JP3412957B2 - Method for manufacturing light receiving member - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreceptor that is sensitive to electromagnetic waves such as light (light in a broad sense and means ultraviolet rays, visible rays, infrared rays, X-rays, rays, etc.). the member is continuously directed <br/> the manufacture how the light-receiving member for stably manufactured.

[0002]

2. Description of the Related Art As a material for forming a photoconductive layer in a solid-state image pickup device, a photoreceptive member for electrophotography in an image forming field, or a document reading device, it is highly sensitive and has an SN ratio [photocurrent (1p) / (1d)]. Of high absorption rate, having absorption spectrum characteristics matched with the spectrum characteristics of electromagnetic waves to be radiated, having fast photoresponsiveness and having a desired dark resistance value, being harmless to the human body when in use, and further solid-state imaging device In the case of (1), characteristics such as that afterimages can be easily processed within a predetermined time are required. Particularly in the case of the electrophotographic light-receiving member used in an office as an office machine, the above-mentioned pollution-free property at the time of use is an important point. Based on this point of view, materials that have been attracting attention include amorphous silicon whose dangling bonds are modified with monovalent elements such as hydrogen and halogen atoms (hereinafter referred to as “a-Si”).
(Japanese Patent Application Laid-Open No. 54-86341) describes application to a light receiving member for electrophotography. Conventionally, as a forming method for forming a light-receiving member made of a-Si on a cylindrical support, a sputtering method, a method of decomposing a raw material gas by heat (thermal CVD method), a method of decomposing a raw material gas by light ( Many are known, such as a photo CVD method) and a method of decomposing a source gas by plasma (plasma CVD method). Among them, the plasma CVD method, that is, the method of decomposing a raw material gas by direct current or high frequency, microwave glow discharge, etc. to form a deposited film on a cylindrical support is currently in practice, such as the method of forming a photoreceptive member for electrophotography. It is very advanced.

FIG. 4 is a schematic sectional view of a typical plasma CVD apparatus. In the figure, (5100) shows the entire vacuum reaction vessel, (5111) is the cathode electrode that also serves as the side wall of the vacuum reaction vessel, (5120) is the gate that is the upper wall of the vacuum reaction vessel,
(5121) is the bottom wall of the vacuum reaction vessel. The cathode electrode (5111) is insulated from the top wall (5120) and the bottom wall (5121) by an insulator (5122). (5112) is a support provided in the vacuum reaction vessel, and the support (5112)
Is grounded to serve as an anode electrode. A heater for heating the support (5113) is installed in the support (5112) to heat the support to a predetermined temperature before film formation or to heat the support to a predetermined temperature during film formation. It is used for maintaining or for annealing the support after film formation.
Reference numeral (5114) is a source gas introduction pipe for forming a deposited film, which is provided with a large number of gas release holes (not shown) for releasing the source gas in the vacuum reaction space. The other end of 5114) communicates with the deposited film forming raw material gas supply system (5200) via a valve (5260). (5119)
Is an exhaust pipe for evacuating the inside of the vacuum reaction container, and a vacuum exhaust device (5117) via an exhaust valve (5118).
Is in communication with. (5115) is a means for applying a voltage to the cathode electrode (5111). The method of operating the deposited film forming apparatus by the plasma CVD method is performed as follows. That is, the gas in the vacuum reaction container is evacuated through the exhaust pipe (5119), and the support (5112) is heated and held at a predetermined temperature by the heater (5113) for heating. Next, for example, in the case of forming an a-SiH deposited film through the source gas introduction pipe (5114), a source gas such as silane is introduced into the vacuum reaction vessel, and the source gas is supplied through the source gas introduction pipe (5114). The raw material gas is discharged into the vacuum reaction container through a hole (not shown). Simultaneously with this, for example, a high frequency is applied from the voltage applying means (5115) between the cathode electrode (5111) and the support (anode electrode) (5112) to generate plasma discharge. Thus, the raw material gas in the vacuum reaction vessel is excited and excited to generate seeds, and radical particles such as Si ^* , SiH ^* ( ^* represents an excited state), electrons, ion particles, etc. are generated,
A chemical interaction between these particles or between these particles and the surface of the support forms a deposited film on the surface of the support.

Conventionally, in order to make uniform the film thickness and film quality required for forming a deposited film having a large area such as a photoconductor for electrophotography by such a deposited film forming method by the plasma CVD method. Have already made various improvements. For example, according to Japanese Patent Laid-Open No. 59-213439, the cylindrical electrode and the gas introducing means are used in common, and gas discharge holes are arranged on the wall surface of the electrode so that the source gas is uniformly discharged into the discharge space. However, a technique for improving the variation in film thickness and film quality is disclosed. Further, in Japanese Unexamined Patent Publication No. 3-44477, in a similar cylindrical electrode also serving as gas introducing means, setting the aperture ratio of the gas discharge hole on the electrode wall surface to a range of 0.1 to 2.0% causes image defects. Techniques for suppressing pile-like protrusions have been disclosed. On the other hand, JP-A-58
According to JP-A-30125, a gas pipe for introducing gas, which is independent of a cylindrical electrode, is used for introducing the raw material gas, and the cross-sectional area and interval of the gas discharge holes provided in the gas pipe are set to the longitudinal direction of the cylindrical support. There is disclosed a technique of improving the film thickness and image unevenness when used as an electrophotographic photoreceptor by changing the direction and discharging the source gas uniformly. JP-A-58-3
According to Japanese Patent No. 2413, even in the cylindrical electrode also serving as the gas introducing means, even when the gas introducing gas pipe is used, the direction of the gas release hole is set so that the raw material gas rotates in a certain direction. , A technique for improving the uniformity of film thickness is disclosed. . According to Japanese Patent Laid-Open No. 63-479, the relationship between the angle between the gas discharge hole of the gas introduction pipe and the cylindrical support, the inner diameter of the cylindrical support, and the distance between the cylindrical support and the gas introduction pipe. Is disclosed, by which the uniformity of film thickness and film quality is improved without rotating the support. According to Japanese Patent Laid-Open No. 63-7373, by using a gas introduction pipe and defining the relationship between the cross-sectional area of the gas introduction pipe and the cross-sectional area of the gas discharge hole and the number, the cylindrical support is not rotated. , A technique for making the thickness of a deposited film to be formed uniform is disclosed.

[0005]

However, in the above-mentioned conventional method for producing a light-receiving member, it is possible to obtain a light-receiving member having practical characteristics and uniformity to some extent, and a vacuum reaction container. Although it is possible to obtain a light-receiving member with few defects if the inside is rigorously cleaned, there are problems in the following points. That is, in these conventional methods for producing a light-receiving member, for products such as a light-receiving member for electrophotography, which requires a large area and a relatively thick deposited film, a uniform film quality and various optical and electrical characteristics are required. There is a problem in that it is difficult to obtain a deposited film that satisfies the above conditions and has few image defects at the time of image formation by an electrophotographic process with high yield. Further, at present, electrophotographic devices are required to have higher image quality, higher speed, and higher durability. As a result, in the electrophotographic light-receiving member, the optical property and the electrical property are further improved, and at the same time, the high chargeability,
It is required to extend durability in all environments while maintaining high sensitivity. Further, in recent years, in order to improve the image characteristics of the electrophotographic apparatus, the optical exposure system, the developing apparatus, and the transfer apparatus in the electrophotographic apparatus have been improved. It has become necessary to improve. Especially as a result of improved image resolution,
There has been a demand for reduction of white spot-like or black spot-like image defects commonly known as “potches”, and particularly for the reduction of microscopic “potches” which has not been a problem in the past.

Furthermore, in order to cope with the speeding up of the electrophotographic apparatus,
It also speeds up the copying process. Therefore, the afterimage that occurs when the light receiving member is repeatedly used, that is, a so-called “ghost” phenomenon is not always a pain in a conventional speed copying system and can be ignored in some cases. High-speed continuous image forming systems such as high-speed copying systems, facsimile systems, printer systems, etc. that use an interference light source, especially digital high-speed continuous image systems, and even full-color image systems that have become popular in recent years, are visually obvious. Therefore, it is a serious problem, and it is one that needs to be solved. Therefore, while the characteristics of the light receiving member itself are improved, it is possible to improve from a comprehensive viewpoint such as the layer configuration, the chemical composition of each layer, and the manufacturing method so that the above problems can be solved. is necessary.

Therefore, the present invention solves various problems in the above-described conventional method for manufacturing a light-receiving member, in particular, an electrophotographic photosensitive member, and can form a light-receiving member which is inexpensive, has a good yield, and has excellent characteristics at high speed. it is an object to provide a manufacturing how the receiving member.

[0008]

The present invention, in order to achieve the above object, provides a method for producing a light-receiving member configured as described in 1 to 3 below. 1. A raw material gas and high-frequency power are introduced into the discharge space of a vacuum-tight cylindrical reaction vessel, the raw material gas is decomposed via an applying means, and the cylindrical support is placed in the discharge space. The method for producing a light receiving member, further comprising the step of forming at least a photoconductive layer without rotating the cylindrical support, wherein the outer diameter of the cylindrical support is R1, and the cylindrical support is R2 is the distance from the raw material gas introduction pipe, and A (W / SCCM) is the discharge power (Power / gas flow rate) with respect to the flow rate of the raw material gas for supplying Si.
When the length of the cylindrical reaction vessel is L1 and the length of the cylindrical support is L2, these are represented by the following formula (1) and
The conditions of the manufacturing method of the light receiving part are set so as to satisfy the expression (2).
A method for manufacturing a light-receiving member, which comprises determining and manufacturing the light-receiving member. 0.12 ≦ R2 / (R1 · A) ≦ 0.6 (1) 0.65 ≦ L2 / L1 ≦ 0.9 2) 2. The conditions of the manufacturing method of the light receiving part are determined so that the R1, the R2, and the A satisfy the following expression (3).
2. The method for producing a light-receiving member as described in 1 above , characterized in that the light-receiving member is produced. 0.33 ≦ R2 / (R1 · A) ≦ 0.5 (3) 3. The above A is in the range of 2.5 to 6.
3. The method for producing the light receiving member according to 1 or 2 above .

[0009]

According to the present invention, as described above, the outer diameter of the cylindrical support, the distance between the cylindrical support and the gas introduction pipe for introducing the raw material gas into the reaction space, The relationship with the discharge power supplied per unit source gas when the photoconductive layer is formed, that is, the curvature of the cylindrical support, the distance between the source gas discharge part and the cylindrical support, and the discharge power applied to the unit source gas. By setting the relationship within a predetermined range, uniformity of film thickness and film quality is improved, and electrophotographic characteristics such as ghost are improved. Further, according to the present invention, it is possible to drastically reduce white spot-like or black spot-like image defects commonly referred to as “potches”, and to form an electrophotographic photoreceptor having improved electrophotographic characteristics at high speed. Became possible.

Regarding the mechanism, the present inventors consider as follows. When, for example, an amorphous silicon deposited film is formed on a support by the plasma CVD method, the reaction includes the decomposition process of the source gas in the vapor phase, the transport process of active species from the discharge space to the support surface, and the surface on the support surface. The reaction process can be divided into three parts.
Here, the discharge power is a parameter that plays a major role in determining the decomposition process of the source gas in the gas phase. In particular, when decomposing the raw material gas, the value of the discharge power given to the unit raw material gas is important. By changing the discharge power applied to the unit source gas, the degree of decomposition of the source gas changes, and the deposition rate can be significantly changed. Further, by changing the discharge power applied to the unit source gas, the quality of the deposited film formed by changing the active species, the ion species, and the energy possessed by them, which are generated in the plasma, are affected. If the discharge power applied to the unit material gas is increased in order to increase the deposition rate, the deposition rate can be increased to some extent, but image defects and uniformity in the circumferential direction are adversely affected. Particularly, this effect is caused by a cylindrical reaction container which also serves as an electrode, a cylindrical support which is installed in the cylindrical reaction container and constitutes an opposite electrode to the electrode in the cylindrical reaction container, the cylindrical reaction container and the cylinder. It is remarkably observed in a deposited film forming apparatus having a raw material gas introduction pipe for forming a deposited film, which is disposed between both electrodes of a strip-shaped support and has a plurality of raw material gas discharge holes on its side wall. The cause is considered as follows.
When the discharge power applied to the unit source gas is increased, the deposition rate gradually becomes more dependent on the flow rate of the source gas from the discharge power. In other words, when the discharge power supplied to the unit raw material gas is low, a slight spatial change in the flow rate of the raw material gas, which can be ignored, becomes apparent by increasing the discharge power supplied to the unit raw material gas. The uniformity of the deposited film is affected.

On the other hand, from the viewpoint of improving the uniformity in the circumferential direction, a method of rotating the cylindrical support has been proposed, but this has the following problems. 1. If it is not rotated with high precision, the plasma in the reaction vessel is disturbed, which adversely affects the uniformity in the circumferential direction and adversely affects the quality of the deposited film. 2. Since it is very difficult to prevent gas leakage at the connection between the rotary shaft and the motor provided outside the reaction vessel, the quality of the film deteriorates under the influence. 3. Providing the rotation mechanism itself leads to high cost of the device and the product, and if it is intended to completely solve the above 1.2, a huge cost will be required. Therefore, in order to improve the quality of the deposited film and further reduce the cost of the apparatus and the product itself, it is necessary to reduce the uniformity in the circumferential direction and the image defects without rotating the cylindrical support. In the case of a cylindrical support, in order to make the source gas spatially uniform with respect to the support, the curvature thereof and the distance from the source gas discharge portion become important. When the distance between the raw material gas discharge portion and the cylindrical support is short, the raw material gas is not sufficiently diffused, and circumferential unevenness occurs depending on the pitch of the raw material gas discharge portion. On the other hand, if the distance between the source gas discharge portion and the cylindrical support is long, the source gas is sufficiently diffused and unevenness in the circumferential direction is reduced, but the deposition rate is reduced and the film quality is also reduced. This is because the active species and ionic species are exhausted before they reach the support due to the distance, and the life of the active species and ionic species affects the life of the active species and ionic species. It is considered that the ionic species do not reach the support efficiently. As described above, in order to form a high-speed and uniform high-quality deposited film, the discharge power applied to the unit source gas, the curvature of the cylindrical support, and the distance between the source gas discharge part and the cylindrical support are extremely important. Is becoming. Therefore, the present inventors have made diligent studies on the discharge power given to the unit source gas, the curvature of the cylindrical support, and the distance between the source gas discharge part and the cylindrical support. The relationship between the discharge power supplied per source gas for supply, the outer diameter of the cylindrical support, and the distance between the cylindrical support and the deposited film forming source gas introduction tube is within a predetermined range. By setting to, discharge in the reaction vessel and gas flow are stabilized, high-speed film formation is possible, and a deposited film with improved uniformity can be formed without rotating the cylindrical support. I found a thing. Further, as an unexpected effect of the present invention, reduction of image defects and improvement of ghost are observed. This mechanism is presumed as follows. The discharge and gas flow were stabilized by the forming method of the present invention. Therefore, in the deposited film, unlike the conventional case where the deposited films having different film qualities are formed adjacent to each other, a uniform film quality and film thickness are deposited. Therefore, it is considered that since the strain in the deposited film is significantly alleviated, the carrier traveling property is improved and the ghost phenomenon is reduced. Similarly, since the discharge is stabilized and uniformed, the internal strain is alleviated even in the deposited film deposited on the source gas introduction pipe, and therefore film peeling occurs especially in the source gas introduction pipe with a large curvature. Since it is significantly reduced, it is considered that image defects are reduced.

The method for forming the light receiving member of the present invention will be described in detail below with reference to the drawings with reference to specific examples.
The manufacturing method of the present invention is performed by a vacuum deposition film forming method. Specifically, for example, the glow discharge method (low frequency CV
D method, AC discharge CVD method such as high frequency CVD method or microwave CVD method, or DC discharge CVD method), sputtering method, vacuum deposition method, ion plating method,
It can be formed by various thin film deposition methods such as a photo CVD method and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be prepared. Since it is relatively easy to control the conditions for producing a photoreceptive member having characteristics, a glow discharge method, especially RF
A high frequency glow discharge method using a power supply frequency in the band or VHF band is suitable. Hereinafter, an apparatus and a method for forming a deposited film by the high frequency plasma CVD method will be described in detail.

FIG. 4 shows a high frequency plasma CVD (hereinafter referred to as "RF
It is a typical block diagram which shows an example of the manufacturing apparatus of the electrophotographic photosensitive member by the method (it describes with -PCVD). The structure of the deposition film manufacturing apparatus by the RF-PCVD method shown in FIG. 4 is as follows. This device is roughly classified into a deposition device (511
0), a source gas supply device (5200), and an exhaust device (5117) for reducing the pressure inside the reaction vessel (5111). In the reaction vessel (5111) in the deposition apparatus (5100), a conductive cylindrical support (5112), a heater for heating the support (5113), a raw material gas introduction pipe (5114) are installed, and a high-frequency matching box is further installed. (5115) is connected. Raw material gas supply device (5200)
Is SiH4, H2, CH4, NO, B2H6, GeH
Raw material gas cylinders (5221-5226) and valves (5231-5)
236, 5241 to 5246, 5251 to 5256) and a mass flow controller (5211 to 5216), and each source gas cylinder is connected to the gas inlet pipe (5114) in the reaction vessel (5111) via the valve (5260). Has been done.

The deposited film can be formed using this apparatus, for example, as follows. First, the reaction vessel (511
A cylindrical support (5112) is installed in 1), and an exhaust device (5117,
The inside of the reaction vessel (5111) is evacuated by, for example, a vacuum pump. Then, the heater for heating the support (5113) is turned on to control the temperature of the cylindrical support (5112) to a predetermined temperature of 250 ° C to 500 ° C. In order to flow the raw material gas for forming the deposited film into the reaction vessel (5111), make sure that the gas cylinder valves (5231 to 5236) and the leak valve (5123) of the reaction vessel are closed. (5251 to 5256), outflow valve (524
1 ~ 5246), make sure that the auxiliary valve (5260) is opened, then first open the main valve (5118) and then the reaction vessel (5111).
And exhaust the gas pipe (5116). Next vacuum gauge (5124)
When the reading of about 5 × 10 ⁻⁶ Torr is reached, the auxiliary valve (5260) and the outflow valve (5251-5256) are closed. afterwards,
Valves (5231 to 523) for each gas from gas cylinders (5221 to 5226)
6) is opened and introduced, and each gas pressure is adjusted (for example, 2 Kg / cm ² ) by the pressure regulator (5261 to 5266). Next, the inflow valves (5241 to 5246) are gradually opened to introduce each gas into the mass flow controllers (5211 to 5216). After the preparation for film formation is completed as described above, the cylindrical support (5112)
Each layer such as a charge injection blocking layer, a photoconductive layer, and a surface layer is formed thereon. When the cylindrical support (5112) reaches a predetermined temperature, the necessary one of the outflow valves (5251 to 5256) and the auxiliary valve (5260) are gradually opened, and the gas cylinder (522
1-5226) introduces a predetermined gas into the reaction vessel (5111) through the gas introduction pipe (5114). Next, the mass flow controllers (5211 to 5216) are adjusted so that each raw material gas has a predetermined flow rate. At that time, the pressure inside the reaction vessel (5111) is adjusted to a predetermined pressure of 1 Torr or less by a vacuum gauge (512
While watching 4), adjust the opening of the main valve (5118). When the internal pressure is stable, the RF power source (not shown) is set to a desired power, and the RF power is introduced into the reaction vessel (5111) through the high frequency matching box (5111) to cause the RF glow discharge. The raw material gas introduced into the reaction vessel is decomposed by this discharge energy, and the cylindrical support
The deposited film containing silicon as a main component is formed on the (5112). After forming the desired film thickness,
The supply of PR power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, an electrophotographic photosensitive member having a multilayer structure is formed. At this time, when the photoconductive layer is formed, the outer diameter R1 of the cylindrical support (5112) is
And the distance R2 between the cylindrical support (5112) and the gas introduction pipe (5114),
And the relationship between the RF power A supplied to the source gas for supplying the unit silicon is set to 0.12 ≦ R2 / (R1 · A) ≦ 0.6. R2 /
If (R1 ・ A) is less than 0.12, there will be uneven potential in the circumferential direction and
Image defects are getting worse. If R2 / (R1 · A) is larger than 0.6, a sufficient deposition rate cannot be obtained. Furthermore, R2 / (R1 ・ A)
By setting the value to 0.33 or more and 0.5 or less, the discharge is extremely stable and the ghost is improved. Therefore, R2 / (R1 ・ A) is 0.12 or more.
0.6 or less is preferable, and 0.33 or more and 0.5 or less is more preferable. The adjustment of the RF power A supplied to the raw material gas for supplying unit silicon is performed by changing the RF power or changing the flow rate of the raw material gas for supplying silicon. Cylindrical support (511
2) Adjust the distance R2 between the gas introduction pipe (5114) and the gas introduction pipe.
Adjust by changing the installation position of (5114). An example of how to change the installation position will be described with reference to FIG. In FIG. 2, (2112) shows a cylindrical support, and (2114) shows a gas introduction pipe. In FIG. 2 (2), the mounting position of the gas introduction pipe (5114) is changed as compared with FIG. 2 (1). 2 (3), the mounting position of the gas introduction pipe (2114) is the same as that of FIG. 2 (1), but the shape of the gas introduction pipe (5114) is changed for adjustment.

In any case, the raw material gas introduction pipe
(2114) is preferably arranged concentrically with the cylindrical support (2112). To adjust the outer diameter R1 of the cylindrical support (5112),
This is performed by changing the outer diameter of the cylindrical support (5112). Needless to say, all of the outflow valves other than the necessary gas are closed when forming each layer, and each gas is supplied to the reaction vessel (5111) and the outflow valves (5251 to 525).
In order to avoid remaining in the pipe from 6) to the reaction vessel (5111), close the outflow valve (5251 to 5256), open the auxiliary valve (5260), and further open the main valve (5118) to fully open the system. If necessary, the inside of the chamber is once evacuated to a high vacuum. It goes without saying that the above-mentioned gas species and valve operation may be changed according to the production conditions of each layer. The heating method of the cylindrical support (5112) may be any heating element having a vacuum specification, and more specifically, an electric resistance heating element such as a winding heater of a sheathed heater, a plate heater, a ceramic heater, or a halogen lamp. Examples include a heat-radiating lamp heating element such as an infrared lamp, and a heating element using a heat exchange means using liquid, gas or the like as a heating medium. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used. In addition to that, a container dedicated to heating is provided in addition to the reaction container (5111), and after heating the cylindrical support (5112), the cylindrical support (5112) in the reaction container (5111) in vacuum.
And the like are used. Figure 3 shows the reaction vessel (511
It is a schematic sectional view of 1).

In FIG. 3, (3111) is a reaction vessel, and (3112)
The cylindrical support (3114) shows the raw material gas introduction pipe, and (3500) shows the blowing direction of the raw material gas. As shown in FIG. 3 (1), the gas release holes may be arranged in one direction toward the reaction vessel (3111) to blow the raw material gas toward the reaction vessel (3111). As described above, when the cylindrical reaction vessel (3111) is symmetrically arranged in the tangential direction and the raw material gas is blown in the tangential direction, the gas is sufficiently mixed in the reaction space, and the film thickness and the film quality are uniform. It is better because it improves.

The support used in the present invention may be either electrically conductive or electrically insulating. As the conductive support, Al, Cr, Mo, Au, In, Nb, T
Examples thereof include metals such as e, V, Ti, Pt, Pd, and Fe, and alloys thereof, such as stainless steel. Further, at least the surface of the electrically insulating support such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, or the like, on which the light receiving layer is formed, of the electrically insulating support such as glass or ceramic. It is also possible to use a support obtained by conducting a conductive treatment. The shape of the support used in the present invention may be a cylindrical shape having a smooth surface or an uneven surface, and its thickness is appropriately determined so that a desired electrophotographic light-receiving member can be formed. When flexibility as a light receiving member for electrophotography is required, it can be made as thin as possible within a range in which the function as a support can be sufficiently exhibited. However, the support is usually 10 μm in terms of manufacturing and handling, mechanical strength and the like.
That is all. In particular, when performing image recording using coherent light such as laser light, unevenness is provided on the surface of the support in order to more effectively eliminate image defects due to so-called interference fringe patterns that appear in visible images. May be. The unevenness provided on the surface of the support is disclosed in JP-A-60-168156.
It is prepared by a known method described in JP-A-60-178457 and JP-A-60-225854. Further, as another method for more effectively eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, the surface of the support may be provided with a concavo-convex shape by a plurality of spherical trace depressions. . That is, the surface of the support has irregularities that are smaller than the resolving power required for the electrophotographic light-receiving member, and the irregularities are due to a plurality of spherical trace depressions. Unevenness due to a plurality of spherical trace depressions provided on the surface of the support is disclosed in JP-A-61-23.
It is prepared by the known method described in Japanese Patent No. 1561.

It is necessary for the photoconductive layer in the production method of the present invention to contain hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms,
This is because it is indispensable for improving the layer quality, particularly for improving the photoconductivity and the charge retention property. Therefore, the content of hydrogen atoms or halogen atoms, or the sum of hydrogen atoms and halogen atoms is calculated as silicon atoms and hydrogen atoms or /
And 10 to 30 atom%, more preferably 15 to 25 atom% with respect to the sum of halogen atoms. Examples of the substance that can be used as the Si-supplying gas in the present invention include those in the gas state of SiH4, Si2H6, Si3H8, Si4H10, etc., or gasifiable silicon hydrides (silanes) that are effectively used. In addition, Si is easy to handle when creating layers, and Si supply efficiency is good.
H4 and Si2 H6 are preferred. Then, structurally introducing hydrogen atoms into the photoconductive layer to be formed, and in order to further facilitate the control of the introduction ratio of hydrogen atoms, in order to obtain the film characteristics to achieve the object of the present invention, these It is necessary to further mix a desired amount of H2 and / or He or a silicon compound gas containing hydrogen atoms with the above gas to form a layer.

Further, each gas may be a mixture of not only a single type but also a plurality of types at a predetermined mixing ratio. Further, a material gas effective for supplying halogen atoms used in the present invention is, for example, a halogen gas, a halide, an interhalogen compound containing a halogen, a halogen-substituted silane derivative, or another gaseous or gasifiable halogen compound. Are preferred. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains silicon atoms and a halogen atom as constituent elements, can also be cited as an effective one. The halogen compound that can be preferably used in the present invention,
Specifically, fluorine gas (F2), BrF, ClF, ClF
There may be mentioned interhalogen compounds such as 3, BrF3, BrF5, IF3 and IF7. As the silicon compound containing a halogen atom, that is, a so-called silane derivative substituted with a halogen atom, silicon fluoride such as SiF4 or Si2F6 can be specifically mentioned as a preferable example.
In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer, for example, the temperature of the support, in the reaction vessel of the raw material used for containing hydrogen atoms and / or halogen atoms, It is sufficient to control the amount to be introduced into, the discharge power, etc.

In the present invention, the photoconductive layer preferably contains atoms for controlling the conductivity, if necessary. Atoms that control conductivity may be contained in the photoconductive layer in a uniformly distributed state, or may be contained in an unevenly distributed state in the layer thickness direction. Good. Examples of the atoms that control the conductivity include so-called impurities in the field of semiconductors, and atoms that belong to Group IIIb of the Periodic Table (hereinafter abbreviated as “Group IIIb atoms”) that give p-type conductivity, or An atom that belongs to Group Vb of the periodic table (hereinafter abbreviated as “Group Vb atom”) that imparts n-type conductivity can be used.
Specific examples of the Group IIIb atom include boron (B),
There are aluminum (Al), gallium (Ga), indium (In), thallium (Tl), etc., especially B, Al.
, Ga are preferred. Specific examples of the Group Vb atom include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and the like, with P and As being particularly preferable.
The content of atoms controlling the conductivity contained in the photoconductive layer is preferably 1 × 10 ⁻² to 1 × 10 ⁴ atoms pp.
m, more preferably 5 × 10 ^{-2 to} 5 × 10 ³ atom pp
m, most preferably 1 × 10 ⁻¹ to 1 × 10 ³ atom ppm.

Atoms that control conductivity, eg, II
In order to structurally introduce the group Ib atom or the group Vb atom, the raw material for introducing the group IIIb atom or the raw material for introducing the group Vb atom is introduced into the reaction vessel in a gas state during the layer formation. It may be introduced together with another gas for forming the photoconductive layer 103. As a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom, a gaseous substance at room temperature and normal pressure or a substance which can be easily gasified under at least a layer forming condition is adopted. Is desirable. As the raw material for introducing such a group IIIb atom, specifically, for introducing a boron atom, B2H6, B4H10, B5H9, B5H11, B
Boron hydride such as 6H10, B6H12, B6H14,
Examples thereof include boron halides such as BF3, BCl3 and BBr3. In addition, AlCl3, GaCl3, Ga (CH3)
3, InCl3, TlCl3 and the like can also be mentioned. V
Effectively used as a raw material for introducing a group b atom are phosphorus hydride such as PH3, P2H4, PH4I, PF3, PF5, PCl3, PCl5, P for introducing a phosphorus atom.
Examples thereof include phosphorus halides such as Br3, PBr5 and PI3. In addition, AsH3, AsF3, AsCl3, AsBr
3, AsF5, SbH3, SbF3, SbF5, SbCl3,
SbCl5, BiH3, BiCl3, BiBr3 and the like can also be mentioned as effective starting materials for introducing a Group Vb atom. Further, these raw material substances for atom introduction for controlling the conductivity may be diluted with H2 and / or He as necessary and used.

Further, in the present invention, it is effective that the photoconductive layer contains carbon atoms and / or oxygen atoms and / or nitrogen atoms. The content of carbon atoms and / or oxygen atoms / and / or nitrogen atoms is preferably 1 with respect to the sum of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms.
× 10 ⁻⁵ to 10 atom%, more preferably 1 × 10 ⁻⁴ to 8
Atomic%, optimally 1 × 10 ^{−3 to} 5 atomic% is desirable. Carbon atom and / or oxygen atom and / or nitrogen atom,
The photoconductive layer may be evenly and uniformly contained, or may have a portion having an uneven distribution such that the content of the photoconductive layer varies in the layer thickness direction. In the present invention, the layer thickness of the photoconductive layer is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economical effects, and is preferably 20 to 50 μm, more preferably 23 to 45 μm.
m, most preferably 25 to 40 μm. In order to achieve the object of the present invention and form a photoconductive layer having desired film characteristics, the mixing ratio of the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power and the temperature of the support are set. It is necessary to set it appropriately. The flow rate of H2 and / or He used as a diluting gas is appropriately selected in accordance with the layer design, but the flow rate of H2 and / or He is usually 3 to 20 times that of the Si supply gas.
It is desirable to control in the range of preferably 4 to 15 times, and most preferably 5 to 10 times. Similarly, the gas pressure in the reaction vessel is appropriately selected according to the layer design, but in the usual case, it is 1 × 10 ^{−4 to} 10 Torr, preferably 5 × 10 ^−4.
˜5 Torr, optimally 1 × 10 ⁻³ ˜1 Torr. Similarly, the discharge power is appropriately selected in accordance with the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 0.7 to 7 times, preferably 2.5 to 6 times, and most preferably 3 times. It is desirable to set the range to 5 times. Further, the temperature of the support is appropriately selected according to the layer design, but in the usual case, it is preferably 200 to 350 ° C., more preferably 230 to 33 ° C.
It is desirable to set it to 0 ° C. In the present invention, the support temperature for forming the photoconductive layer, the range described above as a desirable numerical range of the gas pressure is mentioned, the conditions are not usually independently determined separately, the desired characteristics It is desirable to determine the optimum value on the basis of mutual and organic relationships so as to form a light receiving member having.

In the present invention, it is preferable to further form an amorphous silicon type surface layer on the photoconductive layer. This surface layer has a free surface and is provided mainly for achieving the object of the present invention in moisture resistance, continuous repeated use characteristics, electric pressure resistance, use environment characteristics, and durability.
Further, in the present invention, since each of the amorphous materials forming the photoconductive layer forming the light receiving layer and the surface layer has a common constituent element of a silicon atom, a chemical element is formed at the stacking interface. The stability is fully ensured. The surface layer can be made of any material as long as it is an amorphous silicon-based material. For example, amorphous silicon containing hydrogen atoms (H) and / or halogen atoms (X) and further containing carbon atoms (hereinafter "A-SiC: H,
X "), a hydrogen atom (H) and / or a halogen atom (X), and an amorphous silicon further containing an oxygen atom (hereinafter referred to as" a-SiO: H, X "), a hydrogen atom. (H) and / or halogen atom (X)
Containing a nitrogen atom, amorphous silicon (hereinafter referred to as “a-SiN: H, X”), a hydrogen atom (H) and / or a halogen atom (X), and further containing a carbon atom and oxygen. Amorphous silicon containing at least one of an atom and a nitrogen atom (hereinafter referred to as "a-SiCON:
Materials such as "H, X") are preferably used. In the present invention, in order to effectively achieve the object, the surface layer is formed by a vacuum deposition film forming method by appropriately setting numerical conditions of film forming parameters so that desired characteristics can be obtained. Specifically, for example, glow discharge method (AC discharge CVD method such as low frequency CVD method, high frequency CVD method or microwave CVD method, or DC discharge CVD method),
It can be formed by various thin film deposition methods such as a sputtering method, a vacuum deposition method, an ion plating method, a photo CVD method, and a thermal CVD method.

These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be produced. From the viewpoint of productivity of the light receiving member, it is preferable to use the same deposition method as that for the photoconductive layer. For example, in order to form a surface layer made of a-SiC: H, X by the glow discharge method, basically, a raw material gas for supplying Si capable of supplying silicon atoms (Si) and a carbon atom (C) are used. Source gas for C supply that can be supplied, and source gas for H supply that can supply hydrogen atom (H) and / or halogen atom (X)
The raw material gas for X supply capable of supplying X is introduced in a desired gas state into a reaction vessel capable of depressurizing the inside to cause glow discharge in the reaction vessel, and a photoconductive material previously installed at a predetermined position. A- is formed on the support 101 on which the layer 103 is formed.
It suffices to form a layer of SiC: H, X. The material of the surface layer used in the present invention may be any amorphous material containing silicon, such as carbon, nitrogen,
A compound with a silicon atom containing at least one element selected from oxygen is preferable, and a compound containing a-SiC as a main component is particularly preferable. When the surface layer is composed mainly of a-SiC, the amount of carbon is preferably in the range of 30% to 90% with respect to the sum of silicon atoms and carbon atoms. Further, in the present invention, it is necessary for the surface layer to contain hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, especially the photoconductive property and It is essential in order to improve the charge retention characteristics. The hydrogen content is usually 30 to 70 atom%, preferably 35 to 65 atom%, and most preferably 40 to 60 atom% with respect to the total amount of structural atoms. The content of fluorine atoms is usually 0.01 to 15 atom%, preferably 0.1 to 10 atom%, and most preferably 0.6 to 4 atom%.
It is preferably set to atomic%.

The light-receiving member formed within the range of the hydrogen and / or fluorine content can be sufficiently applied as a remarkably excellent one which has not been heretofore in practice. That is, it is known that defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer adversely affect the characteristics as the electrophotographic light-receiving member. For example, the deterioration of the charging characteristics due to the injection of electric charges from the free surface, the fluctuation of the charging characteristics due to the change of the surface structure under the usage environment, for example, high humidity. This adverse effect is caused by the injection of charges and the trapping of the charges in the defects in the surface layer, resulting in the occurrence of an afterimage phenomenon during repeated use. However, by controlling the hydrogen content in the surface layer to 30 atomic% or more, defects in the surface layer are significantly reduced, and as a result, electrical characteristics and high-speed continuous usability are dramatically improved as compared with the conventional one. Can be achieved. On the other hand, when the hydrogen content in the surface layer is 71 atomic% or more, the hardness of the surface layer decreases, and it becomes impossible to withstand repeated use. Therefore, controlling the hydrogen content in the surface layer to be within the above range is one of the very important factors in obtaining the desired electrophotographic properties that are remarkably excellent. The hydrogen content in the surface layer can be controlled by the flow rate of H2 gas, the support temperature, the discharge power, the gas pressure and the like. Further, by controlling the fluorine content in the surface layer to be in the range of 0.01 atomic% or more, it becomes possible to more effectively achieve the bond between silicon atoms and carbon atoms in the surface layer.

Further, as a function of the fluorine atom in the surface layer, the breaking of the bond between the silicon atom and the carbon atom due to the damage of corona or the like can be effectively prevented. on the other hand,
When the fluorine content in the surface layer exceeds 15 atomic%, most of the effect of generating the bond between the silicon atom and the carbon atom in the surface layer and the effect of preventing the breaking of the bond between the silicon atom and the carbon atom due to damage such as corona are generated. Will not be recognized. Further, since excess fluorine atoms impede the mobility of carriers in the surface layer, the residual potential and image memory are noticeable. Therefore, controlling the fluorine content in the surface layer within the above range is one of the important factors in obtaining desired electrophotographic characteristics. The fluorine content in the surface layer is the same as the hydrogen content, such as H2 gas flow rate, support temperature, discharge power,
It can be controlled by gas pressure or the like. Materials that can be used as a gas for supplying silicon (Si) used in the formation of the surface layer of the present invention include SiH4, Si2H6, Si3H8,
Silicon hydrides (silanes) in a gas state such as Si4H10 or capable of being gasified are mentioned as being effectively used, and SiH4 and Si2H6 are more preferable in view of ease of handling during layer formation and good Si supply efficiency. It is mentioned as a preferable one. In addition, these raw material gases for supplying Si may be diluted with a gas such as H2, He, Ar, or Ne, if necessary.

As a substance that can be used as a carbon supply gas, C
H4, C2H6, C3H8, C4H10, and other gas-state or gasifiable hydrocarbons are effectively used, and CH4 and C2H6 are more easily handled during layer formation and have better Si supply efficiency. It is mentioned as a preferable one. Further, the raw material gas for supplying C may be diluted with a gas such as H2, He, Ar, or Ne, if necessary. As a substance that can be used as a gas for supplying nitrogen or oxygen, NH3, NO, N2O, NO
Compounds in the gas state such as 2, O 2, CO, CO 2, N 2 or the like which can be gasified are mentioned as being effectively used. Further, these raw material gases for supplying nitrogen and oxygen may be diluted with a gas such as H2, He, Ar, Ne or the like, if necessary. Further, in order to make it easier to control the introduction ratio of hydrogen atoms introduced into the formed surface layer, hydrogen gas or a silicon compound gas containing hydrogen atoms is mixed in a desired amount with these gases. It is preferable to form a layer. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio. The effective source gas for supplying halogen atoms is
Preferable examples include gaseous or gasifiable halogen compounds such as halogen gas, halides, halogen-containing interhalogen compounds, and halogen-substituted silane derivatives. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains silicon atoms and a halogen atom as constituent elements, can also be cited as an effective one. Specific examples of the halogen compound that can be preferably used in the present invention include fluorine gas (F2), BrF, ClF, ClF3, BrF3 and BrF.
5, interhalogen compounds such as IF3 and IF7 can be mentioned. As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom, silicon fluorides such as SiF4 and Si2F6 can be specifically mentioned as preferable ones. In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer, for example, the temperature of the support, the reaction material of the raw material used for containing hydrogen atoms and / or halogen atoms, can be introduced. The amount to be introduced and the discharge power may be controlled. The carbon atoms and / or oxygen atoms and / or nitrogen atoms may be uniformly contained in the surface layer, or may have a non-uniform distribution such that the content changes in the layer thickness direction of the surface layer. There may be a part. Further, in the present invention, it is preferable that the surface layer contains an atom for controlling conductivity, if necessary. Atoms that control conductivity may be contained in the surface layer in a uniformly distributed state, or even in the layer thickness direction even if there is a portion that is contained in a non-uniform distribution state. Good. Examples of the atoms that control the conductivity include so-called impurities in the field of semiconductors, which give a p-type conduction characteristic.
An atom belonging to group IIb (hereinafter abbreviated as “group IIIb atom”) or an atom belonging to group Vb of the periodic table (hereinafter abbreviated as “group Vb atom”) that provides n-type conductivity can be used. . As the group b atom, specifically,
Boron (B), Aluminum (Al), Gallium (G
a), indium (In), thallium (Tl), etc., and B, Al, and Ga are particularly preferable. Specific examples of the Vb group atom include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), etc., and particularly P and As.
Is preferred. The content of atoms controlling the conductivity contained in the surface layer is preferably 1 × 10 ⁻³ to 1 × 10 ^3.
3 atom ppm, more preferably 1 × 10 ^{-2 to} 5 × 10 ² atom ppm, optimally 1 × 10 ^-1 to 1 × 10 ² atom ppm
Is desirable. To structurally introduce a conductivity controlling atom, for example, a group IIIb atom or a group Vb atom, a raw material for introducing a group IIIb atom or a group Vb atom for introducing a group IIIb atom is formed during layer formation. The raw material may be introduced in a gas state into the reaction vessel together with another gas for forming the surface layer 104. As a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom, a gaseous substance at room temperature and normal pressure or a substance which can be easily gasified under at least a layer forming condition is adopted. Is desirable. As the raw material for introducing such a group IIIb atom, specifically, for introducing a boron atom, B2H6, B4H10, B5H9, B5H1
1, B6H10, B6H12, B6H14, and other boron hydrides, BF3, BCl3, and BBr3, and other halogenated boron. In addition, AlCl3, GaCl3, Ga (CH
3) 3, InCl3, TlCl3 and the like can also be mentioned. As a raw material for introducing a Group Vb atom, phosphorus hydrides such as PH3, P2H4, etc., PH4I, PF3, PF5, PCl3, PCl are effectively used for introducing a phosphorus atom.
5, phosphorus halides such as PBr3, PBr5, PI3 and the like. In addition, AsH3, AsF3, AsCl3, AsB
r3, AsF5, SbH3, SbF3, SbF5, SbCl
3, SbCl5, BiH3, BiCl3, BiBr3, etc. are also V
It can be mentioned as an effective starting material for introducing a group b atom. In addition, these raw material substances for atom introduction for controlling conductivity may be diluted with a gas such as H2, He, Ar, Ne or the like, if necessary. The thickness of the surface layer in the present invention is usually 0.01 to 3 μm, preferably 0.05 to 2 μm, and most preferably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to abrasion or the like during use of the light receiving member, and if it exceeds 3 μm, the electrophotographic properties such as increase in residual potential are deteriorated. The surface layer according to the present invention is carefully formed so that its required properties are provided as desired. That is, Si, C, and / or N
And / or the substance having O, H, and / or X as a constituent is structurally in the form of crystalline to amorphous depending on its forming condition, and in terms of electrical property, it is from conductive to semiconducting to insulating. And the properties from the photoconductive property to the non-photoconductive property, respectively. Therefore, in the present invention, a compound having a desired property depending on the purpose is formed as desired. The formation conditions are strictly selected. For example, in order to provide the surface layer mainly for the purpose of improving the pressure resistance, the surface layer is formed as a non-single-crystal material having a remarkable electric insulating behavior in the use environment. Further, when a surface layer is provided mainly for the purpose of improving continuous repeated use characteristics and use environment characteristics, the degree of electric insulation described above is relaxed to some extent and has a certain sensitivity to irradiation light. It is formed as a non-single crystal material. In order to form the surface layer having the characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the temperature of the support and the gas pressure in the reaction vessel as desired. Support temperature (Ts)
The optimum range is selected according to the layer design,
In the usual case, the temperature is preferably 200 to 350 ° C, more preferably 230 to 330 ° C, and most preferably 250 to 310 ° C. Similarly, the gas pressure in the reaction vessel is also appropriately selected according to the layer design, but in the normal case,
Preferably 1 × 10 ^{−4 to} 10 Torr, more preferably 5 × 10 ^{−4 to} 5 Torr, most preferably 1 × 10 ^{−3 to} 1Tor.
It is preferably rr. In the present invention, the support temperature for forming the surface layer, the range described above as a desirable numerical range of the gas pressure is mentioned, the conditions are not usually independently determined separately, the desired characteristics It is desirable to determine the optimum value based on the mutual and organic relationships to form the light receiving member.

Further, in the present invention, a blocking layer (lower surface layer) having a carbon atom, oxygen atom, or nitrogen atom content lower than that of the surface layer is provided between the photoconductive layer and the surface layer. It is effective for further improving the characteristics of. Also, carbon atoms and / or between the surface layer and the photoconductive layer
Alternatively, a region where the content of oxygen atoms and / or nitrogen atoms changes so as to decrease toward the photoconductive layer may be provided. This improves the adhesion between the surface layer and the photoconductive layer,
The influence of light reflection at the interface can be further reduced. In the present invention, between the photoconductive layer and the support,
Further, it is preferable to form an amorphous silicon-based charge injection blocking layer. This charge injection blocking layer has a function of blocking the injection of charges from the support side to the photoconductive layer side when the photoreceptive layer receives a charging treatment of a constant polarity on its free surface, and has a reverse 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 contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer. The conductivity-controlling atoms contained in the layer may be evenly distributed in the layer, or they may be uniformly distributed in the layer thickness direction but are nonuniformly distributed. There may be a portion that is contained in a distributed state. When the distribution concentration is non-uniform, it is preferable that the content is so distributed as to be distributed more on the support side. However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary that the content be evenly distributed so that the characteristics in the in-plane direction can be made uniform. Examples of the atoms contained in the charge injection blocking layer that control the conductivity include so-called impurities in the semiconductor field.
Atoms belonging to group IIIb of the periodic table giving p-type conductivity (hereinafter abbreviated as “group IIIb atoms”) or atoms belonging to group Vb of the periodic table giving n-type conductivity (hereinafter “group Vb atoms”). Abbreviated) can be used.
Specific examples of the group IIIb atom include B (boron), Al (aluminum), Ga (gallium), and In.
(Indium), Ta (Thallium), etc., especially B,
Al and Ga are preferred. Specific examples of the group Vb atom include P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), and the like, with P and As being particularly preferable.

In the present invention, the content of atoms controlling the conductivity contained in the charge injection blocking layer is appropriately determined according to need so that the object of the present invention can be effectively achieved, but is preferably. 10 to 1 × 10 ⁴ atoms 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 contains at least one of carbon atom, nitrogen atom and oxygen atom to improve the adhesion with other layers provided in direct contact with the charge injection blocking layer. You can do it even more. The carbon atoms, nitrogen atoms or oxygen atoms contained in the layer may be evenly distributed in the layer,
Alternatively, it may be contained evenly in the layer thickness direction, but there may be a portion containing it in a non-uniformly distributed state. However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary that the content be evenly distributed so that the characteristics in the in-plane direction can be made uniform. Carbon atoms and / or nitrogen atoms contained in the entire layer region of the charge injection blocking layer in the present invention and /
Alternatively, the content of oxygen atoms is appropriately determined so that the object of the present invention can be effectively achieved, but in the case of one kind, as the amount thereof, in the case of two or more kinds, the sum thereof, preferably 1 × 10 5. ^-3 to 50 atom%, more preferably 5 x 10 ^{-3 to} 3
It is desirable that the content is 0 atomic%, optimally 1 × 10 ^-2 to 10 atomic%. Further, hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer in the present invention compensate for dangling bonds existing in the layer and are effective in improving the film quality.
The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the charge injection blocking layer is preferably 1
It is desirable that the content is -50 atom%, more preferably 5-40 atom%, and most preferably 10-30 atom%.

In the present invention, the thickness of the charge injection blocking layer is preferably 0.1 to 5 μm, and most preferably 1 to 4 μm from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
It is desirable to be m. In order to form the charge injection blocking layer having the characteristics capable of achieving the object of the present invention, the mixing ratio of the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power and the temperature of the support are appropriately adjusted. It is necessary to set. The flow rate of H2 and / or He, which is a dilution gas, is appropriately selected according to the layer design,
H2 and / or He is usually 1 to 20 times, preferably 3 to 15 times, and optimally 5 times the Si supply gas.
It is desirable to control in the range of 10 times. Similarly, the gas pressure in the reaction vessel is appropriately selected according to the layer design, but in the usual case, it is 1 × 10 ^{−4 to} 10 Torr, preferably 5 × 10 ^{−4 to} 5 Torr, most preferably 1 × 10 ^{−. 3}
It is preferably set to 1 Torr. Similarly, the discharge power is selected in the optimum range according to the layer design.
It is desirable to set the discharge power with respect to the flow rate of the gas for supplying i in the range of 1 to 7 times, preferably 2 to 6 times, and most preferably 3 to 5 times in the normal case. Furthermore, the temperature of the support is
The optimum range is appropriately selected according to the layer design, but in the usual case, it is preferably 200 to 350 ° C, more preferably 220 to 330 ° C, and most preferably 240 to 310 ° C. In the present invention, the mixture ratio of the diluent gas for forming the charge injection blocking layer, the gas pressure, the discharge power, the range described above as a desirable numerical range of the support temperature, but these layer formation factors are usually. It is not independently determined separately, but it is desirable to determine the optimum value of each layer formation factor based on mutual and organic relationships so as to form a charge injection blocking layer having desired characteristics. The electrophotographic photoreceptor manufactured by the method of the present invention is widely used not only in electrophotographic copying machines but also in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making machines. Can be used.

Experimental examples of the present invention will be described below. (Experimental Example) Using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4, the substrate has a direct line of 108 m made of aluminum having a silicon atom content of 100 ppm.
An amorphous silicon deposited film was formed on the base body under the conditions shown in Table 1 on a mirror-finished aluminum cylinder of m, a length of 358 mm, and a wall thickness of 5 mm.
A blocking type electrophotographic photoreceptor having the layer structure shown in FIG. 1 (a) was produced. In FIG. 1A, (101), (105), (103) and (10
4) shows an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer, respectively. In this experimental example, the photoconductive layer was formed under the following conditions. (A) Distance between cylindrical support and source gas supply pipe (R2) = 46
mm, the outer diameter of the cylindrical support (R1) = 108 mm, and the discharge power (Power / SiH4 flow rate) supplied per unit source gas was changed by changing the Power during the production of the photoconductive layer. (B) The outer diameter (R1) of the cylindrical support was set to 108 mm, the power for producing the photoconductive layer was set to 300 W, and the distance (R2) between the cylindrical support and the source gas supply pipe was changed. The produced electrophotographic photosensitive member was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing), and circumferential potential unevenness, ghost and image defects (white spots) were evaluated by the following methods. Furthermore, the deposition rate was also evaluated.

Regarding "circumferential potential unevenness", an electrophotographic photosensitive member was installed in an experimental device, and a charging device was +6 KV.
Is applied to carry out corona charging, and the surface potential of the electrophotographic photosensitive member is measured by the surface potential meter. Then, the fluctuation range of the obtained dark surface potential is defined as the circumferential potential unevenness. ◎ is “excellently good” ○ is “good” △ is “no problem in practical use” × is “problem in practical use” Regarding the “Ghost”, the Canon Ghost Test Chart (part number: FY9-90)
A copy image when a black circle with a reflection density of 1.1 and a diameter of 5 mm is attached to 40) is placed at the front edge of the image on the platen, and a Canon halftone chart (part number: FY9-9042) is placed on top of it. In, the difference between the reflection density of φ5 mm of the ghost chart observed on the intermediate copy and the reflection density of the halftone portion was measured. ◎ is “especially good” ○ is “good” △ is “no problem in practical use” × is “problem in practical use” About “white spot” Canon full black chart (part number: FY9-907
White spots having a diameter of 0.2 mm or less within the same area of the copy image obtained when 3) was placed on the platen and copied were evaluated. ◎ is “excellently good” ○ is “good” △ is “no problem in practical use” × is “problem in practical use” For each of the conditions ((a) and (b)), R2 / ( Relative evaluation was performed by setting the deposition rate obtained when R1 · A) = 0.1 as 100. ⊚ is 85 <≦ 100 ○ is 70 <≦ 85 Δ is 55 <≦ 70 × is ≦ 55 The results thus obtained are shown in Tables 2 and 3. As is clear from Tables 2 and 3, the distance between the cylindrical support and the source gas supply pipe (R2), the outer diameter of the cylindrical support (R1), and the supply per unit source gas in the production of the photoconductive layer. The relation of discharge power (A = SiH4 flow rate / Power) to be set R2 / (R1 ・ A) is set to 0.12 or more and 0.6 or less, which is effective in improving the uneven potential.
Image defects can be reduced. Furthermore, the uneven potential,
It was found that high-speed film formation is possible with good image defects. Furthermore, it was found that image characteristics such as ghost were improved by setting R2 / (R1 · A) to 0.33 or more and 0.5 or less.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3] The configuration of the present invention was determined by the above experimental example. next,
The present invention will be described more specifically with reference to Examples and Comparative Examples.

[0037]

EXAMPLES Next, examples of the present invention and comparative examples will be specifically described, but the present invention is not limited thereto. [Example 1] An apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 4 was used, and the substrate was made of aluminum having a content of silicon atoms of 100 ppm and a diameter of 108 m.
An amorphous silicon deposited film was formed on the base body under the conditions shown in Table 4 on a mirror-finished aluminum cylinder of m, a length of 358 mm, and a wall thickness of 5 mm.
A blocking electrophotographic photoreceptor having the layer structure shown in FIG. 1 (a) was produced. In FIG. 1 (a), (101), (105), (103) and (104)
Indicate an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer, respectively. In this embodiment, the distance between the cylindrical support and the source gas supply pipe (R2) = 46 mm, the outer diameter of the cylindrical support (R1) = 108 mm, the discharge power (Power / SiH4) supplied per unit source gas. Flow rate) = 1.1, R2 / (R
1 ・ A) = 0.39. The produced electrophotographic photosensitive member was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing), and potential unevenness in the circumferential direction, ghost, and image defects (white spots) were evaluated by the following methods. The deposition rate was also evaluated. With respect to these “circumferential potential unevenness”, “ghost”, and “white spot”, the same results as in Experimental Example 1 were obtained. The results of these evaluations are shown in Table 5. In the table, the deposition rate is shown by relative evaluation with the result of Comparative Example 1 shown below as 100. (Comparative Example 1) Compared with Example 1, in this comparative example, the power at the time of producing the photoconductive layer was 340 (W) and R2 / (R1 · A) = 0.70.
A blocking-type electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the above was adopted. The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The results of these evaluations are shown in Table 5 together with Example 1. (Comparative Example 2) Compared with Example 1, in this comparative example, the power at the time of producing the photoconductive layer was 1000 (W) and the flow rate of SiH4 was 300 (scc).
m), R2 = 36 mm and R2 / (R1A) = 0.10.
A blocking type electrophotographic photoreceptor was prepared in the same manner as in. The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The results of these evaluations are shown in Table 5 together with Example 1. The electrophotographic photosensitive member manufactured by the method for manufacturing an electrophotographic photosensitive member of the present invention showed very good results in all items as compared with the electrophotographic photosensitive member manufactured by the conventional method.

[0038]

[Table 4]

[0039]

[Table 5] [Embodiment 2] Using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
A function-separated electrophotographic photoconductor having a layer structure shown in FIG. 1 (b) was formed by forming an amorphous silicon deposition film on a substrate under the conditions shown in Table 6 on an aluminum cylinder (support) that had been subjected to a mirror finishing of mm. The body was made. In FIG. 1B, (101), (105), (107), (106), (103) and (104)
Indicate an aluminum substrate, a charge injection blocking layer, a charge transport layer, a charge generating layer, a photoconductive layer and a surface layer, respectively. In this example, the distance between the cylindrical support and the source gas supply pipe (R2) = 60 mm, the outer diameter of the cylindrical support (R1) = 108 m
m, discharge power supplied per unit source gas (Power / SiH
(4 flow rate), charge transport layer = 2.0, charge generation layer = 4, R2 / (R1 ・
A) = 0.28 (charge transport layer) and 0.14 (charge generation layer). The produced electrophotographic photoreceptor was evaluated in the same manner as in Example 1. As a result, the result was very good as in Example 1.

[0040]

[Table 6] [Embodiment 3] Using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
An amorphous silicon deposited film is formed on a substrate under the conditions shown in Table 7 on an aluminum cylinder (support) that has been subjected to a mirror finishing of mm to produce an electrophotographic photoreceptor having the layer structure shown in FIG. 1 (C). did. In FIG. 1 (C), (101), (109),
(105), (103) and (104) respectively indicate an aluminum substrate, a charge injection blocking layer, a light long wavelength light absorbing layer, a photoconductive layer and a surface layer. In this example, the distance between the cylindrical support and the source gas supply pipe (R2) = 60 mm, the outer diameter of the cylindrical support (R1) = 80 mm, and the power at the time of producing the photoconductive layer was 225.
(W), 300 (W), 600 (W), 900 (W), and change the discharge power (Power / SiH4 flow rate) supplied per unit raw material gas to 1.5, 2.0, 4.0, 6.0, R2 / (R1・ A) = 0.125, 0.1
An electrophotographic photosensitive member was prepared by changing four types of 9, 0.38, 0, and 5. The prepared electrophotographic photosensitive member was set in an electrophotographic apparatus (NP9330 manufactured by Canon was modified for testing), and potential unevenness in the circumferential direction, ghost and image defects (black spots) were evaluated by the following methods. The deposition rate was also evaluated. Regarding "potential in the circumferential direction", an electrophotographic photosensitive member was installed in the experimental device, and the charging device was +6 KV.
Is applied to carry out corona charging, and the surface potential of the electrophotographic photosensitive member is measured by the surface potential meter. Then, the fluctuation range of the obtained dark surface potential is defined as the circumferential potential unevenness. About Ghost, Canon Ghost Test Chart (Part No. FY9-904
A copy image when a black circle with a reflection density of 1.1 and φ5 mm is attached to (0) is placed at the image front end of the document table, and a Canon halftone chart (part number: FY9-9042) is placed on it. In, the difference between the reflection density of φ5 mm of the ghost chart observed on the intermediate copy and the reflection density of the halftone portion was measured. As for "black spots", black spots having a diameter of 0.2 mm or less within the same area of a copy image obtained when a blank sheet was placed on a platen and copied were evaluated. As a result, all items were very good results as in Example 1.

[0041]

[Table 7] [Example 4] Gas release holes are arranged in the gas introduction pipe so as to be symmetric with respect to the tangential direction of the cylindrical reaction vessel as shown in Fig. 3 (2),
Other than that, using the apparatus shown in Example 1, an electrophotographic photoreceptor was produced under the production conditions shown in Table 1. In this example, the distance between the cylindrical support and the source gas supply pipe (R2) = 46 mm, the outer diameter of the cylindrical support (R1) = 108 mm, the discharge power supplied per unit source gas (Power / SiH4 Flow rate) = 1.1, R2 / (R
1 ・ A) = 0.39. When the produced electrophotographic photosensitive member was evaluated in the same manner as in Example 1, good results were obtained as in Example 1.

[Embodiment 5] A gas release hole is formed in the gas introducing pipe as shown in FIG.
Arranged symmetrically in the tangential direction of the cylindrical reaction container as shown in (2), using the apparatus shown in Example 3 for the other, to produce an electrophotographic photoreceptor under the production conditions shown in Table 7. . In this example, the distance between the cylindrical support and the source gas supply pipe 1 (R2) = 60 mm, the outer diameter of the cylindrical support (R1) = 80 mm, and Power = 600 (W) when the photoconductive layer was formed. And discharge power (Power / SiH4 flow rate) supplied per unit source gas = 4.0, and R2 / (R
An electrophotographic photosensitive member was prepared with 1 · A) = 0.38. When the produced electrophotographic photosensitive member was evaluated in the same manner as in Example 3, the same good results as in Example 3 were obtained.

[Embodiment 6] An embodiment 1 is manufactured by using the apparatus for manufacturing an electrophotographic light-receiving member by the RF-PCVD method shown in FIG.
In the same manner as above, a light receiving member including a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared under the conditions shown in Table 4 on a mirror-finished aluminum cylinder (support) having a diameter of 108 mm. In this example, the length of the cylindrical reaction vessel L1 = 945
(mm), and the length L2 of the cylindrical support was changed. The lengthwise method of the cylindrical support was set so as to be located at the center of the cylindrical reaction vessel. The produced electrophotographic photosensitive member was set in an electrophotographic apparatus (NP6150 manufactured by Canon was modified for testing), and circumferential potential unevenness and ghost were evaluated in the same manner as in Experimental Example 1. Table 8 shows the results of these evaluations. In the table, the deposition rate and the circumferential potential unevenness are shown by relative evaluation with the result of Comparative Example 4 shown below as 100.

(Comparative Example 3) Compared to Example 6 , in this comparative example, the power at the time of forming the photoconductive layer was 340 (W) and R2 / (R1 · A).
A blocking type electrophotographic photosensitive member was produced in the same manner as in Example 6 except that the ratio was set to 0.70. The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 6 . The results of these evaluations are shown in Table 8 together with Example 6 .

(Comparative Example 4) Compared with Example 6 , in this comparative example, the power at the time of forming the photoconductive layer was 1000 (W) and the flow rate of SiH4 was 30.
0 (sccm), R2 = 36 mm and R2 / (R1.
A blocking electrophotographic photosensitive member was produced in the same manner as in Example 6 except that A) = 0.10. The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 6 . The results of these evaluations are shown in Table 8 together with Example 6 . As is clear from Table 8, in the method for producing an electrophotographic photosensitive member of the present invention, the length L1 of the cylindrical reaction container and the length L2 of the cylindrical support are 0.
It was found that it was particularly effective when 65 ≦ L2 / L1 ≦ 0.9. From this result, it is possible to stabilize the discharge and gas flow by making the size (length) of the reaction vessel slightly longer than the length of the support, and as a result, electrophotographic characteristics such as uneven electric potential in the circumferential direction and ghost Since a very excellent electrophotographic photosensitive member can be formed at high speed, it is useful for downsizing of the apparatus and reduction of capital investment.

[0046]

[Table 8]

[0047]

As described above, according to the present invention, the outer diameter of the cylindrical support and the distance between the cylindrical support and the gas introduction pipe for introducing the raw material gas into the reaction space are set as follows. , Relationship with discharge power supplied per unit material gas for supplying silicon during formation of the photoconductive layer, that is, curvature of cylindrical support, distance between source gas discharge part and cylindrical support, unit source gas By setting the mutual relationship of the discharge power given to the inside of the reaction vessel within a predetermined range, it is possible to stabilize the discharge and the gas flow in the reaction vessel, thereby making it possible to inexpensively manufacture without rotating the cylindrical support. The method can be employed, high-speed film formation is possible, and the light-receiving member having improved characteristics of film quality, reduced image defects, and reduced ghost can be manufactured. Further, according to the present invention, the size of the device can be reduced, and the yield can be dramatically improved in mass production.

[Brief description of drawings]

FIG. 1 is a schematic view showing a structure of a light receiving member according to a method for manufacturing a light receiving member of the present invention.

FIG. 2 (1) to (3) are schematic explanatory views showing adjustment of the distance between the cylindrical support and the raw material gas introduction pipe in the method for producing a light receiving member of the present invention.

FIG. 3 is a schematic view showing a cylindrical reaction container that also serves as an electrode, a counter electrode including a cylindrical support, a gas release hole of a gas introduction tube, and a direction of the gas release hole in the method for producing a light receiving member according to the present invention. FIG.

FIG. 4 shows an example of an apparatus for producing a light receiving member according to the present invention, and is a schematic view of an apparatus for producing a photoconductor for electrophotography by an RF glow discharge method.

[Explanation of symbols]

100 Photoreceptive member 101 Conductive support 102 Photoreceptive layer 103 Photoconductive layer 104 Surface layer 105 Charge injection blocking layer 106 Charge generation layer 107 Charge transport layer 109 Long wavelength light absorption layer 110 Free surface 5100 Deposition device 5111, 2111, 3111 Cylindrical reaction vessel 5112, 2112, 3112 Cylindrical support 5113 Support heating heater 5114, 2114, 3114 Raw material gas inlet pipe 5115 Matching box 5116 Raw material gas pipe 5117 Reaction vessel leak valve 5118 Main exhaust valve 5119 Vacuum gauge 5200 Raw material gas Supply device 5211 to 5216 Mass flow controller 5221 to 5226 Source gas cylinder 5231 to 5236 Source gas cylinder valve 5241 to 5246 Gas inlet valve 5251 to 5256 Gas outlet valve 5261 to 5266 Pressure regulator 3500 Source gas outlet direction

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI H01L 31/0248 H01L 31/08 G (56) References JP 63-479 (JP, A) JP 60-176047 ( JP, 56-83746 (JP, A) JP, 5-134438 (JP, A) JP, 5-17312 (JP, B2) JP, 3-68948 (JP, B2) (58) ) Fields investigated (Int.Cl. ⁷ , DB name) C23C 16/00-16/56 H01L 21/205

Claims (3)

(57) [Claims] 1. A raw material gas and high-frequency power are introduced into a discharge space of a vacuum-tight cylindrical reaction vessel, and the raw material gas is decomposed through an applying means and placed in the discharge space. A method for manufacturing a light-receiving member, comprising the step of forming at least a photoconductive layer on a cylindrical support without rotating the cylindrical support, wherein an outer diameter of the cylindrical support is R1, The distance between the cylindrical support and the source gas introduction pipe is R2, and the discharge power (Power / gas flow rate) with respect to the flow rate of the source gas for supplying Si is A (W / SCC).
M), the length of the cylindrical reaction vessel is L1, and the length of the cylindrical support is L2, these are represented by the following formulas.
The photoreceptive part is manufactured so as to satisfy (1) and the following formula (2).
A method of manufacturing a light-receiving member, which comprises manufacturing a light-receiving member by determining conditions of a manufacturing method. 0.12 ≦ R2 / (R1 · A) ≦ 0.6 (1) 0.65 ≦ L2 / L1 ≦ 0.9 2) 2. The conditions of the method for manufacturing a light receiving section are determined so that R1, R2 and A satisfy the following expression (3).
And manufacturing a light-receiving member.
A method for manufacturing the light receiving member according to the item 1. 0.33 ≦ R2 / (R1 · A) ≦ 0.5 (3) 3. The method for producing a light receiving member according to claim 1, wherein the A is in the range of 2.5 to 6.