JPH1097998A - Formation of deposited film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming deposited film by which the sizes of substrates, practically, the diameters of light receiving members for electrophotography can be reduced without increasing the uneven characteristics and structural defects of deposited films. SOLUTION: In a method for forming deposited film, a substrate 102 is set in a reaction vessel 101 which can be reduced in pressure and a deposited film is formed on the substrate 102 by introducing a gaseous starting material and discharged power to the chamber 101 after the substrate 102 is heated. In the chamber 101, a plurality of heating means 103 and 104 is set for heating the substrate 102 in such a way that the first heating means 104 is firstly set in the chamber 101 and the substrate 102 is set against the heating means 103, and then, the second heating means 104 is set against the substrate 102.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a deposited film which is particularly suitable as a semiconductor element such as a light receiving member for electrophotography, a solar cell, a line sensor for image input, an imaging device, a TFT, etc. on a substrate by a plasma CVD method. To a manufacturing method.

[0002] The present invention also relates to a film forming method suitable for miniaturizing a light receiving member for electrophotography.

[0003]

2. Description of the Related Art As one method of producing a deposited film, a CVD method using low-temperature plasma has been spotlighted. In this method, the reaction vessel is depressurized to a high vacuum, the source gas is introduced into the reaction vessel, and then the discharge power is applied to decompose the source gas by glow discharge, and the deposited film is formed on a substrate placed in the reaction vessel. It is applied to the production of an amorphous silicon film, for example.

An amorphous silicon film produced by this method using silane gas (SiH ₄ ) as a film forming material gas has a relatively small number of localized levels in the forbidden band of amorphous silicon, and is doped with impurities. It has been studied that an amorphous silicon electrophotographic photoreceptor capable of controlling valence electrons and having excellent characteristics can be obtained.

Japanese Patent Publication No. Sho 60-35059 discloses a light receiving member for electrophotography in which hydrogenated amorphous silicon is applied to a photoconductive portion.

Japanese Patent Application Laid-Open No. 62-20874 discloses an apparatus for producing a deposited film by plasma CVD for producing such a light receiving member for electrophotography.

In such a plasma processing apparatus, it is common to form a deposited film by heating the substrate of the electrophotographic light receiving member. A heating means is provided inside the substrate of the electrophotographic light receiving member. It is common to provide.

[0008] Japanese Patent Application Laid-Open No. 6-2144 discloses an example in which a cylindrical aluminum substrate is installed and combined with a substrate support to be installed in a heater for heating a substrate in a reaction furnace.

[0009]

SUMMARY OF THE INVENTION The inventor of the present invention has proposed a method of forming a deposited film as described above, in which the diameter of a light receiving member for electrophotography is reduced (small diameter) in order to cope with recent miniaturization of electrophotographic devices. In the method of installing a substrate on a substrate heater via a substrate support, it has been necessary to considerably reduce the size of the substrate heater as the diameter of the substrate becomes smaller. In short, the heating ability of the substrate, particularly the ability to uniformly heat the surface of the substrate, becomes insufficient. If a deposited film is formed on the substrate while the heating temperature of the substrate is not uniform, the electrophotographic light There is a problem that the characteristics of the receiving member also become non-uniform.

On the other hand, in order to improve the performance of the substrate heating heater so that the heating temperature of the substrate surface can be uniformly and sufficiently heated, it is necessary to increase the size of the substrate heating heater. The need arises to reduce the thickness of the base support or to reduce the distance between the base support and the heater for heating the base. As a result, the base support is deformed by heat, Contact with the substrate heating heater, the substrate is deformed, the heating temperature of the substrate surface becomes non-uniform, the discharge becomes non-uniform, and a failure occurs in the deposited film forming apparatus. Or there was a problem.

Therefore, the present inventor studied the method of directly installing the substrate on the substrate heating heater without using the substrate support, and found that the substrate surface was uniformly heated to a sufficient heating temperature. Although it is now possible to do
When the substrate is installed, an image defect is generated in the electrophotographic light receiving member due to generation of dust, or when the substrate heating heater is configured to suppress generation of dust, the surface of the substrate is uniformly heated. There is a problem that it becomes difficult.

Particularly, in recent electrophotographic apparatuses, it is desired to faithfully copy not only character images but also photographic images. Therefore, further improvement in image characteristics such as improvement in reproducibility of intermediate density images is required. Have been. For this purpose, efforts have been made to improve the resolving power of the electrophotographic apparatus in the direction of forming a more faithful latent image on a document image and developing using a developer having a finer particle size. As a result, the deposited film as a light receiving member for electrophotography has uniformity of image density,
In particular, reduction of image defects corresponding to the improvement of the resolution of the electrophotographic apparatus, that is, reduction of structural defects of the deposited film called spherical projections causing image defects, etc., has become an important issue.
It has been difficult for the above-described conventional method for forming a deposited film to sufficiently satisfy the improvement in overall performance of these deposited films.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to reduce the size of a substrate without increasing unevenness in the characteristics of a deposited film and structural defects of the deposited film. An object of the present invention is to provide a method for forming a deposited film, which can reduce the diameter of a receiving member and is excellent in productivity.

[0014]

The above object is achieved by the following means.

That is, the present invention uses a deposition film forming apparatus comprising a reaction vessel capable of reducing pressure and an exhaust unit for exhausting the inside of the reaction vessel, disposing a substrate in the reaction vessel, and heating the substrate. In a deposition film forming method for introducing a source gas and discharge power into the reaction vessel and decomposing the source gas by the discharge power to form a deposition film on the substrate, the substrate heating means includes a plurality of heating means. First, the first heating means is installed in the reaction vessel in advance, then the base is installed on the first heating means, and finally the second heating means is installed on the base, Thereafter, a method of forming a deposited film, wherein the substrate is heated by the first and second heating means, is proposed, wherein the substrate is a plurality of cylindrical substrates, and the substrate is provided in the reaction vessel. On the same circumference Means for rotating the cylindrical substrate, means for introducing a source gas into the circle of the cylindrical substrate, and discharge electrodes for introducing discharge power into the circle of the cylindrical substrate. That the substrate disposed in the reaction vessel is a plurality of cylindrical substrates, and has a plurality of discharge electrodes for introducing discharge power into the reaction vessel,
Arranging the plurality of cylindrical substrates on concentric circles, wherein the first heating unit and / or the second heating unit of the substrate also serves as a cooling unit of the substrate, and the first heating unit and the second heating unit of the substrate That the heating temperature of the second heating means is different, that the base is a cylinder having a diameter of 40 mm or less and 16 mm or more;
The above-mentioned substrate includes a cylindrical shape having a diameter of 30 mm or less and 16 mm or more.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in more detail.

According to the conventional method for forming a deposited film,
As described in JP-A-2214, when a substrate is placed in a reaction vessel, a configuration has been adopted in which a substrate support is combined and placed on a heater for heating a substrate in the reaction vessel.

As described above, the present inventor has conducted a study on a method of directly mounting a substrate on a heater for heating a substrate without using a substrate support in order to cope with a reduction in the diameter of the substrate.
It has been found that structural defects called spherical protrusions of the deposited film occur, and it is difficult to maintain a uniform heating temperature on the surface of the substrate.

Then, the present inventor pursued the cause of the occurrence of a structural defect called a spherical projection in the deposited film, and it was confirmed that the spherical projection started to grow with the nucleus attached to the substrate surface.

Conventionally, the substrate before film formation is strictly cleaned and transported from a dust-controlled environment such as a clean room into the deposited film forming apparatus so that dust is prevented from adhering to the substrate as much as possible. I've been. Although the substrate is transported into the deposition apparatus in a clean state as described above, there is a cause that dust adheres when the substrate is installed in the deposition apparatus.

That is, since the surface of the substrate needs to be kept at the highest degree of cleanness, when the substrate is installed on the heater for heating the substrate in the deposition apparatus, the substrate must be installed without holding the surface of the substrate. Conventionally, the substrate was installed in the heater for heating the substrate via the substrate support, so there was no need to hold the substrate surface.However, when the substrate was installed on the heater for heating the substrate without using the substrate support, In addition, it is necessary to hold and install the substrate surface, which makes the substrate surface easily contaminated and spherical projections are generated. On the other hand, to install the heater on the substrate while holding the inner surface of the substrate,
It is necessary to shorten the length of the substrate heating heater so that the top of the substrate heating heater is lower than the top of the substrate. However, in this case, it becomes difficult to make the heating temperature of the substrate surface uniform. Further, in a state where the top of the substrate heating heater is higher than the top of the substrate so that the heating temperature of the substrate surface becomes uniform, the substrate is put into a part of the substrate heating heater while holding the inner surface of the substrate. A method of removing the inner surface and placing the substrate in the heater for heating the substrate by free-falling the substrate may be used, but in this case, the dust in the reaction vessel flies up and adheres to the surface of the substrate, resulting in spherical projections. The substrate may be bent or deformed.

The inventor of the present invention divided the substrate heating heater into two parts and installed the first substrate heating heater in the reaction vessel in advance such that the top of the first substrate heating heater was lower than the top of the substrate. Then, by installing the substrate on the first substrate heating heater and finally installing the second substrate heating heater on the substrate, without holding the substrate surface and free falling the substrate It has been found that a substrate can be placed in a reaction vessel, and a deposition film forming method capable of maintaining a uniform heating temperature on the substrate surface is possible. Accordingly, it is possible to reduce the size of the substrate, particularly the diameter of the light receiving member for electrophotography, without increasing the characteristic unevenness of the deposited film and the structural defects of the deposited film, so that the deposited film can be formed with high productivity. Became.

Hereinafter, the method of forming a deposited film of the present invention will be described in more detail with reference to the drawings.

FIG. 1 shows a high-frequency plasma CVD method.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view schematically showing a longitudinal section of an example of an apparatus for forming a deposited film of a light receiving member for electrophotography using the deposited film forming method of the present invention.

In FIG. 1, reference numeral 101 denotes a reaction vessel also serving as a high-frequency electrode, which is connected to an exhaust device (vacuum pump) 113 composed of a rotary pump 114 and a mechanical booster pump 115 via an exhaust pipe 111 and an exhaust valve 112. ing.

The reaction vessel 101 may have a vacuum-tight structure, and preferably has a shape conforming to the shape of the substrate 102 of the electrophotographic light-receiving member. If the shape of the substrate 102 is cylindrical, the reaction vessel 101 Similarly, a cylindrical shape is generally used. The material is desirably a metal such as Al or stainless steel from the viewpoint of mechanical strength and also serving as a high-frequency electrode.

The source gas reacts via an introduction valve 108, a gas introduction pipe 107 and a gas supply pipe 105 connected to a source gas supply system (not shown) composed of a cylinder, a pressure regulator, a mass flow controller, a valve and the like. Container 1
01.

The reaction vessel 101 serving also as a high-frequency electrode is supplied with a high-frequency power supply (not shown,
(For example, 13.56 MHz). By applying high-frequency power between the reaction vessel 101 also serving as a high-frequency electrode and the base 102 of the electrophotographic light-receiving member,
Glow discharge is generated in the reaction vessel 101. Substrate 10
2 is heated by a first substrate heating heater 103 and a second substrate heating heater 104 to a temperature required for forming a deposited film.

Next, the procedure for forming a deposited film using the apparatus shown in FIG. 1 will be described. The formation of a deposited film using this apparatus
For example, it can be performed as follows.

First, the first heater 103 for heating the substrate is placed in the reaction vessel 101, and then the substrate 102 which has been degreased and washed is placed on the first heater 103 for heating the substrate. Then, the second substrate heating heater 104 is provided on the substrate 102, and the inside of the reaction vessel 101 is exhausted by the exhaust device 113. Subsequently, the temperature of the substrate 102 is controlled to a desired temperature of, for example, 50 ° C. to 400 ° C. by the first substrate heating heater 103 and the second substrate heating heater 104.

When the temperature of the base 102 reaches a desired temperature, a source gas is supplied from a source gas supply system (not shown) into the reaction vessel 101 through a source gas supply pipe 105. At this time, care should be taken not to cause extreme pressure fluctuation such as gas projection. Next, when the flow rate of the source gas reaches a predetermined flow rate, the evacuation speed of the evacuation device 113 is adjusted while observing the vacuum gauge 110 to obtain a desired internal pressure.

When the internal pressure is stabilized, a high-frequency power supply (not shown) is set to a desired power, and the matching box 1 is set.
A high-frequency power is applied to the reaction vessel 101 also serving as a high-frequency electrode through 06 to generate a glow discharge in the reaction vessel 101. The source gas introduced into the reaction vessel 101 is decomposed by the discharge energy, and a predetermined deposited film is formed on the base 102. At this time, it is also effective to rotate the base 102 at a desired rotation speed by a base rotation motor (not shown) in order to further increase the uniformity of the circumferential film thickness and film characteristics. After the formation of the desired film thickness, the supply of the high-frequency power is stopped, the flow of the source gas into the reaction vessel is stopped, and the formation of the deposited film is completed.

When a deposited film composed of a plurality of layers is formed on a substrate due to the desired properties of the deposited film, a deposited film having a desired layer structure can be obtained by repeating the above operation. .

FIG. 2A is a schematic cross-sectional view of another example of an apparatus for forming a deposited film of a light receiving member for electrophotography using the deposited film forming method of the present invention by a high-frequency plasma CVD method. FIG. FIG. 2B is a diagram schematically showing a longitudinal section of the deposition film forming apparatus.

In FIG. 2, reference numeral 201 denotes a reaction vessel, which is connected to an exhaust device (not shown) via an exhaust pipe 212. The reaction vessel 201 may have any structure as long as it has a vacuum airtight structure, and any shape may be used, but a shape such as a cylinder or a rectangular parallelepiped is generally used. Any material may be used, but metals such as Al and stainless steel are desirable from the viewpoint of mechanical strength and prevention of leakage of high-frequency power.

The source gas is supplied from a source gas supply pipe 208 connected to a source gas supply system (not shown) composed of a cylinder, a pressure regulator, a mass flow controller, a valve and the like to an internal chamber 211 formed by the base 203. Supplied.

The high-frequency electrode 202 is connected to a high-frequency power source 207 via a matching box 206. By applying high-frequency power between the high-frequency electrode 202 and the base 203, a glow discharge is generated in the internal chamber 211. The substrate 203 is supported by a first substrate heating heater 204. Further, the first substrate heating heater 204 is connected to a motor 209 via a gear 210, and a uniform deposition film is formed on the substrate 203 by rotating the substrate 203 by the motor 209. The substrate 203 is provided with the first substrate heating heater 20.
By the fourth and second substrate heating heaters 205, the substrate is heated to a temperature required for forming a deposited film.

Next, a procedure for forming a deposited film using the apparatus shown in FIG. 2 will be described. The formation of a deposited film using this apparatus
For example, it can be performed as follows.

First, a first substrate heating heater 204 is installed in the reaction vessel 201, and then the substrate 203 degreased and washed in advance is installed in the first substrate heating heater 204. Then, a second substrate heating heater 205 is provided on the substrate 203, and the inside of the reaction vessel 201 is exhausted by an exhaust device (for example, a vacuum pump). Subsequently, the first substrate heater 204 and the second substrate heater 205 raise the temperature of the substrate 203 to, for example, 50 ° C. to 4 ° C.
Control to the desired temperature of 00 ° C.

When the temperature of the base 203 reaches a desired temperature, a source gas is supplied from a source gas supply system (not shown) into the internal chamber 211 through a source gas supply pipe 208. At this time, care should be taken not to cause extreme pressure fluctuation such as gas projection. Next, when the flow rate of the raw material gas reaches a predetermined flow rate, an exhaust valve (not shown) is adjusted while watching a vacuum gauge (not shown) to obtain a desired internal pressure.

When the internal pressure is stabilized, the high-frequency power supply 20
7 is set to a desired power, and the matching box 206 is set.
To apply a high-frequency power to the high-frequency electrode 202 to generate glow discharge. The raw material gas introduced into the reaction vessel 201 is decomposed by this discharge energy,
A predetermined deposition film is to be formed on the substrate 03. After the desired film thickness is formed, the supply of high frequency power is stopped,
The flow of the source gas into the reaction vessel is stopped, and the formation of the deposited film is completed.

When a deposited film composed of a plurality of layers is formed on a substrate due to the desired properties of the deposited film, the above operation is repeated to obtain a deposited film having a desired layer structure. .

When, for example, high-frequency power is used as the discharge power in the present invention, the oscillation frequency of the high-frequency power is
Preferably, the frequency may be any range from 0.2 MHz to 450 MHz, and it is appropriately determined according to the configuration of the deposited film forming apparatus and the conditions for forming the deposited film. The high-frequency waveform is not particularly limited, but a sine wave, a rectangular wave, or the like is suitable. The magnitude of the high frequency power is appropriately determined depending on the characteristics of the target deposited film and the like, but is preferably 1 to 5000 W per substrate, and more preferably 5 to 2000 W.

The heater for heating the substrate used in the present invention may be any heater as long as it uses a vacuum. For example, in addition to an electric resistor such as a sheath heater, a plate, or a ceramic heater, a heat radiator such as a halogen lamp, A heating element using a heat exchange means mediated by gas or liquid can be used. The shape of the heater for heating the substrate may be any shape, but since the substrate is directly installed on the heater for heating the substrate, the shape is preferably similar to the shape of the substrate, and the shape is preferably cylindrical.
The material for the surface of the heater for heating the substrate may be any material, but from the viewpoint of mechanical strength, heat resistance, thermal conductivity, etc.
Metals such as 1, stainless steel, Ti, and Inconel are desirable. Further, when rotating the substrate, it is preferable to rotate the entire substrate heating heater. The heating temperature settings of the first substrate heating heater and the second substrate heating heater may be the same or different. In any case, it is desirable to set the heating temperature of the substrate surface to be uniform. Further, depending on the conditions for forming the deposited film, a mechanism for cooling the substrate during the formation of the deposited film may be provided so that the surface of the substrate is not excessively heated. As a cooling method,
Preferably by means of heat exchange mediated by gas or liquid,
It is also preferable to perform both heating and cooling of the substrate by these heat exchange means.

The raw material gas used in the present invention is, for example, in the case of forming an amorphous silicon (hereinafter abbreviated as “a-Si”) film, in a gas state such as SiH ₄ or Si ₂ H ₆ or in a gas state. Silicon hydride obtained (silanes)
Is effectively used as a gas for introducing silicon. In addition to silicon hydride, a silicon compound containing a fluorine atom, a so-called silane derivative substituted with a fluorine atom, specifically, for example, silicon fluoride such as SiF ₄ or Si ₂ F ₆ , SiH ₃ F, A gaseous or gasifiable substance such as fluorine-substituted silicon hydride such as SiH ₂ F ₂ or SiHF ₃ is also effective as the silicon introduction gas of the present invention. In addition, the present invention may be used without any problem even if the raw material gas for introducing silicon is diluted with a gas such as H ₂ , He, Ar, or Ne as necessary.

The effective gas for introducing a halogen atom into the a-Si film is a gas such as a halogen gas, a halide, an interhalogen compound containing a halogen, or a silane derivative substituted with a halogen. Alternatively, gaseous halogen compounds are preferred. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound. Specific examples of the halogen compound that can be preferably used include fluorine gas (F ₂ ), BrF, and Cl.
Interhalogen compounds such as F, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ can be mentioned. Specific examples of the silicon compound containing a halogen atom, ie, a silane derivative substituted with a halogen atom, include, for example, SiF
₄ , silicon fluorides such as Si ₂ F ₆ are preferred.

In the present invention, the gas for introducing halogen is
Containing the above-mentioned halogen compound or halogen atom
Is used as an effective silicon compound
But also halogens such as HF, HCl, HBr, and HI
Hydrogen, SiH_Three F, SiH_Two F_Two , SiHF_Three , S
iH_Two I_Two , SiH_Two Cl_Two , SiHCl_Three , SiH _Two 
Br_Two , SiHBr_Three Halogen-substituted silicon hydride, etc.
Hydrogen atoms in various gaseous states or can be gasified
Halide, one of the elements, is also an effective source gas.
I can do it.

The halide containing these hydrogen atoms is
Since a hydrogen atom is introduced together with a halogen atom, it is used as a suitable halogen atom introduction gas in the present invention.

Further, hydrogen atoms are contained in the a-Si film.
Effective as a gas for introducing hydrogen for
_Two , D_Two Or SiH_Four , Si_Two H₆ , Si_Three H₈ ,
Si _Four H_TenAnd the like.

Further, in addition to the above gases, an element belonging to Group 3 of the Periodic Table (hereinafter abbreviated as “Group 3 element”) or an element belonging to Group 5 of the Periodic Table (hereinafter referred to as “ Group 5 element) can also be used as an element for controlling conductivity, a so-called dopant.

Specific examples of Group 3 elements include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). It is suitable. As the Group 5 element, specifically, phosphorus (P), arsenic (As), antimony (S
b), bismuth (Bi) and the like, and P and As are particularly preferable.

For example, as the boron introducing gas, B ₂ H
₆ , boron hydride such as B ₄ H _{10 and the} like, and boron halide such as BF ₃ and BCl ₃ . Other Group 3 element introduction gases include AlCl ₃ , GaCl ₃ , Ga (CH
₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like.

The gas for introducing phosphorus is PH_Three , P_Two 
H_Four Phosphorus hydride, PH_Four I, PF _Three , PCl_Three , PB
r_Three , PI_Three And the like can be used. Other
AsH element introduction gas, AsH_Three , AsF_Three , A
sCl_Three , AsBr_Three , AsF_Five , SbH_Three , SbF
_Three , SbF_Five , SbCl_Three , SbCl_Five , BiH_Three , B
iCl_Three , BiBr_Three And the like.

Further, the gas for introducing an element for controlling the conductivity may be used after being diluted with H ₂ and / or He as necessary.

In the case of forming amorphous silicon carbide (a-SiC), for example, in addition to the above-mentioned raw material gas, as a gas for introducing carbon atoms, C and H are used as constituent atoms. A saturated hydrocarbon of the formulas 1 to 5,
Ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like can be used. Specifically, as the saturated hydrocarbon, methane (CH ₄ ), ethane (C ₂ H
₆ ) etc., ethylene (C ₂
H _4), propylene (C ₃ H ₆₎ or the like, as the acetylenic hydrocarbon, acetylene (C ₂ H _2), and methyl acetylene (C ₃ H ₄₎ and the like.

In the case of forming amorphous silicon oxide (a-SiO), for example, oxygen (O ₂ ), ozone (O ₂ ) ₃ ), nitric oxide (N
O), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N ₂
O), nitrogen trioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂
O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitric oxide (NO ₃
), Silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H) as constituent atoms, for example, disiloxane (H
₃ SiOSiH _3), trisiloxane (H ₃ SiOSi
H ₂ OSiH ₃ ).

In the present invention, for example, in the case of forming amorphous silicon nitride (a-SiN), nitrogen (N ₂ ), ammonia (NH ₃ ),
Hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ),
Examples include gaseous or gasifiable nitrogen, such as ammonium (NH ₄ N ₃ ), and nitrogen compounds, such as nitrogen and azide. In addition to the introduction of nitrogen atoms,
Nitrogen halide compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be given because a halogen atom can be introduced.

Representative examples of the layer constitution when producing a light receiving member for electrophotography using the present invention are as follows.

FIG. 4 is a schematic configuration diagram for explaining the layer configuration.

The light receiving member 4 for electrophotography shown in FIG.
No. 00 is provided with a photoconductive layer 402 made of a-Si containing hydrogen and / or halogen (hereinafter referred to as “a-Si (H, X)”) and having photoconductivity on a base 401. I have.

The light receiving member 4 for electrophotography shown in FIG.
Reference numeral 00 denotes a photoconductive layer 402 made of a-Si (H, X) and having photoconductivity, and an amorphous silicon-based surface layer 403 formed on a substrate 401.

The light receiving member 4 for electrophotography shown in FIG.
Reference numeral 00 denotes a photoconductive layer 402 made of a-Si (H, X) and having photoconductivity, an amorphous silicon-based surface layer 403, and an amorphous silicon-based charge injection blocking layer 404 formed on a substrate 401. ing.

The light receiving member 4 for electrophotography shown in FIG.
No. 00 has a photoconductive layer 402 provided on a base 401. The photoconductive layer 402 includes a charge generation layer 405 and a charge transport layer 406 made of a-Si (H, X), and an amorphous silicon-based surface layer 403 is provided thereon.

The light receiving member 4 for electrophotography shown in FIG.
Reference numeral 00 denotes a photoconductive layer 402 made of a-Si (H, X) and having photoconductivity, an amorphous silicon-based surface layer 403, an amorphous silicon-based charge injection blocking layer 404, and an amorphous silicon It comprises a system upper blocking layer 407.

<Substrate> The substrate of the electrophotographic light-receiving member may be either conductive or electrically insulating. As the conductive substrate, Al, Cr, Mo, Au, In, Nb, T
Examples include metals such as e, V, Ti, Pt, Pd, and Fe, and alloys thereof, such as stainless steel. Further, a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, etc., at least the surface on the side on which the light-receiving layer is formed of an electrically insulating substrate such as glass, ceramic, etc. A substrate subjected to a conductive treatment can also be used. Further, it is desirable that the side opposite to the side on which the light receiving layer is formed is also subjected to conductive treatment.

The shape of the substrate 401 is preferably cylindrical, and its thickness is appropriately determined so that the electrophotographic light-receiving member 400 can be formed as desired. When flexibility is required, it can be made as thin as possible within a range where the function as the base 401 can be sufficiently exhibited. However, the substrate 401 is usually 10 μm or more in terms of manufacturing, handling, mechanical strength and the like.

The surface shape of the substrate 401 can be a smooth flat surface or an uneven surface. For example, in the case of performing image recording using a coherent light such as a laser beam in a light receiving member for electrophotography or the like, Japanese Patent Application Laid-open No. 16
Nos. 8156, 60-178457 and 60
It may be an uneven surface produced by a known method described in -225854 and the like.

<Photoconductive Layer> The photoconductive layer 402 is
Above, it is created by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics. In order to form the photoconductive layer 402, basically, a gas for introducing silicon and a gas for introducing hydrogen and / or a gas for introducing halogen as described above are introduced into a deposition chamber in a desired gas state. Glow discharge is generated in the deposition chamber, and a-Si (H,
X) is formed.

Further, since the a-Si film in the photoconductive layer 402 contains hydrogen atoms and / or halogen atoms, dangling bonds of Si atoms are compensated for, and the layer quality is improved. This is because it is indispensable to improve the charge retention characteristics. Therefore, the content of the hydrogen atom or the halogen atom, or the content of the sum of the hydrogen atom and the halogen atom is 1 to 40 atom%, more preferably 5 to 35 atom%.
It is desirable to be.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 402, for example, the temperature of the substrate 401, a raw material used to contain hydrogen atoms and / or halogen atoms It is only necessary to control the amount of gas introduced into the deposition chamber, the discharge power, and the like.

It is preferable that the photoconductive layer 402 contains atoms for controlling conductivity as necessary. The element that controls the conductivity may be contained in the photoconductive layer 402 in a state of being uniformly distributed without unevenness, or there may be a part that is contained in the layer thickness direction in a non-uniform distribution state. Is also good.

As the element for controlling the conductivity, the aforementioned Group 3 element or Group 5 element can be used.

The content of the element for controlling the conductivity contained in the photoconductive layer 402 is preferably 1 × 10 ^-2 to 1
× 10 ² atomic ppm, more preferably 5 × 10 ^-2 to 50
Desirably, it is set to atomic ppm, optimally 0.1 to 10 atomic ppm.

In order to structurally introduce an element for controlling conductivity, for example, a Group 3 element or a Group 5 element, the aforementioned Group 3 element introduction gas or Group 5
A group element introduction gas may be introduced into the deposition chamber together with another gas for forming the photoconductive layer 402.

The photoconductive layer 402 has carbon atoms and / or carbon atoms.
Or may contain oxygen and / or nitrogen atoms.
It is valid. Carbon atoms and / or oxygen atoms and / or
Preferably has a nitrogen atom content of 1 × 10^-Five~ 30 atoms
%, More preferably 1 × 10 ^-Four~ 20 atomic%, optimally
1 × 10^-3-10 atomic% is desirable. Carbon atoms and / or
Alternatively, oxygen atoms and / or nitrogen atoms
It may be contained evenly and uniformly in the photoconductive layer 40.
Non-uniform distribution such that the content changes in the thickness direction of layer 2
There may be parts that have been raised.

In order to structurally introduce carbon atoms and / or oxygen atoms and / or nitrogen atoms, the above-mentioned gas for introducing carbon atoms and / or oxygen atoms and / or nitrogen atoms is used during the formation of a layer. It may be introduced together with another gas for forming the photoconductive layer 402.

The thickness of the photoconductive layer 402 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, and is preferably 5 to 80 μm, more preferably 10 to 60 μm, and most preferably 10 to 60 μm. Is desirably 15 to 45 μm.

Photoconductive layer 4 having characteristics capable of achieving the object
To form 02, it is necessary to appropriately set the temperature of the substrate 401 and the gas pressure in the deposition chamber as desired.

The temperature (Ts) of the substrate 401 is appropriately selected in an optimum range according to the layer design, but is usually preferably 50 to 400 ° C., more preferably 150 to 35 ° C.
The temperature is desirably 0 ° C, optimally 200 to 300 ° C.

The gas pressure in the deposition chamber is also appropriately selected in the same manner according to the layer design, but is usually preferably 0.01 to 1000 Pa, more preferably 0.05 to 1000 Pa.
It is preferable that the pressure is set to 500 Pa, most preferably 0.1 to 100 Pa.

Desirable numerical ranges of the substrate temperature and the gas pressure for forming the photoconductive layer 402 include the above-mentioned ranges. In addition, the mixing ratio with the gas for introducing silicon and the gas for introducing other atoms, It is necessary to appropriately set the discharge power and the like. These conditions are usually not independently determined separately, but it is desirable to determine optimum values based on mutual and organic relationships to form an electrophotographic light-receiving member having desired characteristics.

<Surface Layer> It is preferable to further form an amorphous silicon-based surface layer 403 on the photoconductive layer 402 formed on the substrate 401 as described above.
The surface layer 403 is provided mainly for the purpose of improving moisture resistance, continuous repeated use characteristics, electric pressure resistance, use environment characteristics, and durability.

The surface layer 403 can be made of any material as long as it is an amorphous silicon material. For example, the surface layer 403 contains a hydrogen atom (H) and / or a halogen atom (X) and further contains a carbon atom. Amorphous silicon (hereinafter referred to as “a-SiC (H, X)”), amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X), and further containing an oxygen atom (hereinafter referred to as “a
-SiO (H, X) "), amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing a nitrogen atom (hereinafter referred to as" a-SiN ").
(H, X) "), a hydrogen atom (H) and / or a halogen atom (X), and at least one of a carbon atom, an oxygen atom and a nitrogen atom (hereinafter referred to as" a -Si (C, O, N) (H, X) "
And the like are suitably used.

The surface layer 403 is formed by a vacuum deposition film forming method by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics.

For example, in order to form the surface layer 403 made of a-SiC (H, X), basically, a gas for introducing a silicon atom, a gas for introducing a carbon atom, a gas for introducing a hydrogen atom or And / or a halogen atom introducing gas is introduced in a desired gas state into a deposition chamber in which the inside can be decompressed to generate a glow discharge in the deposition chamber to form a photoconductive layer 402 previously set at a predetermined position. Base 4
A layer made of a-SiC (H, X) may be formed on the first layer.

The surface layer 403 is made of a-Si (C, O, N)
Carbon content when (H, X) is the main component and / or
Alternatively, the content of oxygen atoms and / or nitrogen atoms is preferably in the range of 1% to 90%, more preferably 5% to 70%, and most preferably 10% to 50%.

Further, hydrogen atoms or / and / or
And halogen atoms need to be contained, which is a silicon atom or a carbon atom and / or an oxygen atom and / or
Alternatively, it is important for compensating for dangling bonds of nitrogen atoms and improving the layer quality, particularly, the photoconductive characteristics and the charge retention characteristics. The content of hydrogen atoms and / or halogen atoms is usually 1 to 70 atomic%, preferably 10 to 60 atomic%, and most preferably 20 to 50 atomic%.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer 403, for example, the temperature of the substrate 401, the amount of a raw material used to contain hydrogen atoms and / or halogen atoms, The amount to be introduced into the deposition chamber, the discharge power, and the like may be controlled.

The carbon atoms and / or oxygen atoms and / or nitrogen atoms may be evenly and uniformly contained in the surface layer 403, or may be such that the content changes in the thickness direction of the surface layer 403. There may be a portion having a uniform distribution.

Further, the surface layer 403 may contain an element for controlling conductivity as necessary. The element for controlling the conductivity may be contained in the surface layer 403 in a state of being uniformly distributed in the surface layer 403, or even if there is a part contained in the layer thickness direction in a non-uniform distribution state. Good.

As the element for controlling the conductivity, the aforementioned Group 3 element or Group 5 element can be used.

The content of the element controlling the conductivity contained in the surface layer 403 is preferably 1 × 10 ⁻³ to 1 ×.
10 ³ atomic ppm, more preferably 5 × 10 ^{−3 to} 5 × 1
Desirably, the concentration is 0 ² atomic ppm, most preferably 1 × 10 ^-2 to 1 × 10 ² atomic ppm. An element that controls conductivity,
For example, in order to structurally introduce a Group 3 element or a Group 5 element, the above-described Group 3 element introduction gas or Group 5 element introduction gas is introduced into the deposition chamber during the layer formation. It may be introduced together with another gas for forming the layer 403.

The thickness of the surface layer 403 is usually 0.0
1 to 3 μm, preferably 0.05 to 2 μm, and most preferably 0.
It is desirable that the thickness be 1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer 403 is lost due to abrasion or the like during use of the electrophotographic light-receiving member, and if it exceeds 3 μm, deterioration of electrophotographic properties such as increase in residual potential is caused. Can be seen.

The surface layer 403 is carefully formed so that the required characteristics are provided as desired. That is,
The material 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 from electrical property to semiconductor from electrical property. In the present invention, a compound having desired properties according to the purpose is formed, since the properties between the properties and the insulating properties and the properties between the photoconductive properties and the non-photoconductive properties are shown. As such, the choice of the formation conditions is strictly made as desired.

For example, in order to provide the surface layer 403 mainly for the purpose of improving the pressure resistance, the surface layer 403 is formed as a non-single-crystal material having a remarkable electric insulating property in a use environment.

When the surface layer 403 is provided mainly for the purpose of improving the characteristics of continuous and repeated use and the characteristics of the use environment, the above-mentioned degree of electric insulation is alleviated to some extent.
It is formed as a non-single-crystal material having a certain sensitivity to the irradiated light.

The surface layer 40 having characteristics capable of achieving the object
In order to form 3, it is necessary to appropriately set the temperature of the substrate 401 and the gas pressure in the deposition chamber as desired.

The temperature (Ts) of the substrate 401 is appropriately selected in an optimum range according to the layer design, but is usually preferably 50 to 400 ° C., and more preferably 150 to 35 ° C.
The temperature is desirably 0 ° C, optimally 250 to 300 ° C.

Similarly, the gas pressure in the deposition chamber is appropriately selected in an optimum range according to the layer design, but is usually preferably 0.01 to 1000 Pa, more preferably 0.05 to 1000 Pa.
It is preferable that the pressure is set to 500 Pa, most preferably 0.1 to 100 Pa.

A substrate temperature for forming the surface layer 403;
Desirable gas pressure ranges include the above-mentioned ranges, but the conditions are not usually independently determined separately, but are mutually and organically formed to form an electrophotographic light-receiving member having desired characteristics. It is desirable to determine the optimal value based on the relevance.

A region where the content of carbon atoms and / or oxygen atoms and / or nitrogen atoms continuously decreases toward the photoconductive layer 402 may be provided between the surface layer 403 and the photoconductive layer 402. . Thereby, the surface layer and the photoconductive layer 40 are formed.
2, the effect of interference due to light reflection at the interface can be reduced, and at the same time, the trapping of carriers at the interface can be prevented, and the characteristics of the electrophotographic light receiving member can be improved. . <Charge Injection Blocking Layer, Upper Blocking Layer> If necessary, a charge injection blocking layer 404 that functions to block charge injection from the conductive substrate side is provided between the conductive substrate and the photoconductive layer 402. Is also good. That is, the charge injection blocking layer 404 has a function of preventing charges from being injected from the substrate side to the photoconductive layer 402 side when the electrophotographic light-receiving member is subjected to a charging treatment of a fixed polarity on its surface. However, such a function is not exhibited when it is subjected to charging treatment of the opposite polarity, that is, it has a so-called polarity dependency. In order to provide such a function,
The charge injection blocking layer 404 contains a relatively large number of elements for controlling conductivity as compared with the photoconductive layer 402.

Further, if necessary, an upper blocking layer 407 which functions to prevent charge injection from the surface layer side may be provided between the photoconductive layer 402 and the surface layer 403. That is, the upper blocking layer 407 has a function of preventing charges from being injected from the surface layer 403 side to the photoconductive layer 402 side when the electrophotographic light receiving member is subjected to a charging treatment of a fixed polarity on its surface. However, such a function is not exhibited when subjected to a charging treatment of the opposite polarity, that is, it has a so-called polarity dependency. To provide such a function, the upper blocking layer 40
7, the element for controlling conductivity is contained in a relatively large amount as compared with the photoconductive layer 402, similarly to the charge injection blocking layer 404.

The elements for controlling the conductivity contained in the layer may be uniformly distributed in the layer uniformly, or may be uniformly distributed in the thickness direction of the layer, but may be undistributed. 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 substrate side.

However, in any case, it is necessary to uniformly contain the particles in the in-plane direction parallel to the surface of the base in order to make the characteristics uniform in the in-plane direction.

As the element for controlling the conductivity contained in the charge injection blocking layer 404 and / or the upper blocking layer 407, the aforementioned Group 3 element or Group 5 element can be used.

The content of the element for controlling conductivity contained in the charge injection blocking layer 404 and / or the upper blocking layer 407 is appropriately determined as desired, but is preferably 10 to 1 × 10 ⁴ atoms. ppm, more preferably 50
-5 × 10 ³ atomic ppm, optimally 1 × 10 ^{2 -3} × 1
0 ³ desirably are atomic ppm.

Further, the charge injection blocking layer 404 and / or the upper blocking layer 407 contains at least one of carbon atoms, nitrogen atoms and oxygen atoms so that the charge injection blocking layer 404 and / or the upper blocking layer 407 can be formed. Can be further improved in the adhesiveness with another layer provided in direct contact with the substrate.

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

The charge injection blocking layer 404 and / or the upper blocking
The carbon atoms contained in the entire layer region of the stop layer 407 and / or
Is the desired film content of nitrogen and / or oxygen atoms
It is determined as appropriate so that the characteristics can be obtained.
Of two or more species, the sum of
1x10^-3５０50 atomic%, more preferably 5 × 10 ^-3
~ 30 atomic%, optimally 1 × 10^-2To 10 atomic%
Is desirable.

The hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer 404 and / or the upper blocking layer 407 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 404 and / or the upper blocking layer 407 is preferably 1 to 50 atomic%, more preferably 5 to 40 atomic%. Optimally, it is desirably 10 to 30 atomic%.

The thickness of the charge injection blocking layer 404 is preferably from 0.1 to 10 μm, more preferably from 0.3 to 5 from the viewpoints of obtaining desired electrophotographic characteristics and economic effects.
μm, optimally 0.5 to 3 μm.

The thickness of the upper blocking layer 407 is preferably from 0.01 to 3 μm, more preferably from 0.05 to 2 μm, from the viewpoints of obtaining desired electrophotographic characteristics and economic effects.
m, and most preferably 0.1 to 1 μm.

In order to form the charge injection blocking layer 404 and / or the upper blocking layer 407, a vacuum deposition method similar to the method of forming the photoconductive layer 402 described above is employed. As with the photoconductive layer 402, it is necessary to appropriately set the mixing ratio of the gas for introducing silicon atoms to the gas for introducing other atoms, the gas pressure in the deposition chamber, the discharge power, and the temperature of the base 401.

The optimum range of the gas pressure in the deposition chamber is appropriately selected, but is usually 0.01 to 1000 Pa, preferably 0.05 to 500 Pa, and most preferably 0.1 to 100 Pa.
It is preferred that

The layer formation factors such as the mixing ratio of the diluent gas, the gas pressure, the discharge power and the substrate temperature for forming the charge injection blocking layer 404 and / or the upper blocking layer 407 are usually determined independently and separately. Instead, the charge injection blocking layer 404 and / or the upper blocking layer 4 having desired characteristics
It is desirable to determine the optimum value of each layer forming factor based on mutual and organic relationships to form 07.

For the purpose of further improving the adhesion between the substrate 401 and the photoconductive layer 402 or the charge injection blocking layer 404, for example, Si ₃ N ₄ , SiO ₂ , SiO, or silicon atoms are used as a base material. An adhesion layer formed of an amorphous material containing a hydrogen atom and / or a halogen atom and a carbon atom and / or an oxygen atom and / or a nitrogen atom may be provided. Further, a light absorbing layer for preventing the generation of an interference pattern due to light reflected from the base may be provided.

[0117]

The present invention will be described in more detail with reference to the following examples.

(Example 1) In the deposition film forming apparatus shown in FIG.
mm of aluminum cylindrical substrate 102, and then a second substrate heating heater is disposed on the cylindrical substrate 102, and then the inside of the reaction vessel 101 is evacuated.
An a-Si film was formed on the film No. 2 according to the film forming conditions shown in Table 1, and a light receiving member for electrophotography having a layer structure shown in FIG.

(Comparative Example 1-1) In Example 1, except that the second substrate heating heater 104 was not heated, and the cylindrical substrate 102 was heated only by the first substrate heating heater 103. A light receiving member for electrophotography was prepared in the same manner as in Example 1.

(Comparative Example 1-2) In the deposition film forming apparatus shown in FIG. 5, the substrate heating heater 503 was charged while holding the inner surface of the aluminum cylindrical substrate 502,
Finally, after removing the holding of the cylindrical substrate 502 and installing it in the form of dropping it into the substrate heating heater 503, the reaction vessel 5
A light-receiving member for electrophotography was prepared in the same manner as in Example 1 except that the inside of 01 was exhausted.

(Comparative Example 1-3) In the apparatus for forming a deposited film shown in FIG. 5, a heater 503 for heating a substrate was set while holding the outer surface of a cylindrical substrate 502 made of aluminum, and then the inside of the reaction vessel 501 was evacuated. A light receiving member for electrophotography was prepared in the same manner as in Example 1 except for the above.

The light-receiving members for electrophotography prepared in Example 1 and Comparative Example 1 were evaluated by the following methods.

Each of the electrophotographic light receiving members was set in an electrophotographic apparatus (GP55 manufactured by Canon Inc. modified for experiments), and a copy paper manufactured by Canon (product number: EN-
500) is placed on a platen, and the number of black spots having a diameter of 0.2 mm or more in the same area of the copy image obtained when copying is checked, and the average of the number of black spots of each electrophotographic light receiving member is determined. The value was calculated. The smaller the number of black spots, the smaller the number of image defects and the higher the image quality.

Further, Canon Test Sheet NA-7
(Part No. FY9-9060) was placed on a platen and the image density of a halftone portion was measured with an image densitometer (RD91 manufactured by Macbeth Co., Ltd.) in a copy image obtained when copying.
4), the image density in the axial direction of the electrophotographic light receiving member was examined, and the variation in image density of each electrophotographic light receiving member was calculated. The smaller the variation in the image density, the better the characteristic uniformity.

Further, the surface of each light receiving member for electrophotography was observed with an optical microscope, and the diameter per 10 cm square was 1 mm.
The number of spherical protrusions having a size of 5 μm or more was checked, and the average value of the number of spherical protrusions of each electrophotographic light-receiving member was calculated. The smaller the number of spherical projections, the smaller the number of image defects and the higher the image quality.

The above evaluations are shown in Table 2. In Table 2, the evaluation result of Comparative Example 1-1 is shown as a relative value with 1 being set. As can be seen from Table 2, the electrophotographic light-receiving member of Example 1 was better than the electrophotographic light-receiving member of Comparative Example 1.
Less image defects and excellent property uniformity.

From the above results, it has been found that according to the present invention, a deposited film having excellent characteristics can be formed, and a light receiving member for electrophotography can be formed by using this deposited film. did.

[0128]

[Table 1]

[0129]

[Table 2] Note) All values in the table are relative values when the value obtained in Comparative Example 1-1 is set to 1.

(Example 2) In the deposition film forming apparatus shown in FIG.
mm cylindrical aluminum substrate 203 is installed, and then a second substrate heating heater 205 is attached to the cylindrical substrate 203.
Is installed, the inside of the reaction vessel 201 is evacuated, an a-Si film is formed on the cylindrical substrate 203 according to the film forming conditions shown in Table 3, and the electrophotographic light having the layer structure shown in FIG. A receiving member was created.

(Comparative Example 2-1) In Example 2, except that the second substrate heating heater 205 was not heated and the cylindrical substrate 203 was heated only by the first substrate heating heater 204. A light receiving member for electrophotography was prepared in the same manner as in Example 2.

(Comparative Example 2-2) In the deposition film forming apparatus shown in FIG. 6, the inner surface of the cylindrical substrate 603 made of aluminum was inserted into the substrate heating heater 604 while holding the inner surface thereof.
Finally, after the cylindrical substrate 603 is released from the holding and released into the heater 605 for heating the substrate,
A light receiving member for electrophotography was prepared in the same manner as in Example 2 except that the inside of the chamber was exhausted.

(Comparative Example 2-3) In the deposition film forming apparatus shown in FIG. 6, after the outer surface of the aluminum cylindrical substrate 603 was set on the substrate heating heater 604 while holding the outer surface thereof, the inside of the reaction vessel 601 was evacuated. A light receiving member for electrophotography was prepared in the same manner as in Example 2 except for the above.

The electrophotographic light-receiving members prepared in Example 2 and Comparative Example 2 were evaluated in the same procedure as in Example 1. Table 4 shows the results. In Table 4, the evaluation results of Comparative Example 2-1 are shown as relative values with 1 being set. As can be seen from Table 4, Example 2 was applied to the electrophotographic light-receiving member of Comparative Example 2.
The electrophotographic light-receiving member of (1) has less image defects and is excellent in property uniformity.

From the above results, it has been found that according to the present invention, it is possible to form a deposited film having excellent characteristics, and it is possible to form an excellent light receiving member for electrophotography by using this deposited film. did.

[0136]

[Table 3]

[0137]

[Table 4] Note) All values in the table are relative values when the value obtained in Comparative Example 2-1 is set to 1.

Example 3 In the deposited film forming apparatus shown in FIG.
mm of aluminum cylindrical substrate 303, and then a second substrate heating heater 305
Is installed, the inside of the reaction vessel 301 is evacuated, an a-Si film is formed on the cylindrical substrate 303 according to the film forming conditions shown in Table 5, and the electrophotographic light having the layer structure shown in FIG. A receiving member was created.

Comparative Example 3 The procedure of Example 3 was repeated, except that the second substrate heating heater 305 was not heated and the first substrate heating heater 304 was used to heat the cylindrical substrate 303 alone. In the same manner as in No. 3, a light receiving member for electrophotography was prepared.

The electrophotographic light-receiving members prepared in Example 3 and Comparative Example 3 were evaluated in the same procedure as in Example 1. As a result, the light receiving member for electrophotography of Example 3 was 0.69 in black spot number with respect to the light receiving member for electrophotography of Comparative Example 3.
The image density was 0.49, the number of spherical projections was 0.77, and the electrophotographic light-receiving member of Example 3 had less image defects and characteristic uniformity than the electrophotographic light-receiving member of Comparative Example 3. Is excellent.

From the above results, it has been found that according to the present invention, a deposited film having excellent characteristics can be formed, and a light receiving member for electrophotography can be formed by using this deposited film. did.

[0142]

[Table 5] (Embodiment 4) In the deposition film forming apparatus shown in FIG. 2, an aluminum cylindrical substrate 203 having a diameter of 30 mm is installed on a substrate heating heater 204 incorporating a first cooling mechanism. After the substrate heating heater 205 incorporating the second cooling mechanism is installed, the inside of the reaction vessel 201 is evacuated, and an a-Si film is formed on the cylindrical substrate 203 according to the film forming conditions shown in Table 6. An electrophotographic light-receiving member having a layer configuration shown in FIG. 4C was prepared.

(Comparative Example 4) In the deposition film forming apparatus shown in FIG.
04 while holding the inner surface of the aluminum cylindrical substrate 603 while holding the inner surface of the aluminum substrate 603, and finally disposing the cylindrical substrate 603 in a form of dropping it into the substrate heating heater 605 having a cooling mechanism incorporated therein. An electrophotographic light-receiving member was prepared in the same manner as in Example 4, except that the inside was evacuated.

The electrophotographic light-receiving members prepared in Example 4 and Comparative Example 4 were evaluated in the same procedure as in Example 1. As a result, the light receiving member for electrophotography of Example 4 was 0.49 in black spot number with respect to the light receiving member for electrophotography of Comparative Example 4.
The image density was 0.82, the number of spherical projections was 0.55, and the electrophotographic light receiving member of Example 4 had less image defects and the uniformity of characteristics than the electrophotographic light receiving member of Comparative Example 4. Is excellent.

From the above results, it has been found that according to the present invention, it is possible to form a deposited film having excellent characteristics, and it is possible to form an excellent electrophotographic light-receiving member by using this deposited film. did.

[0146]

[Table 6] (Embodiment 5) In the deposition film forming apparatus shown in FIG. 1, an aluminum cylindrical substrate 203 having a diameter of 40 mm is set on a first substrate heating heater 204, and then a second substrate is mounted on the cylindrical substrate 203. After the heater 205 is installed, the inside of the reaction vessel 201 is evacuated, and an a-Si film is formed on the cylindrical substrate 203 by the first substrate heater 20 shown in Table 7.
Film formation was performed according to different film formation conditions with the settings of the fourth and second substrate heating heaters 205 different from each other, and an electrophotographic light-receiving member having a layer configuration shown in FIG.

(Comparative Example 5) In the deposited film forming apparatus shown in FIG. 5, the inside of the reaction vessel 501 was evacuated after being placed on the substrate heating heater 503 while holding the outer surface of the aluminum cylindrical substrate 502. An electrophotographic light-receiving member was prepared in the same manner as in Example 5, except that the setting of the substrate heating heater 503 was the same as that of the first substrate heating heater of Example 5.

The electrophotographic light-receiving members prepared in Example 5 and Comparative Example 5 were evaluated in the same procedure as in Example 1. As a result, the light receiving member for electrophotography of Example 5 was 0.66 in black spot number with respect to the light receiving member for electrophotography of Comparative Example 5,
The image density was 0.62, the number of spherical projections was 0.71, and the electrophotographic light receiving member of Example 5 had less image defects and the characteristic uniformity compared to the electrophotographic light receiving member of Comparative Example 5. Is excellent.

From the above results, it has been found that according to the present invention, it is possible to form a deposited film having excellent characteristics, and it is possible to form an excellent electrophotographic light-receiving member by using this deposited film. did.

[0150]

[Table 7] (Embodiment 6) In the same manner as in Embodiment 2 except that the film-forming conditions shown in Table 8 were used and the aluminum cylindrical base 203 having a diameter of 24 mm was used, FIG.
The light receiving member for electrophotography having the layer constitution shown in the following was prepared.

The electrophotographic light-receiving member prepared in Example 6 was evaluated in the same procedure as in Example 1. As a result, the same image defects and uniformity of characteristics as in Example 1 were obtained, and according to the present invention, a deposited film having excellent characteristics could be formed. It has been found that a light receiving member can be formed.

[0152]

[Table 8] (Example 7) In Example 3, an aluminum cylindrical substrate 303 having a diameter of 16 mm was used, and a first substrate heater 304 and a second substrate heater 305 each having a cooling mechanism were used. An electrophotographic light-receiving member having a layer structure shown in FIG. 4C was prepared in the same manner as in Example 3 except that the film formation conditions were followed.

The electrophotographic light-receiving member prepared in Example 7 was evaluated in the same procedure as in Example 1. As a result, the same image defects and uniformity of characteristics as in Example 1 were obtained, and according to the present invention, a deposited film having excellent characteristics could be formed. It has been found that a light receiving member can be formed.

[0154]

[Table 9]

[0155]

As described above, according to the present invention,
The size of the substrate can be reduced without increasing the unevenness of the characteristics of the deposited film and the structural defects of the deposited film, and in particular, the diameter of the light receiving member for electrophotography can be reduced, which is effective in forming a deposited film with excellent productivity. There is.

[Brief description of the drawings]

FIG. 1 is a schematic view showing one example of a deposited film forming apparatus of the present invention.

FIG. 2A is a schematic top view showing an example of another deposited film forming apparatus of the present invention, and FIG. 2B is a schematic vertical sectional view of FIG. 2A.

FIG. 3A is a schematic top view showing an example of still another deposited film forming apparatus of the present invention, and FIG.
It is a longitudinal cross-sectional schematic diagram of (A).

FIGS. 4 (A) to 4 (E) are schematic structural views showing the layer constitution in the case of producing a light receiving member for electrophotography using the present invention.

FIG. 5 is a schematic view showing an example of a conventional deposited film forming apparatus.

6 (A) is a schematic top view showing another example of a conventional deposited film forming apparatus, and FIG. 6 (B) is a schematic vertical sectional view of FIG. 6 (A).

[Explanation of symbols]

100, 200, 300, 500, 600 Deposited film forming apparatus 101, 201, 301, 501, 601 Reaction vessel 102, 203, 303, 502, 603 Substrate 103, 204, 304 First substrate heating heater (first Heating means) 104, 205, 305 Second substrate heating heater (second heating means) 105, 208, 308, 505, 608 Source gas supply pipes 106, 206, 306, 506, 606 Matching box 107, 507 Gas Inlet pipe 108,508 Inlet valve 110,510 Vacuum gauge 111,212,312,511,612 Exhaust pipe 112,512 Exhaust valve 113,513 Exhaust device 114,514 Rotary pump 115,515 Mechanical booster pump 202,302,602 High frequency Electrodes 207, 07,607 High frequency power supply 209,309,609 Motor 210,310,610 Gear 211,611 Inner chamber 400 Electrophotographic light receiving member 401 Base 402 Photoconductive layer 403 Surface layer 404 Charge injection blocking layer 405 Charge generation layer 406 Charge transport Layer 407 Upper blocking layer 503, 604 Heater for substrate heating

Claims (8)

[Claims] 1. A substrate is disposed in a reaction vessel using a deposition film forming apparatus including a reaction vessel capable of reducing pressure and an exhaust unit for exhausting the inside of the reaction vessel. In a deposition film forming method of forming a deposition film on the substrate by introducing power into the reaction vessel and decomposing the source gas by the discharge power, the substrate heating means includes a plurality of heating means. Is installed in the reaction vessel in advance, then the substrate is installed on the first heating unit, and finally, the second heating unit is installed on the substrate, and then the first And heating the substrate by a second heating means. 2. The method according to claim 1, wherein the substrate is a plurality of cylindrical substrates, and the substrates are arranged on the same circumference in the reaction vessel, and have means for rotating the cylindrical substrates. 2. The method according to claim 1, further comprising: means for introducing discharge power into the circle where the substrate is arranged; and discharge electrodes for introducing discharge power into the circle where the cylindrical substrate is arranged. 3. The deposition film forming method according to claim 1, wherein the substrate disposed in the reaction container is a plurality of cylindrical substrates, and the substrate has a plurality of discharge electrodes for introducing discharge power into the reaction container. . 4. The method according to claim 3, wherein the plurality of cylindrical substrates are arranged concentrically. 5. The deposited film forming method according to claim 1, wherein the first heating unit and / or the second heating unit of the substrate also serves as a cooling unit of the substrate. 6. The deposited film forming method according to claim 1, wherein a heating temperature of the first heating unit and a heating temperature of the second heating unit of the substrate are different. 7. The method according to claim 1, wherein the substrate has a cylindrical shape with a diameter of 40 mm or less and 16 mm or more. 8. The method according to claim 1, wherein the substrate has a cylindrical shape with a diameter of 30 mm or less and 16 mm or more.