JP2719502B2 - Method of manufacturing electrophotographic light-receiving member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to light (here, light in a broad sense).
Indicates ultraviolet light, visible light, infrared light, X-ray, γ-ray, etc.
Photoconductor for electrophotography that is sensitive to electromagnetic waves such as
Used as materialMethod of manufacturing electrophotographic light-receiving memberAbout
I do. [0002] 2. Description of the Related Art An electrophotographic image forming unit in the image forming field.
As the photoconductive material forming the photoconductive layer in the material,
In sensitivity, the S / N ratio [photocurrent (I_p) / (I_d)] Is high,
Absorption matched to the spectral characteristics of the irradiating electromagnetic wave
Having spectral characteristics, fast light response,
It has dark resistance and no
Characteristics such as pollution are required. Especially with office machines
Embedded in electrophotographic equipment used in offices
For electrophotographic imaging members, use
Pollution is an important point. Recently, attention has been focused on this point of view.
Hydrogen (H), halogen atom (X), etc.
With dangling bond modified by monovalent element
Fac silicon (hereinafter a-Si (H, X))
There are, for example, German Patent Publication No. 274667,
No. 2,855,718 discloses an electrophotographic image forming member.
For its excellent photoconductivity, abrasion resistance,
Because of its heat resistance and relatively easy area enlargement,
The application to a true image forming member is expected. In general, light containing a-Si (H, X)
Manufactures a photosensitive drum for electrophotography having a conductive material
In order to obtain good photoconductive properties, a-Si
In the (H, X) film deposition apparatus, the drum-shaped metal
Extremely high temperature compared to the case of Se
A-S on the drum-shaped metal substrate under the condition that heating is continued.
i (H, X) film deposition is formed to a thickness of 1 to 100 μm.
You. Maintaining high temperature heating of this substrate is a
-Necessary for manufacturing a Si photosensitive drum, a-S
Considering the deposition rate of the i (H, X) film,
Currently, maintenance lasts from several hours to over a dozen hours.
You. And a drum-shaped metal substrate and an a-Si (H, X) film
Difference in thermal expansion coefficient of a-Si (H, X) film
Because of the large internal stress of
Deposition of a-Si (H, X) film for maintaining metal substrate at high temperature
Not only during loading, but also when cooling to outside air temperature after deposition,
Deposited a-Si (H, X) film from drum-shaped metal substrate
Peeling was reduced. Further, the photosensitive drum for electrophotography is used.
During use, the drum is heated depending on the ambient temperature
The a-Si (H, X) film is less likely to peel off
It was not lost. According to many experiments by the present inventors, a
In the case of the -Si (H, X) film, the film peeling is performed using a-Si (H,
X) The larger the film thickness, the more likely it is to occur.
Of the photosensitive drum for Se-based electrophotography,
Thermal deformation of the drum-shaped metal substrate (particularly the formation of a photoconductive layer)
A.-Si (H, X) -based feeling
In the case of an optical drum, the difference between the coefficient of thermal expansion and a-Si
(H, X) The peeling of the film occurs due to the magnitude of the internal stress of the film.
This was not the case. a-Si (H, X) film
Of the internal stress of the a-Si (H, X) film
(Type of source gas, gas flow ratio, discharge power,
Heating temperature, internal structure of manufacturing equipment, etc.)
Can be eased, but consider productivity and mass productivity.
It is still insufficient when considered. And this film peeling
When used as a photoreceptor drum for
The cause of the fall is fatal. [0006] In addition, during the production of an a-Si (H, X) film,
Prolonged high-temperature heating of the drum-shaped metal substrate
In addition to causing film peeling,
It is also easy to cause thermal deformation of the body, and this thermal deformation is a-S
Causes non-uniform discharge during the production of i (H, X) deposited film
Thereby, the uniformity of the film thickness of the a-Si (H, X) deposited film is obtained.
Loss of unity causes image defects. [0007] SUMMARY OF THE INVENTION The present invention is directed to the above points.
The electronic copying of a-Si (H, X)
Applicability as photoconductive member used for true image forming member
Intensive research and investigation from the perspective of
As a result, the drum-shaped metal substrate having a specific thickness was a-
By using it as a support for Si (H, X) deposited film
Can solve the above problems such as film peeling
It is based on what was done. [0008] The present invention relates to an a-Si (H, X) deposited film.
High quality images with few image defects such as white spots due to peeling
As a photoconductive member for electrophotography that can obtain
UseElectrophotographic light receiving memberAim to provide
You. Another object of the present invention is to provide an electric, optical, optical,
Conductive properties are always stable and degrade after repeated use
A photoconductive member for electrophotography that does not cause phenomena and has excellent durability
Is to provide. [0010] Means for Solving the Problems That is, according to the present invention,Electronic photography
Mahikari receiving memberofManufactureThe method is more than 2.5mm thickAl
Drum shape made of minium or aluminum alloy
ShapeHeat the metal substrate to 200 ° C to 350 ° C and release the glow.
The raw material gas is decomposed by electrolysis and
Forming deposited films with amorphous material based on silicon atoms
It is characterized by the following. [0011] The present inventionElectrophotographic light receiving memberofManufactureMethod
Is an electrophotographic light source in the preferred embodiment.
Photoconductive layer such as conductive member, barrier layer, surface charge injection prevention
Used as a method for forming a deposited film such as a layer or a protective layer
In this case, the photoconductive layer has a drum shape, that is,
A metal substrate such as a cylindrical A1 or A1 alloy (hereinafter referred to as A1
Based on silicon atoms), preferably
At least one of a hydrogen atom and a halogen atom
As a layer containing an amorphous material containing as its constituent atoms
It is formed. In a photoconductive member for electrophotography,
The electric layer is in contact with the drum-shaped metal substrate,
A surface barrier layer may be provided on the surface of the conductive layer. The metal substrate of the present invention has a thickness of
It is 2.5 mm or more. That is, 2.5 mm or less
By using one having the above thickness, the deposited film
In the a-Si (H, X) film deposition apparatus during the formation of
Is a metal substrate when used as a photoreceptor drum for electrophotography
The degree of thermal deformation of the metal substrate is sufficiently small even if
A-Si (H, X) deposited film
There is no problem within the practical range of the degree of film peeling
Can be reduced to none or none at all
You. To improve productivity and mass productivity, metal substrates
More preferably, it has a thickness of 3.5 mm or more. The metal group preferably used in the present invention
The base material of the body is, for example, NiCr, stainless steel, Al, C
r, Mo, Au, Nb, Ta, V, Ti, Pt, Pd, etc.
Or alloys thereof, especially Al and A
An l-based alloy is preferably used. Drum-shaped metal substrate
Sometimes, aluminum or aluminum as the base material of the base
It is relatively easy to use a round alloy
Quality, surface smoothness, etc. can be obtained.
Easy temperature control of a-Si (H, X) deposition surface
And economical. [0014] The deposited film formed by the method of the present invention is a photoconductive layer.
When the halogen atom which may be contained in the photoconductive layer
As (X), specifically, fluorine, chlorine, bromine, iodine
But chlorine, especially fluorine,
Can be listed as Contained in the photoconductive layer
Components other than silicon, hydrogen, and halogen atoms
Is used as a component to adjust the Fermi unit, the band width, etc.
Group III atoms of the periodic table, such as boron and gallium, (II
Group V), nitrogen, phosphorus, arsenic, etc.
Group atom, (group V atom), oxygen atom, carbon atom,
Contains rumanium atom etc. alone or in appropriate combination
Can be done. When the deposited film is a barrier layer, the barrier layer may be a photoconductive layer.
Improve adhesion between layer and metal substrate or adjust charge acceptance
The barrier layer is provided according to the purpose.
Group III atom, group V atom, oxygen atom, carbon atom, gel
An a-Si (H, X) layer or the like containing manium atoms or the like;
It is composed of a single layer or multiple layers of a crystal-Si layer. A deposition film is provided on the photoconductive layer.
Surface charge injection prevention layer or protective layer
Is based on silicon atoms, carbon atoms, nitrogen atoms, oxygen
Contains a large amount of atoms and the like, preferably hydrogen
A layer made of an amorphous material containing atoms or halogen atoms
Alternatively, it is a layer made of a high-resistance organic material. In the present invention, a-Si is used as a deposited film.
To form a photoconductive layer composed of (H, X)
For example, glow discharge, sputtering, or ion
Various known discharge phenomena such as the plating method
The vacuum deposition method used is applied. Next, it is prepared by a glow discharge decomposition method.
Example of a method for forming a deposited film as a photoconductive member for electrophotography
Will be described. FIG. 1 shows an electrophotographic image formed by a glow discharge decomposition method.
1 shows an apparatus for producing a deposited film as a photoconductive member. Deposition tank 1
Are base plate 2, tank wall 3, top plate 4, etc.
In this deposition tank 1, a cathode electrode 5 is provided.
And an a-Si (H, X) deposited film is formed.
The drum-shaped metal substrate 6 is set at the center of the cathode electrode 5.
And also serves as the anode electrode. Using this manufacturing apparatus, a-Si (H,
X) To form a deposited film on a drum-shaped metal substrate,
First, the raw gas inflow valve 7 and the leak valve 8 are closed,
The exhaust valve 9 is opened, and the inside of the deposition tank 1 is exhausted. Vacuum gauge 1
The reading of 0 is about 5 × 10^-6When the torr reaches
Open the inlet valve 7 and open the mass flow controller 11
Adjusted to a predetermined mixing ratio within, for example, SiH_Fourgas,
Si_TwoH₆Gas, SiF_FourDeposits raw material mixed gas such as gas
It flows into the tank 1. At this time, the pressure in the deposition tank 1 is desired.
While reading the vacuum gauge 10 reading
The opening of the valve 9 is adjusted. And the drum-shaped metal substrate 6
The surface temperature is set to a predetermined temperature by the heater 12.
After confirming that the high-frequency power supply 13 is
Glow discharge is generated in the deposition tank 1 by setting the force. In addition, during the formation of the layer,
In order to achieve uniformity, the drum-shaped metal substrate 6 is
To rotate at a constant speed. In this way the drum shape
A-Si (H, X) deposited film is formed on the metal substrate 6
be able to. [0022] The present invention will now be described in more detail with reference to examples.
I will tell. Embodiment 1 Production of deposited film as photoconductive member for electrophotography shown in FIG.
According to the glow discharge decomposition method described in detail above,
Six types of aluminum with outer diameter of 80mmφ and different thickness
A-S on a drum-shaped substrate made of
An i: H deposited film was formed. [0024]Stacking order of deposited film Raw material gas used Film thickness (μm)           First layer SiH_Four, B_TwoH₆        0.6           Second layer SiH_Four                20           Third layer SiH_Four, C_TwoH_Four        0.1 Drum-shaped substrate temperature: 250 ° C Internal pressure of deposition chamber during deposition film formation: 0.03 Torr Discharge frequency: 13.56 MH_z Deposition film formation speed: 20 ° / sec Discharge power: 0.18 W / cm^Two State of film peeling of electrophotographic photosensitive drum obtained in this way
After observing, 400RE copying machine manufactured by Canon Inc.
These photoreceptor drums were used in an experimental copier modified for experiments.
To display the effect of film peeling.
The image evaluation was performed. Table 1 shows the results. The thickness is 1.5 mm and 2.0 mm.
When the roundness of the photosensitive drum was measured,
The difference between the part that is projected and the part that protrudes most is close to 100 μm
2.5mm and 3.0mm
The difference is about 30 μm and the wall thickness is 3.5 m
m and 5.0 mm for photoreceptor drums
there were. Embodiment 2 Aluminum with an outer diameter of 80mmφ and a thickness of 3.0mm
A-Si: H deposited film as a second layer on a drum-shaped substrate made of
When forming SiH_FourSi instead of gas_TwoH ₆Gas
Except for the fact that it was used,
A true photosensitive drum was prepared. This electrophotographic photosensitive drum
In the same manner as in Example 1, evaluation of the state of film peeling and actual
Image evaluation was performed with the test copying machine installed.
This is also the same as the case of the photosensitive drum having a thickness of 3.0 mm of the first embodiment.
Similarly good results were obtained. Reference Example 1 Using the apparatus for manufacturing a photoconductive member for electrophotography shown in FIG.
According to the glow discharge decomposition method described in detail above, the outer diameter is 80 mmφ.
And 7 kinds of aluminum drum-shaped substrates with different wall thickness
An a-Si deposited film was formed thereon under the following conditions. Material gas used: SiH_Four(10%) / H_Two Film thickness: 35 μm Drum-shaped substrate temperature: 250 ° C Internal pressure of deposition chamber during deposition film formation: 0.03 Torr Discharge frequency: 13.56 MH_z Deposition film formation speed: 20 ° / sec Discharge power: 0.18 W / cm^Two After film formation, gradually leak over 10 minutes to atmospheric pressure.
Then, the mixture was naturally cooled to room temperature. Comparative Example 1 Prepare the same aluminum drum base as in Reference Example 1.
Then, using a commonly used vacuum evaporation apparatus, each substrate
A Se-Te alloy is deposited on the above under the following conditions to form a photoconductive layer.
Was formed. [0030] Evaporation raw material: Se-Te alloy (99.999%) Evaporation source temperature: 290 ° C Substrate temperature: 65 ° C Degree of vacuum during layer formation: 1 × 10^-FiveTorr After film formation, gradually leak over 10 minutes to atmospheric pressure.
Then, the mixture was naturally cooled to room temperature. Comparative Example 2 After forming a film under the same conditions as in Comparative Example 1, gradually over 10 minutes
To the atmospheric pressure, take out dry eye immediately
About 100 ° C in cold and alcoholic refrigerant (-77 ° C)
Forced cooling was performed. This is because after the deposition of the a-Si film,
This is because the strain that occurs during cooling is also given to the Se-Te film.
However, the deposition of the Se-Te film is similar to the deposition of the a-Si film.
Method to perform forced cooling using refrigerant because it cannot be performed at high temperature
Was taken. Reference Example 1 Electrophotographic photoreceptor drums obtained in Comparative Examples 1 and 2
After observing the peeling condition of the film at room temperature,
For experiment, which was modified from 400RE copier manufactured by Co., Ltd.
These photoconductor drums are installed in a copying machine to perform image output.
In addition, image evaluation was performed to show the effect of film peeling. So
Table 2 shows the results. As is clear from Table 2, a-Si deposited film
In the case of an electrophotographic photosensitive drum formed with
If the thickness is less than 2.5 mm, the thickness of 2.4 mm
Even with a substrate, the film is often peeled off, and the image quality is also a practical problem
However, if the thickness is more than 2.5mm,
It can be seen that the number is small and the image quality is almost good. On the other hand, in the case where a Se—Te deposited film is formed,
In the case of the electrophotographic photosensitive drum used,
Even in the case of cooling, a-Si film
Even if the same distortion is given,
Neither did film peeling occur. That is, the Se-Te film
In this case, the film peeling does not depend on the thickness of the drum-shaped metal substrate.
However, in the case of an a-Si deposited film,
Therefore, film peeling depends on the thickness of the drum-shaped metal substrate,
This indicates that the distance needs to be 2.5 mm or more. [0035] [Table 1]Image evaluation criteria: ◎ Very good ○ Good △ Not practical
X × Practical problem A^{* 1}: Size of film peeling part 0.3 mm ≦ φ ≦ 0.6 mm B^{* 2}: Size of film peeling part 0.6 mm <φ [0036] [Table 2] Image evaluation criteria: ◎ Very good ○ Good △ Not practical
X × Practical problem A^{* 1}: Size of film peeling part 0.3 mm ≦ φ ≦ 0.6 mm B^{* 2}: Size of film peeling part 0.6 mm <φ

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an apparatus for producing a deposited film as a photoconductive member by a glow discharge decomposition method. [Description of Signs] 1 Deposition tank 2 Base plate 3 Tank wall 4 Top plate 5 Cathode electrode 6 Drum-shaped metal base 7 Source gas inflow valve 8 Leak valve 9 Exhaust valve 10 Vacuum gauge 11 Mass flow controller 12 Heater 13 High frequency power supply 14 Motor

Claims (1)

(57) [Claims] Aluminum or aluminum with a thickness of 2.5 mm or more
The metal substrate of drum-like shape made of um based alloy 200 ° C. to 3
Was heated to 50 ° C., an electronic copy, characterized in that by decomposing the raw material gas by glow discharge decomposition method to form a deposited film having an amorphous material for the silicon atoms as a matrix on the metal substrate
A method for manufacturing a true light receiving member. 2. Electrodeposition of claim 1 wherein the deposited film having a photoconductive
A method for producing a photoreceptor. 3. The electrophotographic photoreceptor of claim 1, wherein said amorphous material contains at least one of a hydrogen atom and a halogen atom.
Manufacturing method of the member. 4. The amorphous material contains at least one atom belonging to Group III or Group V of the periodic table.
3. The method for producing an electrophotographic light-receiving member according to item 3 . 5. Wherein the amorphous material is an oxygen atom, a manufacturing method of the electrophotographic light-receiving member according to claim 1, 3 also <br/> 4 which contains at least one carbon atom and germanium atom. 6. _2. The electrophotographic light receiving device according to claim 1, wherein the source gas is a gas selected from SiH ₄ , Si ₂ H ₆ and SiF _4.
A method for manufacturing a housing member. 7. The deposited film is a photoconductive layer, a barrier layer, and prevents surface charge injection.
The method according to claim 1, further comprising at least one of a layer and a protective layer.
Method.