JPH08236457A - Formation of deposited film and electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE: To uniformly treat a substrate having a relatively large area with plasma at a high speed by arranging a plurality of cylindrical high-frequency electrodes and causing discharge by alternately applying high-frequency power upon the electrodes. CONSTITUTION: The period of the intermittent outputs of high-frequency power sources 131 and 132 is adjusted to a desired value by means of a high-frequency power source controller 141 and glow discharge is created by supplying electric power of 20-450MHz in frequency to high-frequency electrodes 111 and 112. Matching circuitss 121 and 122 are then adjusted so that reflected waves can become the smallest. The formation of a layer is completed after a depositing chamber 101 is once evacuated to a high vacuum by adjusting the circuits 121 and 122 so that the difference between the high-frequency incident power and reflected power can become the prescribed valve and stopping the glow discharge when a film is deposited to a desired thickness, and then, stopping the flow of a gaseous starting material to the chamber 101 by closing a gaseous starting material introducing valve 107.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline or non-single crystalline functional deposited film which is useful for electrophotographic photoreceptor devices as semiconductor devices, image input line sensors, image pickup devices, photovoltaic devices and the like. The present invention relates to a deposited film forming method for forming an insulating film or a metal wiring as a semiconductor device or an optical element, and particularly to a plasma CVD method.

[0002]

2. Description of the Related Art There are various plasma processing methods used for semiconductors and the like depending on their respective applications. For example, in film formation, various features such as oxide film using plasma CVD method, nitride film formation and amorphous silicon semiconductor film, metal wiring film using sputtering method, fine processing technology using etching method, etc. The method of making the most of is used.

Further, in recent years, there has been a strong demand for improvement in film quality and processing capacity, and various devices have been studied.

Particularly, the plasma process using high frequency power is widely used because it has high discharge stability and various advantages such as being usable for forming an insulating material such as an oxide film or a nitride film. . The oscillation frequency of the high-frequency power supply for discharge that has been conventionally used in plasma processes such as plasma CVD is generally 13.56 MHz.

FIG. 8 shows an example of a plasma CVD apparatus generally used for forming such a conventional deposited film. The plasma CVD apparatus shown in FIG. 8 has an amorphous silicon film (hereinafter referred to as “a-Si” on a cylindrical conductive substrate.
It is a film forming apparatus suitable for producing a photoconductor for electrophotography by depositing a film. Hereinafter, using this device
A method of forming the -Si film will be described.

A cylindrical high frequency electrode 811 and a cylindrical conductive substrate (electrophotographic photosensitive member substrate) 802 as a counter electrode are arranged in a deposition chamber 801 capable of depressurizing. Auxiliary bases 803 and 804 are attached to both ends of the cylindrical conductive base 802, and form a part of a counter electrode. In order to improve the uniformity of the film thickness and the film characteristics, the dimension of the high frequency electrode 811 in the cylinder axis direction is set to be approximately the same as the length of the cylindrical conductive substrate 802 and the auxiliary substrates 803, 804 in the cylinder axis direction. . The cylindrical conductive substrate 802 is heated from the inside by a heater 805 inside. The high frequency power supply 831 is connected to the high frequency electrode 811 via the matching circuit 821. Reference numeral 808 is a vacuum exhaust port, 809 is a main valve, 807 is a source gas introduction valve, and 806 is a source gas introduction port.

A cylindrical conductive substrate 802 is provided in the deposition chamber 801.
Is installed, the main valve 809 is opened, and the inside of the deposition chamber 801 is temporarily evacuated through the exhaust port 808. After that, the raw material gas introduction valve 807 is opened, an inert gas is introduced into the deposition chamber 801 through the raw material gas introduction block 806, and the flow rate is adjusted so as to have a predetermined pressure. The heating heater 805 is energized to heat the cylindrical conductive substrate 802 to a desired temperature. After that, a raw material gas for film formation, for example, a raw material gas such as silane gas, disilane gas, methane gas, ethane gas, or diborane gas is supplied through the raw material gas inlet 806.
Introducing a doping gas such as phosphine gas, several Pa
The evacuation speed is adjusted so as to maintain the pressure at 1 to several hundred Pa.

The high frequency power of 13.56 MHz is supplied from the high frequency power source 831 through the matching circuit 821 to the high frequency electrode 81.
1 to supply a plasma discharge between the high frequency electrode 811 and the cylindrical conductive substrate 802 as the counter electrode to decompose the raw material gas, thereby forming an a-Si film on the cylindrical conductive substrate 802. Deposit. During this time, the cylindrical conductive substrate 802 is maintained at a desired temperature by the heater 805. At that time, the cylindrical conductive substrate 802 may be rotated by a rotation mechanism (not shown) as needed to improve the film thickness distribution in the circumferential direction.

The deposition rate for obtaining an a-Si film satisfying the performance of the electrophotographic photoreceptor by this film forming method is, for example, 1
The deposition rate is about 0.5 to 6 μm per hour, and if the deposition rate is further increased, the characteristics of the photoconductor may not be obtained. In general, when an a-Si film is used as a photoconductor for electrophotography, a film thickness of at least 20 to 30 μm is required to obtain charging ability, and it takes a long time to manufacture the photoconductor for electrophotography. I needed it.
Therefore, there has been a strong demand for a technique for reducing the manufacturing time without deteriorating the characteristics of the photoconductor.

By the way, in recent years, a parallel plate type plasma CV is used.
There is a report of a plasma CVD method using a high frequency power source of 20 MHz or more by a D device (Plasma Chemistry and P
lasma Processing, Vol.7, No.3, (1987) p.267-27
3) It has been noted that increasing the discharge frequency higher than the conventional 13.56 MHz has the potential to improve the deposition rate without degrading the performance of the deposited film, and is drawing attention. In addition, reports of increasing the discharge frequency have also been made in sputtering and the like, and its superiority has been widely studied in recent years.

[0011]

Therefore, the inventors of the present invention set the discharge frequency to the conventional 13.56 M in order to improve the deposition rate.
When a high-frequency power having a frequency higher than Hz was used and the film-forming procedure was performed in the same manner as in the conventional method, it was confirmed that the film could be deposited at a higher deposition rate than the conventional method. However, in this case, it was found that the following problems, which were not a problem at the discharge frequency of 13.56 MHz, may newly occur.

That is, when the film formation is performed while rotating the cylindrical conductive substrate, a film having characteristics substantially equal to those of the conventional film is deposited, and the film thickness distribution in the circumferential direction is naturally evenly deposited. be able to. However, for the purpose of reducing the cost of the film forming furnace and reducing the complexity of maintenance, a cylindrical conductive substrate is formed in a stationary state by using a deposition film forming apparatus in which the rotating mechanism of the cylindrical conductive substrate is omitted. It was found that a large film thickness difference occurs in the circumferential direction. In other words, it did not appear on the surface when the cylindrical conductive substrate was rotated, but in reality, the plasma state in the film formation furnace was considerably unevenly distributed in the circumferential direction, and the deposition rate also greatly varied depending on the location. Became clear.

Furthermore, when an electrophotographic photosensitive member is manufactured by forming a film of a cylindrical conductive substrate in a stationary state, not only the deposition rate but also the electrophotographic characteristics of the deposited film differ depending on the location in the circumferential direction. I found it quite different. Since the unevenness of this characteristic cannot be explained only by the difference in the film thickness of the deposited film, it is presumed that the film quality itself of the deposited film is different in the circumferential direction.

Further, in a portion where the film quality in the circumferential direction is good, the characteristics are superior to those of the electrophotographic photosensitive member formed by rotating the cylindrical conductive substrate, and conversely, in the portion where the film quality in the circumferential direction is poor. Was found to be inferior to the characteristics of the rotated electrophotographic photoreceptor. That is, it is presumed that in the electrophotographic photosensitive member formed by rotating the cylindrical conductive substrate, a film having inferior properties and a film having excellent properties are laminated, and average properties are exhibited.

As described above, in the conventional film formation by the high frequency power having a frequency higher than 13.56 MHz, when the cylindrical conductive substrate is formed in a stationary state, the film thickness and film characteristics in the circumferential direction become uneven, As a result, image unevenness, which is a problem in practical use, may occur in a relatively large area work piece such as an electrophotographic photoreceptor.

Further, in the case of forming a film by rotating the cylindrical conductive substrate, it is inevitable that a film having excellent characteristics and a film having inferior characteristics are laminated due to uneven distribution of plasma, and the film characteristics as a whole. However, there is a problem in that good film characteristics that should be expected cannot be obtained.

Such unevenness of the film thickness (that is, the deposition rate) and the film characteristics are not limited to the electrophotographic photoconductor, but are also single crystal or non-crystalline materials useful for image input line sensors, image pickup devices, photovoltaic devices and the like. This is a big problem when forming a monocrystalline functional deposited film. Furthermore, in other plasma processes such as dry etching and sputtering, similar process unevenness occurs when the discharge frequency is increased,
As it is, it will become a big problem in practical use.

Therefore, an object of the present invention is to overcome the above-mentioned conventional problems and uniformly perform plasma processing on a relatively large-area substrate at a high processing speed which cannot be achieved by the conventional plasma process. Another object of the present invention is to provide a method for forming a deposited film capable of achieving the above, and to provide an electrophotographic photoreceptor having excellent image characteristics.

[0019]

SUMMARY OF THE INVENTION According to the present invention, a cylindrical conductive substrate is arranged in a vacuum-tight deposition chamber provided with an exhaust unit and a source gas introducing unit, and the cylindrical conductive substrate is enclosed and A high-frequency power is applied to a cylindrical high-frequency electrode arranged concentrically with the base to generate a discharge between the high-frequency electrode and the cylindrical conductive base, and the source gas introduced into the deposition chamber is discharged. In the deposited film forming method of forming a deposited film on the cylindrical conductive substrate by disassembling by, the plurality of cylindrical high frequency electrodes are arranged, and high frequency power is alternately applied to each of the high frequency electrodes. Disclosed is a method for forming a deposited film, which is characterized by causing discharge, and an electrophotographic photoreceptor obtained by the method.

The present inventors have solved the film thickness and film characteristic unevenness in the circumferential and axial directions when a film is formed on a cylindrical conductive substrate in a static state using a high frequency of 20 to 450 MHz. In order to do so, we conducted a thorough study.

First, an experiment was conducted to confirm the positional relationship between the film thickness unevenness and the position where the high frequency power is introduced. As a result, contrary to the expectation, a film thickness distribution that was not correlated with the position where the high frequency power was introduced was recognized. The reason for this is currently unknown, but 20 MHz to 450 MH
When using a so-called VHF high frequency called z,
It is considered that this is because the inductance component of the high frequency electrode (cathode) to which the high frequency power is applied cannot be ignored.

However, if only the inductance is a problem, the deposition rate should be high on the side to which the high frequency is applied, and low on the opposite side where the physical distance is far from the application position. The fact that there is no correlation in the positional relationship means that not only the inductance of the high frequency electrode is a problem in this frequency range, but also the capacitance between the high frequency electrode and the cylindrical conductive substrate (anode). There is a nature. That is, 20-450
In the frequency region of MHz, the deposition furnace itself forms a series resonance circuit of inductance and capacitance, and it is speculated that the high-frequency power increases and the decomposition rate of the raw material gas increases at the position where the resonance condition shown by the following formula is satisfied. It

[0023]

Ω = 1 / (L · C) ^{1/2 In the} above formula, ω is the angular velocity, L is the inductance, and C is the capacitance.

Further, when the electric characteristics of the film deposited on the cylindrical conductive substrate after film formation were measured, the film at the place where the deposition rate was high exhibited better properties than the film at the place where the deposition rate was low. It has been found. Usually, the smaller the deposition rate, the better the film properties, but in this case, it is considered that supplying sufficient high-frequency energy to the source gas contributes to the improvement of the film properties.

From the above experiment, in the film formation using the high frequency of 20 to 450 MHz, if the high frequency power can be applied uniformly in the circumferential direction of the high frequency electrode, the cylindrical conductive substrate can be rotated sufficiently without rotating. Since it is considered that the uniformity of the film thickness in the direction can be obtained and sufficient electric power can be supplied, it was concluded that the film quality of the deposited film can be improved.

Therefore, by making the length of the high frequency electrode in the axial direction shorter than that of the cylindrical conductive substrate, it becomes possible to apply the high frequency power more uniformly in the circumferential direction, and as a result, the film thickness in the circumferential direction becomes uniform. It has been revealed that the property is improved and the film quality is also improved. However, particularly when using a long cylindrical conductive substrate, it has become necessary to use a plurality of these high-frequency electrodes in the axial direction in order to ensure uniformity in the axial direction. When using a plurality of high-frequency electrodes, it is possible to ensure uniformity in the axial direction, but depending on the discharge conditions, the discharges from multiple high-frequency electrodes interfere with each other, making it difficult to match the high-frequency power. In some cases, the discharge becomes unstable, or it becomes difficult to generate a uniform discharge over the entire surface of the cylindrical conductive substrate. Therefore, there are cases where the film forming conditions are limited and it is not possible to obtain a deposited film of sufficient film quality, and it is necessary to further improve the film forming method.

Based on the above findings, the present inventor substantially applies discharge power to a plurality of high frequency electrodes to cause discharges alternately between the plurality of high frequency electrodes and the cylindrical conductive substrate, thereby substantially Is to generate a uniform discharge over the entire surface of the cylindrical conductive substrate. In this way, when alternating discharges are generated in multiple high-frequency electrodes, the interference of discharges between the high-frequency electrodes is reduced compared to the case where they are simultaneously discharged, resulting in excellent consistency and stable discharge. It becomes easy to obtain a uniform discharge over the entire surface of the conductive substrate. Furthermore, the stable discharge facilitates the decomposition state of the raw material gas to a desired state, and the quality of the deposited film can be improved.

[0028]

The present invention will be described in detail below with reference to the drawings.

FIG. 1 is a schematic longitudinal sectional view of an example of an apparatus for carrying out the method of the present invention, which is suitable for producing a deposited film on a cylindrical substrate such as an electrophotographic photoreceptor. is there.

In FIG. 1, reference numeral 101 is a deposition chamber for forming a deposited film, and an exhaust chamber 108 and a main valve 10 are provided.
It is connected via 9 to an exhaust device (not shown). 106
Is a source gas introduction port for introducing the source gas into the deposition chamber 101, and introduces the source gas into the deposition chamber 101 from a gas supply system (not shown) via the source gas introduction valve 107. Reference numeral 102 denotes a cylindrical conductive substrate connected to the ground, and auxiliary substrates 103 and 104 are provided above and below the cylindrical conductive substrate. Reference numeral 105 is a heater for heating the substrate to a predetermined temperature. In addition, the cylindrical conductive substrate 102 is
It is possible to make the film thickness in the circumferential direction more uniform by rotating it by a rotating mechanism (not shown) if necessary.

131 and 132 are 20 MHz to 45
A high-frequency power supply that generates a high frequency of 0 MHz, and the high-frequency power supply controller 141 controls the cycle of the high-frequency output intermittently output from each high-frequency power supply 131 and 132 to a predetermined value, and the matching circuits 121 and 122, respectively. High frequency power is alternately applied to each of the high frequency electrodes 111 and 112 via. As shown in the figure, the high frequency electrodes 111 and 112 are arranged at a predetermined interval by the insulating ring 110. The high frequency electrodes 111 and 112 and the insulating ring 110 may also serve as the inner wall of the deposition chamber 101.

FIG. 2 is a schematic cross-sectional view of an example of the device as shown in FIG. In FIG. 2, 2
Reference numeral 01 is a deposition chamber for forming a deposited film, and the high frequency electrodes 211 and 2 are concentrically formed with the cylindrical conductive substrate 202.
12 are arranged. A source gas introduction port 206 is arranged in the deposition chamber 202. Each high-frequency electrode 2 from a high-frequency power source (not shown) via matching circuits 221 and 222.
High frequency power is supplied to 11 and 212. that time,
By introducing the high frequency power from the matching circuits 221 and 222 to the high frequency electrodes 211 and 212 at two locations, it becomes possible to apply the high frequency power more uniformly in the circumferential direction of the high frequency electrodes 211 and 212. .

As the material used for the high-frequency electrodes 111 and 112, any material having high conductivity can be used, but for the purpose of minimizing the inductance of the electrode itself, the material used should have a low magnetic permeability. preferable. Specific materials include Cu, Al, A
u, Ag, Pt, Pb, Ni, Co, Fe, Cr, M
Metals such as o and Ti and alloys thereof (for example, stainless steel) are preferable.

Cooling means may be provided to the high frequency electrodes 111 and 112 as required. As specific cooling means, water, air, liquid nitrogen, a Peltier element, or the like is used as necessary.

The high-frequency electrodes 111 and 112 are preferably shaped so that the surface area is as large as possible in consideration of the skin effect of high-frequency power. In consideration of ease of matching and processing, etc. The flat plate shape is optimal.

The length of the high frequency electrodes 111 and 112 in the axial direction is the same as that of the cylindrical conductive substrate 10 which is an opposing electrode.
2 and the lengths of the auxiliary bases 103 and 104, and further the wiring from the matching circuit to the high-frequency power introducing means is appropriately set. The length of the cylindrical conductive base 102 and the lengths of the auxiliary bases 103 and 104 are set. The total length is preferably 1/2 or less, more preferably 1/3 or less.

As the material used for the insulating ring 110, any material can be used as long as it has the strength to hold a vacuum and has a high insulating property, but it should not affect the high frequency power applied to the high frequency electrodes 111 and 112. Therefore, a material having a high dielectric breakdown voltage and a small dielectric loss tangent is preferable. Specific materials include Teflon (trade name; DuPont), alumina, silicon oxide, silicon carbide, silicon nitride,
Examples thereof include boron nitride, aluminum nitride and polystyrene.

High frequency power supplies 115 and 116 used
Can use anything if the oscillation frequency is 20 MHz to 450 MHz, but 50 MHz to 450 MH
Oscillation frequencies in the z range are more preferred. Oscillation frequency is 2
If it is less than 0 MHz, the discharge may become unstable depending on the conditions, and the conditions for forming the deposited film may be limited. In particular, when the pressure inside the deposition chamber is low, the discharge tends to be unstable. On the other hand, if it is higher than 450 MHz, the transmission characteristic of high frequency power is deteriorated, and further, the leakage of high frequency power is likely to occur during transmission, and in some cases, it may be difficult to generate glow discharge itself.

The high frequency waveform is not particularly limited, but a sine wave, a rectangular wave or the like is suitable. The output is 10W to 10k.
Any output can be used as long as it can generate electric power suitable for the device in the range of W.

The high frequency electric power intermittently output from each of the high frequency electric power sources 131 and 132 is alternately output in a cycle as shown in FIG. 7, for example.

That is, in FIG. 7A, the electric power output from each high frequency power source is alternately changed in a sine wave shape.

In FIG. 7B, the electric power output from each high-frequency power source is alternately changed in a triangular wave shape.

In FIG. 7C, the electric power output from each high-frequency power source is alternately changed to a rectangular wave (trapezoidal wave) shape.

In FIG. 6D, the electric power output from each high-frequency power source is alternately changed into a rectangular wave (trapezoidal wave) having a small duty ratio.

Matching circuits 121 and 122 used
Can be suitably used in any configuration as long as it can match the load with the high frequency power supplies 131 and 132. Further, as a method for obtaining matching, an automatically adjusted method is suitable for avoiding complication during manufacturing, but even if manually adjusted, the effect of the present invention can be achieved. it can. Regarding the position where the matching circuit is placed, it does not matter where it is placed within the range where matching can be achieved, but it should be placed so that the inductance of the wiring from the matching circuit to the high frequency power introducing means is made as small as possible. However, it is desirable because it can be matched under a wide load condition.

The procedure of an example of the method for forming a deposited film of the present invention will be described below.

First, the auxiliary substrates 103 and 1 are formed on the cylindrical conductive substrate 102 whose surface is mirror-finished by a lathe, for example.
04, and a heater 10 for heating in the deposition chamber 101.
5, the cylindrical conductive substrate 102 and the auxiliary substrate 1
Insert 03.104.

Next, the raw material gas introduction valve 107 is closed, the main valve 109 is opened, and the inside of the deposition chamber 101 is temporarily evacuated through the exhaust air 108, and then the raw material gas introduction valve 107 is opened to open the heating chamber. An active gas (for example, argon) is introduced into the deposition chamber 101 from the source gas introduction unit 106, and the flow rate of the heating gas is adjusted so that the inside of the deposition chamber 101 has a predetermined pressure. Then, a temperature controller (not shown) is operated to heat the cylindrical conductive substrate 102 by the heating heater 105, and the cylindrical conductive substrate 102 is heated.
Is heated to a predetermined temperature, the raw material gas introduction valve 107 is closed to stop the gas flow into the deposition chamber 101.

The source gas introduction valve 107 is used to form the deposited film.
Is opened and a predetermined source gas is introduced into the deposition chamber 101 from the source gas introduction port 106, and 0.01 Pa to 1000 Pa
Adjust the pumping speed to maintain the desired pressure in the range. After the pressure stabilizes, the high frequency power supplies 131 and 132
Power is turned on, the high-frequency power supply control device 141 adjusts the intermittent output cycle of the high-frequency power supplies 131 and 132 to a desired value, and power of a frequency of 20 MHz to 450 MHz is supplied to the high-frequency electrodes 111 and 112 to cause glow discharge. Raise it. At this time, the matching circuits 121 and 122 are adjusted so as to minimize the reflected wave. The value obtained by subtracting the reflected power from the high frequency incident power is adjusted to a predetermined value, the glow discharge is stopped when the deposited film is formed with a desired film thickness, and the source gas introduction valve 107 is closed. The flow of the source gas into the deposition chamber 101 is stopped, the inside of the deposition chamber 101 is once evacuated to a high vacuum, and then the layer formation is completed. When stacking deposited films having various functions, the above operation is repeated.

The source gas used in the present invention is, for example, SiH when forming amorphous silicon.
₄ , a gas state such as Si ₂ H ₆ or a gasifiable silicon hydride (silanes) is effectively used as a gas for introducing silicon. In addition to silicon hydride, a silicon compound containing fluorine, a so-called fluorine-substituted silane derivative, specifically, silicon fluorides such as SiF ₄ and Si ₂ F ₆ , SiH ₃ F, and SiH are used. Gaseous or gasifiable substances such as fluorine-substituted silicon hydride such as ₂ F ₂ and SiHF ₃ are also effective as the gas for introducing silicon of the present invention. In addition, if necessary, the raw material gas for introducing silicon may be H ₂ , H
Even if it is diluted with a gas such as e, Ar or Ne and used, there is no problem in the present invention.

The halogen-introducing gas for containing a halogen atom in the a-Si film is, for example, a halogen gas, a halide, an interhalogen compound containing halogen, a silane derivative substituted with halogen, or the like. Preferable are halogen compounds which can be gasified. Further, a silicon hydride compound containing halogen, which is composed of silicon and a halogen element and which can be gasified or gasified, can be cited as an effective one.

Specific examples of the halogen compound that can be preferably used include fluorine gas (F ₂ ), BrF, ClF and C.
_{lF 3, BrF 3, BrF 5} , may be mentioned IF _3, IF ₇ or the like interhalogen compounds of. As a silicon compound containing halogen, that is, a so-called halogen-substituted silane derivative, silicon fluorides such as SiF ₄ and Si ₂ F ₆ can be specifically mentioned as preferable examples.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the halogen-introducing gas. In addition to these, halogens such as HF, HCl, HBr and HI are used. Hydrogen fluoride; SiH ₃ F, SiH ₂ F ₂ , SiHF ₃ , SiH
₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , S
Halides containing halogen-substituted silicon hydride such as iHBr ₃ or the like, which can be gasified or which contains hydrogen as a constituent element, can also be cited as an effective source gas.

These halogen-containing halides are used as a preferred halogen atom-introducing gas in the present invention because hydrogen atoms are introduced together with the halogen atoms.

Further, in addition to the above, H ₂ , D ₂ or SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ are effective as hydrogen introducing gas for containing hydrogen atoms in the a-Si film.
Examples thereof include silicon hydride such as H ₁₀ .

Furthermore, 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 " It is also possible to use an element that controls the conductivity (abbreviated as “group 5 element”) as a so-called dopant.

Specific examples of the Group 3 element include boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), etc., and particularly B, Al, and Ga. It is suitable. Specific examples of the group 5 element include phosphorus (P), arsenic (As), antimony (S)
b), bismuth (Bi), etc., and P and As are particularly preferable. For example, as a gas for introducing boron, B ₂ H ₆ , B ₄
Examples thereof include boron hydride such as H ₁₀ and boron halide such as BF ₃ and BCl ₃ . Other gas for introducing a Group 3 element is AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl.
₃ , TlCl _{3 and the} like can also be mentioned.

Further, as a gas for introducing phosphorus, PH ₃ , P ₂ H
Phosphorus hydride such as ₄ , PH ₄ I, PF ₃ , PCl ₃ , PBr ₃ ,
A phosphorus halide such as PI3 can be used. As other group 5 element introduction gases, AsH ₃ , AsF ₃ , AsCl
3, ASBr3, AsF5, SbH3, SbF3, Sb
F5, SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , B
iBr ₃ etc. can also be mentioned.

Further, these element introducing gases for controlling the conductivity may be diluted with H ₂ and / or He as necessary and used.

In addition, 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, C and H having constituent elements such as carbon, for example, carbon. A saturated hydrocarbon of the numbers 1 to 5,
Ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms and the like can be used. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C
₂ H ₆ ) etc., ethylene (C
₂ H ₄ ), propylene (C ₃ H ₆ ) and the like, acetylene hydrocarbons include acetylene (C ₂ H ₂ ) and methylacetylene (C ₃ H ₄ ).

When forming amorphous silicon oxide (a-SiO), for example, oxygen (O ₂ ), ozone (O ₂ ) and ozone (O ₂ ) can be used as a gas for introducing oxygen atoms in addition to the above-mentioned raw material gas. ₃ ), air monoxide (N
O), nitrogen dioxide (NO ₂ ), nitrogen dioxide (N ₂ O), nitrous oxide (N ₂ O ₃ ), nitrous oxide (N ₂ O ₄ ), nitrous oxide (N ₂ O ₅ ). , Nitric oxide (NO ₃ ); silicon (Si), oxygen (O) and hydrogen (H) as constituent elements, for example, disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ), etc. And lower siloxanes thereof.

In the present invention, for example, in the case of forming amorphous silicon nitride (a-SiN), nitrogen (N ₂ ) and ammonia can be used as a gas for introducing nitrogen atoms in addition to the above-mentioned raw material gas. (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), and other nitrogen compounds such as nitrogen, nitrogen compounds and azides that can be gasified. There are many things to list. In addition to this, in addition to the introduction of nitrogen atoms,
Nitrogen halide compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be mentioned from the viewpoint that a halogen atom can be introduced.

FIG. 6 shows a typical example of the layer structure when an electrophotographic photosensitive member is produced using the present invention.

An electrophotographic photosensitive member 600 shown in FIG. 6A.
Is provided with a photoconductive layer 602 having photoconductivity, which is made of a-Si containing hydrogen and / or halogen (hereinafter referred to as “a-Si (H, X)”) on the base 601. .

An electrophotographic photoreceptor 600 shown in FIG. 6B.
Is composed of a photoconductive layer 602 made of a-Si (H, X) and having photoconductivity and an amorphous silicon-based surface layer 603 on a base body 601.

An electrophotographic photosensitive member 600 shown in FIG. 6C.
Is composed of a photoconductive layer 602 made of a-Si (H, X) and having photoconductivity, an amorphous silicon-based surface layer 603, and an amorphous silicon-based charge injection blocking layer 604 on a substrate 601. There is.

Electrophotographic photoreceptor 600 shown in FIG. 6D.
A photoconductive layer 602 is provided on the base 601. The photoconductive layer 602 is composed of a charge generation layer 605 made of a-Si (H, X) and a charge transport layer 606, and an amorphous silicon based surface layer 603 is provided thereon.

Next, the substrate will be described.

The substrate of the electrophotographic photoreceptor may be either conductive or electrically insulating. As the conductive substrate,
Al, Cr, Mo, Au, In, Nb, Te, V, T
Examples thereof include metals such as i, Pt, Pd, and Fe, and alloys thereof (for example, stainless steel). Also, a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, or polyamide,
It is also possible to use a substrate in which at least the surface of the electrically insulating substrate such as glass or ceramic on which the light receiving layer is formed is subjected to a conductive treatment. 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 base 601 preferably has a cylindrical shape, and the thickness of the base 601 is as desired.
0 is formed appropriately, but when flexibility as the electrophotographic photoreceptor 600 is required, the base 6
It can be made as thin as possible within a range where the function as 01 can be sufficiently exhibited. However, the substrate 601 is usually 1 in terms of manufacturing and handling, mechanical strength, and the like.
It is set to 0 μm or more.

The surface shape of the substrate 601 can be a smooth flat surface or an uneven surface. For example, in the case of recording an image on a photoconductor for electrophotography using coherent light such as laser light, in order to eliminate an image defect due to an interference fringe pattern appearing in a visible image, JP-A-60-16881 is used.
56, 60-178457 and 60-2.
It can be an uneven surface produced by a known method described in Japanese Patent No. 25854.

The photoconductive layer 602 is formed on the substrate 601 by appropriately setting the numerical conditions of film forming parameters so that desired characteristics can be obtained. In order to form the photoconductive layer 602, basically, a gas for introducing silicon as described above,
A gas for introducing hydrogen and / or a gas for introducing halogen,
It is introduced into the deposition chamber in a predetermined gas state to cause glow discharge in the deposition chamber, and a layer made of a-Si (H, X) is formed on the substrate 601 installed in a predetermined position in advance.

Further, by containing hydrogen atoms and / or halogen atoms in the a-Si film in the photoconductive layer 602, the dangling bonds of Si atoms are compensated, and the layer quality is improved, especially the photoconductive and This is because it is essential to improve the charge retention characteristics. Therefore, the content of hydrogen atoms or halogen atoms, or the sum of hydrogen atoms and halogen atoms is 10 to 40 atom%, more preferably 15 to 2 with respect to the sum of silicon atoms, hydrogen atoms and / or halogen atoms.
It is desirable to set it to 5 atom%.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 602, for example, the temperature of the substrate 601, the raw material used for containing hydrogen atoms and / or halogen atoms. The amount of gas introduced into the deposition chamber, discharge power, etc. may be controlled.

It is preferable that the photoconductive layer 602 contains an element for controlling the conductivity, if necessary. The conductivity controlling element may be contained in the photoconductive layer 602 in a uniformly distributed state, or may be contained in a nonuniformly distributed state in the layer thickness direction. Good.

As the element for controlling the conductivity, the above-mentioned Group 3 element or Group 5 element can be used.

The content of the element controlling the conductivity contained in the photoconductive layer 602 is preferably 1 × 10 ⁻² to 1
× 10 ⁴ atomic ppm, more preferably 5 × 10 ^{-2 to} 5 ×
It is desirable that the concentration is 10 ³ atom ppm, optimally 1 × 10 ⁻¹ to 1 × 10 ³ atom ppm.

In order to structurally introduce an element for controlling conductivity, for example, a Group 3 element or a Group 5 element, the above-mentioned Group 3 element introduction gas or Group 5 element introduction is performed during layer formation. The working gas may be introduced into the deposition chamber together with another gas for forming the photoconductive layer 602.

Further, it is also effective that the photoconductive layer 602 contains carbon atoms, oxygen atoms and / or nitrogen atoms. The content of carbon atom, oxygen atom and / or nitrogen atom is preferably 1 × 10 ⁻⁵ to 10 atom%, based on the sum of silicon atom, carbon atom, oxygen atom and nitrogen atom,
More preferably 1 × 10 ^-4 to 8 atom%, optimally 1 × 1
0 ^over 3-5 atomic% is desirable. The carbon atoms, oxygen atoms and / or nitrogen atoms may be evenly contained in the photoconductive layer 602 evenly, or may be non-uniform such that the content changes in the layer thickness direction of the photoconductive layer 602. There may be a portion with a distribution.

In order to structurally introduce carbon atoms, oxygen atoms and / or nitrogen atoms, the above-mentioned gas for introducing carbon atoms, oxygen atoms and / or nitrogen atoms is introduced into the deposition chamber at the time of layer formation by light irradiation. It may be introduced together with another gas for forming the conductive layer 602.

The layer thickness of the photoconductive layer 602 is appropriately determined in view of desired electrophotographic characteristics and economic effects, and is preferably 1 to 100 μm, more preferably 10 to 50 μm, and most preferably 20 to 40 μm. Is desirable.

In order to form the photoconductive layer 602 having desired characteristics, it is necessary to properly set the temperature of the substrate 601 and the gas pressure in the deposition chamber.

The temperature (Ts) of the substrate 601 is appropriately selected in accordance with the layer design, but is usually preferably 1
The temperature is 50 to 350 ° C, more preferably 200 to 330 ° C, and most preferably 250 to 300 ° C.

Similarly, the gas pressure in the deposition chamber is appropriately selected according to the layer design, but is usually preferably 0.0.
1-1000 Pa, more preferably 0.05-500 P
a, optimally 0.1 to 100 Pa.

The above-mentioned ranges are mentioned as desirable numerical ranges of the substrate temperature and the gas pressure for forming the photoconductive layer 602. In addition, the mixing ratio with a gas for introducing silicon or a gas for introducing other atoms, It is necessary to appropriately set the discharge power and the like. These conditions are not usually independently determined separately, but it is desirable to determine the optimum value based on the mutual organic relationship to form an electrophotographic photosensitive member having desired characteristics.

Next, the surface layer will be described.

It is preferable to further form an amorphous silicon-based surface layer 603 on the photoconductive layer 602 formed on the substrate 601 as described above. The surface layer 603 is provided mainly for the purpose of improving moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.

The surface layer 603 can be made of any material as long as it is an amorphous silicon type material. For example, amorphous silicon containing hydrogen (H) and / or halogen (X) and further containing carbon ( Hereinafter, referred to as "a-SiC (H, X)"; amorphous silicon containing hydrogen (H) and / or halogen (X), and further containing oxygen (hereinafter "a-SiO (H,
X) ”); amorphous silicon containing hydrogen (H) and / or halogen (X) and further containing nitrogen (hereinafter referred to as“ a-SiN (H, X) ”); hydrogen (H ) And / or halogen (X) and further at least one of carbon, oxygen and nitrogen (hereinafter referred to as “a-Si (C, O,
N) (denoted as (H, X) ”) and the like are preferably used.

The surface layer 603 is formed by the vacuum deposition film forming method by appropriately setting the numerical conditions of film forming parameters so that desired characteristics can be obtained.

For example, in order to form the surface layer 603 made of a-SiC (H, X), basically, the above-mentioned silicon atom introducing gas, carbon atom introducing gas, hydrogen atom introducing gas and And / or a gas for introducing a halogen atom,
A substrate 60 having a photoconductive layer 602 formed in advance at a predetermined position by introducing a predetermined gas state into a deposition chamber whose inside can be decompressed to cause glow discharge in the deposition chamber.
A layer of a-SiC (H, X) may be formed on the first layer.

When the surface layer 603 is composed mainly of a-SiC, the amount of carbon is preferably in the range of 10% to 90% with respect to the sum of silicon atoms and carbon atoms.

When the surface layer 603 is composed mainly of a-SiO, the amount of oxygen is preferably in the range of 10% to 90% with respect to the sum of silicon atoms and oxygen atoms.

When the surface layer 603 is composed mainly of a-SiN, the amount of nitrogen is preferably in the range of 10% to 90% with respect to the sum of silicon atoms and carbon atoms.

Further, in the surface layer 603, hydrogen atoms and / or
Or, it is necessary that a halogen atom is contained,
This is important for compensating dangling bonds of silicon atoms, carbon atoms, oxygen atoms and / or nitrogen atoms, and improving the layer quality, especially the photoconductive property and the charge retention property.

The hydrogen content is usually 10 to 70 atom%, preferably 20 to 65 atom%, and most preferably 30 to 60 atom% with respect to the total amount of the constituent atoms. In addition, the content of fluorine atoms is usually 0.01 to
It is desirable that the amount is 15 atom%, preferably 0.1 to 10 atom%, and most preferably 0.6 to 4 atom%.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer 603, for example, the temperature of the substrate 601 and the amount of the source material used for containing hydrogen atoms and / or halogen atoms can be controlled. The amount introduced into the deposition chamber, discharge power, etc. may be controlled.

The carbon atom, the oxygen atom and / or the nitrogen atom may be uniformly contained in the surface layer 603, or may be non-uniform such that the content varies in the layer thickness direction of the surface layer 603. There may be a portion with a distribution.

Further, the surface layer 603 may contain an element for controlling conductivity, if necessary. The conductivity controlling element may be contained in the surface layer 603 in a uniformly distributed state, or may be contained in an unevenly distributed portion in the layer thickness direction. .

As the element for controlling the conductivity, the above-mentioned Group 3 element or Group 5 element can be used.

The content of the element for controlling the conductivity contained in the surface layer 603 is preferably 1 × 10 ⁻³ to 1 ×.
10 ⁵ atomic ppm, more preferably 1 × 10 ^-2 to 1 × 1
0 ⁴ atom ppm, optimally 1 × 10 ⁻¹ to 1 × 10 ³ atom p
pm is desirable. In order to structurally introduce an element that controls conductivity, for example, a Group 3 element or a Group 5 element, the above-described Group 3 element introduction gas or Group 5 element introduction gas during layer formation The surface layer 6 in the deposition chamber.
It may be introduced together with other gas for forming 03. The layer thickness of the surface layer 603 is usually 0.01 to 3
μm, preferably 0.05 to 2 μm, optimally 0.1 to 1
μm. If the layer thickness is less than 0.01 μm, the surface layer 603 is lost due to abrasion or the like during use of the electrophotographic photoreceptor, and if it exceeds 3 μm, the electrophotographic characteristics are deteriorated such as increase in residual potential. To be

The surface layer 603 is carefully formed so as to obtain the required characteristics. That is, a substance having Si; C, N and / or O; and H and / or X as a constituent element structurally takes a form from crystalline to amorphous depending on its forming condition, and is electrically conductive from an electrically conductive state. In the present invention, a compound having properties depending on the purpose can be exhibited since it can exhibit properties ranging from semiconducting properties to insulating properties, and a wide range of properties ranging from photoconductive properties to non-photoconductive properties. The formation conditions are strictly selected so that they are formed.

For example, when the surface layer 603 is provided mainly for the purpose of improving the electrical withstand voltage, it is manufactured as a non-single crystal material that exhibits a remarkable electrical insulating property in the use environment.

When the surface layer 603 is provided mainly for the purpose of improving continuous repeated use characteristics and use environment characteristics, the above-mentioned electric insulation is not so remarkable,
It is formed as a non-single crystal material that has some sensitivity to the light it illuminates.

Surface layer 6 having desired characteristics suited to the purpose
In order to form 03, it is necessary to appropriately set the temperature of the substrate 601 and the gas pressure in the deposition chamber.

The temperature (Ts) of the substrate 601 is appropriately selected in accordance with the layer design, but is usually preferably 1
The temperature is 50 to 350 ° C, more preferably 200 to 330 ° C, and most preferably 250 to 300 ° C.

Similarly, the gas pressure in the deposition chamber is appropriately selected in accordance with the layer design, but is usually preferably 0.0.
1-1000 Pa, more preferably 0.05-500 P
a, optimally 0.1 to 100 Pa.

Substrate temperature for forming surface layer 603,
The above-mentioned ranges are mentioned as desirable numerical ranges of the gas pressure, but the conditions are not usually decided independently and independently of each other, and the mutual and organic relations are required to form an electrophotographic photoreceptor having desired characteristics. It is desirable to determine the optimum value based on the sex.

A region in which the content of carbon atoms, oxygen atoms and / or nitrogen atoms continuously decreases toward the photoconductive layer 602 may be provided between the surface layer 603 and the photoconductive layer 602. As a result, the adhesion between the surface layer and the photoconductive layer 602 can be improved, and the influence of interference due to the reflection of light at the interface can be further reduced. At the same time, carrier trapping at the interface can be prevented and the photoreceptor characteristics can be improved. Can be achieved.

Next, the charge injection blocking layer will be described.

A conductive substrate and a photoconductive layer 602, if necessary.
A charge injection blocking layer 604 having a function of blocking injection of charges from the conductive substrate side may be provided between and. That is, the charge injection blocking layer 604 has a function of blocking the injection of charges from the substrate side to the photoconductive layer 602 side when the surface of the photoconductor is charged with a constant polarity, and the opposite polarity. Such a function is not exhibited when it is subjected to the charging treatment of 1. In order to impart such a function, the charge injection blocking layer 604 contains a relatively large amount of an element that controls conductivity as compared with the photoconductive layer 602.

The conductivity controlling element contained in the charge injection blocking layer may be uniformly distributed in the layer, or may be contained uniformly in the layer thickness direction. There may be a portion containing the non-uniformly distributed state. When the concentration distribution is non-uniform, it is preferable that the content be contained so as to be distributed more on the substrate side.

However, in any case, it is necessary that the content be uniformly distributed in the in-plane direction parallel to the surface of the substrate in order to obtain uniform characteristics in the in-plane direction.

As the element for controlling the conductivity contained in the charge injection blocking layer 604, the above-mentioned Group 3 element or Group 5 element can be used.

The content of the element for controlling the conductivity contained in the charge injection blocking layer 604 is appropriately determined as desired, but is preferably 10 to 1 × 10 ⁴ atom pp.
m, more preferably 50 to 5 × 10 ³ atomic ppm, most preferably 1 × 10 ² to 1 × 10 ³ atomic ppm.

Further, the charge injection blocking layer 604 contains at least one kind of carbon atom, nitrogen atom and oxygen atom, so that the charge injection blocking layer 604 is provided in direct contact with the charge injection blocking layer 604. It is possible to further improve the adhesion.

The carbon atoms, nitrogen atoms or oxygen atoms contained in the charge injection blocking layer may be uniformly distributed in the layer, or they may be uniformly distributed in the layer thickness direction. However, there may be a portion containing the non-uniformly distributed state. However, in any case, it is necessary that the content be uniformly distributed in the in-plane direction parallel to the surface of the substrate in order to make the characteristics uniform in the in-plane direction.

The content of carbon atoms, nitrogen atoms and / or oxygen atoms contained in the entire region of the charge injection blocking layer 604 is appropriately determined so that desired film characteristics can be obtained.
The total sum of those elements is preferably 1 × 10 ⁻³ to 50
Atomic%, more preferably 5 × 10 ⁻³ to 30 at%, optimally 1 × 10 ⁻² to 10 at%.

The hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer 604 are effective in compensating for dangling bonds existing in the layer and 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 604 is preferably 1 to 50 atom%, more preferably 5 to 40 atom%, most preferably 10 to 30. Atomic%

The layer thickness of the charge injection blocking layer 604 is determined in view of desired electrophotographic characteristics and economic effects, and is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm.
m, optimally 0.5 to 3 μm.

To form the charge injection blocking layer 604, a vacuum deposition method similar to the method of forming the photoconductive layer 602 described above is adopted. Similar to the photoconductive layer 602, it is necessary to appropriately set the mixing ratio of the silicon atom introduction gas and the other atom introduction gas, the gas pressure in the deposition chamber, the discharge power, and the temperature of the substrate 601.

The gas pressure in the deposition chamber is appropriately selected in an optimum range. In the usual case, it is 0.01 to 1000 Pa, preferably 0.05 to 500 Pa, and most preferably 0.1 to 100 Pa.
And

The layer forming factors such as the mixing ratio of the diluent gas for forming the charge injection blocking layer 604, the gas pressure, the discharge power, the substrate temperature and the like are usually not individually and independently determined, but desired characteristics can be obtained. It is desirable to determine the optimum value of each layer formation factor on the basis of mutual and organic relations to form the charge injection blocking layer 604.

For the purpose of further improving the adhesion between the substrate 601 and the photoconductive layer 602 or the charge injection blocking layer 604, for example, Si ₃ N ₄ , SiO ₂ , SiO, or a silicon atom is used as a base material, An adhesion layer made of an amorphous material containing hydrogen and / or halogen and carbon, oxygen and / or nitrogen may be provided. Further, a light absorption layer may be provided to prevent the occurrence of an interference pattern due to the reflected light from the substrate.

[0124]

EXAMPLES The present invention will now be described in more detail by way of examples.

(Example 1) An oscillation frequency of 105 M was obtained using the deposited film forming apparatus using the two high frequency electrodes shown in FIG.
Alternating high frequency power of 10 Hz with a cycle of 10 kHz
The pattern shown in (c) was applied to each high-frequency electrode.

A cylindrical conductive substrate made of aluminum was used, and the discharge conditions were SiH ₄ gas flow rate of 100 sccc.
m, discharge power 200 W, pressure in discharge space was changed to the conditions shown in Table 1, and an a-Si film of about 10 μm was deposited on a cylindrical conductive substrate made of aluminum to prepare a film thickness distribution measuring drum. did.

Further, a single crystal silicon substrate was placed at the center in the axial direction on a cylindrical conductive substrate made of aluminum, and an a-Si film of about 1 μm was formed under the same manufacturing conditions.
A sample for infrared spectroscopy measurement was prepared.

In all the film formations, the substrate was formed in a stationary state.

(Comparative Example 1) Using a deposited film forming apparatus using two high frequency electrodes shown in FIG.
A film thickness distribution measuring drum and an infrared spectroscopic measurement sample were prepared under the same film forming conditions as in Example 1 except that high frequency power of Hz was applied to each high frequency electrode at the same timing with a cycle of 10 kHz.

(Comparative Example 2) An oscillation frequency of 105 M was obtained using the deposited film forming apparatus using the two high frequency electrodes shown in FIG.
A film thickness distribution measuring drum and an infrared spectroscopic measurement sample were prepared under the same film forming conditions as in Example 1 except that continuous high frequency power of Hz was applied to each high frequency electrode.

The film thickness distribution measuring drum and the infrared spectroscopic measuring sample produced in Example 1, Comparative Example 1 and Comparative Example 2 were evaluated by the following methods.

(1) Evaluation of film thickness distribution For each film thickness distribution measuring drum, the film thickness at 15 locations in the axial direction was measured by an eddy current film thickness meter (manufactured by Kett Scientific Research Institute) to obtain the maximum film thickness and the minimum film thickness. The film thickness distribution ratio was calculated by dividing the film thickness difference by the average film thickness. Then, evaluation was performed with a relative value with the film thickness distribution ratio of the film thickness distribution measuring drum of Comparative Example 2 being 1. That is, the smaller the value is, the more the film thickness unevenness is improved.

(2) Evaluation of film quality An infrared spectrophotometer sample was measured with an infrared spectrophotometer (Perkin E
It is installed at 1720-X manufactured by Lmer Co., Ltd., and the infrared absorption spectra of Si—H _n (n = 1 to 3) appearing at around 2000 cm ⁻¹ are obtained by Si—H at around 2000 cm ⁻¹ and Si—H. ₂ and waveform separated by around 2100 cm _-1 due to the Si-H _3, was determined the ratio of each of the infrared absorption sectional area (the absorption cross section of the absorption cross-section / 2000 cm around _-1 around 2100 cm _-1). Then, the evaluation was performed by the relative value with the infrared absorption cross-sectional area ratio of Comparative Example 2 being 1. That is,
The smaller the value is, the smaller the absorption cross-sectional area around 2100 cm ₋₁ indicates that the film quality is improved.

The above results are summarized in Table 1. As can be seen from Table 1, the film thickness distribution measuring drum and the infrared spectroscopic measurement sample manufactured in Comparative Example 1 and 2 were compared with the film thickness distribution measuring drum and the infrared spectroscopic measurement sample manufactured in Example 1. In either case, a good result is obtained in any evaluation, that is, the film thickness difference in the axial direction is small and the characteristics are excellent.

From the above results, it has been found that the manufacturing method of the present invention makes it possible to form a deposited film having a uniform film thickness in the axial direction and a good film quality.

[0136]

[Table 1] Note) All the values in the table are relative values when the value obtained in Comparative Example 2 is set to 1. (Example 2) The pressure in the discharge space is 0.5 Pa, and the high frequency power is alternately applied to the two high frequency electrodes. Table 2 shows the cycle applied to
A film thickness distribution measuring drum and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 1 except that the conditions shown in FIG.

(Comparative Example 3) The pressure in the discharge space was set to 0.5 P.
a, and the conditions for applying high-frequency power to the two high-frequency electrodes at the same timing under the conditions shown in Table 2 were the same as in Comparative Example 1 except that the film thickness distribution measurement drum and the infrared spectroscopy measurement sample were used. Was produced.

With respect to the film thickness distribution measuring drum and the infrared spectroscopic measurement sample produced in Example 2 and Comparative Example 3, the film thickness distribution ratio and the infrared absorption cross section ratio were determined by the same procedure as in Example 1. . The results are shown in Table 2. As can be seen from Table 2, Example 2 is superior to Comparative Example 3 in any evaluation (that is, the difference in film thickness in the axial direction is small and the characteristics are excellent).

From the above results, it has been found that according to the manufacturing method of the present invention, the film thickness in the axial direction can be made uniform and a deposited film of good film quality can be formed.

[0140]

[Table 2] Note) All values in the table are relative values when the value obtained in Comparative Example 3 is set to 1 (Example 3) The pressure in the discharge space is 0.7 Pa, and the high frequency power is alternately applied to the two high frequency electrodes. Applied to the cycle of 10
A film thickness distribution measuring drum and an infrared spectroscopic measurement sample were produced under the same conditions as in Example 1 except that the frequency was set to kHz and the frequency of the high frequency power was set to the conditions shown in Table 3.

(Comparative Example 4) The pressure in the discharge space was set to 0.7 P.
a, the frequency of applying high frequency power to two high frequency electrodes at the same timing was 10 kHz, and the frequency of the high frequency power was set to the conditions shown in Table 3, under the same conditions as in Comparative Example 1 for measuring the film thickness distribution. A drum and a sample for infrared spectroscopy measurement were prepared.

With respect to the film thickness distribution measuring drum and the infrared spectroscopic measurement sample produced in Example 3 and Comparative Example 4, the film thickness distribution ratio and the infrared absorption cross-sectional area ratio were determined by the same procedure as in Example 1. It was Table 3 shows the results. As can be seen from Table 3, Example 3 is superior to Comparative Example 4 in any evaluation (that is, the difference in film thickness in the axial direction is small and the characteristics are excellent).

From the above results, it was found that according to the manufacturing method of the present invention, the film thickness in the axial direction can be made uniform, and the deposited film of good film quality can be formed.

[0144]

[Table 3] Note) All the values in the table are relative values when the value obtained in Comparative Example 4 is set to 1. (Example 4) In the deposited film forming apparatus shown in FIG. An a-Si film is formed on a cylindrical base body made of aluminum, and then, as shown in FIG.
An electrophotographic photoreceptor having the layer structure shown in was prepared.

In this embodiment, two high frequency electrodes are used, and
High frequency power was alternately supplied in the pattern shown in FIG. 7C at a cycle of 0 kHz.

The film formation was performed according to the film forming conditions shown in Table 4.

[0147]

[Table 4] (Comparative Example 5) Except that the deposited film forming apparatus using the two high frequency electrodes shown in FIG. 1 was used and high frequency power with an oscillation frequency of 105 MHz was applied to each high frequency electrode at the same timing in a cycle of 10 kHz. Under the same film forming conditions as in Example 4, a-Si was formed on an aluminum cylindrical conductive substrate.
A film was deposited to prepare an electrophotographic photoreceptor.

(Comparative Example 6) An oscillation frequency of 105 M was obtained using the deposited film forming apparatus using the two high frequency electrodes shown in FIG.
An a-Si film was deposited on a cylindrical conductive substrate made of aluminum under the same film forming conditions as in Example 4 except that continuous high frequency power of Hz was applied to each high frequency electrode. Was produced.

Example 4, Comparative Example 5 and Comparative Example 6 described above
Each of the electrophotographic photoreceptors prepared in 1. was set in an electrophotographic apparatus (NP6060 manufactured by Canon Inc. was modified for experiments), and the charging ability was evaluated as the initial electrophotographic characteristics as follows.

The photoconductor for electrophotography is installed in an electrophotographic apparatus, a high voltage of +6 kV is applied to a charger to perform corona charging, and the surface potential meter is used to measure the surface potential of the dark portion in the axial direction of the photoconductor for electrophotography. The ratio of the dark surface potential was calculated by measuring and dividing the difference between the maximum and minimum dark surface potentials by the average dark surface potential. Then, the evaluation was carried out by a relative value with the dark area surface potential ratio of the electrophotographic photosensitive member of Comparative Example 6 being 1. In other words, the smaller the numerical value is, the more the dark part surface potential unevenness is improved.

Further, the average dark surface potential was calculated by dividing the average dark surface potential by the average film thickness to eliminate the influence of the film thickness, and the average dark surface potential was calculated. The evaluation was performed by the relative value obtained by dividing the dark surface potential by each average dark surface potential. That is, the smaller the value is, the more the average dark surface potential is improved.

The above results are summarized in Table 5. From this table, it can be seen that the electrophotographic photosensitive member manufactured in Example 4 has a smaller axial film thickness difference and excellent characteristics than the electrophotographic photosensitive members manufactured in Comparative Examples 5 and 6. .

From the above results, it has been found that according to the manufacturing method of the present invention, the film thickness in the axial direction can be made uniform and a deposited film of good film quality can be formed.

[0154]

[Table 5] Note) All values in the table are relative values when the value obtained in Comparative Example 6 is set to 1. (Example 5) Oscillation was performed using the deposited film forming apparatus using three high frequency electrodes shown in FIG. Electrophotographic sensitization under the same conditions as in Example 4 except that high frequency power of 105 MHz was alternately applied to each high frequency electrode in a pattern similar to the pattern shown in FIG. 7C at a cycle of 5 kHz. The body was made.

(Comparative Example 7) An oscillation frequency of 105 M was obtained using the deposited film forming apparatus using the three high frequency electrodes shown in FIG.
An electrophotographic photoreceptor was produced under the same conditions as in Example 5 except that high frequency power of Hz was applied to each high frequency electrode at the same timing with a cycle of 5 kHz.

(Comparative Example 8) An oscillation frequency of 105 M was obtained using the deposited film forming apparatus using the three high frequency electrodes shown in FIG.
An electrophotographic photosensitive member was produced under the same conditions as in Example 5 except that continuous high frequency power of Hz was applied to each high frequency electrode.

Example 5, Comparative Example 7 and Comparative Example 8 described above
The electrophotographic photosensitive member prepared in 1. was evaluated for dark surface potential unevenness and average dark surface potential in the same procedure as in Example 4. Table 6 shows the results. As can be seen from Table 6, Example 5
The electrophotographic photoconductor of (1) has a small difference in film thickness in the axial direction and has excellent characteristics.

From the above results, it was found that according to the manufacturing method of the present invention, the film thickness in the axial direction can be made uniform, and the deposited film of good film quality can be formed.

[0159]

[Table 6] Note: All values in the table are relative values when the value obtained in Comparative Example 8 is set to 1. (Example 6) Using the four high-frequency electrodes shown in FIG.
Using a deposited film forming apparatus in which two aluminum cylindrical conductive substrates are stacked in the axial direction, high-frequency power having an oscillation frequency of 105 MHz is alternately arranged at a cycle of 20 kHz in a pattern similar to that shown in FIG. 7C. An electrophotographic photosensitive member was produced under the same conditions as in Example 4, except that the voltage was applied to the high frequency electrode and the film forming conditions shown in Table 7 were followed.

[0160]

[Table 7] (Comparative Example 9) The four high frequency electrodes shown in FIG.
The same as Example 6 except that a deposited film forming apparatus in which two aluminum-made cylindrical conductive substrates were stacked in the axial direction was used, and high-frequency power having an oscillation frequency of 105 MHz was applied to each high-frequency electrode at a cycle of 20 kHz at the same timing. An electrophotographic photoreceptor was prepared under various conditions.

(Comparative Example 10) Using the four high frequency electrodes shown in FIG. 4, a deposited film forming apparatus in which two aluminum cylindrical conductive substrates were axially stacked was used, and an oscillation frequency of 10
An electrophotographic photosensitive member was produced under the same conditions as in Example 6 except that continuous high frequency power of 5 MHz was applied to each high frequency electrode.

Example 6, Comparative Example 9 and Comparative Example 1 described above
With respect to the three electrophotographic photoconductors manufactured in No. 0, the dark part surface potential unevenness and the average dark part surface potential were evaluated in the same procedure as in Example 4. Table 8 shows the results. As can be seen from Table 8, the electrophotographic photosensitive member of Example 6 has a small axial film thickness difference and excellent characteristics.

From the above results, it was found that according to the manufacturing method of the present invention, the film thickness in the axial direction can be made uniform, and a deposited film of good film quality can be formed.

[0164]

[Table 8] Note: All values in the table are relative values when the value obtained in Comparative Example 10 is set to 1. (Example 7) Outer circumference of the insulating ring 510 made of the insulating material (alumina ceramics) shown in FIG. Using a deposited film forming apparatus using two high frequency electrodes 511 and 512, a high frequency power with an oscillation frequency of 105 MHz is set to 30 kHz.
An electrophotographic photosensitive member was produced under the same conditions as in Example 4, except that the high frequency electrodes were alternately applied in the pattern shown in FIG.

(Comparative Example 11) A deposited film forming apparatus using two high frequency electrodes 511 and 512 on the outer periphery of an insulating ring 510 made of an insulating material (alumina ceramics) shown in FIG. An electrophotographic photoreceptor was produced under the same conditions as in Example 7, except that high frequency power was applied to each high frequency electrode at the same timing with a cycle of 30 kHz.

COMPARATIVE EXAMPLE 12 A deposited film forming apparatus using two high frequency electrodes 511 and 512 on the outer circumference of an insulating ring 510 made of an insulating material (alumina ceramics) shown in FIG. An electrophotographic photoreceptor was produced under the same conditions as in Example 7, except that continuous high frequency power was applied to each high frequency electrode.

With respect to the electrophotographic photoconductors produced in Example 7, Comparative Example 11 and Comparative Example 12, the dark surface potential unevenness and the average dark surface potential were evaluated in the same procedure as in Example 4. The results are shown in Table 9. As can be seen from Table 9, the electrophotographic photosensitive member of Example 7 has a small axial film thickness difference and excellent characteristics.

From the above results, it was found that according to the manufacturing method of the present invention, the film thickness in the axial direction can be made uniform, and a deposited film of good film quality can be formed.

[0169]

[Table 9] Note) All the values in the table are relative values when the value obtained in Comparative Example 12 is set to 1. (Example 8) A deposited film forming apparatus using the two high frequency electrodes 111 and 112 shown in FIG. A cylindrical conductive substrate made of aluminum was rotated by a rotation mechanism (not shown), and high frequency power having an oscillation frequency of 105 MHz was alternately applied to each high frequency electrode in a pattern of 5 kHz at a cycle of 5 kHz. A photoconductor for electrophotography was manufactured under the same conditions as in Example 4.

(Comparative Example 13) Using a deposited film forming apparatus using the two high frequency electrodes 111 and 112 shown in FIG. 1, an aluminum cylindrical conductive substrate is rotated by a rotation mechanism (not shown) to generate an oscillation frequency of 105 MHz. An electrophotographic photosensitive member was produced under the same conditions as in Example 8 except that the high frequency power of 1 was applied to each high frequency electrode at the same timing with a cycle of 5 kHz.

(Comparative Example 14) Using a deposited film forming apparatus using the two high frequency electrodes 111 and 112 shown in FIG. 1, an aluminum cylindrical conductive substrate was rotated by a rotation mechanism (not shown) to generate an oscillation frequency of 105 MHz. An electrophotographic photosensitive member was produced under the same conditions as in Example 8 except that continuous high frequency power of was applied to each high frequency electrode.

With respect to the electrophotographic photoconductors produced in Example 8, Comparative Example 13 and Comparative Example 14, the dark surface potential unevenness and the average dark surface potential were evaluated in the same procedure as in Example 4. The results are shown in Table 10. As can be seen from Table 10, the electrophotographic photosensitive member of Example 8 has a small axial film thickness difference and excellent characteristics.

From the above results, it has been found that according to the manufacturing method of the present invention, the film thickness in the axial direction can be made uniform and a deposited film of good film quality can be formed.

[0174]

[Table 10] Note) All values in the table are relative values when the value obtained in Comparative Example 14 is 1.

[0175]

As described above, according to the manufacturing method of the present invention, electric power can be uniformly supplied to each high-frequency electrode to be used, so that the discharge stability in the deposition chamber is improved and the discharge distribution becomes uniform. It is possible to form a deposited film having a uniform film thickness and excellent characteristics in a short time, and an excellent electrophotographic photoreceptor can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic vertical cross-sectional view of an example of a deposited film forming apparatus used in a deposited film forming method of the present invention.

FIG. 2 is a schematic cross-sectional view of an example of a deposited film forming apparatus used in the deposited film forming method of the present invention.

FIG. 3 is a schematic vertical cross-sectional view of another example of a deposited film forming apparatus used in the deposited film forming method of the present invention.

FIG. 4 is a schematic vertical cross-sectional view of still another example of the deposited film forming apparatus used in the deposited film forming method of the present invention.

FIG. 5 is a schematic vertical sectional view of still another example of a deposited film forming apparatus used in the deposited film forming method of the present invention.

FIG. 6 is a schematic view showing some examples of the layer structure of the electrophotographic photosensitive member produced by the deposited film forming method of the present invention.

FIG. 7 is a pattern diagram showing some examples of change patterns of electric power periodically output from a high frequency power source in the deposited film forming method of the present invention.

FIG. 8 is a schematic vertical sectional view showing an example of a deposited film forming apparatus used in a conventional deposited film forming method.

[Explanation of symbols]

101, 201, 301, 401, 501, 801
Deposition chamber 102, 202, 302, 402, 502, 802
Cylindrical conductive substrate 103, 303, 403, 503, 803 Auxiliary substrate 104, 304, 404, 504, 804 Auxiliary substrate 105, 305, 405, 505, 805 Heating heater 106, 206, 306, 406, 506, 806
Raw material gas introduction port 107, 307, 407, 507, 807 Raw material gas introduction valve 108, 308, 408, 508, 808 Exhaust port 109, 309, 409, 509, 809 Main valve 110, 310, 410, 510 Insulation ring 111, 211, 311, 411, 511, 811
High frequency electrodes 112, 212, 312, 412, 512 High frequency electrodes 121, 221, 321, 421, 521, 821
Matching circuit 122, 222, 322, 422, 522 Matching circuit 131, 331, 431, 531, 831 High frequency power source 132, 332, 432, 532 High frequency power source 333, 433, 434 High frequency power source 141, 341, 441, 541 Phase control device 600 Electrophotographic Photoreceptor 601 Substrate 602 Photoconductive Layer 603 Surface Layer 604 Charge Injection Blocking Layer 605 Charge Generation Layer 606 Charge Transport Layer

Claims (13)

[Claims] 1. A cylindrical conductive substrate is arranged in a vacuum-tight deposition chamber equipped with an exhaust unit and a source gas introducing unit,
High-frequency power is applied to a cylindrical high-frequency electrode that encloses the cylindrical conductive substrate and is arranged concentrically with the substrate to generate discharge between the high-frequency electrode and the cylindrical conductive substrate, and deposit In the deposited film forming method of forming a deposited film on the cylindrical conductive substrate by decomposing the source gas introduced into the chamber by its discharge, a plurality of the cylindrical high frequency electrodes are arranged, A deposited film forming method, characterized in that discharge is generated while alternately applying high-frequency power to each of them. 2. The oscillation frequency of the high frequency power is 20 MH
The deposited film forming method according to claim 1, which has a frequency of z to 450 MHz. 3. The oscillating frequency of the high frequency power is 50 MH.
The deposited film forming method according to claim 1, which has a frequency of z to 450 MHz. 4. The deposited film forming method according to claim 1, wherein the cycle of the high frequency power applied alternately to the plurality of high frequency electrodes is 0.1 to 100 kHz. 5. The plurality of cylindrical high frequency electrodes are arranged in the axial direction of the cylindrical conductive substrate.
The method for forming a deposited film according to any one of 1. 6. The deposited film forming method according to claim 1, wherein the deposited film is formed by keeping the cylindrical conductive substrate stationary. 7. The deposited film forming method according to claim 1, wherein the deposited film is formed while rotating the cylindrical conductive substrate in the circumferential direction of the cylindrical conductive substrate. 8. The method of forming a deposited film according to claim 1, wherein a plurality of the cylindrical conductive substrates are stacked in the axial direction of the conductors and arranged in the deposition chamber. 9. The deposited film forming method according to claim 1, wherein the high-frequency power is applied from a plurality of positions symmetrical with respect to the axis of the cylindrical conductive substrate. 10. The method for forming a deposited film according to claim 1, wherein the high frequency power is periodically changed in a sine wave and applied. 11. The method for forming a deposited film according to claim 1, wherein the high frequency power is periodically changed in a triangular wave and applied. 12. The method for forming a deposited film according to claim 1, wherein the high frequency power is periodically changed in a rectangular wave and applied. 13. An electrophotographic photosensitive member obtained by forming a deposited film on a conductive substrate by the method according to claim 1.