JPH11343573A - Deposited film forming device and its method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deposited film forming device and method using plasma CVD method by which a deposited film is formed to the axial direction of a substrate in the state where the irregularity in the film thickness and the irregularity in a film quality are reduced, the leaking of plasma generated on the inside of an adhesion- preventive member to the outside of the adhesion-preventive member is prevented and the manufacture of a good quality electrophotographic photoreceptor is available. SOLUTION: A reacting vessel 110 for evacuatably housing the substrate is internally provided with a gaseous starting material introducing pipe 113 for the formation of the deposited film having a discharge electrode, a heater 112 for heating the substrate and a rotatable cylindrical supporting body 111, which is installed so as to involve the heater for heating the substrate and also surves as the discharge electrode, installed along the longitudinal direction of the cylindrical supporting body and supplying the gaseous starting material to the reacting vessel, a power supplying means for exciting the gaseous starting material and a means for evacuating the reacting vessel. A partial region of a cylindrical adhesion-preventive member, which is installed so as to involve the cylindrical supporting body and the gaseous starting material introducing pipe in a reaction space of the reacting vessel, has a plurality of holes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and a method for forming a deposited film by a plasma CVD method, and more particularly to a method for forming an amorphous semiconductor film for forming a photoconductive member of an electrophotographic photosensitive member. Related devices and methods.

[0002]

2. Description of the Related Art As one of thin film forming methods, there is a CVD method utilizing discharge energy. An amorphous thin film (for example, amorphous silicon compensated by hydrogen and / or halogen) formed by this method is used for electrophotography. Photoconductor,
Applications to semiconductor devices such as semiconductor devices and TFTs have been proposed, and some of them have been put to practical use. FIGS. 6, 7 and 8 show typical examples of an apparatus for manufacturing a photoconductor for electrophotography by a plasma CVD method used by the inventor before reaching the present invention. FIGS. 6 (A), 7 (A) and 8 (A) are views from the side of a reaction vessel for accommodating the substrate in each apparatus and forming a deposited film on the substrate, and FIG. 6 (B). 7 (B) and FIG. 8 (B) are views of the respective devices as viewed from directly above. This apparatus is roughly classified into a source gas supply device (not shown) and a reaction vessel 110 in which a cylindrical substrate is installed.
And an exhaust device (not shown) for reducing the pressure inside the reaction vessel 110. FIG. 6 (A) and FIG. 6 (B)
In the apparatus shown in (1), a single rotatable cylindrical support 111 that is provided so as to include the substrate heating heater 112 and also serves as a discharge electrode is disposed at the center of the reaction vessel, and the cylindrical support is centered. A plurality of discharge electrodes 118 and a plurality of source gas introduction tubes 113 are arranged on the circumference of the axis.

In the apparatus shown in FIGS. 7A and 7B, one discharge electrode is arranged in the center of a reaction vessel, and a plurality of source gas introduction pipes are arranged on the same coaxial circumference. Further, on the coaxial circumference of the discharge electrode, a heater for heating the substrate is included, and a plurality of rotatable cylindrical supports and a plurality of source gas introduction tubes also serving as the discharge electrodes include the source gas introduction tube. Are located in The device shown in FIGS. 8A and 8B has a single discharge electrode 318 in the center of the reaction vessel.
Are arranged, and a plurality of source gas introduction pipes 313 are arranged on a circumference having the discharge electrode as a central axis. Further, a substrate is provided on the outer circumference of the source gas introduction pipe with the discharge electrode as a central axis. A plurality of rotatable cylindrical supports enclosing a heating heater and serving also as discharge electrodes are arranged, and the raw material gas introduction tube and the cylindrical shape are further arranged with a discharge electrode arranged in the center of the reaction vessel as a central axis. A plurality of discharge electrodes 319 and a plurality of source gas introduction tubes 314 are arranged on the outer circumference of the support.

[0004] SiH ₄ , H ₂ , CH in a source gas supply device
₄ , the raw material gas supplied from the gas cylinder such as B ₂ H ₆ , PH ₃ is adjusted to an appropriate flow rate of the required raw material gas by passing through a valve, a pressure regulator and a mass flow controller. The raw material gas is fed into a reaction vessel that has been evacuated to a vacuum by an exhaust device in advance through a raw gas introduction pipe. A cylindrical substrate 1 is placed in a reaction vessel.
Reference numeral 19 denotes a rotatable cylindrical support, and the base is controlled to a predetermined temperature by a base heater 112. The pressure in the reaction vessel after the introduction of the raw material gas is monitored by a vacuum gauge 116, and is controlled to a predetermined value by adjusting the opening of the throttle valve 120. When the environment for forming a predetermined deposited film is ready, the frequency is 105 MHz.
Box 11 from a VHF power supply (not shown)
High-frequency power is introduced into the reaction vessel through the four and one or more discharge electrodes to generate glow discharge. The source gas is decomposed by the energy of the glow discharge to form a thin film on the cylindrical substrate. Further, in order to prevent the formation of a film on the inner surface of the reaction vessel, the cylindrical deposition-preventing member 117 whose surface has been roughened includes a cylindrical substrate, a substrate heater, a cylindrical support, and a raw material gas introduction pipe. The raw material gas introduced into the cylindrical deposition preventing member is exhausted through a plurality of exhaust holes formed on the entire side surface of the cylindrical deposition preventing member. FIG. 11 is a schematic view of the cylindrical deposition prevention member 117.

When a deposited film used for an electrophotographic photosensitive member is formed using such a deposited film forming apparatus,
The raw material gas is exhausted from the lateral direction of the reaction vessel, but the distribution of the raw material gas is uneven between the upper and lower portions and the central portion in the cylindrical deposition-inhibiting member, and therefore, the deposited film formed on the surface of the cylindrical substrate The film thickness unevenness in the axial direction and the film quality unevenness in the axial direction may occur. Therefore, it has been found by close examination by the present inventors that it is desirable to solve the above-described phenomenon and make the distribution of the raw material gas in the reaction vessel uniform in the axial direction. For example, according to Japanese Patent Application Laid-Open No. 61-6277, a source gas suction portion is disposed near both ends of a plurality of cylindrical substrates disposed between a pair of parallel flat plates for supplying a source gas, thereby forming a cylindrical shape. The gas density around the substrate becomes uniform throughout,
A technique for making the thickness and quality of a deposited film formed uniform has been disclosed.

[0006]

However, when an exhaust means for exhausting a raw material gas disposed near both ends of a cylindrical substrate as described in Japanese Patent Application Laid-Open No. 61-6277 is used, It is necessary to connect exhaust pipes to the upper and lower parts of the container, and the configuration of the apparatus becomes complicated and large. Therefore, a large-scale and complicated operation is required in the deposited film forming process, and there is room for improvement in terms of improving productivity. Further, since the raw material gas inlets are provided near both ends of the cylindrical substrate, there is room for improvement in terms of plasma stability and uniformity. In addition, since the cylindrical deposition prevention member shown in FIG. 11 has exhaust holes on the entire surface,
Since a large amount of plasma generated inside the cylindrical deposition prevention member leaks to the outside of the cylindrical deposition prevention member, the stability of the plasma may be reduced or the quality of the deposited film to be formed may be degraded. Further, when the deposited film is formed on the substrate, the film adheres to the inner surface of the reaction vessel, and these films are separated and fly to the surface of the cylindrical substrate, hitting the deposited film formed on the substrate surface, and as a result, the deposited film has defects. May occur, which may cause image defects. In addition, it is necessary to clean the film adhered to the inner surface of the reaction vessel at regular intervals, which necessitates regular equipment maintenance, which is not preferable in terms of productivity.

Accordingly, the present invention provides a method for forming a deposited film in a state in which unevenness in film thickness and film quality in the axial direction of a substrate is reduced without complicating the apparatus configuration and the step of forming a deposited film. It is an object of the present invention to provide an apparatus and a method for forming a deposited film by a plasma CVD method, which prevent plasma generated inside a member from leaking to the outside of a deposition-inhibiting member and enable to manufacture a high-quality electrophotographic photosensitive member. And

[0008]

In order to achieve the above object, the present invention is characterized in that an apparatus and a method for forming a deposited film are constituted as follows. That is, the deposited film forming apparatus of the present invention is installed so as to include a reaction vessel for storing a substrate that can be depressurized, a discharge electrode, a substrate heater, and the substrate heater in the reaction vessel. A rotatable cylindrical support serving also as a discharge electrode, and a source gas introduction pipe for depositing film formation provided along the longitudinal direction of the cylindrical support and supplying a source gas to the reaction vessel; A deposition film forming apparatus by plasma CVD, comprising: a power supply unit for exciting a gas; and a unit for exhausting the inside of the reaction vessel, and forming a deposition film on the substrate supported by the cylindrical support. It is characterized in that a partial region of a cylindrical deposition-inhibiting member installed so as to include the cylindrical support and the source gas introduction pipe in the reaction space of the reaction vessel has a plurality of holes. Further, the deposited film forming apparatus according to the present invention is characterized in that the minus region is provided on at least one of the upper side surface and the lower side surface of the cylindrical deposition prevention member. Further, the deposited film forming apparatus according to the present invention is characterized in that an aperture ratio in the minus portion region is larger than an aperture ratio in a central portion of the cylindrical deposition prevention member. Further, the deposited film forming apparatus of the present invention,
The area S of one of the holes formed in the cylindrical shield member
[Mm ² ] is in the range of 0.5 ≦ S ≦ 250. Further, in the deposited film forming apparatus of the present invention, the axial length of the cylindrical deposition prevention member is L, and the width of the first partial region provided on the upper side surface of the cylindrical deposition prevention member is 1a. Assuming that the width of the second partial region provided below the side surface of the cylindrical deposition-inhibiting member is 1b, (1a + 1
b) / L is in the range of 0.1 ≦ (1a + 1b) /L≦0.6. Further, the deposited film forming apparatus of the present invention is characterized in that the distance d [mm] between the inner surface of the reaction vessel and the outer surface of the cylindrical deposition-proof member is in the range of 5 ≦ d ≦ 500. Further, in the deposited film forming apparatus according to the present invention, the power supply unit may have a frequency of 50 MHz.
It is characterized in that high-frequency discharge energy of 450 MHz or less is applied.

Further, the method for forming a deposited film according to the present invention comprises a discharge electrode provided in a reaction vessel which can be decompressed, a substrate heater, and a rotary electrode provided so as to include the substrate heater and serving also as the discharge electrode. A possible cylindrical support, a source gas introduction pipe for forming a deposited film provided along a longitudinal direction of the cylindrical support, and an electric power supply for exciting the source gas supplied into the reaction vessel Means and a means for evacuating the inside of the reaction vessel, wherein a deposition film is formed on the substrate supported by the cylindrical support by a plasma CVD method. A cylindrical deposition member is installed so as to include the cylindrical support and the raw material gas introduction pipe, and the cylindrical deposition member is inserted through a plurality of holes provided in a partial area of the cylindrical deposition member. Included in the member It is characterized by forming a deposition film on said substrate from that space by evacuating the raw material gas. Further, in the method for forming a deposited film according to the present invention, the negative region is provided on at least one of an upper side surface and a lower side surface of the cylindrical deposition prevention member. Further, the method of forming a deposited film according to the present invention is characterized in that an aperture ratio in the negative portion region is larger than an aperture ratio in a central portion of the cylindrical deposition prevention member. Further, the deposited film forming method of the present invention comprises:
The area S of one of the holes formed in the cylindrical shield member
[Mm ² ] is in the range of 0.5 ≦ S ≦ 250. Further, in the method of forming a deposited film according to the present invention, the axial length of the cylindrical deposition prevention member is L, the width of the first partial region provided on the cylindrical deposition prevention member is 1a, A second provided at the lower part of the side surface of the cylindrical deposition-proof member
If the width of the partial region is 1b, (1a + 1b) /
L is in the range of 0.1 ≦ (1a + 1b) /L≦0.6. In the method of forming a deposited film according to the present invention, a distance d [mm] between the inner surface of the reaction vessel and the outer surface of the cylindrical deposition-inhibiting member is in a range of 5 ≦ d ≦ 500. Further, in the method for forming a deposited film according to the present invention, the power supply means has a frequency of 50 MHz or more.
It is characterized by a frequency of 50 MHz or less.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The inventors of the present invention have made intensive studies to overcome the above-mentioned problems in the conventional apparatus and method for forming a deposited film and to achieve the object of the present invention. By configuring the members as described above, it is possible to suppress the non-uniformity of the source gas during the deposition film formation in the axial direction without making the apparatus configuration and the deposition film formation process large and complicated, that is, It has been found that it is possible to improve the film thickness unevenness and film quality unevenness of the deposited film in the axial direction. As a result, it has been found that a high quality electrophotographic photoreceptor can be manufactured with good productivity, and the yield can be dramatically improved when mass production is performed. The present invention has been completed based on this finding.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. (First Embodiment) FIG. 1 is a diagram schematically showing the shape of a cylindrical deposition-inhibiting member attached to a deposited film forming apparatus according to a first embodiment of the present invention. In FIG. 1, the cylindrical shield member is a hole band (hereinafter, referred to as an exhaust hole band 501) composed of a plurality of holes (hereinafter, referred to as an exhaust hole) in a part of the cylindrical shield member, that is, in the upper side surface and the lower side surface. ) Is provided, and the raw material gas is exhausted from a space included in the cylindrical deposition-proof member through the exhaust hole band.

In the case of using such a cylindrical protective member, it is important that the area S of one exhaust hole formed on the side surface of the cylindrical protective member is within a certain range, for example, the area of one exhaust hole. When S is extremely small, dust generated due to peeling of a film adhered to the cylindrical support or the discharge electrode during formation of the deposited film may be clogged in the exhaust hole, and the pressure in the reaction vessel cannot be stably controlled. There are cases. As a result, the reproducibility of the formed deposited film may be reduced, and the productivity is undesirably reduced. Also,
Area S of one exhaust hole formed on the side surface of the cylindrical attachment member
Is extremely large, the amount of plasma generated inside the cylindrical deposition-proof member leaks out to the outside of the cylindrical deposition-proof member, leading to a decrease in plasma stability and a decrease in film quality of a deposited film to be formed. There is fear. Further, films adhere to the inner surface of the reaction vessel, and these films peel off during the formation of the deposited film and fly to the surface of the cylindrical substrate, thereby causing a defect in the deposited film formed on the surface of the substrate and causing image defects. It may be. In addition, it is necessary to clean the film adhered to the inner surface of the reaction vessel at regular intervals, which necessitates regular equipment maintenance, which is not preferable in terms of productivity. Of the present invention,
When using the cylindrical deposition prevention member shown in FIG. 1, the area Smm of one exhaust hole formed on the side surface of the cylindrical deposition prevention member is shown.
² is in a range of 0.5 ≦ S ≦ 250 mm ² , and a more preferable range is 5 ≦ S ≦ 100 mm ² .

When the cylindrical deposition-inhibiting member of the present invention is used, the length of the cylindrical deposition-inhibiting member in the axial direction is L, and the width of the exhaust hole band provided above the cylindrical deposition-inhibiting member is 1a. Assuming that the width of the exhaust hole band provided at the lower portion of the cylindrical deposition-inhibiting member is 1b, (1
It is important that (a + 1b) / L is within a certain range. For example, when (1a + 1b) / L is extremely small, the exhaust resistance of the cylindrical deposition-inhibiting member becomes extremely large, and the pressure in the reaction vessel becomes desired. Cannot be maintained, and the desired film quality may not be obtained. Further, (1a)
When + 1b) / L is extremely large, the amount of plasma generated inside the cylindrical deposition-preventing member leaks to the outside of the cylindrical member, so that the stability of the plasma decreases and the quality of the deposited film decreases. May be caused. Further, films adhere to the inner surface of the reaction vessel, and these films peel off during the formation of the deposited film and fly to the surface of the cylindrical substrate, thereby causing a defect in the deposited film formed on the surface of the substrate and causing image defects. It may be. In addition, it is necessary to clean the film adhered to the inner surface of the reaction vessel at regular intervals, which necessitates regular equipment maintenance, which is not preferable in terms of productivity. When a deposited film is formed on a cylindrical substrate using the cylindrical deposition member shown in FIG. 1 of the present invention, the axial length of the cylindrical deposition member is L, and the side surface of the cylindrical deposition member is Assuming that the width of the exhaust hole band provided at the upper part is 1a and the width of the exhaust hole band provided at the lower part of the side surface of the cylindrical attachment member is 1b, the relationship is preferably 0.1 ≦ (1a + 1b) / L. ≦ 0.6, more preferably 0.2 ≦ (1a + 1b) /L≦0.4. As a result, the cylindrical blocking member of the present invention has an opening ratio, that is, a ratio of the total area of the holes to the area of the arbitrary region in the arbitrary region of the cylindrical preventing member, in which the opening ratio of the upper side surface to the lower side surface is cylindrical. It is characterized in that it is larger than the opening ratio of the deposition-inhibiting member.

When such a cylindrical deposition-inhibiting member is used, the distance d between the inner surface of the reaction vessel and the outer surface of the cylindrical deposition-inhibiting member is set.
When [mm] (see FIGS. 6 (B), 7 (B), 8 (B)) is extremely small, the distribution of the raw material gas in the circumferential direction in the cylindrical deposition-inhibiting member becomes uneven, so that In some cases, the thickness of the deposited film formed on the surface of the cylindrical substrate is uneven in the circumferential direction and the quality of the film is uneven in the circumferential direction. When the distance d is extremely large, plasma may be generated between the inner surface of the reaction vessel and the outer surface of the cylindrical deposition-inhibiting member, and the stability of the plasma may be reduced, and the quality of the deposited film may be deteriorated. is there. Therefore, when a deposited film is formed on a cylindrical substrate using the deposited film forming apparatus shown in FIGS. 6, 7 and 8, the distance dmm between the inner surface of the reaction vessel and the outer surface of the cylindrical deposition-inhibiting member is preferably set. 5 ≦ d ≦ 500 mm, more preferably 30 ≦ d ≦ 300
mm.

When the cylindrical deposition-inhibiting member of the present invention is used, it is important that the frequency of the high-frequency discharge energy applied to decompose the raw material gas is within a certain range, for example, a frequency of 50 MHz or less. In such a case, polysilane or the like generated by the gas phase reaction may clog the exhaust holes, making it impossible to stably control the pressure in the reaction vessel. This may cause the reproducibility of the deposited film to be formed, which is not preferable because the productivity is reduced. When the frequency is 450 MHz or more, stable control of the plasma is not easy, and the productivity may decrease. Therefore, when the cylindrical deposition-inhibiting member shown in FIG. 1 is used, the frequency of the high-frequency discharge energy applied to excite and seed the raw material gas is desirably in the range of 50 MHz to 450 MHz.

The deposited film forming apparatus of the present invention has holding means for fixing and holding the cylindrical deposition-inhibiting member of the present invention. Since the hole band 501 is provided slightly apart from the end of the cylindrical stopper member, a screw hole (not shown) is provided between the exhaust hole member 501 and the end of the cylindrical stopper member to accumulate the present invention. It may be fixed to the cylindrical deposition-proof member holding means of the film forming apparatus. Further, for example, a groove is provided in the deposited film forming apparatus of the present invention as the cylindrical deposition-proof member holding means of the present invention, and is fitted and fixed in the groove to one of the ends of the cylindrical deposition-resistant member holding means of the present invention. You can do it. Alternatively, the cylindrical deposition-inhibiting member may be placed on the bottom 130 as it is, for example, using the bottom 130 of the deposited film forming apparatus shown in FIG.
In addition, the cylindrical deposition prevention member used in the present invention may not only be provided with a hole only in a partial region, but also, for example, may be provided with a hole in the central portion of the cylindrical deposition prevention member. When a hole is provided in the center portion, for example, a hole provided in the center portion is provided only in the center portion, or a hole provided in the center portion extends over a partial region. However, regarding the above-described aperture ratio, it is desirable that the aperture ratio in some regions is larger than the aperture ratio in the central portion.

The cylindrical deposition-inhibiting member used in the present invention may be either conductive or electrically insulating. As the conductive deposition preventing member, Al, Cr, Mo, Au, In,
Examples include metals such as Nb, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof, such as stainless steel.
In addition, as the electrically insulating deposition preventing member, Al ₂ O ₃ , Mg
Ceramics such as O, ZrO ₂ , SiO ₂ , and Si ₃ N ₄ are exemplified. In particular, it is preferable to use alumina ceramic as the material of the cylindrical deposition-inhibiting member held by the deposited film forming apparatus of the present invention, since the power consumption during discharge can be reduced. Further, the shape of the exhaust hole formed in the cylindrical deposition prevention member used in the present invention is not particularly limited, such as a circle, an ellipse, and a square. Further, as the cylindrical deposition-inhibiting member used in the present invention, it is desirable that the surface is subjected to a roughening treatment in order to enhance the adhesion of the formed film. Further, the diameter of the cylindrical deposition preventing member used in the present invention is 2,000 [m] in order to maintain the stability of plasma generated inside the cylindrical deposition preventing member.
m] or less. The raw material gas introduction pipe used in the present invention may be either conductive or electrically insulating. Al, Cr, M
o, Au, In, Nb, Te, V, Ti, Pt, Pd,
Examples include metals such as Fe and alloys thereof, for example, stainless steel. As the electrically insulating gas pipe, A
Ceramics such as l ₂ O ₃ , MgO, ZnO ₂ , SiO ₂ , and Si ₃ N ₄ are exemplified.

The substrate used in the present invention includes:
It may be conductive or electrically insulating. As the conductive substrate, Al, Cr, Mo, Au, In, Nb, Te,
Examples include metals such as V, Ti, Pt, Pd, and Fe, and alloys thereof, such as stainless steel. Phosphor bronze can also be used. In addition, at least the surface of the electrically insulating substrate such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide or the like on the side on which the light receiving layer is formed of an electrically insulating substrate such as glass, ceramics, etc. Conductive treated substrates can also be used.

The shape of the substrate used in the present invention may be a cylindrical surface having a smooth surface or an uneven surface, and its thickness is appropriately determined so that a desired electrophotographic photosensitive member can be formed. When flexibility as an electrophotographic photoreceptor is required, it can be made as thin as possible as long as the function as a substrate can be sufficiently exhibited. However, the substrate is usually at least 10 μm in view of production, handling, mechanical strength and the like.

The substances that can be used as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , Si
Silicon hydrides (silanes) in a gas state such as H ₈ , Si ₄ H ₁₀ or the like, which can be gasified, are effectively used, and furthermore, ease of handling at the time of forming a deposited film, and excellent Si supply efficiency. In view of the above, SiH ₄ and Si ₂ H ₆ are preferred. Then, hydrogen atoms are structurally introduced into the deposited film to be formed, and the control of the introduction ratio of hydrogen atoms is further facilitated. In order to obtain a film characteristic that achieves the object of the present invention, these are used. The gas further contains H ₂ and / or
Alternatively, the layer may be formed by mixing a desired amount of He or a silicon compound gas containing a hydrogen atom. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

The raw material gas for supplying halogen atoms used in the present invention is, for example, a halogen gas, a halide, an interhalogen compound containing halogen,
A gaseous or gasifiable halogen compound such as a silane derivative substituted with halogen is preferably exemplified. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound. Specific examples of the halogen compound that can be suitably used in the present invention include fluorine gas (F ₂ ), BrF, 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 fluoride such as Si ₂ F ₆ is a preferred example. In the present invention, the deposited film preferably contains atoms for controlling conductivity as necessary. The atoms controlling the conductivity may be contained in the deposited film in a uniformly distributed state, or may be present in the layer thickness direction in a non-uniform distribution state. .

Examples of the atoms for controlling the conductivity include so-called impurities in the semiconductor field.
An atom belonging to Group IIIb of the Periodic Table giving p-type conduction characteristics (hereinafter abbreviated as “Group IIIb atom”) or an atom belonging to Group Vb of the Periodic Table giving n-type conduction characteristics (hereinafter “V
abbreviated as "group b atom"). II
As the group Ib atom, specifically, boron (B), aluminum (Al), gallium (Ga), indium (I
n), thallium (Tl), etc., especially B, Al, Ga
Is preferred. Specific examples of group Vb atoms include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and the like, and P and As are particularly preferable. The parts per million of the content of the atoms controlling the conductivity contained in the deposited film is preferably 1 × 10 ⁻² to 1 × 10 ⁴ atoms pp.
m, more preferably 5 × 10 ^{-2 to} 5 × 10 ³ atoms pp
m, most preferably 1 × 10 ^-1 to 1 × 10 ³ atomic ppm.

Atoms controlling conductivity, eg IIIb
To structurally introduce a group V atom or a group Vb atom,
In forming the layer, a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom may be introduced in a gaseous state into the reaction vessel together with another gas for forming a deposited film. Raw material for introducing group IIIb atoms or Vb
It is desirable that a material that can be a raw material for introducing group atoms be a gaseous material at normal temperature and normal pressure or a material that can be easily gasified at least under layer forming conditions.

As such a raw material for introducing a group IIIb atom, specifically, for introducing a boron atom, B ₂ H ₆ ,
_{B 4 H 10, B 5 H} 9, B 5 H 11, B 6 H 12, B 6 H 10, B 6 H
₁₄ borohydride; and boron halide such as BF ₃ , BCl ₃ , and BBr ₃ . In addition, AlCl ₃ , Ga
Cl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like can also be mentioned. The source material for introducing a group Vb atom is effectively used as a source material for introducing a phosphorus atom.
₃ , hydrogenated phosphorus such as P ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ , PC
and phosphorus halides such as l ₃ , PCl ₅ , PBr ₃ , PBr ₅ and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsC
l ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , Sb
F ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , B
iBr _{3 and the} like can also be mentioned as effective starting materials for introducing Group Vb atoms. These raw materials for introducing atoms for controlling conductivity may be diluted with H ₂ and / or He as necessary.

In the present invention, an amorphous silicon-based surface layer excellent in moisture resistance, continuous repeated use characteristics, electric pressure resistance, use environment characteristics, and durability is formed on the surface of the deposited film to be formed. Is preferred. The surface layer can be made of any material as long as it is an amorphous silicon material. For example, amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing a carbon atom can be used. Materials are preferably used. S
Substances that can be i supply gas include SiH ₄ , Si ₂
Silicon hydrides (silanes) in a gas state such as H ₆ , SiH ₈ , and Si ₄ H ₁₀ or capable of being gasified can be used effectively.
SiH _4, Si ₂ H ₆ in terms of and Si-feeding efficiency can be mentioned as preferred. In addition, these source gases for supplying Si may be diluted with a gas such as H ₂ and / or He if necessary.

Examples of the substance that can serve as the C supply gas include gaseous hydrocarbons such as CH ₄ , C ₂ H ₂ , C ₂ H ₆ , C ₃ H ₈ , and C ₄ H ₁₀ or hydrocarbons that can be gasified. CH ₄ , C ₂ H ₂ , C ₂ H _{6 in} terms of ease of handling at the time of forming a deposited film and good C supply rate.
Are preferred. If necessary, the raw material gas for supplying C may be replaced with H ₂ and / or He, if necessary.
May be used after being diluted with such a gas. (Second Embodiment) In a deposition film forming apparatus according to a second embodiment of the present invention, as shown in FIGS. 9A and 9B, a single source gas introduction pipe 513 is provided in a reaction vessel. It is characterized by being arranged at 510. Others are the same as those of the deposited film forming apparatus shown in FIGS. 8A and 8B described in the first embodiment. FIG. 9A is a schematic sectional view showing a deposited film forming apparatus according to a second embodiment of the present invention from the side. FIG. 9B is a schematic sectional view showing a deposited film forming apparatus according to the second embodiment of the present invention from above. As shown in FIG.
13 is arranged in the reaction vessel 510 by itself. The plurality of cylindrical supports 511 are arranged concentrically at equal intervals around the position of the source gas introduction pipe 513, and the distance between each cylindrical support 511 and the source gas introduction pipe 513 is the same. Also, the discharge electrodes 518 are arranged concentrically at a plurality of equal intervals around the arrangement position of the source gas introduction pipe 513, and the distance between each discharge electrode 518 and the source gas introduction pipe 513 is the same. Further, the cylindrical deposition prevention member 517 is arranged so as to include the raw material gas introduction pipe 513 and the discharge electrode 518. Further, the substrate heating heater 512 is disposed so as to be located inside the cylindrical substrate 519, and the matching box 514, the raw material gas pipe 515, the vacuum gauge 516, and the throttle valve 520 are shown in FIG.
It is arranged similarly to the deposited film forming apparatus described in (B). The apparatus for forming a deposited film according to the present embodiment is the same as that shown in FIG.
Since two, three, and four cylindrical deposition members can be used, a high-quality deposited film can be deposited on the cylindrical substrate, similarly to the deposited film forming apparatus described in the first embodiment. This is because the cylindrical deposition-preventing member prevents scattered matters and the like which are separated and scattered from the inside of the reaction vessel from obstructing the growth of deposits on the cylindrical substrate. In addition, since the number of source gas introduction pipes in the discharge space is small, discharge occurs more uniformly. Further, since the number of source gas introduction pipes is as small as one, maintenance becomes extremely easy. In addition, in the deposited film forming apparatus of the present invention, in addition to this, for example, as shown in FIGS. 10A and 10B, one raw material gas introduction pipe 513 is disposed in the reaction vessel 510 and the discharge electrode 518 A mode in which the cylindrical deposition-inhibiting member 517 is arranged between the source gas introduction pipe 513 and the source gas introduction pipe 513 is also preferable. In this case, since the discharge electrode 518 is arranged outside the cylindrical deposition-inhibiting member and there is only one gas introduction pipe and the cylindrical substrate in the cylindrical deposition-inhibiting member 517, the growth of the deposit on the substrate is achieved. Almost no splatters disturb the air, and the above-mentioned FIGS.
Since three or four cylindrical deposition members can be used, a high-quality deposited film can be deposited on the cylindrical substrate in the same manner as the deposited film forming apparatus described in the first embodiment.

[0027]

EXAMPLES Hereinafter, the apparatus and method of the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. (Example 1) Using an aluminum holder (cylindrical support) on which a mirror-finished aluminum cylinder (cylindrical substrate) having a length of 360 mm and an outer diameter of 80 mm was mounted, the apparatus shown in FIG. 6 was used. , Oscillation frequency 105M
Using a high-frequency power source of 1 Hz, a light receiving layer comprising a charge injection blocking layer, a photoconductive layer and a surface layer was formed on a cylindrical substrate.
Was formed under the following manufacturing conditions.

[0028]

[Table 1] In this example, as a comparative example, a cylindrical deposition member shown in FIGS. 2, 3, 4, and 11 was prepared, and a cylindrical deposition member of the present invention shown in FIG. 1 was prepared. The characteristics of the substrate formed and having the deposited film are evaluated. The method of forming a deposited film on a substrate is divided into the following (a) to (f). That is, (a) a method for forming a deposited film without installing a cylindrical deposition member, and (b) a cylindrical deposition member (FIG. 11) provided with a plurality of exhaust holes on the entire side surface to deposit the deposited film. How to form,
(C) A method of forming a deposited film by installing a cylindrical deposition-inhibiting member (FIG. 2) provided with a plurality of exhaust holes at the center of the side surface, and (d) From a plurality of exhaust holes at the upper side. A method of forming a deposited film by installing a cylindrical deposition member (FIG. 3) provided with an exhaust hole band, and (e) a cylindrical deposition member having an exhaust hole band formed of a plurality of exhaust holes at the lower side surface. (FIG. 4) A method of forming a deposited film by setting up, (F) Installing and depositing a cylindrical deposition-inhibiting member (FIG. 1) provided with an exhaust hole band composed of a plurality of exhaust holes at the upper side and the lower side. An electrophotographic photoreceptor was manufactured by the above-described six methods of forming a film. The produced electrophotographic photoreceptor was evaluated for axial thickness unevenness, electrophotographic characteristics in the axial direction unevenness, and image characteristics. Table 2 shows the results. From Table 2, it was found that a good electrophotographic photosensitive member was obtained by using the cylindrical deposition-inhibiting member shown in FIG. 1 and provided with a plurality of exhaust holes at the upper and lower sides. .

[0029]

[Table 2] The evaluation criteria for the evaluation ranks A, B, C, and D shown in the table are as follows for each evaluation item.

"Axial film thickness non-uniformity" The film thickness was measured using an eddy current type film thickness measuring device. From the difference between the maximum value (Max) and the minimum value (Min), and the average value (Ave) of the 11 measured points, the ratio of the difference between the maximum value and the minimum value and the average value (Max−Min) / Ave Asked,
By comparing the deposited film formed by each method of (a) to (f) with the deposited film formed by the method described in (b) of Example 1, the axial direction of the deposited film formed by each method is compared. The film thickness unevenness was classified into the following ranks. A Reduction of 40% or more compared to (B) of Example 1 B Reduction of 20% or more and less than 40% compared to (B) of Example 1 C Equivalent to (B) of Example 1 More than less than 20% reduction D Increase compared to (b) of Example 1 Each of the electrophotographic photoreceptors produced was set in an electrophotographic apparatus (a Canon NP6550 was modified for experiment), and The electrophotographic properties were evaluated. Charging ability measurement method Process speed 380 mm / sec, pre-exposure halogen lamp light) 4 luxsec, charger current value 1000μ
Under the condition of A, the surface potential of the dark portion at the developing device position of the electrophotographic photosensitive member is measured by a surface voltmeter. Sensitivity measurement method The dark area surface potential at the developing position of the electrophotographic photoreceptor is set to 400 V
To be charged. Then, using a filter as an image exposure light source, a halogen lamp light having an intensity peak around 550 nm is irradiated, and the light amount is adjusted so that the surface potential of the bright portion at the developing position of the electrophotographic photosensitive member becomes a predetermined value. The sensitivity is measured based on the amount of light at this time. Evaluation Method of Axial Charging Ability Nonuniformity and Axial Sensitivity Unevenness Evaluation A total of 11 charging abilities and sensitivities were measured at 3 cm intervals from the upper end to the lower end in the axial direction of each produced photoconductor, and the maximum value (Max) and the minimum value (Max) Min) and the average value (Ave) of the 11 measured points, the difference between the maximum value and the minimum value and the average value ratio (Max−Min) / Ave were determined. By comparison, it was classified into the following ranks. Axial charging ability unevenness A A reduction of 40% or more compared to (B) of Example 1 B Reduction of 20% or more and less than 40% compared to (B) of Example 1 C (B) of Example 1 D Equivalent to or less than 20% reduction compared to D D Increase in comparison to (B) of Example 1 Axial sensitivity unevenness A 40% or more reduction compared to (B) of Example 1 B B Example 1 20% to less than 40% reduction compared to (b) C Reduction equivalent to or less than 20% compared to (b) of Example 1 D Increase compared to (b) of Example 1 Full black chart (part number FY9-907)
A solid black image was formed using 3), and white spots having a diameter of 0.2 [mm] or more within an arbitrary constant area of the obtained image were evaluated. The ranks are as follows: A Reduced to less than 50% compared to (B) of Example 1 B Reduced to 50% or more and less than 75% compared to (B) of Example 1 C (B) of Example 1 D Reduced to 75% or more and less than equivalent compared to D D Equal to or greater than (b) of Example 1 (Example 2) Mirror-finished aluminum cylinder 360 mm in length and 80 mm in outer diameter Using an aluminum holder (cylindrical support) on which the (cylindrical substrate) is mounted, the device shown in FIG.
Using a high-frequency power source of 1 Hz, a light-receiving layer composed of a charge injection blocking layer, a photoconductive layer and a surface layer was formed on a cylindrical substrate under the conditions shown in Table 1. In this example,
The cylindrical stopper member provided with a plurality of exhaust holes at the upper and lower side surfaces shown in FIG. 1 is used. (A) The area of one exhaust hole formed in the cylindrical stopper member To 0.3
mm ² (b) The area of the exhaust hole is 0.5 m
those with m ^2, (c) those of the area of the exhaust hole was 5 mm ^2, (d) said that the 30 mm ² area of the exhaust hole, which was 100 mm ² area of the exhaust hole (e) (V) Electrophotographic photoreceptor was manufactured using the above-described exhaust hole having an area of 250 mm ² and (g) having the exhaust hole having an area of 300 mm ² . The produced electrophotographic photoreceptor was evaluated for electrophotographic characteristics, reproducibility of electrophotographic characteristics, and white spots. Table 3 shows the results. From Table 3, the area S [mm ² ] of one exhaust hole formed on the side surface of the cylindrical deposition-inhibiting member is defined as 0.5 ≦ S ≦ 250.
As a result, a favorable electrophotographic photosensitive member could be obtained.

[0031]

[Table 3] The measuring method of each characteristic is the same as that of Example 1, and the evaluation criteria of the evaluation ranks A, B, and C shown in the table are as follows for each evaluation item.

Method for Evaluating Charging Ability and Sensitivity Ten electrophotographic photosensitive members were prepared by the method described in Example 1, and the charging ability, sensitivity, and optical memory of each photosensitive member were measured, and the average value was determined. Each of them was classified into the following ranks by comparing with (a) of Example 2. Charging ability A: 10% or more improvement compared to (A) of Example 2 B: 5% to less than 10% improvement compared to (A) of Example 2 C: Compared to (A) of Example 2 D Equal to or less than 5% improvement D Less than (A) of Example 2 Sensitivity A 10% or more improvement compared to (A) of Example 2 B 5% or more compared to (A) of Example 2 Improvement of less than 10% C Improvement equivalent to or less than 5% compared to (A) of Example 2 D Evaluation of reproducibility of charging ability and sensitivity by the method described in Example 1 Ten electrophotographic photoreceptors are prepared, the charging ability and sensitivity of each photoreceptor are measured, and the average value is determined. The lower limit is -5% from the average value for each, and +
Set a standard with an upper limit of 5%, and from that standard,
By comparing the ratio of the number of photoconductors whose sensitivity value deviated with that of Example 2 (a), the photoconductors were classified into the following ranks. Reproducibility of charging ability A Ratio of non-standard number of less than 25% compared to (A) of Example 2 B Ratio of non-standard number of 25% or more compared to (A) of Example 2 50 Less than 50% C The ratio of the out-of-specification number is 50% or more and less than the equivalent as compared to (A) of Example 2. D The ratio of the out-of-specification number is equal to or greater than that of (A) of Example 2. Reproducibility A The ratio of the number of non-standard pieces is less than 25% as compared with (A) of Example 2. B The ratio of the number of non-standard numbers is 25% or more and less than 50% as compared with (A) of Example 2. C The ratio of the number out of the standard is 50% or more and less than the equivalent as compared with (a) of Example 2. D The percentage of the number out of the standard is equal or increased as compared with (a) of Example 2. B Reduced to less than 50% as compared to (A) of Example 2 B Reduced to 50% or more and less than 75% as compared to (A) of Example 2 C Example 75% or less and less than equivalent to (a) of D. D Increase to equivalent or more than that of (a) of Example 2 (Example 3) Mirror finish of 360 mm in length and 80 mm in outer diameter Using an aluminum holder (cylindrical support) on which an aluminum cylinder (cylindrical substrate) was placed, the oscillation frequency was set to 105 M in the apparatus shown in FIG.
Using a high-frequency power source of 1 Hz, a light-receiving layer composed of a charge injection blocking layer, a photoconductive layer and a surface layer was formed on a cylindrical substrate under the conditions shown in Table 1. (However, when a desired pressure cannot be obtained because the exhaust resistance of the deposition-inhibiting member is large, the deposited film is formed under the pressure condition when the throttle valve is fully opened.) In this example, FIG. indicated, using a cylindrical deposition preventing member provided with an exhaust hole band comprising a plurality of exhaust holes on the upper side surface and lower side surface, the area of the exhaust hole in one to be drilled in the cylindrical deposition preventing member side and 40 mm ^2, (A) The axial length L of the cylindrical attachment member, the width 1a of the exhaust hole band provided on the upper side surface of the cylindrical attachment member, and the exhaust hole band provided on the lower side surface of the cylindrical attachment member. The relation (1a + 1b) / L of 1b is set to 0.0
5, (b) the (1a + 1b) / L is 0.1, (c) the (1a + 1b) / L is 0.2, and (d) the (1a + 1)
b) / L is 0.3, (e) the above (1a + 1b) / L is 0.4, (f) the (1a + 1b) / L is 0.6,
(G) An electrophotographic photoreceptor was manufactured using seven types of cylindrical deposition-inhibiting members in which (1a + 1b) / L was 0.8. The electrophotographic photosensitive member thus produced was evaluated for electrophotographic characteristics and white spots. Table 4 shows the results. From Table 4, it can be seen that the axial length L of the cylindrical attachment member, the width 1a of the exhaust hole band provided on the upper side of the cylindrical attachment member, and the exhaust hole provided on the lower side surface of the cylindrical attachment member. By setting the relationship of the band 1b to 0.1 ≦ (1a + 1b) /L≦0.6, a favorable electrophotographic photosensitive member could be obtained.

[0033]

[Table 4] The methods for measuring the charging ability, sensitivity, and whiteness are the same as those in Examples 1 and 2, and the evaluation methods are as follows.

Evaluation method for white spots, charging ability and sensitivity Charging ability A 10% or more improvement as compared to (A) of Example 3 B 5% or more and less than 10% as compared to (A) of Example 3 Improvement C Improvement equal to or more than 5% as compared to (A) of Example 3 D Sensitivity A (A) and lower than (A) of Example 3 B Improvement of 10% or more compared to (A) of Example 3 5% or more and less than 10% improvement as compared to (a) of Example 3 C Improvement of equivalent or more and less than 5% as compared with (a) of Example 3 D (a) or less of Example 3 Reduced to less than 50% compared to (a) of Example 3 B Reduced to 50% or more and less than 75% compared to (a) of Example 3 C 75% or more equivalent to (a) of Example 3 D Reduced to less than D Equivalent to or more than (a) of Example 3 (Example 4) A mirror surface with a length of 360 mm and an outer diameter of φ80 mm Using the alms this aluminum cylinder aluminum holder was placed on (cylindrical substrate) (cylindrical support), in the apparatus shown in FIG. 6, the oscillation frequency 105M
Using a high-frequency power source of 1 Hz, a light-receiving layer composed of a charge injection blocking layer, a photoconductive layer and a surface layer was formed on a cylindrical substrate under the conditions shown in Table 1. In this example,
Using the cylindrical stopper member provided with a plurality of exhaust holes formed on the upper side and the lower side of the side shown in FIG. 1, the area of one exhaust hole provided on the side of the cylindrical stopper is 40 m.
m ² , the axial length L of the cylindrical attachment member, the width 1a of the exhaust hole band provided on the upper side of the cylindrical attachment member, and the exhaust hole provided on the lower side of the cylindrical attachment member. The relation (1a + 1b) / L of the band 1b is set to 0.3, (a) the distance d between the inner surface of the reaction vessel and the outer surface of the cylindrical stopper member is 3 mm, (b) the distance d is 5 mm, and (c) the distance d. Is 30 mm,
(D) the distance d is 100 mm, and (e) the distance d is 3
The electrophotographic photoreceptor was manufactured under seven conditions of 00 mm, (f) the distance d was 500 mm, and (g) the distance d was 700 mm. The electrophotographic characteristics of the produced electrophotographic photosensitive member were evaluated. Table 5 shows the results. As shown in Table 5, by setting the distance d [mm] between the inner surface of the reaction vessel and the outer surface of the cylindrical deposition preventing member to be 5 ≦ d ≦ 500, a favorable electrophotographic photoreceptor could be obtained.

[0035]

[Table 5] The methods for measuring electrophotographic characteristics and white spots are the same as those in Examples 1, 2 and 3.

The evaluation criteria of the respective evaluation ranks of the charging ability, sensitivity, circumferential thickness unevenness, circumferential charging unevenness and circumferential thickness unevenness evaluation method are as follows. Charging ability A: 10% or more improvement compared to (a) of Example 4 B B: 5% to less than 10% improvement compared to (a) of Example 4 C: Compared to (a) of Example 4 D Improvement of not less than 5% in Example 4 D Sensitivity A 10% or more improvement in comparison with (A) of Example 4 B 5% or more in comparison with (A) of Example 4 Improvement of less than 10% C Improvement equivalent to or less than 5% compared to (A) of Example 4 D Less than (A) of Example 4 Non-uniform thickness in the circumferential direction Among the prepared photoconductors, FIG. As shown in the figure, a total of eight film thicknesses were measured at 45 degrees in the circumferential direction at the portion Q of the photoconductor facing the center line P of the exhaust pipe connected to the reaction vessel (axial position in the axial direction), and the maximum value ( Max) and the minimum value (M
in) and the average of the eight measured points (Ave), the ratio of the difference between the maximum value and the minimum value to the average value (Max-Mi)
n) / Ave was obtained, and each was classified into the following ranks by comparing with (a) of Example 4. A Reduction of 40% or more compared to (A) of Example 4 B Reduction of 20% or more and less than 40% compared to (A) of Example 4 C Equivalent to (A) of Example 4 D Less than 20% D Increase in comparison with (a) of Example 4. Circumferential charging ability and sensitivity unevenness Estimated charging ability and sensitivity at a total of 8 points were measured at every 45 degrees in the circumferential direction of each photoconductor produced. (Axial position), maximum value (Ma
x), the ratio of the difference between the maximum value and the minimum value and the average value (Max−Min) / Ave was determined from the difference between the minimum value (Min) and the average value (Ave) of the eight measured points. It was classified into the following ranks by comparing with (a) of No. 4. Circumferential charging ability unevenness A A reduction of 40% or more as compared with (A) of Example 4 B Reduction of 20% or more and less than 40% as compared with (A) of Example 4 C (A) of Example 4 D Equivalent to less than 20% reduction compared to D D Increase in sensitivity compared to (A) of Example 4 Circumferential sensitivity unevenness A 40% reduction or more compared to (A) of Example 4 B B Example 4 20% or more and less than 40% reduction as compared with (A) C Reduction equal to or more than 20% as compared with (A) of Example 4 D Increase as compared with (A) of Example 4 (Example 5) In the deposition film forming apparatus shown in FIG. 6, an amorphous semiconductor film was formed on an aluminum-made cylindrical substrate having a diameter of 80 mm according to the conditions shown in Table 6 by using a high-frequency power supply having an oscillation frequency of 105 MHz. An electrophotographic photoreceptor was prepared. Further, in this embodiment, a cylindrical stopper member provided with an exhaust hole band including a plurality of exhaust holes at the upper side and the lower side of the side shown in FIG. 1 is used, the area of the exhaust hole is 40 mm ² , and the cylindrical stopper is provided. The relationship between the width 1a of the exhaust hole band on the upper side of the member, the length of the exhaust hole band 1b on the lower side, and the length L of the cylindrical deposition prevention member (1a
+ 1b) /L=0.3, the distance between the inner surface of the reaction vessel and the outer surface of the cylindrical deposition prevention member was 50 mm, and the diameter of the cylindrical deposition prevention member was 4
It is 50 mm. The prepared electrophotographic photoreceptor was installed in a Canon copier NP6550 modified for experiment,
As in the case of Examples 1 to 4, when the film thickness unevenness, electrophotographic characteristics, electrophotographic characteristics unevenness, reproducibility of electrophotographic characteristics, and white spots were evaluated, good results were obtained. Further, the obtained photoreceptor was remodeled for experiments, and a Canon copier NP655 was used.
When the image was set at 0 and an image was output, a uniform image was obtained without unevenness in the halftone image. Further, when the text original was copied, a clear image having a high black density was obtained. Also, when copying a photographic original, a clear image faithful to the original could be obtained.

[0037]

[Table 6] (Comparative Example 1) In this example, the deposited film forming apparatus shown in FIG. 6 was used as in Example 5, and instead of the cylindrical deposition-inhibiting member shown in FIG. Using a cylindrical deposition member provided with an exhaust hole, and using a high-frequency power source having an oscillation frequency of 105 MHz, a cylindrical substrate made of aluminum and having a diameter of 80 mm was formed according to the conditions shown in Table 6 in the same manner as in Example 5. A crystalline film was formed to produce an electrophotographic photoreceptor. Further, in this example, the area of the exhaust hole is 40 mm ² , the distance between the inner surface of the reaction vessel and the outer surface of the cylindrical stopper member is 50 mm, and the diameter of the cylindrical stopper member is 450 mm. Canon copier NP65 modified from electrophotographic photoreceptor manufactured for experiment
The electrophotographic photosensitive member produced in Example 5 was compared with the electrophotographic photosensitive member produced in Example 5 for thickness unevenness, electrophotographic characteristics, electrophotographic characteristics irregularity, reproducibility of electrophotographic characteristics, and white spots. The photoreceptor exhibited better electrophotographic properties.

Embodiment 6 In this embodiment, a high-frequency power source having an oscillation frequency of 105 MHz is used in the deposited film forming apparatus shown in FIG. 7 instead of the deposited film forming apparatus shown in FIG. 6 used in Embodiment 5. According to the conditions shown in Table 6, an amorphous semiconductor film was formed on a cylindrical substrate made of aluminum and having a diameter of 80 mm to produce a photoconductor for electrophotography. Further, in this example, a cylindrical stopper member provided with an exhaust hole band including a plurality of exhaust holes in the upper side surface and the lower side surface shown in FIG. 1 is used, the area of the exhaust hole is 40 mm ² , and the cylindrical stopper member is used. Relation (1a + 1b) /L=0.3 between the width 1a of the exhaust hole band on the upper side, the length of the exhaust hole band 1b on the lower side, and the length L of the cylindrical attachment member, between the inner surface of the reaction vessel and the outer surface of the cylindrical attachment member. Is 50 mm and the diameter of the cylindrical deposition-inhibiting member is 700 mm instead of 450 mm in the fifth embodiment. The produced electrophotographic photoreceptor was installed in a Canon copier NP6550 modified for experiments, and the film thickness unevenness, electrophotographic characteristics, electrophotographic characteristics unevenness, reproducibility of electrophotographic characteristics and When evaluated for white spots, good results were obtained. Further, the obtained photoreceptor was modified for experiment for use by a Canon copier NP6.
When the image was set at 550 and an image was output, a uniform image was obtained without unevenness in the halftone image. Further, when the text original was copied, a clear image having a high black density was obtained.
Also, when copying a photographic original, a clear image faithful to the original could be obtained.

(Embodiment 7) In this embodiment, a high-frequency power source having an oscillation frequency of 105 MHz is used in the deposited film forming apparatus shown in FIG. 8 instead of the deposited film forming apparatus shown in FIG. In accordance with the conditions shown in Table 6, an amorphous semiconductor film was formed on a cylindrical substrate made of aluminum and having a diameter of 80 mm to produce an electrophotographic photoreceptor. Further, in this embodiment, a cylindrical stopper member provided with an exhaust hole band including a plurality of exhaust holes at the upper side and the lower side of the side shown in FIG. 1 is used, the area of the exhaust hole is 40 mm ² , and the cylindrical stopper is provided. Relation (1a + 1b) /L=0.3 between the width 1a of the exhaust hole band on the upper side of the member, the length of the exhaust hole band 1b on the lower side, and the length L of the cylindrical stopper member, and the inner surface of the reaction vessel and the outer surface of the cylindrical stopper member. The distance between them is 50 mm, and the diameter of the cylindrical attachment member is 800 mm instead of 700 mm in the sixth embodiment. The produced electrophotographic photoreceptor was installed in a Canon copier NP6550 modified for experiments, and the film thickness unevenness, electrophotographic characteristics, electrophotographic characteristics unevenness, reproducibility of electrophotographic characteristics and When evaluated for white spots, good results were obtained. Further, when the obtained photoreceptor was installed in a Canon copier NP6550 modified for experiment and an image was output, a uniform image was obtained without unevenness in the halftone image. Further, when the text original was copied, a clear image having a high black density was obtained. Also, when copying a photographic original, a clear image faithful to the original could be obtained.

(Embodiment 8) In the deposited film forming apparatus shown in FIG. 8, a high-frequency power source having an oscillation frequency of 105 MHz was used.
In this embodiment, the aluminum diameter 80 m shown in Embodiment 7 is used.
An amorphous semiconductor film was formed on a cylindrical substrate having a diameter of 30 mm in accordance with the conditions shown in Table 6 in place of the cylindrical substrate having a thickness of m, thereby producing a photoconductor for electrophotography. In this embodiment,
A cylindrical deposition-inhibiting member provided with a plurality of exhaust holes at the upper side and lower side shown in FIG. 1 was used. The area of the exhaust hole was 20 mm ² instead of 40 mm ² shown in the seventh embodiment. The relationship between the width 1a of the exhaust hole band at the upper part of the side surface of the cylindrical stopper member, the length L of the exhaust hole band 1b at the lower part of the side surface and the length L of the cylindrical stopper member is (1a + 1b) /L=0.3, and the inner surface of the reaction vessel The distance between the outer surface of the cylindrical deposition-inhibiting member is 40 mm instead of the 50 mm shown in Example 7, and the diameter of the cylindrical deposition-inhibiting member is in Example 7.
Is set to 600 mm instead of 800 mm. The produced electrophotographic photoreceptor was installed in a Canon copier NP6030 modified for experiment, and the film thickness unevenness, electrophotographic characteristics, electrophotographic characteristics unevenness, reproducibility of electrophotographic characteristics and When evaluated for white spots, good results were obtained. Further, when the obtained photoreceptor was set in a Canon copier NP6030 modified for experiment and an image was output, a uniform image was obtained without unevenness in the halftone image. Further, when the text original was copied, a clear image having a high black density was obtained. Also, when copying a photographic original, a clear image faithful to the original could be obtained.

(Embodiment 9) In the deposition film forming apparatus shown in FIG. 6, a high-frequency power source having an oscillation frequency of 105 MHz was used, and aluminum was used according to the conditions shown in Table 7 in place of Table 6 shown in Example 5. An amorphous semiconductor film was formed on a cylindrical substrate having a diameter of 80 [mm] to produce a photoconductor for electrophotography. Further, in this embodiment, a cylindrical stopper member provided with a plurality of exhaust holes at the upper and lower side surfaces shown in FIG. 1 is used. The area of the exhaust hole is 40 mm ² , and the cylindrical stopper member is used. Exhaust hole band 1a at the upper side, exhaust hole band 1 at the lower side
relation between b and the length L of the cylindrical deposition preventing member (1a + 1b) /
L = 0.3, the distance between the inner surface of the reaction vessel and the outer surface of the cylindrical deposition prevention member is 50 mm, and the diameter of the cylindrical deposition prevention member is 450 mm. The prepared electrophotographic photoreceptor was installed in a Canon copier NP6550 modified for experiment, and
Evaluation of film thickness unevenness, electrophotographic characteristics, electrophotographic characteristics non-uniformity, reproducibility of electrophotographic characteristics, and white spots was performed in the same manner as in Example 4. was gotten. Further, when the obtained photoreceptor was installed in a Canon copier NP6550 modified for experiment and an image was output, a uniform image was obtained without unevenness in the halftone image. When I copied the text manuscript further,
A clear image with a high black density was obtained. Also, when copying a photographic original, a clear image faithful to the original could be obtained.

[0042]

[Table 7] (Embodiment 10) In the deposition film forming apparatus shown in FIG.
An amorphous semiconductor film was formed on a cylindrical substrate made of aluminum and having a diameter of 80 [mm] according to the conditions shown in Table 7 by using a high-frequency power supply having an oscillation frequency of 50 MHz instead of the oscillation frequency of 105 MHz in Example 9. An electrophotographic photoreceptor was prepared. Further, in this embodiment, a cylindrical stopper member provided with an exhaust hole band including a plurality of exhaust holes at the upper side and the lower side of the side shown in FIG. 1 is used, the area of the exhaust hole is 40 mm ² , and the cylindrical stopper is provided. The relationship between the width 1a of the exhaust hole band on the upper side of the member, the length of the exhaust hole band 1b on the lower side, and the length L of the cylindrical deposition prevention member (1a + 1)
b) /L=0.3, the distance between the inner surface of the reaction vessel and the outer surface of the cylindrical shield member was 50 mm, and the diameter of the cylindrical shield member was 450.
mm. The produced electrophotographic photoreceptor was installed in a Canon copier NP6550 modified for experiments, and the film thickness unevenness, electrophotographic characteristics, electrophotographic characteristics unevenness, reproducibility of electrophotographic characteristics and When evaluated for white spots, good results were obtained. Further, when the obtained photoreceptor was installed in a Canon copier NP6550 modified for experiment and an image was output, a uniform image was obtained without unevenness in the halftone image. Further, when the text original was copied, a clear image having a high black density was obtained. Also, when copying a photographic original, a clear image faithful to the original could be obtained.

(Embodiment 11) In the deposition film forming apparatus shown in FIG. 6, a high-frequency power source having an oscillation frequency of 450 MHz was used instead of the oscillation frequency of 105 MHz of the ninth embodiment.
According to the conditions shown in the above, aluminum diameter 80m
m, an amorphous semiconductor film was formed on the cylindrical substrate to prepare a photoconductor for electrophotography. In this embodiment, a cylindrical deposition-inhibiting member provided with a plurality of exhaust holes at the upper and lower side surfaces shown in FIG. 1 is used, and the area of the exhaust holes is 40 mm.
^2. The relationship between the width 1a of the exhaust hole band at the upper side of the cylindrical attachment member, the length L of the exhaust hole band 1b at the lower side surface, and the length L of the cylindrical attachment member (1a + 1b) /L=0.3. The distance between the outer surfaces of the cylindrical deposition preventing member is 50 mm, and the diameter of the cylindrical deposition preventing member is 450 mm. The produced electrophotographic photoreceptor was installed in a Canon copier NP6550 modified for experiment, and the film thickness unevenness, electrophotographic characteristics,
When the evaluation was made on the unevenness of the electrophotographic characteristics, the reproducibility of the electrophotographic characteristics, and the white spots, good results were obtained. Further, the obtained photoreceptor is modified for experiment for use by a Canon copier NP.
When placed at 6550 and an image was output, a uniform image was obtained without unevenness in the halftone image. Further, when the text original was copied, a clear image having a high black density was obtained. Also, when copying a photographic original, a clear image faithful to the original could be obtained.

(Embodiment 12) In this embodiment, instead of the deposition film forming apparatus shown in FIG. 6 used in Embodiment 9, as shown in FIG. In the deposited film forming device disposed between the
Using a high-frequency power source of 1 Hz and according to the conditions shown in Table 7, an amorphous semiconductor film was formed on a cylindrical substrate made of aluminum and having a diameter of 80 mm to produce a photoconductor for electrophotography. In this embodiment, an alumina ceramic cylindrical deposition-inhibiting member having a plurality of exhaust holes at the upper side and the lower side shown in FIG. 1 is used.
0 mm ² , width 1 of exhaust hole band at the top of the side surface of the cylindrical deposition prevention member
a, the relationship between the length L of the exhaust hole band 1b at the lower side surface and the length of the cylindrical deposition prevention member (1a + 1b) /L=0.3, and the distance between the inner surface of the reaction vessel and the exterior surface of the cylindrical deposition prevention member is shown in Example 9. 50mm
Is set to 200 mm, and the diameter of the cylindrical prevention member is set to 600 mm instead of 450 mm shown in the ninth embodiment.
In the deposited film forming apparatus of the present invention used in this embodiment, the discharge electrode is arranged between the cylindrical deposition-inhibiting member and the reaction vessel, so that the power can be confined in the cylindrical deposition-inhibiting member. The produced electrophotographic photoreceptor was installed in a Canon copier NP6550 modified for experiments, and the film thickness unevenness, electrophotographic characteristics, electrophotographic characteristics unevenness, reproducibility of electrophotographic characteristics and When evaluated for white spots, good results were obtained. Further, when the obtained photoreceptor was installed in a Canon copier NP6550 modified for experiment and an image was output, a uniform image was obtained without unevenness in the halftone image. Further, when the text original was copied, a clear image having a high black density was obtained. Also, in copying a photographic original, a clear image faithful to the original could be obtained.

[0045]

According to the apparatus and method for forming a deposited film of the present invention, a cylindrical support member and a cylindrical deposition member installed so as to enclose a raw material gas introduction pipe in a reaction vessel are provided at the upper side surface and the lower side surface. By forming the deposited film by exhausting the raw material gas through the plurality of exhaust holes provided, without complicating the apparatus configuration and the deposited film forming process when manufacturing the electrophotographic photosensitive member. In addition, it is possible to realize a deposition film forming apparatus and method capable of reducing unevenness in film thickness and film quality in the axial direction due to non-uniformity of the source gas during the formation of the deposited film in the axial direction.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view showing a cylindrical deposition preventing member in a deposition film forming apparatus using a plasma CVD method of the present invention.

FIG. 2 is a schematic explanatory view showing a cylindrical deposition prevention member used in an embodiment of the present invention.

FIG. 3 is a schematic explanatory view showing a cylindrical deposition prevention member used in the embodiment of the present invention.

FIG. 4 is a schematic explanatory view showing a cylindrical deposition prevention member used in the embodiment of the present invention.

FIG. 5 is an example of a deposited film forming apparatus for forming a light receiving layer of an electrophotographic light receiving member that can be used in the present invention, and is a schematic view of an apparatus for manufacturing an electrophotographic light receiving member by a plasma CVD method. FIG. (A) is a diagram of the device viewed from the side, and (B) is a diagram of the device viewed from directly above.

FIG. 6 is an example of a deposited film forming apparatus for forming a light receiving layer of an electrophotographic light receiving member that can be used in the present invention, and is a schematic view of an apparatus for manufacturing an electrophotographic light receiving member by a plasma CVD method. FIG. (A) is a diagram of the device viewed from the side, and (B) is a diagram of the device viewed from directly above.

FIG. 7 is an example of a deposited film forming apparatus for forming a light receiving layer of an electrophotographic light receiving member that can be used in the present invention, and is a schematic view of an apparatus for manufacturing an electrophotographic light receiving member by a plasma CVD method. FIG. (A) is a diagram of the device viewed from the side, and (B) is a diagram of the device viewed from directly above.

FIG. 8 is an example of a deposited film forming apparatus for forming a light receiving layer of an electrophotographic light receiving member that can be used in the present invention, and is a schematic view of an apparatus for manufacturing an electrophotographic light receiving member by a plasma CVD method. FIG. (A) is a diagram of the device viewed from the side, and (B) is a diagram of the device viewed from directly above.

FIG. 9 is an example of a deposited film forming apparatus for forming a light receiving layer of an electrophotographic light receiving member that can be used in the present invention, and is a schematic view of an apparatus for manufacturing an electrophotographic light receiving member by a plasma CVD method. FIG. (A) is a diagram of the device viewed from the side, and (B) is a diagram of the device viewed from directly above.

FIG. 10 is an example of a deposited film forming apparatus for forming a light receiving layer of an electrophotographic light receiving member that can be used in the present invention, and is a schematic view of an apparatus for manufacturing an electrophotographic light receiving member by a plasma CVD method. FIG. (A) is a diagram of the device viewed from the side, and (B) is a diagram of the device viewed from directly above.

FIG. 11 is a schematic explanatory view showing a cylindrical deposition-inhibiting member having an exhaust hole formed in the entire surface thereof in a conventional apparatus for manufacturing an electrophotographic light-receiving member by a plasma CVD method.

[Explanation of symbols]

 110, 510: reaction vessel 111, 511: cylindrical support 112, 512: substrate heating heater 113, 513: source gas introduction pipe 114, 514: matching box 115, 515: source gas pipe 116, 516: vacuum gauge 117 517: Cylindrical deposition preventing member 118, 518: Discharge electrode 119, 519: Cylindrical base 120, 520: Throttle valve 130: Bottom 313: Source gas inlet tube 314: Source gas inlet tube 318: Discharge electrode 319: Discharge electrode 501: Exhaust hole zone

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshiyasu Shirasuna 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Hitoshi Murayama 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Takashi Otsuka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Tatsuyuki Aoike 3-30-2, Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (14)

[Claims] 1. A reaction vessel which can be decompressed and accommodates a substrate, a discharge electrode, a substrate heating heater, and a rotary electrode which is installed in the reaction vessel so as to include the substrate heating heater and also serves as a discharge electrode. Having a cylindrical support capable of being provided along a longitudinal direction of the cylindrical support, for supplying a source gas to the reaction vessel, a source gas introduction pipe for forming a deposition film, and for exciting the source gas. Plasma CVD comprising a power supply unit and a unit for exhausting the inside of the reaction vessel, and forming a deposited film on the substrate supported by the cylindrical support
In the deposition film forming apparatus by the method, in the reaction space of the reaction vessel, a partial region of a cylindrical deposition prevention member installed to include the cylindrical support and the raw material gas introduction pipe has a plurality of holes. An apparatus for forming a deposited film, comprising: 2. The deposited film forming apparatus according to claim 1, wherein said partial region is provided on at least one of a side upper portion and a side lower portion of said cylindrical deposition preventing member. 3. The deposited film forming apparatus according to claim 1, wherein an aperture ratio in said partial region is larger than an aperture ratio in a central portion of said cylindrical deposition-inhibiting member. 4. The method according to claim 1, wherein an area S [mm ² ] of one of the holes formed in the cylindrical deposition-inhibiting member is within the range of the following formula (I). Deposition film forming equipment. 0.5 ≦ S ≦ 250 (I) 5. An axial length of the cylindrical deposition-inhibiting member is L,
The width of the first partial area provided on the upper side surface of the cylindrical attachment member is 1a, and the width of the second partial area provided on the lower side surface of the cylindrical attachment member is 1b. Then
2. The deposited film forming apparatus according to claim 1, wherein (1a + 1b) / L is within the range of the following formula (II). 0.1 ≦ (1a + 1b) /L≦0.6 (II) 6. The method according to claim 1, wherein a distance d [mm] between the inner surface of the reaction vessel and the outer surface of the cylindrical deposition-inhibiting member is within the range of the following formula (III). An apparatus for forming a deposited film according to claim 1. 5 ≦ d ≦ 500 (III) 7. The power supply means has a frequency of 50 MHz.
The high frequency discharge energy of not less than 450 MHz and not more than 450 MHz is applied.
Item 6. The deposited film forming apparatus according to Item 1. 8. A discharge electrode provided in a reaction vessel which can be decompressed, a substrate heater, a rotatable cylindrical support which is provided so as to include the substrate heater and serves also as a discharge electrode, and A source gas introduction pipe for depositing film formation provided along the longitudinal direction of the cylindrical support, power supply means for exciting the source gas supplied into the reaction vessel, and exhausting the inside of the reaction vessel Means for depositing a deposited film on a substrate supported by the cylindrical support by plasma C
In a method of forming a deposited film by a VD method, a cylindrical deposition member is installed in a reaction space of the reaction vessel so as to include the cylindrical support and the source gas introduction pipe, Forming a deposition film on the substrate by exhausting the raw material gas from a space included in the cylindrical deposition prevention member through a plurality of holes provided in a partial region of the deposition member. . 9. The method according to claim 8, wherein the partial region is provided on at least one of an upper side surface and a lower side surface of the cylindrical deposition-inhibiting member. 10. The method according to claim 8, wherein an aperture ratio in the partial region is larger than an aperture ratio in a central portion of the cylindrical deposition-inhibiting member. 11. The method according to claim 8, wherein an area S [mm ² ] of one of the holes formed in the cylindrical deposition-inhibiting member is within the range of the following formula (I). A method for forming a deposited film. 0.5 ≦ S ≦ 250 (I) 12. The axial length of the cylindrical attachment member is L, the width of the first partial region provided above the cylindrical attachment member is 1a, and the width of the cylindrical attachment member is 1a. Assuming that the width of the second partial region provided at the lower part of the side surface is 1b, (1
The method according to any one of claims 8 to 11, wherein a + 1b) / L is within the range of the following formula (II). 0.1 ≦ (1a + 1b) /L≦0.6 (II) 13. The method according to claim 8, wherein a distance d [mm] between the inner surface of the reaction vessel and the outer surface of the cylindrical deposition-inhibiting member is within the range of the following formula (III). The method for forming a deposited film according to claim 1. 5 ≦ d ≦ 500 (III) 14. The power supply means has a frequency of 50 MHz.
The method according to any one of claims 8 to 13, wherein the frequency is equal to or more than z and equal to or less than 450 MHz.