCON: H, X) containing at least one of a carbon atom, an oxygen atom, and a nitrogen atom is preferably used.

In the present invention, in order to effectively achieve the object, the surface layer 204 is manufactured by a vacuum deposition film forming method by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics. . 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 the manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the light receiving member to be manufactured. From the productivity of the receiving member, it is preferable to use the same deposition method as that for the photoconductive layer. For example, in order to form the surface layer 204 made of a-SiC: H, X by a glow discharge method, it is basically possible to supply a source gas for supplying Si capable of supplying silicon atoms Si and a carbon atom C. A source gas for supplying C and a source gas for supplying H that can supply hydrogen atoms H and / or a source gas for supplying X that can supply halogen atoms X are placed in a reaction vessel capable of reducing the pressure inside a reaction vessel. Introduced in a gaseous state, a glow discharge is generated in the reaction vessel, and the photoconductive layer 20 previously set at a predetermined position is formed.
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. a
Those containing -SiC as a main component are preferable. A-Si for surface layer
When C is a main component, the amount of carbon atoms is preferably in the range of 30 to 90% based on the sum of silicon atoms and carbon atoms.

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

The light-receiving member formed within the above range of hydrogen and / or fluorine content 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 have an adverse effect on 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 3
By controlling the content to 0 atomic% or more, defects in the surface layer are significantly reduced, and as a result, the electrical characteristics and the high-speed continuous usability can be dramatically improved as compared with the related art.

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

Further, by controlling the fluorine content in the surface layer to be in the range of 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 breakage of the bond between silicon atoms and carbon atoms 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 which can be a silicon Si supply gas used in forming the surface layer of the present invention is SiH.
Silicon hydrides (silanes) in a gas state such as ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ or capable of being gasified can be used effectively. Ease,
SiH ₄ and Si ₂ H ₆ are preferred in terms of 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 substances that can serve as a carbon supply gas include:
CH_Four, C_TwoH_Two, C_TwoH₆, C_ThreeH₈, C_FourH _TenEtc. in the gas state,
Or that gaseous hydrocarbons are used effectively
In addition, ease of handling at the time of layer production, Si supply
CH in terms of supply efficiency etc._Four, C_TwoH_Two, C_TwoH₆Is preferred
Are listed. In addition, these raw materials for supplying C
H gas as needed_TwoDiluted with gases such as He, Ar, Ne, etc.
You may use it after appointment.

Substances that can be nitrogen or oxygen supply gas include NH ₃ , NO, N ₂ O, NO, O ₂ , CO, CO ₂ , N ₂
Compounds in a gaseous state or capable of being gasified are effectively used. Also, these nitrogens,
H ₂ , He, Ar, Ne may be used as the source gas for supplying oxygen if necessary.
May be used after being diluted with such a gas.

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

Examples of the effective source gas for supplying a halogen atom include a gaseous or gasifiable halogen compound such as a halogen gas, a halide, an interhalogen compound containing halogen, and a silane derivative 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.

The halogen compounds which can be suitably used in the present invention include, specifically, fluorine gas F ₂ , BrF, ClF,
Inter-halogen compounds such as ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ can be mentioned. As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, specifically, for example, silicon fluoride such as SiF ₄ or Si ₂ F ₆ is preferable.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the 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, the discharge power and the like may be controlled.

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

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

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors, and atoms belonging to Group IIIb of the Periodic Table giving p-type conduction characteristics (hereinafter abbreviated as Group IIIb atoms). Atoms belonging to Group IIIb of the Periodic Table giving n-type conduction characteristics (hereinafter referred to as V
(abbreviated as group b atom) can be used.

Examples of Group IIIb atoms include boron B, aluminum Al, gallium Ga, and indium I.
n, thallium Tl, etc., and B, Al, Ga are particularly preferable. Specific examples of group Vb atoms include phosphorus P and arsenic A.
s, antimony Sb, bismuth Bi, etc., especially P, As
Is preferred.

The content of atoms for controlling conductivity contained in the surface layer 204 is preferably 1 × 10 ⁻³ to 1 ×.
10 ³ atomic ppm, more preferably 1 × 10 ^{-2 to} 5 × 1
0 ² atom ppm, optimally 1 × 10 ^-1 to 1 × 10 ² atom p
pm. In order to structurally introduce an atom for controlling conductivity, for example, a group IIIb atom or a group Vb atom, a source material for introducing a group IIIb atom or a group material for introducing a group Vb atom during layer formation. The raw material may be introduced in a gaseous state into the reaction vessel together with another gas for forming the surface layer 204. As a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom, a gaseous substance at ordinary temperature and pressure, or
It is desirable to employ one 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, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ ,
Examples include boron hydride such as B ₆ H ₁₄ 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.

As a raw material for introducing a group Vb atom, those which can be effectively used include PH ₃ , P
Phosphorus hydride such as ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ , PCl ₃ , PC
phosphorus halides such as l ₅ , PBr ₃ , PBr ₅ and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ ,
SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , Sbl ₅ , BiH ₃ , BiCl ₃ ,
BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing Group Vb atoms. In addition, these raw materials for introducing atoms for controlling the conductivity may be replaced with H ₂ , He,
It may be used after being diluted with a gas such as Ar or Ne.

The thickness of the surface layer 204 in the present invention is usually 0.01 to 3 μm, preferably 0.05 to 2 μm,
Optimally, the thickness is desirably 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, resulting in a loss of 3 μm.
If it exceeds m, a decrease in electrophotographic characteristics such as an increase in residual potential is observed.

The surface layer 204 according to the present invention is carefully formed so that its required properties are provided as desired. That is, a substance containing Si, C and / or N and / or O, H and / or X as a constituent element takes a form from crystalline to amorphous depending on its forming condition, and has electrical conductivity as conductive. From semiconductive to insulating properties, and from the photoconductive property to the non-photoconductive property, respectively, in the present invention, in the present invention, a compound having desired properties according to the purpose, The formation conditions are strictly selected as desired to be formed.

For example, in order to provide the surface layer 204 mainly for the purpose of improving the pressure resistance, the surface layer 204 is formed as a non-single-crystal material having a remarkable electric insulating property in a use environment. Also,
When the surface layer 204 is provided mainly for the purpose of improving the continuous repetitive use characteristics and the use environment characteristics, the degree of the above-mentioned electrical insulation is alleviated to some extent, and the non-conductive layer has a certain sensitivity to irradiated light. Formed as a single crystal material.

In order to form the surface layer 204 having characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the temperature of the support 201 and the gas pressure in the reaction vessel as desired. The temperature (Ts) of the support 201 is appropriately selected in an optimum range according to the layer design. In a normal case, the temperature (Ts) is preferably 200 to 350 ° C., and more preferably 230 to 33 ° C.
The temperature is desirably 0 ° C, optimally 250 to 300 ° C.

[0097] When be appropriately selected within an optimum range in accordance with the gas pressure even with the designing of layer configuration of the reaction vessel of generally preferably 1.0 × 10 ^{over 2 ~1.0} × 10 ³ Pa, more preferably 5 0.0 × 10 ^{-1 to} 5.0 × 10 ² Pa, optimally 1.0 ×
Preferably 10 ^over 1 ~1.0 × 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. It is desirable to determine the optimum value based on mutual and organic relationships to form a light receiving member having the following characteristics.

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

A region in which the content of carbon atoms and / or oxygen atoms and / or nitrogen atoms changes so as to decrease toward photoconductive layer 203 may be provided between surface layer 204 and photoconductive layer 203. Good. As a result, the adhesion between the surface layer and the photoconductive layer is improved, the movement to the surface of the photocarrier becomes smooth, and the influence of interference due to light reflection at the interface between the photoconductive layer and the surface layer can be further reduced. .

(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 for 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. 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 compound 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 uniform in the in-plane direction. . As the atoms for controlling conductivity contained in the charge injection blocking layer, there can be mentioned so-called impurities in the field of semiconductors, and atoms belonging to Group IIIb of the Periodic Table that provide p-type conduction characteristics (hereinafter referred to as Group IIIb atoms) May be used. Specific examples of Group IIIb atoms include B (boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium), and the like, with B, Al, and Ga being particularly preferred. is there.

In the present invention, the content of atoms for controlling conductivity contained in the charge injection blocking layer is appropriately determined as desired so that the object of the present invention can be effectively achieved. 10-1 × 10 ⁴ atom pp
m, more preferably 50 to 5 × 10 ³ atomic ppm, and most preferably 1 × 10 ^{2 to} 3 × 10 ³ atomic ppm. Furthermore, by including at least one of carbon atoms, nitrogen atoms and oxygen atoms in the charge injection blocking layer, the adhesion between the charge injection blocking layer and another layer provided in direct contact with the charge injection blocking layer can be improved. We can do even better.

The carbon atoms, nitrogen atoms or oxygen atoms contained in the layer may be uniformly distributed throughout the layer, or may be evenly distributed in the layer thickness direction. May be present in a non-uniformly distributed state. However, in any case, it is necessary to uniformly contain the particles in the in-plane direction parallel to the surface of the support from the viewpoint of making 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 at%, 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
It is desirable that the content be 5 to 50 atomic%, more preferably 5 to 40 atomic%, and most preferably 10 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. , And most preferably 0.5 to 3 μm. When the layer thickness is less than 0.1 μm, the ability to prevent charge injection from the support is insufficient, and sufficient charging ability cannot be obtained. Even if the layer thickness is more than 5 μm, improvement in electrophotographic properties cannot be expected, Only the production cost is increased due to the extension of the production time.

In the present invention, in order to form the charge injection blocking layer, a vacuum deposition method similar to the above-described method of forming the photoconductive layer is employed. 'To form the charge injection blocking layer 205 having characteristics capable of achieving the object of the present invention, the photoconductive layer 2
03, the mixture ratio of the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power, and the
It is necessary to appropriately set the temperature of No. 1.

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. It is appropriately selected within an optimum range in accordance with the gas pressure inside the reactor even with the designing of layer configuration, usually 1.0 × 10 ^{over from 2} to 1.0
× 10 ³ Pa, preferably 5.0 × 10 ^over 1 to 5.0 × 10 ²
Pa, and most preferably 1.0 × 10 ^{-1 to} 1.0 × 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. Furthermore, the temperature of the support 201 is appropriately selected in an optimum range according to the layer design. In a normal case, the temperature is preferably 200 to 350 ° C., more preferably 23 ° C.
Desirably, the temperature is 0 to 330 ° C, most preferably 250 to 310 ° C.

In the present invention, the preferable 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. The factors are not usually independently determined separately, but it is desirable to determine the optimum value of each layer forming factor based on mutual and organic relations to form a surface layer having desired properties.

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

In the light receiving member of the present invention, the support 201 and the photoconductive layer 203 or the charge injection blocking layer 2
For example, Si ₃ N ₄ , Si ○ ₂ , SiO, or a silicon atom is used as a base, and a hydrogen atom and / or a halogen atom, a carbon atom and / or a An adhesion layer formed of an amorphous material containing oxygen atoms and / or 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.

Next, an apparatus and a film forming method for forming the light receiving layer will be described in detail. FIG. 3 shows a high-frequency plasma CVD method using an RF band as a power supply frequency (hereinafter referred to as an RF band).
FIG. 2 is a schematic configuration diagram illustrating an example of a light-receiving member manufacturing apparatus using -PCVD. The configuration of the manufacturing apparatus shown in FIG. 3 is as follows.装置 This device is roughly divided into
A deposition device (3100), a source gas supply device (320)
0), and an exhaust device (not shown) for reducing the pressure inside the reaction vessel (3111). Deposition equipment (31
00), a cylindrical support (3112), a heater for heating the support (3113), a raw material gas introduction pipe (3114) are installed, and a high-frequency matching box (3115) is connected. ing.

The source gas supply device (3200) is provided with Si
_{H 4, GeH 4, H 2} , CH 4, B 2 H 6, a cylinder of the source gas PH _3, etc. (3221 to 3226) and a valve (3231-32
36, 3241 to 246, 3251 to 256) and mass flow controllers (3211 to 216), and a cylinder for each raw material gas is supplied via a valve (3260) to a gas introduction pipe (311) in the reaction vessel (3111).
4) is connected.

The formation of a deposited film using this apparatus can be performed, for example, as follows. First, the reaction vessel (3
111), a cylindrical support (3112) is set therein, and an evacuation device (for example, a vacuum pump) (not shown) is used for the reaction vessel (3112).
111) is evacuated. 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).

A source gas for forming a deposited film is supplied to a reaction vessel (31).
In order to make the gas flow into 11), the gas cylinder valve (323)
1-3237), leak valve of reaction vessel (3117)
Check that the valve is closed, and check the inlet valve (32
41-3246), outflow valve (3251-325)
6) After confirming that the auxiliary valve (3260) is open, first open the main valve (3118) and exhaust the reaction vessel (3111) and the inside of the gas pipe (3116).

Next, the reading of the vacuum gauge (3119) was about 5 × 1.
Auxiliary valve when it becomes 0 ^over 6 Torr (3260),
Close the outlet valves (3251 to 256). afterwards,
Each gas is introduced from a gas cylinder (3221 to 226) by opening a valve (3231 to 236), and each gas pressure is adjusted to 2 kg / cm by a pressure regulator (3261 to 266).
Adjust to ² . Next, the inflow valves (3241 to 324)
6) is gradually opened, and each gas is introduced into the mass flow controllers (3211 to 216).

After the preparation for film formation is completed as described above, each layer is formed by the following procedure. Cylindrical support (3
When the temperature reaches a predetermined temperature, the outflow valve (3)
251 to 256) and the auxiliary valve (3260) are gradually opened, and the gas cylinder (3221 to 2561) is opened.
From 3226), a predetermined gas is introduced into the reaction vessel (3111) via the gas introduction pipe (3114). Next, each raw material gas is adjusted by a mass flow controller (3211 to 3216) so as to have a predetermined flow rate. that time,
The opening of the main valve (3118) is adjusted while watching the vacuum gauge (3119) so that the pressure in the reaction vessel (3111) becomes a predetermined pressure of 1 Torr or less. When the internal pressure becomes stable, an RF power source (not shown) having a frequency of 13.56 MHz is set to a desired power, and RF power is supplied into the reaction vessel (3111) through the high frequency matching box (3115).
Power is introduced to cause glow discharge.

The raw material gas introduced into the reaction vessel is decomposed by the discharge energy, and the gas is introduced into the cylindrical support (311).
2) A deposited film mainly containing predetermined silicon is formed thereon. After the desired thickness is formed, R
The supply of the F power is stopped, the outflow valve is closed, the flow of gas into the reaction vessel is stopped, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a light receiving layer having a desired multilayer structure is formed. When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed, and each gas flows into the reaction vessel (3111) and outflow valve (3).
251 to 256) to avoid remaining in the pipe from the reaction vessel (3111) to the outflow valve (32
51 to 256), the auxiliary valve (3260) is opened, the main valve (3118) is fully opened, and the inside of the reaction vessel is once evacuated to a high vacuum as required.

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

The temperature of the support during the formation of the deposited film is desirably 200 ° C. to 350 ° C., preferably 230 ° C. to 330 ° C., more preferably 250 ° C. to 310 ° C. The heating method of the support may be a heating element having a vacuum specification, and more specifically, an electric resistance heating element such as a winding heater of a sheath heater, a plate heater, or a ceramic heater, a halogen lamp, an infrared lamp, or the like. Heat-emitting lamp heating element, a heating element using a liquid, a gas or the like as a heating medium and a heat exchange means. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum, and copper, ceramics, heat-resistant polymer resins, and the like can be used. In addition, a method is also used in which a container dedicated to heating is provided in addition to the reaction container, and after heating, the support is transferred into the reaction container in a vacuum.

[Test Examples] The effects of the present invention will be specifically described with reference to 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, a photoconductive layer was formed in the order of the first layer region and the second layer region from the charge injection blocking layer side.

On the other hand, instead of the aluminum cylinder,
Using a cylindrical sample holder with a groove for mounting the sample substrate, a glass substrate (Corning
7059) and an a-Si film having a thickness of about 1 μm was deposited on the Si wafer under the above-mentioned conditions for forming the photoconductive layer. For the deposited film on the glass substrate, after measuring the optical band gap Eg, a skewer electrode of Cr was deposited, the characteristic energy Eu of the exponential function tail was measured by CPM, and the deposited film on the Si wafer was hydrogen by FTIR. The content Ch was measured.

In the example of Table 1, the first layer region is Ch, Eg,
Eu was 23 at%, 1.72 eV and 53 meV, respectively, and Ch, Eg and Eu were 29 at%, 1.83 eV and 59 meV, respectively, in the second layer region.

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

As an element belonging to Group IIIb of the Periodic Table, B
Was linearly changed in each layer. The thicknesses of the first photoconductive layer and the second layer region were fixed at 9 μm and 21 μm, respectively. The prepared light receiving member was set in an electrophotographic apparatus (NP-6550 manufactured by Canon Inc. was modified for testing), and the potential characteristics were evaluated.

At this time, the process speed was 380 mm / s
ec, pre-exposure (565nm wavelength LED) 4lux · s
ec, the surface voltmeter (TREK) set at the developing device position of the electrophotographic apparatus under the conditions 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. Further, the temperature was changed from room temperature (about 25 ° C.) to 50 ° C. by a drum heater incorporated in the light receiving member, and the charging ability was measured under the above conditions. Temperature characteristics were used. As the memory potential, a potential difference between a surface potential in a non-exposure state and a potential after being exposed and then charged again was measured by a similar potential sensor under the above conditions.

FIGS. 4, 5 and 6 show the relationship between Eu and Eg of this example and charging ability, temperature characteristics and memory, respectively. Regarding each characteristic, the photoconductive layer (total film thickness 30μ)
m) is shown as a relative value when 1 is defined as the case where only the second layer region is formed. The points are shown in addition to the improvement in characteristics.
As is clear from FIGS. 4, 5 and 6, Eg is 1.65 eV or more and 1.75 eV or less in the first layer region.
Under the condition that Eu is 50 meV or more and 55 meV or less,
It was found that good characteristics could be obtained in all of the charging ability, temperature characteristics and memory.

[0132]

[Table 1] (Test Example 2) Using an apparatus for manufacturing a photoreceptor member by the RF-PCVD method shown in FIG. 3, under the same conditions as in Test Example 1, a table was placed on an 80 mm-diameter mirror-finished aluminum cylinder (support). Various light-receiving members comprising a charge injection blocking layer, a photoconductive layer and a surface layer were prepared under the conditions shown in FIG.

On the other hand, instead of the aluminum cylinder,
Using a cylindrical sample holder with a groove for mounting the sample substrate, a glass substrate (Corning
7059) and an a-Si film having a thickness of about 1 μm was deposited on the Si wafer under the above-mentioned conditions for forming the photoconductive layer. For the deposited film on the glass substrate, after measuring the optical band gap Eg, a skewer electrode of Cr was deposited, the characteristic energy Eu of the exponential function tail was measured by CPM, and the deposited film on the Si wafer was hydrogen by FTIR. The content Ch was measured.

In the example of Table 2, the first layer region is Ch, Eg,
Eu was 20 at%, 1.67 eV and 52 meV, respectively, and Ch, Eg and Eu were 32 at%, 1.84 eV and 61 meV, respectively, in the second layer region.

In Test Example 2 instead of Test Example 1, the content of B element was increased on the substrate side in each of the first layer region and the second layer region. At that time, the minimum content of the first layer region and the maximum content of the second layer region were set to be the same. The thicknesses of the first photoconductive layer and the second layer region were fixed at 9 μm and 21 μm, respectively.

The produced light-receiving member was evaluated in the same manner as in Test Example 1, and the relationships among Eu and Eg of this example and the charging ability, temperature characteristics, and memory are shown in FIGS. 7, 8, and 9, respectively. . Each characteristic is shown as a relative value when the B element produced in Test Example 1 is fixed at 1 when it is constant.

As is clear from FIGS. 7, 8 and 9, in the first layer region, the Eg is 1.65 eV or more.
The charging ability, the temperature characteristic, and the memory are kept constant by containing 75 eV or less and Eu being 50 meV or more and 55 meV or less and by adding the B element of the element belonging to Group IIIb of the periodic table so as to increase on the substrate side in each layer region. It was found that significantly better characteristics can be obtained than in the case of containing.

[0138]

[Table 2] (Test Example 3) Using the apparatus for manufacturing a light receiving member by the RF-PCVD method shown in FIG.
Various light-receiving members comprising a charge injection blocking layer, a photoconductive layer, and a surface layer were produced on an 80 mm-diameter mirror-finished aluminum cylinder (support) under the same conditions as in Test Example 1.

In Test Example 3 instead of Test Example 2, the minimum and maximum contents of the first layer region and the second layer region were varied as shown in Table 3. The distribution was changed linearly. At this time, 1.0 from the surface side of the second layer region.
In the region up to μm, elements belonging to Group IIIb of the periodic table were not added. The thicknesses of the first photoconductive layer and the second layer region were fixed at 9 μm and 21 μm, respectively.

The produced light receiving member was evaluated in the same manner as in Test Example 1, and the charging ability, temperature characteristics, memory, and residual potential were measured. The evaluation results are shown in FIG. It was shown as a relative value when it was set to 1 based on what was produced under the conditions of Table 2 of Test Example 2. When the charging ability is increased by 10% or more with respect to the reference, 0.1 point is added. When the charging ability is reduced by 10% or more with respect to the reference, 0.1 point is deducted. The memory was evaluated as a 0.1 point deduction, and the memory was evaluated as a 0.1 point deduction at 10 V or more where the density difference of the image became large, and a 0.1 point deduction when the residual potential was higher than 40 V.

As is clear from FIG. 10, the periodic table II
The minimum content of the element belonging to Group Ib in the first layer region is 0.1
Not less than 15 ppm and the maximum content is not less than 0.5 and not more than 50.
ppm or less, the maximum content of the second layer region is 0.01 to 20 ppm, and in the region from the surface side of the second layer region to 0.5 to 1.5 μm, the periodic table IIIb It was found that by making the elements belonging to the group extremely small (no addition in this test), it exhibited generally good characteristics as an electrophotographic light-receiving member.

[0142]

[Table 3] (Test Example 4) On a mirror-finished aluminum cylinder (support) having a diameter of 80 mm under the same conditions as in Table 2 of Test Example 2, using the apparatus for manufacturing a light receiving member by the RF-PCVD method shown in FIG. Then, a light receiving member including a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared. At this time, the first layer region and the second layer region were stacked in this order from the charge injection blocking layer side.

In Test Example 3, the total thickness of the photoconductive layer was 3
The thickness was fixed to 5 μm, the thickness ratio of the first layer region and the entire photoconductive layer was set to 0.005 to 0.6, and the thickness of each layer region was determined to produce various light receiving members. At this time, in the area from the surface side of the second layer area to 0.5 μm, the periodic table I
No element belonging to Group IIb was added.

The same evaluation as in Test Example 1 was performed on each of the produced light-receiving members. The charging ability, temperature characteristics, memory, sensitivity, and residual potential were measured, and the evaluation results of the charging ability are shown in FIG. . The values are shown as relative values when the film thickness ratio 0.3 produced under the conditions in Table 2 of Test Example 2 is set to 1.

As is apparent from FIG. 11, by setting the thickness ratio of the first layer region and the entire photoconductive layer to 0.01 to 0.3, it is possible to obtain a good overall light-receiving member for electrophotography. It was found to exhibit properties.

[0146]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below more specifically with reference to the drawings. 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 by 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 layer region and the second layer region from the charge injection blocking layer side.

Table 4 shows the conditions for producing the light receiving member at this time. At this time, 0.8 μm from the surface side of the second layer region.
In the region up to m, elements belonging to Group IIIb of the periodic table were not added. Then, the portion where the B element was contained in each layer region was changed in the content as shown in FIG.

In the present example, C in the first layer region of the photoconductive layer
h, Eg, and Eu are respectively 16 atomic%, 1.66 eV, 5
As a result, 2 meV and Ch, Eg, and Eu in the second layer region were 30 atomic%, 1.85 eV, and 64 meV, respectively.

The prepared light receiving member was set in an electrophotographic apparatus (a Canon NP-6550 modified for testing) in the same manner as in Test Example 1, and the potential characteristics were evaluated. Good characteristics were obtained for both memories.
Further, when the produced light receiving member was positively charged and the image was evaluated, no optical memory was observed on the image, and good electrophotographic characteristics were obtained also with respect to other image characteristics (pockets, image deletion).

That is, even when the photoconductive layer is arranged in the order of the first layer region and the second layer region from the side of the charge injection blocking layer, the first layer region of the photoconductive layer has a structure of Ch, Eg, Eu.
10 to 25 at% and 1.65 eV to 1.75 eV, respectively, 50 to 55 meV, and Ch, Eg, and Eu in the second layer region are each 1
5 to 30 atomic%, 1.75 eV to 1.85 eV, 55 meV to 65 meV, and
The content of the group IIIb element is increased on the substrate side in each layer region, and the minimum content of the group IIIb element of the periodic table in the first layer region is 0.1 to 15 ppm and the maximum content is 0.1.
5 to 50 ppm, the maximum content of the second layer region of Group IIIb element of the periodic table in the range of 0.01 to 20 ppm, and 0.5 to 1.5 μm from the surface of the second layer region. In the following areas, Periodic Table IIIb
It has been found that by making the content of the element belonging to the group extremely small, the light receiving member for electrophotography exhibits generally good characteristics.

[0151]

[Table 4] [Embodiment 2] In the present embodiment, the photoconductive layer is arranged in the order of the first layer region and the second layer region from the charge injection blocking layer side. A surface layer was provided in which the carbon atom content was unevenly distributed in the layer thickness direction.

Table 5 shows the conditions for producing the light receiving member at this time. At that time, 1.2 seconds from the surface side of the second layer region.
In the region up to μm, the content of the element belonging to Group IIIb of the periodic table was set to 0.1 ppm. Then, in the portion where the B element is contained in each layer region, the content was changed as shown in FIG. 12B.

In this example, the C layer in the first layer region of the photoconductive layer
h, Eg, and Eu are respectively 22 atomic%, 1.74 eV, 5
As a result, 5 meV and Ch, Eg, and Eu of the second layer region were obtained as 24 atom%, 1.78 eV, and 61 meV, respectively. When the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, the photoconductive layer is arranged in the order of the first layer region and the second layer region from the charge injection blocking layer side, and the content of silicon atoms and carbon atoms in the surface layer is unevenly distributed in the layer thickness direction. Even when the surface layer in the state is provided, Ch, Eg, and Eu are each set to 1 in the first layer region of the photoconductive layer.
0 to 25 atomic% or less, 1.65 eV to 1.75 eV or less, 50 meV to 55 meV, and each of Ch, Eg, and Eu in the second layer region is 15 to 30 atomic%.
In the following, the content of Group IIIb element in the periodic table is increased from 1.75 eV to 1.85 eV, from 55 meV to 65 meV in each layer region, and the content of the element in the periodic table is increased.
The minimum content of the IIIb group element in the first layer region is 0.1 or more and 1
5 ppm or less, and the maximum content is 0.5 or more and 50 pp
m and the maximum content of the second layer region of the Group IIIb element of the periodic table in the range from 0.01 to 20 ppm and from the surface side of the second layer region to from 0.5 to 1.5 μm. It has been found that, in the region of No. 3, by setting the content of the element belonging to Group IIIb of the periodic table to an extremely small value, the overall light-receiving member for electrophotography exhibits excellent characteristics.

[0155]

[Table 5] [Embodiment 3] In this embodiment, the photoconductive layer is arranged in the order of the first layer region and the second layer region from the charge injection blocking layer side. A surface layer in which the content of carbon atoms was unevenly distributed in the layer thickness direction was provided, and all the layers contained fluorine atoms, boron atoms, carbon atoms, oxygen atoms, and nitrogen atoms.

Table 6 shows the conditions for manufacturing the light receiving member at this time. At this time, 1.0 from the surface side of the second layer region.
In the region up to μm, elements belonging to Group IIIb of the periodic table were not added. Then, the portion where the B element is contained in each layer region was changed in the content as shown in FIG.

In this example, C in the first layer region of the photoconductive layer
h, Eg, and Eu are each 12 atomic%, 1.65 eV, 5
As a result, 1 meV and Ch, Eg, and Eu of the second layer region were 16 atomic%, 1.76 eV, and 58 meV, respectively.

When the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained. That is, the photoconductive layer is arranged in the order of the first layer region and the second layer region from the charge injection blocking layer side, and the content of silicon atoms and carbon atoms in the surface layer is in a non-uniform distribution state in the layer thickness direction. Even when a surface layer is provided and all layers contain fluorine atoms, boron atoms, carbon atoms, oxygen atoms, and nitrogen atoms, Ch, Eg, and Eu are each 10% in the first layer region of the photoconductive layer. Not less than 25 atomic%,
1.65 eV to 1.75 eV, 50 meV to 55
meV or less, and Ch, Eg, Eu in the second layer region.
From 15 to 30 atomic%, 1.75 eV to 1.85 eV, 55 meV to 65 meV, respectively.
The content of the Group IIIb element of the periodic table is increased on the substrate side in each layer region, and the minimum content of the group IIIb element of the periodic table in the first layer region is 0.1 to 15 ppm and the maximum content. From 0.5 to 50 ppm, the maximum content of the second layer region from 0.01 to 20 ppm, and 0.5 or more from the surface side of the second layer region of Group IIIb element of the periodic table. It has been found that, in the region up to 1.5 μm or less, the content of the element belonging to Group IIIb of the periodic table is made very small, so that the overall light-receiving member for electrophotography exhibits good characteristics.

[0159]

[Table 6] [Embodiment 4] In this embodiment, the photoconductive layer is arranged in the order of the first layer region and the second layer region from the charge injection blocking layer side, and nitrogen atoms are used instead of carbon atoms as atoms constituting the surface layer. It was provided so as to be contained in the surface layer.

Table 7 shows the conditions for producing the light receiving member at this time. At that time, 1.4 from the surface side of the second layer region.
In the region up to μm, the content of the element belonging to Group IIIb of the periodic table was adjusted to 0.05 ppm. Then, in the portion where the B element is contained in each layer region, the content was changed as shown in FIG.

In the present example, C in the first layer region of the photoconductive layer
h, Eg, and Eu are respectively 15 atomic%, 1.68 eV, 5
As a result, 4 meV and Ch, Eg, and Eu of the second layer region were 26 atom%, 1.82 eV, and 63 meV, respectively. Further, when the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, the photoconductive layer is formed in the order of the first layer region and the second layer region from the charge injection blocking layer side, and the surface layer contains nitrogen atoms instead of carbon atoms as atoms constituting the surface layer. Even when a layer is provided, Ch, Eg, and Eu are each set to 10 or more and 25 in the first layer region of the photoconductive layer.
Atomic% or less, 1.65 eV to 1.75 eV, 50 m
eV or more and 55 meV or less, and C in the second layer region.
h, Eg, and Eu are respectively 15 or more and 30 at% or less;
75 eV or more and 1.85 eV or less, 55 meV or more and 65 m
eV or less, and the content of Group IIIb element in the periodic table is increased on the substrate side in each layer region, and the minimum content of the first layer region of the Group IIIb element in the periodic table is set to 0.1 to 15 pp.
m and a maximum content of 0.5 to 50 ppm and a maximum content of the second layer region of the Group IIIb element of the periodic table of 0.01 to 20 ppm and a surface of the second layer region. In the region from 0.5 to 1.5 μm from the side, the content of elements belonging to Group IIIb of the Periodic Table is made very small, so that it shows good overall properties as an electrophotographic light-receiving member. I understood.

[0163]

[Table 7] Example 5 In this example, the photoconductive layer was arranged in the order of the first layer region and the second layer region from the charge injection blocking layer side, and the surface layer contained nitrogen atoms and oxygen atoms. Table 8 shows the manufacturing conditions of the light receiving member at this time. At this time, no element belonging to Group IIIb of the periodic table was added in the region from the surface side of the second layer region to 0.6 μm. And
FIG. 12 shows the content of the B element in each layer region.
The content was changed as shown in (e).

In the present embodiment, the C layer in the first layer region of the photoconductive layer
h, Eg, and Eu are respectively 24 atomic%, 1.74 eV, 5
As a result, 5 meV and Ch, Eg, and Eu of the second layer region were obtained at 29 atomic%, 1.83 eV, and 64 meV, respectively. Further, when the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, the photoconductive layer is arranged in the order of the first layer region and the second layer region from the charge injection blocking layer side, and a surface layer containing nitrogen atoms and oxygen atoms as atoms constituting the surface layer is used. Even in the case of providing, in the first layer region of the photoconductive layer, each of Ch, Eg, and Eu is 10 to 25 atomic%, 1.65 eV to 1.75 eV, and 50 meV.
Not less than 55 meV, and Ch,
Eg and Eu are respectively 15 or more and 30 at% or less, 1.75
eV to 1.85 eV, 55 meV to 65 meV
In the following, the content of the Group IIIb element in the periodic table is increased on the substrate side in each layer region, and the minimum content of the first layer region of the Group IIIb element in the periodic table is 0.1 to 15 ppm and The maximum content is 0.5 to 50 ppm,
The maximum content of the group IIIb element of the periodic table in the second layer region is not less than 0.01 and not more than 20 ppm, and in the region from the surface side of the second layer region to not less than 0.5 and not more than 1.5 μm. It has been found that by making the content of the element belonging to Group IIIb of the periodic table very small, the overall light-receiving member for electrophotography exhibits excellent characteristics.

[0166]

[Table 8] [Embodiment 6] In this embodiment, CH ₄ was used as a carbon source in the photoconductive layer.
The gas was used to form a first layer region and a second layer region containing carbon atoms and a surface layer. Table 9 shows the manufacturing conditions of the light receiving member at this time. At that time, no element belonging to Group IIIb of the periodic table was added in a region from the surface side of the second layer region to 1.0 μm. The content of the B element in each of the layer regions is shown in FIG.
The content was changed as shown in (f).

In this example, C in the first layer region of the photoconductive layer
h, Eg, and Eu are respectively 21 atomic%, 1.71 eV, 5
As a result, 3 meV and Ch, Eg, and Eu of the second layer region were 23 atomic%, 1.80 eV, and 60 meV, respectively. When the produced light-receiving member was evaluated in the same manner as in Example 1, similarly good electrophotographic characteristics were obtained.

That is, a carbon layer is contained in the photoconductive layer, a first layer region and a second layer region are arranged in this order from the charge injection blocking layer side, and carbon atoms are contained in the photoconductive layer. Also, in the first layer region of the photoconductive layer, Ch, Eg, and Eu are each set to 10 to 25 atomic%, 1.65 eV to 1.75 eV, 50 meV to 55 meV, and the second layer region. In Ch, Eg,
Eu is not less than 15 and not more than 30 atomic%, respectively, 1.75 eV
At least 1.85 eV or less, 55 meV or more and 65 meV or less, and the content of Group IIIb element in the periodic table is increased on the substrate side in each layer region, and the minimum content of the first layer region of the Group IIIb element in the periodic table is increased. The amount is from 0.1 to 15 ppm and the maximum content is from 0.5 to 50 ppm, and the maximum content of the group IIIb element of the periodic table in the second layer region is 0.0.
In the region from 0.5 to 1.5 μm from the surface side of the second layer region, the content of the element belonging to Group IIIb of the periodic table is made very small, and the electron content is increased. It has been found that the photoreceptor for photographic materials has good overall characteristics.

[0169]

[Table 9]

[0170]

According to the present invention, the temperature characteristics of the light receiving member in the operating temperature range are remarkably improved, and the occurrence of optical memory can be substantially eliminated.
The stability of the light receiving member with respect to the use environment is improved, and a light receiving member for electrophotography can be obtained in which a halftone is clearly produced and a high-quality image with high resolution can be stably obtained.

Therefore, the a-Si light receiving member of the present invention has a specific structure as described above, and
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, the photoconductive layer is divided into layer regions having different optical band gaps and levels in the gap, and the conductivity in each of the layer regions is controlled in the periodic table.
The group IIIb element is contained so as to increase on the substrate side, and in the region from 0.5 to 1.5 μm from the surface side of the second layer region, the content of the element belonging to Group IIIb of the periodic table is reduced. By making it extremely small, the chargeability is high, and furthermore, the change in surface potential due to a change in the surrounding environment is suppressed, and the device has extremely excellent potential characteristics and image characteristics.

[Brief description of the drawings]

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

FIG. 2 is a schematic explanatory diagram 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 is a graph showing the relationship between the characteristic energy Eu of the Urbach tail in the first layer region of the photoconductive layer and the charging ability in the light receiving member of the present invention.

FIG. 5 is a graph showing the relationship between the characteristic energy Eu of the Urbach tail in the first layer region of the photoconductive layer and the temperature characteristic in the light receiving member of the present invention.

FIG. 6 is a graph showing the relationship between the characteristic energy Eu of the Urbach tail in the first layer region of the photoconductive layer and the memory in the light receiving member of the present invention.

FIG. 7 is a graph showing the relationship between the characteristic energy Eu of the Urbach tail in the first layer region of the photoconductive layer and the charging ability in the photoreceptor member in which the Group IIIb element of the periodic table of the present invention is distributed. FIG.

FIG. 8 is a graph showing the relationship between the characteristic energy Eu of the Urbach tail in the first layer region of the photoconductive layer and the temperature characteristic in the photoreceptor member in which the group IIIb element of the periodic table is distributed according to the present invention. .

FIG. 9 is a graph showing the relationship between the characteristic energy Eu of the Urbach tail in the first layer region of the photoconductive layer and the memory in the photoreceptor member in which the group IIIb element of the periodic table of the present invention is distributed.

FIG. 10 shows a combination of a minimum content and a maximum content of a first layer region and a second layer region in a photoreceptor member in which a Group IIIb element of the periodic table is distributed according to the present invention, and comprehensive electrons. FIG. 4 is a graph showing a relationship with photographic characteristics.

FIG. 11 shows the relationship between the film thickness ratio of the first layer region and the entire photoconductive layer and the overall electrophotographic characteristics in the light receiving member in which the Group IIIb element of the periodic table of the present invention is distributed. Graph diagram.

FIG. 12 is a periodic table III in the light receiving member of the present invention.
The schematic diagram which shows distribution of a group b element.

[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 211 first layer region 212 second layer region 210 free surface 3100,4100 deposition device 3111,4111 reaction vessel 3112, 4112 Cylindrical support 3113, 4113 Heater for support heating 3114 Source gas introduction pipe 3115, 4116 Matching box 3116 Source gas piping 3117 Reaction vessel leak valve 3118 Main exhaust valve 3119 Vacuum gauge 3200 Source gas supply device 3211 to 3216 Mass flow Controllers 3221-226 Source gas cylinders 3231-236 Source gas cylinder valves 3241-246 Gas inlet valves 3251-256 Gas outlet valves 3261-266 Pressure regulators

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

Claims (12)

[Claims] 1. An electrophotographic light-receiving member comprising a photoconductive layer comprising an amorphous material containing hydrogen atoms and / or halogen atoms and containing silicon atoms as a host,
Content of hydrogen atom and / or halogen atom (Ch)
Is 10 atomic% or more and 25 atomic% or less, optical band gap (Eg) is 1.65 eV or more and 1.75 eV or less, and photon energy (hν) is an independent variable, and absorption coefficient (α) of light absorption spectrum is a dependent variable. The characteristic energy (Eu) obtained from the linear relationship part (exponential function tail) of the function represented by the following formula (I) 1nα = (1 / Eu) · hν + α1 (I) is 50 meV or more and 55 me
V and a first layer region of not more than V, and
0 atomic% or less, Eg of 1.75 eV or more and 1.85 eV or less, and Eu of 55 meV or more and 65 meV or less, and the photoconductive layer is formed on the surface of a conductive support. One layer region, stacked in the order of the second layer region, while containing at least one element belonging to Group IIIb of the periodic table, the contained element is the first layer region, the second layer region A light-receiving member for electrophotography, wherein the light-receiving member is increased on the substrate side in each of the layer regions. 2. The photoconductive layer according to claim 1, wherein a ratio of a layer thickness of the first layer region to a layer thickness of the entire photoconductive layer is 0.01 or more and 0.3 or less. The light receiving member according to any one of the preceding claims. 3. In the region from 0.5 to 1.5 μm from the surface side of the second layer region, the periodic table III
The light receiving member according to claim 1, wherein the average content of the element belonging to group b is 0 or more and 0.1 ppm or less. 4. The method according to claim 1, wherein the minimum content of an element belonging to Group IIIb of the periodic table in the first layer region is 0.1 ppm or more and 15 pm or less with respect to silicon atoms. Light receiving member. 5. The method according to claim 1, wherein a maximum content of an element belonging to Group IIIb of the periodic table in the first layer region is not less than 0.5 ppm and not more than 50 pm with respect to silicon atoms. Light receiving member. 6. The method according to claim 1, wherein a maximum content of an element belonging to Group IIIb of the periodic table in the second layer region is 0.01 ppm or more and 20 pm or less with respect to silicon atoms. Light receiving member. 7. The photoconductive layer, wherein carbon is contained in the photoconductive layer.
Characterized by containing at least one of oxygen and nitrogen,
The light receiving member according to claim 1. 8. 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 a surface of the photoconductive layer. The light receiving member according to claim 1. 9. The charge injection blocking layer, wherein the photoconductive layer is formed of a 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. Provided on the surface of
9. The light-receiving member according to claim 8, wherein the 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. . 10. The surface layer has a layer thickness of 0.01 to 0.01.
The light receiving member according to claim 8, wherein the light receiving member has a thickness of 3 μm. 11. The light receiving member according to claim 9, wherein said charge injection blocking layer has a thickness of 0.1 to 5 μm. 12. The photoconductive layer has a thickness of 20 to 50 μm.
The light receiving member according to claim 1, wherein: