JPH11172450A - Method and apparatus for forming deposited film - Google Patents

Abstract

(57) Abstract: The present invention enables a deposited film to be formed efficiently and at low cost without deteriorating the characteristics, and allows a plurality of types of deposited films to be produced without lowering production efficiency. An object of the present invention is to provide a method and an apparatus for forming a deposited film that can be produced and have excellent productivity. The present invention relates to a method or an apparatus for forming a deposited film, in which a source gas is decomposed by discharge power to form a deposited film on a substrate, comprising a reaction vessel capable of reducing pressure and a heating vessel capable of reducing pressure. After individually heating the substrate disposed in the heating container to a desired temperature, the heating container and the reaction container are connected, and the substrate in the heating container is moved into the reaction container to move the substrate. Installing the substrate in a reaction vessel, introducing a source gas and discharge power into the reaction vessel, and decomposing the source gas by the discharge power to form a deposited film on the substrate. is there.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a film deposited on a substrate by a plasma CVD method, in particular, a light receiving member for electrophotography,
Solar cells, image input line sensors, imaging devices,
The present invention relates to a method and an apparatus for forming a deposited film for forming a deposited film such as a semiconductor element such as a TFT.

[0002]

2. Description of the Related Art As one method of forming a deposited film, a CVD method using low-temperature plasma has been spotlighted. In this method, the pressure inside the reaction vessel is reduced to a high vacuum, the raw material gas is introduced into the reaction vessel, and then the discharge power is applied to decompose the raw material gas by glow discharge, and the deposited film is deposited on a substrate placed in the reaction vessel. Is applied to, for example, formation of an amorphous silicon film. In this method, silane gas (Si
An amorphous silicon film formed using H ₄ ) as a film-forming source gas has relatively few localized levels existing in the forbidden band of amorphous silicon, and can control valence electrons by doping impurities. Investigations have been continued to obtain photosensitive members having excellent characteristics.

[0003] Japanese Patent Publication No. 60-35059 discloses an electrophotographic light receiving member in which hydrogenated amorphous silicon is applied to a photoconductive portion. In addition, JP-A-62-2
Japanese Patent Publication No. 20874 discloses an apparatus for forming a deposited film by a plasma CVD method for forming such a light receiving member for electrophotography.

In such an apparatus for forming a deposited film by the plasma CVD method, it is common to form a deposited film by heating a substrate of an electrophotographic light-receiving member. It is common to provide a heating means inside. Japanese Patent Application Laid-Open No. 60-184678 discloses that a substrate of an electrophotographic light receiving member is heated and formed into a film while moving the substrate of the electrophotographic light receiving member between a plurality of vacuum containers using a vacuum container dedicated to transport. -An example of cooling is disclosed. Japanese Patent Publication No. 4-82186 discloses an example of moving a clean chamber and moving the semiconductor-related product between a plurality of clean chambers when processing and assembling a semiconductor-related product.

[0005]

SUMMARY OF THE INVENTION The present inventors have been studying a method of forming a deposited film having higher production efficiency in the above-described method of forming a deposited film.
In the method of performing the heating, film-forming, and cooling steps while moving the substrate of the electrophotographic light-receiving member between a plurality of vacuum containers using a dedicated vacuum container for transport, the timing of transporting the substrate is intimate, and the substrate transport is performed. Wait time occurs,
When electrophotographic light-receiving members of different prescriptions are formed by the same deposition film forming apparatus, the transfer sequence of the substrate becomes very complicated due to the different film formation time of each prescription, and the transfer sequence is reduced. It became apparent that problems such as the necessity of producing while changing each time, which complicates production. To cope with these problems, it is possible to provide a plurality of vacuum vessels dedicated to transport, but this requires extra equipment costs and workers, which raises the problem of increasing production costs.

Further, when a substrate is moved between a plurality of vacuum containers by using a vacuum container dedicated to the transfer, when the substrate is moved in the transfer container or between the transfer container and the vacuum container, dust is attached to the surface of the substrate. Adhered, and the dust adhered to the surface of the substrate caused an increase in the number of defects in the deposited film.
In particular, in recent years, in electrophotographic apparatuses, there has been a wide range of demands for miniaturization of electrophotographic light-receiving members as electrophotographic apparatuses are downsized, and improvement in characteristics of electrophotographic light-receiving members as copying speeds are increased. In response to these demands, there is a need for a method of flexibly and efficiently producing a plurality of types of light receiving members for electrophotography and at a low cost.

Accordingly, the present invention solves the above-mentioned problems, and enables a deposited film to be formed efficiently and at low cost without deteriorating characteristics. It is an object of the present invention to provide a method and an apparatus for forming a deposited film having excellent productivity, which can be produced without causing the generation.

[0008]

According to the present invention, in order to solve the above-mentioned problems, a method and an apparatus for forming a deposited film are constituted as follows. That is, the method for forming a deposited film of the present invention is a method for forming a deposited film in which a raw material gas is decomposed by discharge power to form a deposited film on a substrate, comprising a reaction vessel capable of reducing pressure and a heating vessel capable of reducing pressure. Individually, after heating the substrate disposed in the heating container to a desired temperature, connecting the heating container and the reaction container, moving the substrate in the heating container into the reaction container The method is characterized in that the substrate is placed in the reaction vessel, a source gas and discharge power are introduced into the reaction vessel, and the source gas is decomposed by the discharge power to form a deposited film on the substrate. In the method for forming a deposited film according to the present invention, the connection between the heating container and the reaction container is performed by moving one of the reaction container and the heating container to a position where the other container is installed. It is characterized by having. Further, the method of forming a deposited film according to the present invention is characterized in that the heating vessel and the reaction vessel each include an exhaust unit for individually exhausting the inside of the vessel. Further, the method of forming a deposited film according to the present invention is characterized in that the substrate disposed in the reaction vessel is constituted by a plurality of cylindrical substrates. Further, the method of forming a deposited film according to the present invention is characterized in that the plurality of cylindrical substrates are arranged concentrically. Further, the method for forming a deposited film of the present invention comprises:
The discharge power is introduced into the reaction vessel by a plurality of discharge electrodes arranged in the reaction vessel. Further, in the method of forming a deposited film according to the present invention, the heating container is characterized in that heating means for heating a substrate disposed in the heating container to a desired temperature is arranged around the substrate. I have. Further, the method for forming a deposited film according to the present invention is characterized in that the reaction vessel is provided with cooling means for cooling a substrate provided in the reaction vessel to a desired temperature.

Further, the apparatus for forming a deposited film according to the present invention is a deposited film forming apparatus for decomposing a raw material gas by discharge power to form a deposited film on a substrate, comprising at least a raw material gas and discharge power introduction means; Substrate support means, a decompressible reaction container having an exhaust portion for exhausting the inside, and at least a heating means, a decompressible heating container having an exhaust portion for exhausting the inside, each separately provided, and in the heating container After heating the arranged substrate to a desired temperature, the heating container and the reaction container are connected, the substrate in the heating container is moved into the reaction container, and the substrate is placed in the reaction container. A source gas and discharge power are introduced into the reaction vessel, and the source gas is decomposed by the discharge power to form a deposited film on the substrate. In the apparatus for forming a deposited film according to the present invention, the connection between the heating container and the reaction container may include a moving unit that moves one of the reaction container and the heating container to an installation position of the other container. It is characterized by being performed via Further, the apparatus for forming a deposited film according to the present invention is characterized in that the substrate disposed in the reaction vessel is constituted by a plurality of cylindrical substrates. Further, the apparatus for forming a deposited film according to the present invention is characterized in that the plurality of cylindrical substrates are arranged concentrically. Further, the apparatus for forming a deposited film according to the present invention is characterized in that the introduction of discharge power into the reaction vessel is performed by a plurality of discharge electrodes arranged in the reaction vessel.
Further, in the apparatus for forming a deposited film of the present invention, the heating vessel may include:
A heating means for heating a substrate disposed in the heating vessel to a desired temperature is disposed around the substrate. Further, the apparatus for forming a deposited film according to the present invention is characterized in that the reaction vessel is provided with cooling means for cooling a substrate provided in the reaction vessel to a desired temperature.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the present invention relates to a method for heating a substrate disposed in a separate reaction vessel and a heating vessel to a desired temperature. And the substrate in the heating vessel is moved into the reaction vessel to form a deposited film so as to achieve the above-mentioned object of the present invention. This is the result of the following intensive studies.
Usually, formation of a deposited film on a substrate is performed through steps of heating, film formation, and cooling. Therefore, rather than performing these steps continuously in one reaction vessel, performing the reaction vessels (vacuum vessels) separately for each step can shorten the overall tact time and improve productivity. . However, in order to move the substrate between the heating, film formation and cooling steps, a substrate is conventionally transferred from the heating vacuum container to the vacuum transfer container and then transferred into the reaction container using a vacuum transfer container. Then, it was necessary to use a procedure in which the substrate was temporarily transferred from the inside of the reaction container to the vacuum transfer container, and then transferred to the cooling vacuum container.

In the case where the vacuum transfer container is used as described above, dust floating in the vacuum transfer container may adhere to the surface of the substrate and cause a defect of the deposited film to increase. Also,
When a plurality of reaction vessels are provided in order to increase production efficiency or to cope with multi-product production, the sequence of transferring the substrates using a vacuum transfer container becomes complicated, and the timing for transferring the substrates to a plurality of reaction vessels becomes complicated. When they coincide with each other, there is a case where a waiting time for transporting the substrate occurs and the production efficiency is reduced. In particular, when producing a deposited film of a plurality of types of formulations using the same deposited film forming apparatus, the sequence of transferring the substrate by the vacuum transport container becomes more complicated, and the waiting time increases and the sequence is frequently increased. Or had to change. As a method for addressing this problem, there is a method using a plurality of vacuum transfer containers, but this causes an increase in investment amount and an increase in the number of workers, which causes a rise in production costs. was there.

On the basis of the above findings, the present inventors use at least one of a heating vacuum vessel and a reaction vessel, and connect them to use a means for directly transferring a substrate from the heating vacuum vessel to the reaction vessel. Thus, the above-described problem can be solved. That is, by not using the vacuum transfer container, it is possible to prevent dust from adhering to the substrate generated in the vacuum transfer container, and to reduce a factor of increasing the number of defects in the deposited film. Further, since the step of taking the substrate in and out of the vacuum transfer container is omitted, the tact time can be shortened accordingly, and the production efficiency can be increased. Also,
At the time when the heating is completed in the heating vacuum container, the substrate can be appropriately transferred into the reaction container. Therefore, the timing for transferring the substrate using the vacuum transfer container coincides, and a waiting time occurs. Such a problem does not occur.

Further, due to the miniaturization of the electrophotographic light receiving member, especially when a plurality of electrophotographic light receiving members are simultaneously formed in the same furnace, the substrate between the vacuum transfer container and the reaction container is required. High precision is required for the transfer of the liquid, it takes a long time to adjust the position of the vacuum transfer container and the reaction container,
There is a problem such as a need to transfer the substrate at a low speed, thereby lowering productivity, and reducing the number of times the substrate is transferred is a great merit. In addition, in the case where the substrate is cooled after the formation of the deposited film on the substrate in the reaction container is completed, the substrate is transferred from the reaction container to the cooling vacuum container in the same manner as in the case of heating the substrate. Alternatively, the production efficiency can be improved by separating the reaction vessel from the deposition film forming apparatus and cooling the substrate, and attaching a separate reaction vessel to the deposition film forming apparatus to form the deposition film. It is also possible to improve
According to the present invention, it is possible to flexibly change the production sequence as needed to obtain optimal production efficiency. In particular, when a plurality of types of reaction vessels are prepared to form a variety of electrophotographic light-receiving members, production tact is hardly affected by the type of electrophotographic light-receiving members, so that stable production can be achieved. It is effective for

The method of forming a deposited film according to the present invention will be described in more detail with reference to the drawings. FIG. 1 shows an apparatus 1 for forming a deposited film of a light receiving member for electrophotography using the deposited film forming method of the present invention.
It is the figure which showed the longitudinal cross section of the example typically. The formation of a deposited film using this apparatus can be performed, for example, as follows. In FIG. 1, reference numeral 101 denotes a heating vessel, which is connected to an exhaust device (vacuum pump) 107 via an exhaust pipe 106. The heating container 101 may have any structure as long as it has a vacuum-tight structure, and any shape may be used, but a shape such as a cylinder or a rectangular parallelepiped is generally used. The material is preferably a metal such as Al or stainless steel from the viewpoint of mechanical strength and the like.

The base 102 of the light receiving member for electrophotography installed in the heating vessel 101 is heated to a desired temperature, for example, 50 to 400 ° C. by the heater 103. At this time, if necessary, an inert gas such as nitrogen gas, Ar gas, or He gas is supplied from an inert gas supply system (not shown) to the heating vessel 10.
1 may be flowed. Reference numeral 111 denotes a reaction vessel provided in the heating area 110 for forming a deposited film, and is connected to an exhaust device (vacuum pump) 117 via an exhaust pipe 116. The reaction container 111 may have a vacuum-tight structure, and the shape thereof may be a base 112 of a light-receiving member for electrophotography.
When the shape of the base 112 is cylindrical or when a plurality of bases 112 are arranged on the same circumference, the cylindrical shape of the reaction vessel 111 is also generally used. Can be The material is desirably a metal such as Al or stainless steel from the viewpoint of mechanical strength and when the electrode also serves as a high-frequency electrode.

Gate valve 10 provided in heating vessel 101
After connecting the gate valve 114 provided in the reaction vessel 111 to the gate valve 104, the gate valves 104 and 114 are opened, and the substrate 102 of the light receiving member for electrophotography in which heating in the heating vessel 101 is completed is moved by the substrate moving device 105. It is transferred into the reaction vessel 111 and installed. Base 112 of electrophotographic light-receiving member
Is completed, the gate valve 114 is closed, and the reaction vessel 111 moves to a predetermined film formation area 120. A source gas introduction pipe 125 connected to a source gas supply system (not shown) including a source gas cylinder, a pressure regulator, a mass flow controller, a valve, and the like is connected to a reaction vessel 121 provided in the film formation area 120. To supply the source gas. 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 desired flow rate, the evacuation speed of the evacuation device 127 connected via the evacuation pipe 126 is adjusted while observing the vacuum gauge 128 to obtain a desired internal pressure. The substrate 122 is heated to a temperature required for forming a deposited film, for example, 50 to 400 ° C., by a substrate heating heater 123 provided as needed.
Alternatively, a substrate cooling mechanism 123 provided as needed
Thereby, the substrate is cooled so that the temperature of the substrate does not rise to a desired temperature or more when the deposited film is formed.

A reaction vessel 121 also serving as a high-frequency electrode is connected to a high-frequency power supply (not shown, via a matching box 129).
(For example, 0.2 to 450 MHz). When the internal pressure in the reaction vessel 121 is stabilized, the high-frequency power supply is set to a desired power, and high-frequency power is supplied between the reaction vessel 121 also serving as a high-frequency electrode through the matching box 129 and the base 122 of the electrophotographic light-receiving member. By applying the voltage, a glow discharge is generated in the reaction vessel 121. The source gas introduced into the reaction vessel 121 is decomposed by the discharge energy, and a predetermined deposited film is formed on the base 122. At this time, in order to further increase the uniformity of the film thickness and film characteristics in the circumferential direction, the substrate 1 is rotated at a desired rotation speed by a substrate rotation motor (not shown).
It is also effective to rotate 22. After the formation of the desired film thickness, the supply of the high-frequency power is stopped, and the reaction vessel 12 is turned off.
The flow of the source gas into 1 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 configuration can be obtained by repeating the above operation.

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 in the heating vessel used in the present invention and the heater for heating the substrate optionally provided in the reaction vessel may be any of those having a vacuum specification, such as a sheath heater, a plate-shaped heater, and a ceramic heater. In addition to an electric resistor such as the above, a heat radiator such as a halogen lamp, a heating element using a heat exchange means mediated by gas or liquid, or the like can be used. The shape of the heater for heating the substrate may be any shape, but when heating the substrate from the inside, it is preferably similar to the shape of the substrate, and is preferably cylindrical. Further, when the substrate in the heating vessel is externally heated, a shape corresponding to the arrangement of the substrate is desirable, and when a plurality of substrates are disposed on the same circumference, a cylindrical shape is desirable. The material for the surface of the heater for heating the substrate may be any material, but metals such as Al, stainless steel, Ti, and inconel are desirable from the viewpoint of mechanical strength, heat resistance, thermal conductivity and the like. Furthermore, depending on the conditions for forming the deposited film in the reaction vessel, a mechanism for cooling the substrate during the formation of the deposited film may be provided so that the temperature of the substrate surface does not rise excessively.
As a method of cooling the substrate, it is preferable to use a heat exchange means mediated by a gas or a liquid, and 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 referred to as "a-Si") film, in a gas state such as SiH ₄ or Si ₂ H ₆ , or in a gas state. Silicon hydride (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, or SiH ₃ F A gaseous or gasifiable substance such as fluorine-substituted silicon hydride such as SiH ₂ F ₂ and SiHF ₃ is also effective as a silicon-introducing gas of the present invention.

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. Also effective as a gas for introducing a halogen for causing the a-Si film to contain a halogen atom are, for example, a halogen gas,
Gaseous or gasifiable halogen compounds such as halides, interhalogen compounds containing halogen, and silane derivatives substituted with halogen 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, ClF, ClF ₃ , B
Inter-halogen compounds such as rF ₃ , BrF ₅ , IFF ₃ and IF ₇ can be mentioned. As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, specifically, for example, silicon fluoride such as SiF ₄ or Si ₂ F ₆ can be mentioned as a preferable example.

In the present invention, the above-mentioned halogen compound or a silicon compound containing a halogen atom is effectively used as the halogen-introducing gas. In addition, HF, HCl, HBr, HI, etc. Hydrogen halide, SiH ₃ F, SiH ₂ F ₂ , SiHF ₃ , SiH
₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , S
Halogen-substituted silicon hydrides such as iHBr ₃ , and halides in which a hydrogen atom is one of the constituent elements in a gas state or capable of being gasified can also be mentioned as an effective source gas. In these halides containing hydrogen atoms, since hydrogen atoms are introduced together with the halogen atoms, they are used as a suitable halogen atom introduction gas in the present invention. Further, other than the above, H ₂ , D ₂ or SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H _10, etc. are effective as a hydrogen introduction gas for causing the a-Si film to contain hydrogen atoms. Silicon hydride.

Further, in addition to the above-mentioned gas, 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 “A”), if necessary. An element that controls conductivity,
It can also be used as a so-called dopant.

Specific examples of the Group 3 element 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, B ₂ H ₆ , B ₄
Borohydride of H _10, etc., BF _3, boron halides such as BCl ₃ and the like. Other Group 3 element introduction gases include AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl
₃ , TICl _{3 and the} like. Phosphorus-introducing gases include phosphorus hydride such as PH ₃ and P ₂ H ₄ , PH ₄ I, P
Phosphorus halides such as F ₃ , PCl ₃ , PBr ₃ and Pl ₃ can be used. As another Group 5 element introduction gas, AsH
_{3, AsF 3, AsCl 3,} AsBr 3, AsF 5, Sb
_{H 3, SbF 3, SbF 5} , SbCl 3, SbCl 5, Bi
H ₃ , BiCl ₃ , BiBr _{3 and the} like can also be mentioned.

The gas for introducing an element for controlling the conductivity may be used after being diluted with H ₂ and / or He, if necessary. For example, in the case of forming amorphous silicon carbide (a-SiC), in addition to the above-mentioned raw material gas, as a gas for introducing carbon atoms,
For example, saturated hydrocarbons having 1 to 5 carbon atoms, ethylene-based hydrocarbons having 2 to 4 carbon atoms, acetylene-based hydrocarbons having 2 to 3 carbon atoms, and the like having C and H as constituent atoms can be used. Specifically, methane (CH ₄ ), ethane (C ₂ H ₆ ) and the like as saturated hydrocarbons, and ethylene (C ₂ H ₄ ) and propylene (C ₃ H ₆ ) as ethylene-based hydrocarbons. Examples of the acetylene hydrocarbon include acetylene (C ₂ H ₂ ) and methyl acetylene (C ₃ H ₄ ).

Also, for example, amorphous silicon oxide
When (a-SiO) is formed, the above-mentioned raw material gas
In addition, one that can be used as a gas for introducing oxygen atoms
And oxygen (O_Two),ozone( O_Three), Nitric oxide (N
O), nitrogen dioxide (NO_Two), Nitrogen monoxide (N_TwoO),
Nitrogen dioxide (N_TwoO_Three), Nitrogen tetroxide (N_TwoO_Four)
Nitric oxide (N_TwoO_Five), Nitric oxide (NO_Three),silicon
Atoms (Si), oxygen atoms (O) and hydrogen atoms (H)
For example, disiloxane (H_ThreeSiOSi
H_Three), Trisiloxane (H_ThreeSiOSiH_TwoOSiH_Three)
And the like.

In the present invention, when amorphous silicon nitride (a-SiN) is formed, for example, nitrogen (N ₂ ), ammonia Nitrogen compounds such as gaseous or gasifiable nitrogen, such as (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), and ammonium (NH ₄ N ₃ ), nitrogen and azide. be able to. In addition, nitrogen trifluoride (F ₃
N) and nitrogen halide compounds such as nitrogen tetrafluoride (F ₄ N ₂ ).

The following are typical examples of the layer structure when a light-receiving member for electrophotography is prepared by using the present invention. FIG. 4 is a schematic configuration diagram for explaining a layer configuration. The electrophotographic light receiving member 400 shown in FIG.
A containing hydrogen and / or halogen on a substrate 401
A photoconductive layer 402 made of -Si (hereinafter, referred to as "a-Si (H, X)") and having photoconductivity is provided.
An electrophotographic light receiving member 400 shown in FIG. 4B has a photoconductive layer 402 made of a-Si (H, X) and having photoconductivity, an amorphous silicon-based surface layer 403 formed on a base 401. It is composed of An electrophotographic light-receiving member 400 shown in FIG.
Photoconductive layer 402 made of i (H, X) and having photoconductivity
, An amorphous silicon-based surface layer 403, and an amorphous silicon-based charge injection blocking layer 404. An electrophotographic light receiving member 400 shown in FIG.
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).
An amorphous silicon-based surface layer 403 is provided thereon. The electrophotographic light receiving member 40 shown in FIG.
0 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 is composed of a system upper blocking layer.

The substrate of the light receiving member for electrophotography 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 the thickness thereof is appropriately determined so that a desired electrophotographic light-receiving member 400 can be formed. 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 base 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, etc., in order to eliminate image defects due to interference fringe patterns appearing in a visible image, Japanese Patent Application Laid-Open No. No. 168156, 60-178
No. 457, No. 60-225854 and the like.

The photoconductive layer in the layer structure of the electrophotographic light-receiving member will be described. The photoconductive layer 402 is formed on a substrate 401 by appropriately setting the film forming parameters so as to obtain desired characteristics. Is done. Photoconductive layer 4
In order to form 02, a gas for introducing silicon and a gas for introducing hydrogen and / or a gas for introducing halogen as described above are basically introduced into a deposition chamber in a desired gas state.
A glow discharge is generated in the deposition chamber, and a-Si discharges on a predetermined substrate 401 previously set at a predetermined position.
A layer made of (H, X) is formed. Also, the photoconductive layer 4
02 contains hydrogen atoms and / or halogen atoms in the a-Si film to compensate for dangling bonds of Si atoms and to improve layer quality, particularly to improve photoconductivity and charge retention characteristics. It is indispensable. 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 desirably 1 to 40 atom%, and more preferably 5 to 35 atom%.

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. Photoconductive layer 402
Preferably contains an element for controlling conductivity as necessary. The element that controls the conductivity is the photoconductive layer 40.
2 may be contained in a state of being uniformly distributed without unevenness, or there may be a part contained in a non-uniform distribution state in the layer thickness direction.

As the element for controlling the conductivity, the aforementioned
Group 3 element or Group 5 element can be used.
You. Element for controlling conductivity contained in photoconductive layer 402
Is preferably 1 × 10^-2~ 1 × 10^Two
Atomic ppm, more preferably 5 × 10^-2~ 50 atom pp
m, optimally 0.1 to 10 atomic ppm
New Elements that control conductivity, such as Group 3 elements
Alternatively, in order to introduce the Group V element structurally,
The gas for introducing a Group 3 element or the Group 5 element
The introduction gas was introduced into the deposition chamber to form the photoconductive layer 402.
It may be introduced together with other gases.

Further, carbon atoms and / or
Alternatively, it is also effective to contain an oxygen atom and / or a nitrogen atom. The content of carbon atoms and / or oxygen atoms / and / or nitrogen atoms is preferably 1 × 10 ⁻⁵ to 30 at%, more preferably 1 × 10 ^{−4 to} 20 at%, and most preferably 1 × 10 ⁻³ to 10 at% is desirable. Carbon atoms and / or
Alternatively, oxygen atoms and / or nitrogen atoms are
2 may be uniformly contained in the photoconductive layer 4.
02 may have a non-uniform distribution such that the content changes in the thickness direction.

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 layer 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 6 μm.
It is desirable that the thickness be 0 μm, most preferably 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 optimal range of the temperature (Ts) of the base 401 is appropriately selected according to the layer design.
It is desirable that the temperature be 400 ° C, more preferably 150 to 350 ° C, and most preferably 200 to 300 ° C. Similarly, the gas pressure in the deposition chamber is appropriately selected in an optimum range according to the layer design.
a, more preferably 0.05 to 500 Pa, and most preferably 0.1 to 100 Pa. Photoconductive layer 40
Desirable numerical ranges of the substrate temperature and the gas pressure for forming 2 include the above-mentioned ranges. In addition, the mixing ratio with the gas for introducing silicon and the gas for introducing other atoms, the discharge power, and the like are appropriately set. It is necessary to. These conditions are not usually 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.

The surface layer in the layer structure of the electrophotographic light-receiving member will be described.
It is preferable to further form an amorphous silicon-based surface layer 403 on the photoconductive layer 402 formed on the photoconductive layer 01. 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-based material. For example, amorphous silicon (H) and / or halogen atom (X) and further contains carbon atoms Hereinafter, referred to as “a-SiC (H, X)”), a hydrogen atom (H) and / or a halogen atom (X)
And further contains an oxygen atom-containing amorphous silicon (hereinafter referred to as “a-SiO (H, X)”), a hydrogen atom (H) and / or a halogen atom (X),
It further contains amorphous silicon containing nitrogen atoms (hereinafter referred to as “a-SiN (H, X)”), hydrogen atoms (H) and / or halogen atoms (X), and further contains carbon atoms, oxygen atoms, and nitrogen atoms. Amorphous silicon containing at least one of the atoms (hereinafter referred to as “a-Si (C, O,
N) (H, X) ").

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, a-SiC
In order to form the surface layer 403 made of (H, X), basically, the above-described gas for introducing a silicon atom, the gas for introducing a carbon atom, the gas for introducing a hydrogen atom and / or the gas for introducing a halogen atom are used. Is introduced in a desired gas state into a deposition chamber in which the inside can be reduced in pressure to generate a glow discharge in the deposition chamber, and a photoconductive layer 40 previously set at a predetermined position is generated.
A layer made of a-SiC (H, X) may be formed on the base 401 on which the substrate 2 is formed. The surface layer 403 is a-Si
When (C, O, N) (H, X) is the main component, the content of carbon and / or oxygen and / or nitrogen is preferably in the range of 1% to 90%, and more preferably 5% to 7%.
0% is more preferable, and optimally 10% to 50% is desirable.

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 raw material used to contain the hydrogen atoms and / or halogen atoms, and the like into a deposition chamber. The amount to be introduced, 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 may be contained in the layer in the 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
0 ² atomic ppm, optimally 1 × 10 ^-2 to 1 × 10 ² atomic p
pm. In order to structurally introduce an element for controlling conductivity, for example, a group 3 element or a group 5 element, the above-mentioned gas for introducing a group 3 element or a gas for introducing a group 5 element may be used in forming a layer. May be introduced into the deposition chamber together with another gas for forming the surface layer 403. The layer thickness of the surface layer 403 is usually 0.01 to
3 μm, preferably 0.05-2 μm, optimally 0.1-
It is desirable that the thickness be 1 μm. Layer thickness is 0.0
If the thickness is less than 1 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 m, a decrease in electrophotographic characteristics such as an increase in residual potential is observed.

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, to provide the surface layer 403 mainly for the purpose of improving the pressure resistance,
It is made as a non-single-crystal material with a remarkable electrical insulating behavior in the use environment. In the case where the surface layer 403 is provided for the purpose of mainly improving continuous repetition use characteristics and use environment characteristics, the degree of the above-described electrical insulation is reduced to some extent, and a certain degree of sensitivity to irradiated light is obtained. Is formed as a non-single-crystal material. In order to form the surface layer 403 having characteristics capable of achieving the purpose, 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 250 to 300 ° C.
Similarly, the gas pressure in the deposition chamber is appropriately selected in an optimum range according to the layer design.
~ 1000Pa, more preferably 0.05 ~ 500P
a, optimally, 0.1 to 100 Pa is preferable.
Desirable numerical ranges of the substrate temperature and the gas pressure for forming the surface layer 403 include the above-mentioned ranges. However, the conditions are usually not independently determined separately, and the electrophotographic light having desired characteristics is usually not separately determined. It is desirable to determine the optimum value based on mutual and organic relationships to form the receiving member. Further, 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 adhesion between the surface layer and the photoconductive layer 402 can be improved, the influence of interference due to the reflection of light at the interface can be reduced, and at the same time, the trapping of carriers at the interface can be prevented. An improvement in the properties of the receiving member can be achieved.

The charge injection preventing layer in the layer structure of the electrophotographic light receiving member functions to prevent the injection of charges from the conductive substrate side between the conductive substrate and the photoconductive layer 402, if necessary. A charge injection blocking layer 404 having a shape may be provided. That is, the charge injection blocking layer 404 has a function of preventing charge from being injected from the substrate side to the photoconductive layer 402 side when the electrophotographic photoreceptor 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 is provided with an element for controlling conductivity in the photoconductive layer 40.
The content is relatively large compared to 2.

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 throughout the layer, or may be uniformly distributed in the layer thickness direction. 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 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.

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 atomic ppm, Preferably 50 to
5 × 10 ³ atomic ppm, optimally 1 × 10 ^{2 to} 3 × 10 ³
Desirably, it is set to 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 directly contacted. It is possible to further improve the adhesiveness with another layer provided. 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.

The content of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in the entire region of the charge injection blocking layer 404 and / or the upper blocking layer 407 is appropriately determined so as to obtain desired film characteristics. However, in the case of one kind, the amount is used, and in the case of two or more kinds, the sum is preferably 1 × 10 ⁻³ to 50 at%, more preferably 5 × 10 ³ atomic%.
^-3 to 30 atomic%, optimally 1 × 10 ^-2 to 10 atomic%. Further, the charge injection blocking layer 404 and / or
Alternatively, hydrogen atoms contained in upper blocking layer 407 and / or
Alternatively, the halogen atom compensates for dangling bonds existing in the layer and is 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 as follows:
Preferably, it is 1 to 50 at%, more preferably 5 to 40 at%, and most preferably 10 to 30 at%.

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 0.01 from the viewpoints of obtaining desired electrophotographic characteristics and economical effects.
It is desirable that the thickness be 3 to 3 μm, more preferably 0.05 to 2 μm, 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 gas pressure in the deposition chamber is appropriately selected in an optimum range, 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 Layer formation factors such as a mixing ratio of a diluent gas, a gas pressure, a discharge power, a substrate temperature, and the like for forming the charge injection blocking layer 404 and / or the upper blocking layer 407 are not usually independently determined separately. It is desirable to determine the optimum value of each layer formation factor based on mutual and organic relationships to form the charge injection blocking layer 404 and / or the top blocking layer 407 having desired properties. For the purpose of further improving the adhesion between the base 401 and the photoconductive layer 402 or the charge injection blocking layer 404, for example, Si ₃ N ₄ , SiO ₂ , SiO, or a silicon atom as a base, An adhesion layer made of an amorphous material containing a halogen atom and / or 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.

[0051]

Embodiments of the present invention will be described below. Example 1 In the deposition film forming apparatus shown in FIG. 1, an aluminum cylindrical substrate 102 having a diameter of 80 mm was set in a heating vessel 101, and the cylindrical substrate 102 was heated to 300 ° C. by a heater 103. Next, the heating container 10
1 and the reaction vessel 111 were connected, and the cylindrical substrate 102 in the heating vessel 101 was transferred into the reaction vessel 112. Next, the reaction vessel 111 is moved to the film formation area 120 and the cylindrical substrate 1 is moved.
An a-Si film was formed on the film 22 according to the film forming conditions shown in Table 1 to prepare a light receiving member for electrophotography having a layer structure shown in FIG. Five sets of the reaction vessels 121 are installed, and
By repeating this process 20 times, 20 light receiving members for electrophotography were prepared.

Comparative Example 1-1 In the deposited film apparatus shown in FIG. 5, an aluminum cylindrical substrate 502 having a diameter of 80 mm was set in a heating vessel 501, and a heater 503 was used.
Thereby heating the cylindrical substrate 502 to 300 ° C. next,
The heating container 501 and the transfer container 511 are connected to each other to
01 was transferred into the transfer container 511. Next, the transfer container 511 is moved to a position above the reaction container 521, the transfer container 511 is connected to the reaction container 521, and the cylindrical substrate 512 in the transfer container 511 is transferred into the reaction container 521. A light receiving member for electrophotography was prepared according to the same film forming conditions as in Example 1 with a -Si film. Five sets of the reaction vessels 521 were set up, and this operation was repeated four times to produce 20 electrophotographic light-receiving members.

(Comparative Example 1-2) In the deposited film apparatus shown in FIG. 6, an aluminum cylindrical substrate 602 having a diameter of 80 mm was set in a heating vessel 601, and a heating heater 603.
The cylindrical substrate 602 was heated to 300.degree. next,
The heating container 601 is connected to the transfer container 611, and the heating container 6
The cylindrical substrate 602 in the container 01 was transferred into the transfer container 611. Next, the transfer container 611 is moved to above the reaction container 621, the transfer container 611 is connected to the reaction container 621, and the cylindrical substrate 612 in the transfer container 611 is transferred into the reaction container 621, and a is placed on the cylindrical substrate 622. A light receiving member for electrophotography was prepared according to the same film forming conditions as in Example 1 with a -Si film. Two sets of the transfer containers 611 and five sets of the reaction containers 621 were provided, and this operation was repeated four times to produce 20 electrophotographic light-receiving members.

The light receiving members for electrophotography prepared in Example 1 and Comparative Example 1 were evaluated by the following methods. The surface of each light receiving member for electrophotography is observed with an optical microscope, the number of spherical protrusions having a diameter of 10 μm or more per 10 cm square is checked, and the average value of the number of spherical protrusions of each light receiving member for electrophotography is calculated. did. The smaller the number of spherical projections, the smaller the number of image defects and the higher the image quality. As a result, the number of spherical projections of the electrophotographic light receiving member of Example 1 was 0.89 times the number of spherical projections of the electrophotographic light receiving member of Comparative Example 1-1. The number of spherical projections of the light receiving member for photography is 1.03.
As compared with the electrophotographic light receiving member of Comparative Example 1, it was found that the electrophotographic light receiving member of Example 1 had less image defects.

Further, in Example 1, the same number of electrophotographic light-receiving members as in Comparative Example 1-1 were used to prepare the same number of electrophotographic light-receiving members.
It was created in 93 times the time. In contrast to Comparative Example 1-2, in Example 1, it took approximately the same time to produce the same number of electrophotographic light receiving members, but in Comparative Example 1-2, an extra number of transport containers 611 and workers were required. It was necessary to prepare it, and the deposition film forming method of Example 1 was more excellent in production efficiency. From the above results, according to the present invention, it is possible to efficiently form a deposited film having excellent properties, and it is possible to form an excellent electrophotographic light-receiving member at low cost by using this deposited film. There was found.

[0056]

[Table 1] [Example 2] In Example 1, three sets of reaction vessels 121 were used.
The same electrophotographic light-receiving member as in Example 1
This was prepared, and two sets of reaction vessels 121 were used to obtain a diameter of 1
Eight electrophotographic light-receiving members were prepared using a 08 mm aluminum cylindrical substrate 122 under the film forming conditions shown in Table 2.

(Comparative Example 2) In Comparative Example 1-1, twelve electrophotographic light-receiving members similar to those of Comparative Example 1-1 were prepared using three sets of reaction vessels 521, and two sets of reaction vessels were further prepared. 5
21 and a cylindrical substrate 522 made of aluminum having a diameter of 108 mm in accordance with the film forming conditions shown in Table 2.
An electrophotographic light-receiving member for a book was prepared. The light receiving member for electrophotography produced in Example 2 and Comparative Example 2 was evaluated in the same procedure as in Example 1. As a result, the number of spherical projections of the electrophotographic light receiving member of Example 2 was 0.91 times the number of spherical projections of the electrophotographic light receiving member of Comparative Example 2. In No. 2, the same number of light receiving members for electrophotography could be prepared in 0.85 times as long. From the above results, according to the present invention, it is possible to efficiently form a deposited film having excellent properties, and it is possible to form an excellent electrophotographic light-receiving member at low cost by using this deposited film. There was found.

[0058]

[Table 2] Example 3 In the deposition film forming apparatus shown in FIG. 2, an aluminum cylindrical body 202 having a diameter of 80 mm was set in a heating vessel 201, and the cylindrical body 202 was heated to 300 ° C. by a heater 203. Next, the heating container 20
1 to the film formation area 220 and connect the heating vessel 201 and the reaction vessel 221 to connect the cylindrical substrate 2 in the heating vessel 201.
02 was transferred into the reaction vessel 221, and a light receiving member for electrophotography was formed on the cylindrical substrate 222 in the same manner as in Example 1.
Five sets of the reaction vessels 221 were set up, and this operation was repeated four times to produce 20 electrophotographic light-receiving members.
The light receiving member for electrophotography prepared in Example 3 was evaluated in the same procedure as in Example 1. As a result, a light receiving member for electrophotography having the same characteristics as in Example 1 could be prepared in the same time as in Example 1. From the above results, according to the present invention, it is possible to efficiently form a deposited film having excellent properties, and it is possible to form an excellent electrophotographic light-receiving member at low cost by using this deposited film. There was found.

Example 4 In the deposition film forming apparatus shown in FIG. 3, ten cylindrical substrates 302 made of aluminum having a diameter of 30 mm were set in a heating vessel 301, and the cylindrical substrates 302 were heated by a heater 303. Heated to ° C. Next, the heating vessel 301 and the reaction vessel 311 are connected, and the cylindrical substrate 302 in the heating vessel 301 is connected to the reaction vessel 311.
It was transferred inside. Next, the reaction vessel 311 is placed in the film formation area 320.
Then, a light receiving member for electrophotography was prepared in the same manner as in Example 1 except that the film was formed on the cylindrical substrate 322 according to the film forming conditions shown in Table 3. Three sets of the reaction vessels 321 are set up, and this operation is repeated 5 times to obtain 15 lots (150 pieces).
Was prepared.

COMPARATIVE EXAMPLE 3 In the deposition film apparatus shown in FIG. 7, ten cylindrical substrates 702 made of aluminum having a diameter of 30 mm were set in a heating vessel 701 and a heating heater
03 heated the cylindrical substrate 702 to 250 ° C. Next, the heating container 701 and the transfer container 711 were connected, and the cylindrical substrate 702 in the heating container 701 was transferred into the transfer container 711. Next, the transfer container 711 is moved to a position above the reaction container 721, the transfer container 711 is connected to the reaction container 721, the cylindrical substrate 712 in the transfer container 711 is transferred into the reaction container 721, and a is placed on the cylindrical substrate 722. A photoreceptor member for electrophotography was prepared according to the same film forming conditions as in Example 4 using a -Si film. Three sets of the reaction vessels 721 were set up, and this operation was repeated five times to produce 15 lots (150 pieces) of electrophotographic light-receiving members. The light receiving member for electrophotography produced in Example 4 and Comparative Example 3 was evaluated in the same procedure as in Example 1. As a result, the number of spherical projections of the electrophotographic light receiving member of Example 4 was 0.87 times the number of spherical projections of the electrophotographic light receiving member of Comparative Example 3. In No. 4, the same number of electrophotographic light receiving members could be formed in 0.81 times as long. based on the above results,
According to the present invention, it has been found that a deposited film having excellent properties can be efficiently formed, and that an excellent light receiving member for electrophotography can be formed at a low cost by using this deposited film.

[0061]

[Table 3] Fifth Embodiment The third embodiment is the same as the deposition film forming apparatus shown in FIG. 3 except that a substrate cooling mechanism 323 is provided inside a cylindrical substrate 322 in a reaction vessel 321 and the film is formed under the film forming conditions shown in Table 4. A light-receiving member for electrophotography was prepared in the same manner as described above. Three sets of the reaction vessels 321 were set up, and this operation was repeated six times to produce 18 lots (180 pieces) of electrophotographic light receiving members. The light receiving member for electrophotography prepared in Example 5 was evaluated in the same procedure as in Example 4. As a result, a light receiving member for electrophotography having the same characteristics as in Example 4 could be produced in the same time as in Example 4. From the above results, according to the present invention, it is possible to efficiently form a deposited film having excellent properties, and it is possible to form an excellent electrophotographic light-receiving member at low cost by using this deposited film. There was found.

[0062]

[Table 4]

[0063]

As described above, according to the present invention, the reaction vessel and the heating vessel are separately provided, and after heating the substrate disposed in the heating vessel to a desired temperature, the heating vessel and the reaction vessel are heated. And connecting the substrate directly from the heating vacuum container to the reaction container without using a vacuum transfer container, thereby preventing dust generated in the vacuum transfer container from adhering to the substrate. It is possible to reduce the cause of the increase in the number of defects in the deposited film. Further, in the present invention, the above configuration eliminates the step of taking the substrate in and out of the vacuum transfer container, so that the tact time can be reduced by that amount, and the production efficiency can be increased. At the time when the heating is completed, it is possible to appropriately transfer the substrate into the reaction vessel, particularly when preparing a plurality of types of reaction vessels to form a multi-type electrophotographic light-receiving member, As in the case of using a vacuum transfer container, the timing for transferring the substrates does not coincide with each other, so that a waiting time does not occur, and a deposited film having excellent characteristics is stably produced without lowering the production efficiency. It becomes possible. Further, in the present invention, the above configuration eliminates the step of taking the substrate in and out of the vacuum carrying container, so that the size of the electrophotographic light receiving member can be reduced, and in particular, a plurality of electrophotographic light receiving members can be used. In the case of simultaneous film formation in the same furnace, for example, when a vacuum transfer container is used, high precision is required for transferring the substrate between the vacuum transfer container and the reaction container. It is possible to efficiently produce a deposited film without causing a problem that a long time is required for the adjustment.

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

FIG. 3 is a schematic view showing one example of a deposited film forming apparatus of the present invention.

FIG. 4 is a schematic view showing an example of a layer configuration of a light receiving member for electrophotography prepared according to the present invention.

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

FIG. 6 is a schematic view showing an example of a conventional deposited film forming apparatus.

FIG. 7 is a schematic view showing an example of a conventional deposited film forming apparatus.

[Explanation of symbols]

101, 201, 301, 501, 601, 701: Heating vessel 102, 202, 302, 502, 602, 702: Substrate 103, 203, 303, 503, 603, 703: Heating heater 104, 204, 304, 504, 604 , 704: Gate valve 105, 205, 305, 515, 615, 715: Substrate moving device 106, 206, 306, 506, 606, 706: Exhaust pipe 107, 207, 307, 507, 607, 707: Exhaust device 108, 208, 308, 508, 608, 708: Vacuum gauge 110, 310: Heating area 111, 311, 511, 611, 711: Reaction vessel 112, 312, 512, 612, 712: Substrate 113, 313: Heater 114, 314 , 514, 614, 714: Gate valves 116, 316, 516, 616, 716: Exhaust pipe 117, 317, 517, 617, 717: Exhaust device 118, 318, 518, 618, 718: Vacuum gauge 120, 220, 320: Film formation area 121, 221, 321, 521, 621 , 721: Reaction vessel 122, 222, 322, 522, 622, 722: Substrate 123, 223, 323, 523, 623, 723: Heating / substrate cooling mechanism 124, 224, 324, 524, 624, 724: Gate valve 125, 225, 325, 525, 625, 725: source gas introduction pipe 126, 226, 326, 526, 626, 726: exhaust pipe 127, 227, 327, 527, 627, 727: exhaust device 128, 228, 328, 528, 628, 728: Vacuum gauge 129, 229, 529, 629: Ching boxes 319, 329, 729: Discharge electrodes 519: Transport rail 400: Photoreceptor for electrophotography 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

 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Kazuhiko Takada 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Ryuji Okamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor: Toshiyasu Shirasuna 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (15)

[Claims] 1. A method for forming a deposited film, wherein a source gas is decomposed by discharge power to form a deposited film on a substrate, the method comprising separately providing a decompressible reaction vessel and a decompressible heating vessel, After heating the substrate disposed in the container to a desired temperature, the heating container and the reaction container are connected, and the substrate in the heating container is moved into the reaction container, and the substrate is placed in the reaction container. Wherein a source gas and discharge power are introduced into the reaction vessel, and the source gas is decomposed by the discharge power to form a deposited film on the substrate. 2. The connection between the heating vessel and the reaction vessel,
2. The method according to claim 1, wherein one of the reaction container and the heating container is moved to an installation position of the other container. 3. The deposition film forming method according to claim 1, wherein the heating vessel and the reaction vessel each have an exhaust portion for individually exhausting the inside of the vessel. . 4. The formation of a deposited film according to claim 1, wherein the substrate disposed in the reaction vessel is composed of a plurality of cylindrical substrates. Method. 5. The method according to claim 4, wherein the plurality of cylindrical substrates are arranged on concentric circles. 6. The method according to claim 1, wherein the introduction of the discharge power into the reaction vessel is performed by a plurality of discharge electrodes arranged in the reaction vessel. The method for forming a deposited film according to the above. 7. The heating container according to claim 1, wherein a heating means for heating a substrate disposed in the heating container to a desired temperature is disposed around the substrate. 6
The method for forming a deposited film according to any one of the above items. 8. The reaction vessel according to claim 1, wherein said reaction vessel is provided with a cooling means for cooling a substrate provided in said reaction vessel to a desired temperature. The method for forming a deposited film according to the above. 9. A deposition film forming apparatus for decomposing a source gas by a discharge power to form a deposition film on a substrate, comprising: at least a source gas and a discharge power introduction unit; a substrate support unit; A pressure-reducing reaction vessel having at least a heating means and a pressure-reducing heating vessel having an exhaust part for exhausting the inside of the reaction vessel, wherein the substrate disposed in the heating vessel is heated to a desired temperature. After that, the heating vessel and the reaction vessel are connected to each other, the substrate in the heating vessel is moved into the reaction vessel, and the substrate is placed in the reaction vessel. A deposition film formed on the base by decomposing a source gas by the discharge power and forming a deposition film on the substrate. 10. The connection between the heating vessel and the reaction vessel is made via a moving means for moving one of the reaction vessel and the heating vessel to a position where the other vessel is installed. The apparatus for forming a deposited film according to claim 9. 11. The apparatus for forming a deposited film according to claim 9, wherein the substrate disposed in the reaction vessel is constituted by a plurality of cylindrical substrates. 12. The deposition film forming apparatus according to claim 11, wherein said plurality of cylindrical substrates are arranged on concentric circles. 13. The method of introducing discharge power into the reaction vessel,
The apparatus for forming a deposited film according to any one of claims 9 to 12, wherein the deposition is performed by a plurality of discharge electrodes arranged in the reaction vessel. 14. The heating container according to claim 9, wherein a heating means for heating a substrate disposed in the heating container to a desired temperature is disposed around the substrate. The apparatus for forming a deposited film according to any one of claims 13 to 13. 15. The reaction vessel according to claim 1, wherein the reaction vessel is provided with cooling means for cooling a substrate provided in the reaction vessel to a desired temperature. An apparatus for forming a deposited film as described in the above.