JP3143027B2 - Method for manufacturing light receiving member - Google Patents

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.). The present invention relates to a method for manufacturing 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, a high SN ratio [photocurrent (Ip) / dark current (Id)], and irradiation. Characteristics such as having an absorption spectrum suitable for the spectral characteristics of the electromagnetic waves to be emitted, having a fast light response, having a desired dark resistance value, and being harmless to the human body during use. In particular, in the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used in an office as an office machine, the above-described non-polluting property at the time of use is important. Hydrogen amorphous silicon (hereinafter abbreviated as "a-Si: H") is a photoconductive material exhibiting excellent properties in this respect. For example, Japanese Patent Publication No. 60-35059 discloses an electrophotographic light-emitting material. Application as a receiving member is described. The light receiving member for electrophotography generally has a substrate at 50 ° C to 40 ° C.
Heated to 0 ° C., and deposited on the substrate by vacuum evaporation, sputtering, ion plating, thermal CVD, photo CVD
A photoconductive layer made of a-Si is formed by a film forming method such as a plasma CVD method or a plasma CVD method. Among them, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency, or microwave glow discharge to form an a-Si deposited film on a substrate has been put to practical use as a suitable method. Also, in JP-A-54-83746,
A-Si containing a substrate and a halogen atom as a constituent element
An electrophotographic light-receiving member comprising a photoconductive layer (hereinafter referred to as "a-Si: X") has been proposed. In this publication, a-Si contains 1 to 40 atom% of a halogen atom. In addition, a technique relating to a light receiving member for electrophotography having high heat resistance and excellent electrical and optical characteristics is disclosed.

However, such conventional a-Si
For electrophotographic light-receiving members having a photoconductive layer composed of a series material, electrical, optical, photoconductive properties such as dark resistance value, photosensitivity, photoresponsiveness, and use environment properties, as well as stability over time, In terms of properties and durability, individual characteristics have been improved for some time, but in recent years it has become impossible to respond to recent demands for comprehensive characteristics improvement.
In particular, high image quality, high speed, and high durability of electrophotographic devices are rapidly expanding, and even in light receiving members for electrophotography,
In addition to the need to further improve electrical and photoconductive properties, it is not only required to significantly extend the performance in all environments while maintaining the charging ability and sensitivity, as well as the layer composition and chemical composition of each layer. For example, it is necessary to improve the characteristics of the a-Si material itself while improving the characteristics from a comprehensive viewpoint. For example, Japanese Patent Application Laid-Open No. Sho 54-86341 discloses a method using a-Si for a photoconductive layer.
A technique relating to an electrophotographic light-receiving member having excellent electrical properties is described. Japanese Patent Application Laid-Open No. 62-168161 discloses that a silicon layer and a carbon atom are used as a surface layer.
A technique using a material composed of an amorphous material containing a hydrogen atom of ７０70 atomic% as a constituent element is described. As a method for forming such an amorphous electrophotographic light-receiving member, plasma CV by glow discharge is used.
D method (hereinafter simply referred to as plasma CVD method). For example, Japanese Patent Application Laid-Open No. 60-186849 discloses a method for forming a deposited film by a microwave plasma CVD method using a microwave having a frequency of 2.45 GHz as a decomposition source of a source gas. According to the publication,
By forming a plurality of cylindrical members in the deposition chamber, an inner chamber is formed, and a raw material gas is introduced into the inner chamber, thereby increasing the gas use efficiency and forming a deposited film that improves productivity. A method is disclosed. Further, Japanese Patent Application Laid-Open No. Hei 3-219081 discloses a method of forming a deposited film of higher quality by applying a DC electric field to a plasma space and controlling a plasma potential. With such a technique, it has become possible to supply a light receiving member for electrophotography having good electric characteristics.

[0004]

However, today, the performance of copying machines has been further improved, and digital machines,
With the spread of color machines, light-receiving members for electrophotography
Higher image quality and higher quality than ever have been demanded. In particular, since these copying machines mainly use a halftone image instead of a conventional copy image mainly composed of only characters, it has become indispensable to form a clearer halftone image. Further, from the viewpoints of high charging ability and high durability, a-SiC containing carbon atoms in the photoconductive layer is used.
A system material is used. In the a-SiC-based material, as the content of carbon atoms with respect to silicon atoms increases, electric charges hardly run in the photoconductive layer. Therefore, the remaining charge is prevented from being generated by adding a large amount of a charge controlling agent such as boron. However, in a layer design in which carbon atoms are distributed in the thickness direction, the amount of boron contained in each region must be determined by trial and error.
An excessive number of experiments was required. It is necessary to be able to design a layer by a simple method without the need for trial and error and to improve the characteristics.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for manufacturing a light receiving member which has solved the above-mentioned problems in the conventional electrophotographic light receiving member having a light receiving layer made of a-Si. Is what you do. In other words, the main object of the present invention is to improve the image quality of a light-receiving member for electrophotography with the spread of color machines and the high-performance digital copying machines in recent years. It is an object of the present invention to provide a light receiving member capable of forming an image and a method for manufacturing the same.

[0006]

According to the present invention, in order to achieve the above object, a source gas containing silicon atoms and a source gas containing an element belonging to Group III or V of the periodic table are introduced into a reaction space. Atoms on the substrate and periodic table II
A method for manufacturing a light-receiving member, comprising the step of forming a photoconductive layer made of an amorphous material containing an element belonging to Group I or Group V, wherein the member belongs to Group III or Group V of the periodic table A source gas containing an element is introduced while being continuously changed using a spline function.

[0007] In the present invention, it is preferable that a source gas containing an element selected from the group consisting of a carbon atom, an oxygen atom and a nitrogen atom is further introduced in the step.

Next, the present invention will be described in detail with reference to the drawings. FIG. 1A is a schematic configuration diagram illustrating a layer configuration of the electrophotographic light-receiving member of the present invention. FIG. 1 (a)
The light receiving member for electrophotography 100 shown in FIG. 1 has a light receiving layer 102 provided on a substrate 101 for a light receiving member. The light receiving layer 102 is made of a-Si: H or a-Si.
It comprises a photoconductive layer 103 made of C: H and having photoconductivity, a charge injection blocking layer 104 that functions to block charge injection, and an amorphous silicon-based surface layer 105. FIG. 1B is a schematic configuration diagram for explaining another layer configuration of the electrophotographic light-receiving member of the present invention. FIG.
In the electrophotographic light receiving member 100 shown in FIG. 1B, a light receiving layer 102 is provided on a base 101 for a light receiving member. The light receiving layer 102 includes a photoconductive layer 103 and an amorphous silicon-based surface layer 105. The photoconductive layer 103 includes a first region 106 serving as a charge transporting layer made of a-SiC: H and a-Si: H or a.
-Second region 1 serving to generate electric charge composed of -SiC: H
07.

[0009] Such a photoconductive layer 103 is formed 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 (low-frequency CVD method, high-frequency C
AC discharge CVD such as VD method or microwave CVD method
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 electrophotographic light-receiving member to be produced. In the present invention, the glow discharge method, particularly the microwave plasma CVD method using a frequency of 2.45 GHz, the frequency, RF using 13.56 MHz
The plasma CVD method is effective. The formation of the photoconductive layer 103 by the glow discharge method is basically performed using silicon atoms (S
source gas for supplying Si capable of supplying i), source gas for supplying C capable of supplying carbon atoms (C), and I-th of the periodic table
A source gas containing an element belonging to Group II or Group V, and a source gas for supplying H that can supply hydrogen atoms (H) are introduced in a desired gas state into a reaction vessel in which the inside can be reduced in pressure, A glow discharge is generated in the reaction vessel, and a-glow discharge is generated on a predetermined substrate 101 which is previously set at a predetermined position.
The method is performed by forming a layer composed of Si: H and a-SiC: H. The present invention relates to a method in which a source gas containing an element belonging to Group III or Group V of the periodic table is converted to a spline function. It is characterized in that it is introduced while being continuously changed by using.

That is, in the step of forming the photoconductive layer, when introducing a source gas containing an element belonging to Group III or Group V of the periodic table as doping while continuously changing the gas flow rate, In the case of 5,
As shown in FIGS. 7, 9 and 11, several points were linearly connected to the time axis to change the flow rate. However, with such an introduction method, an appropriate doping amount could not be obtained. In particular,
In the case of a thick semiconductor film such as a photoconductive layer of a photoreceptor for electrophotography, it is not sufficient to meet the recent demands described above for obtaining a high-quality deposited film with carrier mobility. Was. In the present invention, as shown in FIGS. 4, 6, 8, and 10, each point is continuously changed using a spline function so that an appropriate doping amount can be obtained, so that the traveling of the carrier can be obtained. While improving the
It is also possible to obtain a high quality deposited film. In particular, in the case of a thick-film semiconductor such as a photoconductive layer of an electrophotographic light-receiving member, in order to form a clearer halftone image as described above, the carrier mobility in a low electric field must be improved. It is particularly important to improve the electric field in the photoconductive layer and to form the electric field in the photoconductive layer more uniformly. According to the present invention, the group III or V in the periodic table at the time of forming the conductive layer is used. By more smoothly doping the element belonging to the above, it becomes possible to form a more uniform electric field in the photoconductive layer.

Next, the operation procedure will be described with reference to FIGS. FIG. 2 shows a microwave plasma CVD method (hereinafter referred to as “MW-PCVD”) using a frequency of 2.45 GHz.
FIG. 2A is a schematic cross-sectional view, and FIG. 2B is a vertical cross-sectional view of one example of an apparatus for manufacturing an electrophotographic light-receiving member according to the present invention. First, a cylindrical substrate 20 previously degreased and washed is placed in a reaction vessel 201.
2, the base 202 is rotated by the driving device 203, and the inside of the reaction vessel 201 is evacuated through the exhaust pipe 204 by an exhaust device (for example, a vacuum pump) (not shown). Adjust to ^-6 Torr or less.
Subsequently, the temperature of the substrate 202 is maintained at a predetermined temperature of 20 ° C. to 500 ° C. by the substrate heating heater 205.
In order to allow the source gas for forming the light receiving member to flow into the reaction vessel 201, the valves of the gas cylinder and various valves are operated, and the source gas is introduced into the discharge space 207 from the source gas introduction pipe 206 via a mass flow controller (not shown). Introduce. After the preparation for film formation is completed as described above, the photoconductive layer and the surface layer are formed on the cylindrical substrate 202. When the temperature of the cylindrical base 202 reaches a predetermined temperature, necessary ones of the outflow valves are gradually opened, and the raw material gas is discharged through the introduction pipe 206 into the discharge space 2 in the reaction vessel 201.
07. Next, each raw material gas is adjusted to a predetermined flow rate by a mass flow controller (not shown). At this time, the opening of the main valve (not shown) is adjusted while watching the vacuum gauge (not shown) so that the pressure in the discharge space 207 becomes a predetermined pressure of 1 Torr or less. After the pressure is stabilized, when a predetermined voltage is applied from a bias power source 208 to a bias electrode 206 (also used as a source gas introduction tube in this figure) 206, a microwave power source (not shown) simultaneously applies a microwave of 2.45 GHz. Is generated and set to a desired power, and microwave energy is introduced into the discharge space 207 through the waveguide 209 and the microwave introduction window 210 to generate a glow discharge. In this way, the source gas is excited and dissociated by microwave energy, and a predetermined light receiving member is formed on the base 202. At this time, the layer is rotated at a desired rotation speed by the driving means 203 in order to achieve uniform layer formation. After the formation of the desired film thickness, the supply of the bias voltage and the microwave power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed. By repeating the same operation several times,
A light-receiving layer having a desired multilayer structure is formed. The procedure for forming the photoconductive layer is as described above. In the present invention, when each of the raw material gases is introduced into the discharge space 207 in the reaction vessel 201 through the introduction pipe 206, the periodicity A source gas containing an element belonging to Group III or Group V of the table is introduced while continuously changing using a spline function.

FIG. 3 is a schematic explanatory view showing an example of an apparatus for manufacturing an electrophotographic light-receiving member by a high-frequency plasma CVD method using RF frequencies (hereinafter abbreviated as "RF-PCVD"). This device is roughly composed of a deposition device (3100), a source gas supply device (3200), and an exhaust device (not shown) for reducing the pressure inside the reaction vessel (3111). A cylindrical substrate (3112) is provided in a reaction vessel (3111) in the deposition apparatus (3100).
Substrate heating heater (3113), source gas inlet pipe (3
114), and a high-frequency matching box (3115) is further connected. Source gas supply device (3
200) is SiH4, GeH4, H2, CH4, B2
Cylinders (3221-322) of source gases such as H6 and PH3
6) and valves (3231-336, 3241-324)
6, 3251 to 256) and a mass flow controller (3221 to 216), and a cylinder for each source gas is supplied to the reaction vessel (31) via a valve (3260).
11) is connected to the gas inlet pipe (3114).
The formation of a deposited film using this apparatus can be performed, for example, as follows. First, the base (3112) is set in the reaction vessel (3111), and the inside of the reaction vessel (3111) is evacuated by an exhaust device (not shown) (for example, a vacuum pump).
Subsequently, the temperature of the substrate (3112) is controlled to a predetermined temperature of 200 ° C. to 350 ° C. by the substrate heating heater (3113). The source gas for forming the deposited film is supplied to the reaction vessel (3
111), the gas cylinder valve (32
31 to 2237), a leak valve of the reaction vessel (311).
7) is closed, and the inflow valves (3241 to 246) and the outflow valves (3251 to 32)
56) 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 gauge (3119) reads about 5 × 10 ^-6 To.
When rr is reached, the auxiliary valve (3260) and the outflow valves (3251 to 256) are closed. Thereafter, each gas is supplied from a gas cylinder (3221 to 226) to a valve (3231).
~ 3236) to open and introduce the pressure regulator (3261-
3266), each gas pressure is adjusted to ² kg / cm ² . Next, the inflow valves (3241 to 246) are gradually opened to allow each gas to flow through the mass flow controller (3211).
~ 3216). After the preparation for film formation is completed as described above, each layer is formed by the following procedure. When the temperature of the base (3112) reaches a predetermined temperature, necessary ones of the outflow valves (3251 to 256) and the auxiliary valve (3260) are gradually opened, and the gas cylinder (3221 to 3211) 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 source gas introduced into the reaction vessel is decomposed by this discharge energy, and a deposited film mainly containing silicon is formed on the base (3112). After the formation of the desired film thickness, the supply of the RF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed. In the present invention, when each source gas is introduced into the discharge space in the reaction vessel through the introduction pipe, the source gas contains an element belonging to Group III or Group V of the periodic table. It goes without saying that the source gas is introduced while being continuously changed using the spline function, as in the case of the MV-PCVD. By repeating the same operation a plurality of times, a light receiving layer having a desired multilayer structure is formed. When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed, and each gas is placed in the reaction vessel (3111).
From the outflow valve (3251 to 256), the reaction vessel (31)
In order to avoid remaining in the piping to 11), the outflow valves (3251 to 256) are closed, the auxiliary valve (3260) is opened, and the main valve (3118) is opened.
Is fully opened and the system is once evacuated to a high vacuum as required. It is also effective to rotate the base (3112) at a predetermined speed by a driving device (not shown) during the layer formation in order to make the film formation uniform. Further, it goes without saying that the above-described gas types and valve operations are changed according to the respective layer forming conditions.

The substances that can be used as the Si supply gas used in the present invention include SiH4, Si2H6 and SiH4.
Silicon hydrides (silanes) in a gas state such as 3H8, Si4H10, or the like, which can be gasified, are effectively used. Further, SiH4 is used in terms of easy handling at the time of forming a layer, good Si supply efficiency, and the like. , Si2H6 are preferred. In the present invention, the atoms for controlling the conductivity introduced into the photoconductive layer 103 by using a spline function include so-called impurities in the semiconductor field, and the periodic table III.b which gives p-type conduction characteristics can be given. Group (hereinafter abbreviated as "group III.b atom") or an atom belonging to group V.b group of the periodic table giving n-type conduction properties (hereinafter abbreviated as "group V.b atom") ) Can be used. Specific examples of Group III.b atoms include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl), with B, Al, and Ga being particularly preferred. It is. Group V.b atoms include:
Specifically, phosphorus (P), arsenic (As), antimony (S
b), bismuth (Bi) and the like, and P and As are particularly preferable. In order to structurally introduce an atom for controlling conductivity, for example, a group III.b atom or a group V.b atom, it is necessary to form a layer III.b. An atomic substance for introducing a group b atom or a raw material for introducing a group Vb atom may be introduced into the reaction vessel in a gas state together with another gas for forming the photoconductive layer 103. III. As a source material for introducing a group b atom or a source material for introducing a group Vb atom, a material which is gaseous at ordinary temperature and normal pressure or which can be easily gasified at least under layer forming conditions is employed. Is desirable. Such III. As a raw material for introducing a group b atom, specifically, for introducing a boron atom,
B2H6, B4H10, B5H9, B5H11, B6H
10, borohydride such as B6H12 and B6H14, BF
3, boron halides such as BCl3 and BBr3. In addition, AlCl3, GaCl3, Ga (CH
3) 3, InCl3, TlCl3, and the like. Section V. Effectively used as a raw material for introducing a group b atom are PH3 and P2H4 for introducing a phosphorus atom.
Such as phosphorus hydride, PH4I, PF3, PF5, PCl3,
Phosphorus halides such as PCl5, PBr3, PBr5, PI3 and the like. In addition, AsH3, AsF3, AsC
l3, AsBr3, AsF5, SbH3, SbF3, S
bF5, SbCl3, SbCl5, BiH3, BiCl
3, BiBr3, etc. It can be mentioned as an effective starting material for introducing a group b atom. In addition, these raw materials for introducing atoms for controlling the conductivity may be used after being diluted with H2 and / or He as necessary. Further, in the present invention, the photoconductive layer 103 may contain at least one of carbon atoms, oxygen atoms, and nitrogen atoms uniformly in the photoconductive layer, or may be formed in the thickness direction of the photoconductive layer. May be provided with a non-uniform distribution such that the content changes.

Substances that can serve as a carbon supply gas include:
The gaseous hydrocarbons such as CH4, C2H6, C3H8, and C4H10 or hydrocarbons that can be gasified are used effectively.
CH4 and C2H6 are preferred in terms of good supply efficiency and the like. Further, these raw material gases for supplying C may be diluted with a gas such as H2, He, Ar, Ne or the like as necessary. In addition, examples of a starting material that can be effectively used as a source gas for introducing oxygen atoms (O) include oxygen (O2), ozone (O3), and carbon dioxide (CO2). Similarly, a starting material that is effectively used as a source gas for introducing a nitrogen atom (N) is one that has N as a constituent atom, or N and H as constituent atoms, for example, nitrogen gas (N2 ), Ammonia (NH 3), hydrazine (H 2 NNH 2), hydrogen azide (HN 3), ammonium azide (NH 4 N 3), and other gaseous or gasifiable nitrogen, and nitrides such as nitrides and azides. In addition, as a source gas into which oxygen atoms (O) and nitrogen atoms (N) can be introduced simultaneously, nitrogen monoxide (NO), nitrogen dioxide (NO2), nitrous oxide (N2O), nitrous oxide (N2O) N2O3), nitrous oxide (N2O4), nitrous oxide (N2O5), nitric oxide (NO3) and the like. Further, these raw materials for introducing atoms may be used after being diluted with H2 and / or He as necessary.

In the present invention, the thickness of the photoconductive layer 103 is determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, and is preferably 15
The thickness is desirably about 50 μm, more preferably about 20 to 45 μm, and most preferably about 25 to 40 μm. In order to achieve the object of the present invention and to form the photoconductive layer 103 having desired film properties, the mixing ratio of the Si supply gas and the dilution gas, the gas pressure in the reaction vessel, the discharge power, and the substrate temperature are appropriately adjusted. It is necessary to set. The flow rate of H2 used as the diluent gas is appropriately selected in an optimum range according to the layer design.
It is desirable to control to change in a range of 2 times, preferably 2 to 15 times, and optimally 3 to 10 times. Similarly, the optimum range of the gas pressure in the reaction vessel is appropriately selected depending on the layer design and the deposition method, but usually 1 × 10 −4 to 10 To.
rr, preferably 5 × 10 −4 to 5 Torr, optimally 1
It is preferable to set it to 10-3 to 1 Torr. Similarly, the discharge power is also appropriately selected in an optimum range depending on the layer design and the deposition method. The discharge power with respect to the flow rate of the gas for supplying Si is usually 2 to 7 times, preferably 2.5 times. ~ 6
It is desirable to set it in the range of 2 times, optimally 3 to 5 times. Further, the temperature of the base 101 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 230 to 330 ° C.
Most preferably, the temperature is set to 250 to 310 ° C. In the present invention, the above-mentioned range is mentioned as a desirable numerical range of the substrate temperature and the gas pressure for forming the photoconductive layer, but the conditions are not usually independently determined separately, and the desired characteristics are not usually determined. It is desirable to determine the optimum value based on mutual and organic relationships to form a light receiving member having the same.

The substrate used in the present invention includes:
It may be conductive or electrically insulating. As a substrate,
Al, Cr, Mo, Au, In, Nb, Te, V, T
Metals such as i, Pt, Pd, and Fe, and alloys thereof, such as stainless steel. Also, polyester,
Polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene,
It is also possible to use an electrically insulating substrate such as a film or sheet of a synthetic resin such as polyamide, glass, ceramic, or the like, on which at least the surface on the side on which the light receiving layer is formed is subjected to a conductive treatment. The shape of the substrate 101 used in the present invention may be a cylindrical or plate-like endless belt having a smooth surface or an uneven surface, and the thickness thereof may form the electrophotographic light-receiving member 100 as desired. In this case, when the flexibility as the electrophotographic light receiving member 100 is required, the thickness can be made as thin as possible within a range where the function as the base 101 can be sufficiently exhibited. However, the substrate 101 is usually set to 10 μm or more in terms of production, handling, mechanical strength and the like. In particular, when performing image recording using coherent light such as laser light, in order to more effectively eliminate image defects due to a so-called interference fringe pattern appearing in a visible image, irregularities are provided on the surface of the substrate 101. You may. The irregularities provided on the surface of the base 101 are described in JP-A-60-168156 and JP-A-60-168156.
It is prepared by a known method described in JP-A-78457, JP-A-60-225854 and the like.

As another method for more effectively eliminating image defects due to interference fringe patterns when coherent light such as laser light is used, a concave and convex shape formed by a plurality of spherical trace depressions is provided on the surface of the substrate 101. You may. That is, the base 101
Has fine irregularities smaller than the resolution required for the electrophotographic light receiving member 100, and the irregularities are caused by a plurality of spherical trace depressions. Unevenness due to a plurality of spherical trace depressions provided on the surface of the base 101 is disclosed in
It is prepared by a known method described in JP-A-231561.

In the electrophotographic light-receiving member of the present invention, it is more preferable to provide a charge injection blocking layer between the substrate and the photoconductive layer, which has a function of preventing charge injection from the side of the substrate light-receiving member. It is effective. That is, the charge injection blocking layer has a function of preventing charge from being injected from the substrate 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 exerted when it is subjected to a charging treatment of, for example, 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 that control the conductivity contained in the layer may be uniformly distributed throughout the layer, or may be uniformly distributed in the layer thickness direction, but may be unevenly distributed. There may be a part contained in the state where it does. When the distribution concentration is non-uniform, it is preferable that the compound be contained so as to be distributed more on the substrate side. However, in any case, it is necessary to uniformly contain the particles in a direction in a plane parallel to the surface of the substrate in order to make the characteristics uniform in the direction in the plane.

Also, there is no problem in changing and introducing the source gas containing the conductive control atoms using the spline function of the present invention in the charge injection blocking layer. 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.
Atom belonging to group (hereinafter abbreviated as "Group IIIb atom")
Alternatively, an atom belonging to Group Vb of the Periodic Table that gives n-type conduction characteristics (hereinafter abbreviated as “Vb Group atom”) can be used. As the Group IIIb atom, specifically, B
(Boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium), and the like, and B, Al, and Ga are particularly preferable. Specific examples of group Vb atoms include P (phosphorus), As (arsenic), and Sb.
(Antimony), Bi (bismuth) and the like.
As is preferred. 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, but is preferably from 10 to 1 It is desirable that the concentration is set to × 10 ⁴ atomic ppm, more preferably 50 to 5 × 10 ³ atomic ppm, and most preferably 1 × 10 ² to 1 × 10 ³ ppm. Furthermore, by including at least one of a nitrogen atom and an oxygen atom in addition to carbon atoms in the charge injection blocking layer, adhesion between the charge injection blocking layer and another layer provided in direct contact with the charge injection blocking layer is improved. Can be further improved. The carbon atoms, nitrogen atoms, or oxygen atoms contained in the layer may be uniformly distributed throughout the layer, or may be uniformly distributed in the layer thickness direction, but may be unevenly distributed. There may be a portion contained in a distributed state. However, in any case, it is necessary to uniformly contain the particles in a direction in a plane parallel to the surface of the substrate in order to make the characteristics uniform in the direction in the plane. Further, the hydrogen atoms contained in the charge injection blocking layer in the present invention are effective in improving the film quality by compensating the terminal bonds existing in the layer. In the present invention, the thickness of the charge injection blocking layer is such that desired electrophotographic characteristics can be obtained,
And 0.1 to 5 μm, more preferably 0.3 to 4 μm, and most preferably 0.5 to 3 μm from the viewpoint of economic effect.
It is desirable to be.

In the present invention, to form the charge injection blocking layer, a vacuum deposition method similar to the above-described method of forming the photoconductive layer is employed. To form the charge injection blocking layer 104 having characteristics capable of achieving the object of the present invention, the photoconductive layer 10
3, the mixing ratio between the gas for supplying Si and the diluting gas,
It is necessary to appropriately set the gas pressure in the reaction vessel, the discharge power, and the temperature of the substrate 101. H as a dilution gas
The optimum range of the flow rate of 2 and / or He is appropriately selected according to the layer design.
It is desirable to control He and / or He in a range of usually 1 to 20 times, preferably 3 to 15 times, and most preferably 5 to 10 times. Similarly, the optimum range of the gas pressure in the reaction vessel is appropriately selected according to the layer design.
× 10 −4 to 10 Torr, preferably 5 × 10 −4 to 5 T
orr, optimally 1 × 10 −3 to 1 Torr. Similarly, the optimum range of the discharge power is appropriately selected according to the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 1 to 7 times, preferably 2 to 7 times.
It is desirable to set the range to 6 times, optimally 3 to 5 times. Further, the temperature of the base 101 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 230 to 330 ° C.
Most preferably, the temperature is set to 250 to 310 ° C. In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the mixing ratio of the diluent gas, the gas pressure, the discharge power, and the substrate temperature for forming the charge injection blocking layer, but these layer forming factors are usually independent. However, it is desirable that the optimum value of each layer forming factor be determined based on mutual and organic relationships in order to form a surface layer having desired properties. In the electrophotographic light-receiving member of the present invention, for the purpose of further improving the adhesion between the substrate 101 and the photoconductive layer 103 or the charge injection blocking layer 105, for example, Si3N4, SiO2, An adhesion layer made of an amorphous material or the like containing SiO or silicon atoms as a base and containing hydrogen atoms and / or halogen atoms, and carbon atoms and / or oxygen atoms and / or nitrogen atoms may be provided. Further, a light absorbing layer for preventing an interference pattern from being generated by light reflected from the base may be provided.

In the present invention, it is preferable to further form an amorphous silicon-based surface layer 105 on the photoconductive layer 103 formed on the base 101 as described above. The surface layer 105 may be made of any material as long as it is an amorphous silicon-based material. For example, amorphous silicon (H) and / or halogen atom (X) and further containing carbon atoms Amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing an oxygen atom (hereinafter referred to as “a-SiC: H, X”).
SiO: H, X "), a hydrogen atom (H) and / or
Alternatively, amorphous silicon containing a halogen atom (X) and further containing a nitrogen atom (hereinafter referred to as “a-SiN: H,
X), amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing at least one of a carbon atom, an oxygen atom and a nitrogen atom (hereinafter referred to as “a-SiCON: H , X ") are suitably used.

In the present invention, in order to effectively achieve the object, the surface layer 105 is formed by a vacuum deposition film forming method by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics. Is done. The specific formation method can be formed by a number of thin film deposition methods similar to those of the photoconductive layer described above. 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 electrophotographic receiving member to be produced. It is preferable to use the same deposition method as that for the photoconductive layer from the viewpoint of productivity. The material of the surface layer used in the present invention may be any amorphous material containing silicon, but is preferably a compound with a silicon atom containing at least one element selected from carbon, nitrogen and oxygen. Those containing -SiC as a main component are preferable. Substances that can serve as a silicon (Si) supply gas used in forming the surface layer of the present invention include SiH4, Si2H6, Si3H8, and Si4.
Silicon hydrides (silanes) in a gas state such as H10 or the like can be effectively used. In addition, SiH4, Si2H6 can be used in terms of ease of handling at the time of forming a layer, and high Si supply efficiency. Are preferred. Further, these source gases for supplying Si may be diluted with a gas such as H2, He, Ar, Ne or the like, if necessary. As a substance that can be a carbon supply gas, a gaseous hydrocarbon such as CH 4, C 2 H 6, C 3 H 8, C 4 H 10 or a gasifiable hydrocarbon can be effectively used.
CH4 and C2H6 are preferred in terms of good supply rate. Further, these raw material gases for supplying C may be diluted with a gas such as H2, He, Ar, Ne or the like as necessary. The layer thickness of the surface layer 104 in the present invention is usually 0.01 to 3 μm, preferably 0.03 μm.
It is desirable that the thickness be 5 to 2 μm, most preferably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to abrasion or the like during use of the light receiving member, and if it exceeds 3 μm, the electrophotographic characteristics such as an increase in residual potential are reduced.

[0023]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. [Example 1] Outer diameter 108 mm, length 358 mm, wall thickness 5
2 mm aluminum cylinder is mirror-finished, degreased and washed, and used as a substrate. The apparatus shown in FIG. A light receiving member was created. Note that B2H
The six gases were introduced using a spline function with a change in flow rate as shown in FIG.

[0024]

[Table 1] This drum is mounted on an electrophotographic apparatus (NP606, manufactured by Canon Inc.).
0) was modified for this test), and the following electrophotographic characteristics and image quality were evaluated by the following methods. Sensitivity: The electrophotographic light-receiving member is charged to a constant dark-area surface potential. Then, the light image is immediately emitted. The light image is 550 nm using a halogen lamp light source and a filter.
Irradiate light excluding light in the following wavelength ranges. At this time, the surface potential of the bright portion of the electrophotographic light-receiving member is measured by a surface electrometer. The exposure amount was adjusted so that the bright portion surface potential became a predetermined potential, and the exposure amount at this time was used as sensitivity to evaluate. Regarding the sensitivity ◎ indicates “particularly good” ○ indicates “good” Δ indicates “no problem in practical use” x indicates “problem in practical use” Residual potential: The drum is charged to a constant dark area surface potential.
Then, a relatively intense light of a constant light amount is immediately applied. The light image was obtained using a halogen lamp light source and a filter.
Light excluding light in a wavelength range of 0 nm or less was applied. At this time, the surface potential of the light portion of the electrophotographic light-receiving member is measured by a surface electrometer. Regarding residual potential indicates “especially good” ○ indicates “good” Δ indicates “no problem in practical use” x indicates “problem in practical use” EV linearity: The drum is charged to a constant dark area surface potential. Irradiation is performed while changing the amount of light. The light image is 550 nm using a halogen lamp light source and a filter.
Irradiation was performed except for light in the following wavelength ranges. At this time, the surface potential of the light portion of the electrophotographic light-receiving member is measured with a surface electrometer, and the relationship between the light portion surface potential and the amount of light is measured. Regarding EV linearity ◎ indicates “particularly good” ○ indicates “good” 「indicates“ no problem in practical use ”X indicates“ problem in practical use ” Halftone roughness: The roughness of an image obtained when an intermediate chart (part number: FY9-9042) manufactured by Canon Inc. was placed on a platen and copied was visually evaluated. Regarding the roughness, は indicates “particularly good”, は indicates “good”, Δ indicates “no problem in practical use”, and x indicates “problem in practical use”. Comparative Example 1 A blocking type electrophotographic light-receiving member was prepared in the same manner as in Example 1 under the conditions shown in Table 1.
The same evaluation was performed. Note that the B2H6 gas was introduced at a flow rate change connecting each point with a straight line as shown in FIG. The results of Example 1 and Comparative Example 1 are shown in Table 3 below. As shown in Table 2, in the present invention, good results were obtained in all items.

[0025]

[Table 2] Example 2 Using the same aluminum cylinder as in Example 1, using the apparatus shown in FIG. 2, and under the conditions shown in Table 3, according to the procedure shown above, a function-separated type electrophotographic photoreceptor was used. Created a member. The B2H6 gas in the first region was introduced using a spline function with a change in flow rate as shown in FIG.

[0026]

[Table 3] Comparative Example 2 In the same manner as in Example 2, a function-separated electrophotographic light-receiving member was prepared under the conditions shown in Table 3, and the same evaluation as in Example 1 was performed. Note that the B2H6 gas was introduced at a flow rate change connecting each point with a straight line as shown in FIG. Table 4 below shows the results of Example 2 and Comparative Example 2 together.
Shown in As shown in Table 4, the present invention obtained good results in all items.

[0027]

[Table 4] (Example 3) Outer diameter 108 mm, length 358 mm, wall thickness 5
3 mm aluminum cylinder is mirror-finished, degreased and washed, and used as a base. The apparatus shown in FIG. A light receiving member was created. Note that B2H
The six gases were introduced at a flow rate change as shown in FIG. 8 using a spline function.

[0028]

[Table 5] (Comparative Example 3) A blocking type electrophotographic light-receiving member was prepared in the same manner as in Example 3 using the apparatus shown in FIG. 3 under the conditions shown in Table 5, and evaluated in the same manner as in Example 1. went. Note that the B2H6 gas was introduced at a flow rate change connecting each point with a straight line as shown in FIG. Hereinafter, Example 3 and Comparative Example 3
Table 6 also shows the results. As shown in Table 4,
In the present invention, good results were obtained in all items.

[0029]

[Table 6] Example 4 Using the same aluminum cylinder as in Example 1 and using the apparatus shown in FIG. 3 under the conditions shown in Table 7 and according to the procedure described above, a function-separated type electrophotographic photoreceptor was used. Created a member. The B2H6 gas in the first region was introduced using a spline function with a change in flow rate as shown in FIG.

[0030]

[Table 7] Comparative Example 4 In the same manner as in Example 4, a function-separated electrophotographic light-receiving member was prepared under the conditions shown in Table 7 and evaluated in the same manner as in Example 1. Note that the B2H6 gas was introduced at a flow rate change connecting each point with a straight line as shown in FIG. Table 8 below shows the results of Example 4 and Comparative Example 4 together.
Shown in As shown in Table 8, in the present invention, good results were obtained in all items.

[0031]

[Table 8] Example 5 Using the same aluminum cylinder as in Example 1, using the apparatus shown in FIG. 2, and under the conditions shown in Table 9, the blocking type electrophotographic light-receiving member according to the above-described procedure. It was created. The B2H6 gas in the photoconductive layer was introduced at a flow rate change as shown in FIG. 6 using a spline function.

[0032]

[Table 9] Example 6 Using the same aluminum cylinder as in Example 1, using the apparatus shown in FIG.
According to the procedure described above, a blocking type electrophotographic light-receiving member was prepared. The B2H6 gas in the photoconductive layer was introduced at a flow rate change as shown in FIG. 6 using a spline function.

[0033]

[Table 10] The electrophotographic light-receiving members prepared in Examples 5 and 6 were evaluated in the same manner as in Example 1. In addition, image defects and durability were also evaluated. Image defect: Canon halftone chart (part number: FY
9-9042) was placed on a platen, and the number of white spots having a diameter of 0.5 mm or less within the same area of the copied image obtained when copying was counted. Regarding Image Defects は: “0 to 2 pieces, not bothersome” ○: “3 to 5 pieces, not bothersome” △: “6 to 10 pieces, slightly anxious” ×: “11 pieces Above, I am worried. " Durability: After measuring various electrophotographic characteristics, an accelerated durability test corresponding to 100,000 sheets was performed, and a change in each electrophotographic characteristic was measured thereafter. Regarding the durability ◎ indicates that there is little change from the initial characteristics. ○ indicates that there is a change but no problem at all. △ indicates that there is some change. X indicates that there is a significant change. The results of Example 5 and Example 6 are shown in Table 11 below. Table 11 also shows the evaluation of the electrophotographic light-receiving member prepared in Example 1 for comparison with the present example. As shown in Table 11, in the present invention, good results were obtained in all items.

[0034]

[Table 11]

[0035]

According to the present invention, a more uniform electric field can be formed in the photoconductive layer by doping the element belonging to Group III or V of the periodic table more smoothly during the formation of the conductive layer. And a light receiving member with improved carrier running properties can be obtained, whereby a clear halftone image can be formed.
In particular, when this is used for a light receiving member for electrophotography, the performance of a copying machine body has recently been improved. In particular, it can contribute more effectively to providing a clearer halftone image. Further, the light receiving member obtained according to the present invention is excellent in electrophotographic properties, particularly, sensitivity, residual potential, EV linearity, etc., and contains carbon, oxygen, and nitrogen atoms in the photoconductive layer. The defect can be reduced and the durability can be further improved.

[0036]

[Brief description of the drawings]

FIG. 1 is a schematic layer configuration diagram for explaining the layer configuration of a preferred embodiment of the light receiving member of the present invention. FIG. 2 is an example of an apparatus for forming a light receiving layer of the light receiving member of the present invention, and is a schematic explanatory view of a light receiving member manufacturing apparatus by a glow discharge method using a microwave. FIG. 3 is an example of an apparatus for forming a light receiving layer of the light receiving member of the present invention, and is a schematic explanatory view of a device for manufacturing a light receiving member by a glow discharge method using a high frequency in an RF band.
2A is a cross-sectional view thereof, and FIG. 2B is a longitudinal cross-sectional view thereof. FIGS. 4, 6, 8, and 10 show the I-th part of the periodic table using a spline function for forming the light-receiving layer of the present invention.
5 is a graph showing an example of a change in flow rate of a source gas containing an element belonging to Group II or Group V. 5, 7, 9, and 11 are graphs showing an example of a change in the flow rate of a source gas containing an element belonging to Group III or Group V of the periodic table that forms the conventional light receiving layer. is there. REFERENCE SIGNS LIST 100 light receiving member 101 base 102 light receiving layer 103 photoconductive layer 104 charge injection blocking layer 105 surface layer 106 photoconductive layer first area 107 photoconductive layer second area 201 reaction vessel 202 base 203 rotating mechanism 204 exhaust hole 205 Heating heater 206 Source gas supply tube / electrode 207 Internal chamber 208 Power supply 209 Waveguide 210 Dielectric window 3100 Deposition device 3111 Reaction vessel 3112 Base 3113 Base heating heater 3114 Source gas introduction pipe 3115 Matching box 3116 Source gas pipe 3117 Reaction Vessel leak valve 3118 Main exhaust valve 3119 Vacuum gauge 3200 Source gas supply device 3211-216 Mass flow controller 3221-226 Source gas cylinder 3231-236 Source gas cylinder valve 3241-3246 Gas inflow valve 3251-3256 Gas outflow valve 3261-3266 Pressure regulator

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) H01L 21/205 C23C 16/50 C23C 16/52 G03G 5/08 360 H01L 31/0248

Claims (2)

(57) [Claims] A raw material gas containing silicon atoms and a raw material gas containing an element belonging to Group III or Group V of the periodic table are introduced into a reaction space, and silicon atoms and a compound of the periodic table II are placed on a substrate.
A method for manufacturing a light-receiving member, comprising the step of forming a photoconductive layer made of an amorphous material containing an element belonging to Group I or Group V, wherein the member belongs to Group III or Group V of the periodic table A method for producing a light receiving member, wherein a source gas containing an element is introduced while being continuously changed using a spline function. 2. The method according to claim 1, wherein a source gas further containing an element selected from the group consisting of carbon atoms, oxygen atoms and nitrogen atoms is introduced in said step. Method.