JPS61295563A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member having excellent electrostatic chargeability, low residual potential, high sensitivity over a wide wavelength region, good adhesiveness to a substrate and excellent environment resistance by using microcrystalline silicon in at least part of the photoconductive member. CONSTITUTION:This photoconductive member has a conductive base 21, a barrier layer 22 formed on the base 21 and a photoconductive layer 23 formed on the barrier layer 22. At least parts of the barrier layer 22 is formed of the amorphous silicon contg. the element belonging to the group III or V of the periodic table and at least part of the photoconductive layer 23 is formed of the microcrystalline silicon contg. the element belonging to the group III or V of the periodic table. The proper region on the conductive base side of the barrier layer 22 and/or the proper region on the surface side of the photoconductive layer contains at least one kind of element selected from carbon, oxygen and nitrogen. The photoconductive member which has high resistance and excellent electrostatic charge characteristic, has the high photosensitive characteristic in visible light and near IR region, permits easy production and has high practicability is thus obtd.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention is used for electrophotographic photoreceptors, etc., and has charging characteristics,
The present invention relates to a photoconductive member having excellent photosensitivity characteristics, environmental resistance, etc.

[Technical background of the invention and its problems] Conventionally, inorganic materials such as CdS, ZnO, Se, 5e-Te, or amorphous silicon, or poly-N- Organic materials such as vinyl carbazole (PVCz) or trinitrofluorene (TNF) have been used. However, these conventional photoconductive materials have various problems in terms of photoconductive properties and manufacturing, and it is necessary to use these materials depending on the purpose of use, sacrificing some of the characteristics of the photoreceptor system. There is.

For example, Se and CdS are materials that are harmful to the human body, and special consideration must be given to safety measures when manufacturing them. Therefore, there are problems in that the manufacturing equipment becomes complicated and the manufacturing cost is high, and in particular, Se needs to be recovered, which adds to the recovery cost. Also,
In the Se or 5e-Te system, the crystallization temperature is 65°C
Therefore, during repeated copying, problems with photoconductive properties arise due to residual copies, and as a result, the service life is short, making it impractical.

Furthermore, ZnO is susceptible to oxidation-reduction and is significantly affected by the environmental atmosphere, resulting in a problem of low reliability in use.

Furthermore, organic photoconductive materials such as PVCz and TNF are suspected to be carcinogens and present human health concerns, and organic materials have low thermal stability and abrasion resistance. , has the disadvantage of short lifespan.

On the other hand, amorphous silicon (hereinafter abbreviated as a-3i)
has recently attracted attention as a photoconductive conversion material, and is being actively applied to solar cells, thin film transistors, and image sensors. As part of the application of 'a-S i, attempts have been made to use a-3i as a photoconductive material for electrophotographic photoreceptors, and photoreceptors using a-8i are non-polluting materials. It has advantages such as no need for recovery treatment, higher spectral sensitivity in the visible light region than other materials, high surface hardness, and excellent abrasion resistance and impact resistance.

This a-5t is being studied as a photoreceptor based on the Carlson method, but in this case, the photoreceptor characteristics are required to be high resistance and photosensitivity. Since it is difficult to satisfy the requirements with a photoreceptor, we created a laminated structure in which a barrier layer is provided between the photoconductive layer and the conductive support, and a surface charge retention layer is provided on the photoconductive layer. , satisfies these requirements.

By the way, a-3i is usually formed by a glow discharge decomposition method using silane gas, but at this time, a-3i is
Hydrogen is incorporated into the 5i film, and the electrical and optical characteristics vary greatly due to the difference in the amount of hydrogen. That is, as the amount of hydrogen that enters the a-3i film increases, the optical bandgap increases and the resistance of a-3t increases, but as a result, the photosensitivity to long wavelength light decreases. For example, it is difficult to use it in a laser beam printer equipped with a semiconductor laser. In addition, if the hydrogen content in the a-3i film is high, depending on the film formation conditions, (S
iH) and SiH2 having a bond n structure may occupy most of the area in the film. In this case, voids increase and silicon dangling bonds increase, resulting in deterioration of photoconductive properties and rendering the material unusable as an electrophotographic photoreceptor. Conversely, when the amount of hydrogen penetrating into a-3t decreases, the optical bandgap becomes smaller and its resistance decreases, but the photosensitivity to longer wavelength light increases. However, when the hydrogen content is low, there is less hydrogen to combine with and reduce silicon dangling bonds. For this reason, the mobility of the generated carriers is reduced, the life span is shortened, and the photoconductive properties are deteriorated, making it difficult to use as an electrophotographic photoreceptor.

In addition, as a technique to increase the sensitivity to long wavelength light, there is a method of mixing silane-based gas and germane G e H4 and decomposing it by glow discharge to produce a film with a narrow optical band gap. system gas and G
Since the optimum substrate temperature is different between eH4 and H4, the produced film has many structural defects and cannot obtain good photoconductive properties. Moreover, since the waste gas of G e H4 becomes toxic gas when oxidized, the waste gas treatment is also complicated. Therefore,
Such technology is impractical.

[Objective of the Invention] This invention was made in view of the above circumstances, and has excellent charging ability, low residual potential, high sensitivity over a wide wavelength range, and good adhesion to the substrate. An object of the present invention is to provide a photoconductive member with excellent environmental resistance.

[Summary of the Invention] A photoconductive member according to the present invention includes an electrically conductive support, a barrier layer formed on the electrically conductive support, a photoconductive layer formed on the barrier layer, In the photoconductive member having a photoconductive member, the barrier layer contains hydrogen and group Ⅰ or V of the periodic table.
The photoconductive layer is formed of amorphous silicon containing an element belonging to group I or V of the periodic table, and at least a part of the photoconductive layer is formed of microcrystalline silicon containing an element belonging to group I or V of the periodic table. , a suitable region of the barrier layer on the conductive support side and/or a suitable region on the surface side of the photoconductive layer contains at least one element selected from carbon, oxygen and nitrogen.

This invention was achieved through various experimental studies by the inventors of the present invention in order to overcome the drawbacks of the prior art described above and to develop a photoconductive member that has both excellent photoconductive properties (electrophotographic properties) and environmental resistance. As a result, microcrystalline silicon (hereinafter referred to as μC)
The present invention was completed based on the idea that this object could be achieved by using a photoconductive material (abbreviated as -3t) for at least a portion of a photoconductive member.

[Embodiments of the Invention] The present invention will be specifically described below. The feature of this invention is that μC-3i is used instead of the conventional a-3i. That is, whether all or part of the region of the photoconductive layer is formed of microcrystalline silicon (μC-3i) or a mixture of microcrystalline silicon and amorphous silicon (a-3t); Alternatively, it is formed of a laminate of microcrystalline silicon and amorphous silicon. In addition, in a functionally separated photoconductive member, μC is added to the charge generation layer.
-5i is used.

μC-3i is a-
3i and polycrystalline silicon (polycrystalline silicon)
clearly distinguished from That is, in X-ray diffraction measurement, since a-3i is amorphous, only a halo appears;
Although no diffraction pattern can be observed, μC-6i shows a crystal diffraction pattern with a 2θ of around 27 to 28.5°. Also, while polycrystalline silicon has a dark resistance of 106Ω, μC-5i has a dark resistance of 1011Ω.
- Has a dark resistance of cm or more. This μC-3i is formed by an aggregation of microcrystals having a grain size of approximately several tens of angstroms or more.

A mixture of μC-3i and a-8i is one in which the crystalline region of μC-5i is mixed in a-3t, and μC-5i and a-3L exist in the same volume ratio. means. In addition, most of the laminate of μC-3t and a-3L is a-
A layer consisting of 3t and a layer filled with μC-8t are laminated.

A photoconductive layer having such μC-3t can be produced by depositing μC-3i on a conductive support using silane gas as a raw material using a high-frequency glow discharge decomposition method in the same way as a-3i. can. In this case, if the temperature of the support is set higher than when forming a-Si and the high frequency power is also set higher than when forming a-3i, μC
-3i becomes easier to form. Furthermore, by increasing the support temperature and high frequency power, the flow rate of source gas such as silane gas can be increased, and as a result, the film formation rate can be increased. Further, by using a gas obtained by diluting a high-order silane gas such as SiH or S 1 2 He as a raw material gas with hydrogen, μC-5t can be formed with higher efficiency.

FIG. 1 is a diagram showing an apparatus for manufacturing a photoconductive member according to the present invention. Gas cylinders 1, 2, and 3°4 contain, for example, S iH, B H, and N2, respectively.

A raw material gas such as CH4 is contained. The gas in these gas cylinders 1.2.3.4 is controlled by a valve 6 for adjusting the flow rate.
and is supplied to a mixer 8 via a pipe 7. Each cylinder is equipped with a pressure gauge 5, and by monitoring the pressure gauge 5 and adjusting the valve 6, the flow rate and mixing ratio of each raw material gas supplied to the mixer 8 can be adjusted. can. The gases mixed in the mixer 8 are supplied to a reaction vessel 9. At the bottom 11 of the reaction vessel 9,
A rotating shaft 10 is attached to be rotatable around the vertical direction, and a disk-shaped support 12 is attached to the upper end of this rotating shaft 10.
is fixed with its surface perpendicular to the rotating shaft 10. Inside the reaction vessel 9, a cylindrical electrode 13 is installed on the bottom 11 with its axial center aligned with the axial center of the rotating shaft 10. A drum base 14 of a photoreceptor is placed on a support base 12 with its axial center aligned with the axial center of the rotating shaft 10,
A heater 15 for heating the drum base is disposed inside the drum base 14. Electrode 13 and drum base 14
A high frequency power source 16 is connected between the electrode 1 and
A high frequency current is supplied between the drum base member 14 and the drum base member 14 . The rotating shaft 10 is rotationally driven by a motor 18. The pressure inside the reaction vessel 9 is monitored by a pressure gauge 17, and the reaction vessel 9 is connected via a gate valve 18 to an appropriate evacuation means such as a vacuum pump.

When manufacturing a photoreceptor using the apparatus configured as described above, after installing the drum base 14 in the reaction vessel 9, the gate valve 19 is opened to control the inside of the reaction vessel 9 at approximately 0.1 Torr. Evacuate to below pressure. Next, cylinder 1
, 2.3.4, the required reaction gases are mixed at a predetermined mixing ratio and introduced into the reaction vessel 9. In this case, reaction vessel 9
The gas flow rate introduced into the reaction vessel 9 is such that the pressure inside the reaction vessel 9 is 0.1.
Set it so that it is between 1 Torr and 1 Torr. Next, the motor 18
is activated to rotate the drum base 14, the heater 15 heats the drum base 14 to a constant temperature, and the high frequency power supply 16 supplies a high frequency current between the electrode 13 and the drum base 14 to create a glow between them. form a discharge.

As a result, microcrystalline silicon (μC-5i) is deposited on the drum base 14. Note that N2O, NH, NH, NO, N2. CH4゜CH,
By using O gas etc., these elements can be reduced to μC-
3i.

In this way, the photoconductive member according to the present invention is similar to the conventional a-
Like those using 3t, it can be manufactured using closed system manufacturing equipment, so it is safe for the human body. Further, since this photoconductive member has excellent heat resistance, moisture resistance, and abrasion resistance, it has the advantage of having a long service life with little deterioration even after repeated use over a long period of time. Furthermore, since a long wavelength sensitizing gas such as G e H4 is not required, there is no need to provide waste gas treatment equipment, and industrial productivity is extremely high.

It is preferable that μC-5i contains 0.1 to 30 at % of hydrogen. As a result, the dark resistance and bright resistance become harmonious, and the photoconductive properties are improved. μC-
For example, when doping hydrogen into the 8L layer by a glow discharge decomposition method, a silane-based raw material gas such as SiH and S L 2 He and a carrier gas such as hydrogen are introduced into a reaction vessel and a glow discharge is performed. Discharge or S iF 4
A mixed gas of a silicon halide such as and S i Cl 4 and hydrogen gas may be used, or a mixed gas of a silane gas and a silicon halide may be used. Furthermore, the μC-8L layer can be formed not only by the glow discharge decomposition method but also by a physical method such as sputtering. In view of photoconductive properties, the photoconductive layer containing μC-3t preferably has a thickness of 1 to 80 μm, and more preferably 5 to 50 μm.

Substantially all areas of the photoconductive layer may be formed of μC-5i, or may be formed of a mixture or a laminate of a-3L and μC-3i. The charging ability is higher in the laminate,
Although the photosensitivity depends on the volume ratio, the mixture is higher in the long wavelength region of the infrared region, and the two are almost the same in the visible light region. Therefore, depending on the use of the photoreceptor, substantially all the regions may be made of μC-8t, or may be made of a mixture or a laminate.

Preferably, μC-5i is doped with at least one element selected from nitrogen (N), carbon (C), and oxygen (0). Thereby, the dark resistance of μC-5i can be increased and the photoconductive properties can be improved.

These elements precipitate at the grain boundaries of μC-5i and act as terminators for silicon dangling bonds,
It is thought that the density of states existing in the band-to-band region is reduced, thereby increasing the dark resistance.

In this invention, a barrier layer is provided between the conductive support and the photoconductive layer. This barrier layer comprises a conductive support and
By suppressing the flow of charge between the photoconductive layer and the photoconductive layer, the charge retention function on the surface of the photoconductive member is enhanced, and the charging ability of the photoconductive member is enhanced. In the Carlson method, when the surface of the photoreceptor is positively charged, the barrier layer is made p-type in order to prevent electrons from being injected from the support side to the photoconductive layer. On the other hand, when the surface of the photoreceptor is negatively charged, the barrier layer is made n-type in order to prevent holes from being injected from the support side to the photoconductive layer. It is also possible to form an insulating film on the support as a barrier layer. The barrier layer may be formed using μC-5i, or may be formed using a-Sf.

In order to make μC-3i and a-3i p-type, it is preferable to dope them with elements belonging to Group Ⅰ of the periodic table, such as boron B1 aluminum AI, gallium Ga, indium In, and thallium TI. , μC-3i
To make the layer n-type, an element belonging to group V of the periodic table, such as nitrogen N1 phosphorus P1 arsenic As1 antimony S
It is preferable to dope with B, bismuth Bi, or the like.

This doping with p-type impurities or nM impurities prevents charges from moving from the support side to the photoconductive layer.

Preferably, a surface layer is provided on top of the photoconductive layer.

Since μC-3t of the photoconductive layer has a relatively large refractive index of 3 to 4, light reflection easily occurs on the surface. When such light reflection occurs, the proportion of the amount of light absorbed by the photoconductive layer decreases, increasing optical loss. For this reason, it is preferable to provide a surface layer to prevent reflection. Also, by providing the surface layer, the photoconductive layer is protected from damage. Furthermore, by forming a surface layer, charging ability is improved,
The surface becomes more charged. The materials forming the surface layer are SiN, SiO, and SiC.

AI O, a-3iN; H,, a-SiO; H.

and a-3iC;H, and organic materials such as polyvinyl chloride and polyamide.

As described above, a photoconductive member applied to an electrophotographic photoreceptor is formed by forming a barrier layer on a support, a photoconductive layer on this barrier layer, and a surface layer on this photoconductive layer. A charge transport layer (CTL) is formed on the support.
It is also possible to form a functionally separated structure in which a charge generation layer (CGL) is formed on a charge transport layer. In this case, a barrier layer may be provided between the charge transport layer and the support. The charge generation layer generates carriers upon irradiation with light. This charge generation layer is preferably made of microcrystalline silicon μC-3i in part or in its entirety, and has a thickness of 0.1 to 10 μm.

The charge transport layer is a layer that allows carriers generated in the charge generation layer to reach the support side with high efficiency, and therefore, the carriers must have a long life, high mobility, and high transportability. The charge transport layer may be formed of a-5i or μ
It may be formed of C-5f. In order to increase dark resistance and improve chargeability, it is preferable to light-dope with an element belonging to either Group Ⅰ or Group V of the periodic table.

Furthermore, in order to further improve the charging ability and to have the functions of both a charge transport layer and a charge generation layer, one or more of the elements C, N, and 0 may be contained. If the charge transport layer is too thin or too thick, it will not perform its function satisfactorily.

Therefore, the thickness of the charge transport layer is preferably 3 to 80 μm. By providing a barrier layer, even in a functionally separated photoconductive member having a charge transport layer and a charge generation layer, its charge retention function can be enhanced and charging ability can be improved. Note that whether the barrier layer is p-type or n-type is determined depending on its charging characteristics. This barrier layer may be formed of a-Si or μC-8i.

The invention according to this application is characterized in that at least a portion of the photoconductive layer is formed of μC-3i, and the barrier layer is a hydrogen-containing a
-3i, and the photoconductive layer and barrier layer contain an element belonging to Group Ⅰ or Group V of the periodic table. 2 and 3 are cross-sectional views of a photoconductive member embodying the present invention. In FIG. 2, a barrier layer 22 is formed on a conductive support 21;
'' Second, a photoconductive layer 23 is formed. On the other hand, in FIG. 3, a surface layer 24 is further formed on the photoconductive layer 23. At least a portion of the photoconductive layer 23 has μ
The barrier layer 22 is made of a-3i containing hydrogen.
Consisting of 3t. These photoconductive layer 23 and barrier layer 22 contain an element belonging to Group 1 or Group V of the periodic table.

By forming the photoconductive layer mainly of μC-5t, it is possible to increase the sensitivity of the photoconductive member from the visible light region to the near-infrared region (for example, around 790 nm, which is the oscillation wavelength of a semiconductor laser). This allows the photoconductive member to be used in both PPC (plain paper copiers) and laser printers. μC-3i itself is
Although it is slightly n-type, the photoconductive layer mainly made of μC-5i is lightly doped (10 to 10-3 at.
The photoconductive layer 23 becomes an l-type (intrinsic) semiconductor, has a high dark resistance, and improves the S/N ratio and charging ability. Also,
The photoconductive layer preferably has a thickness of 3 to 80 μm, more preferably 10 to 40 μm.

Further, a-5i constituting the barrier layer 22 is also doped with an element belonging to Group Ⅰ or Group V of the periodic table, making the barrier layer 22 a p-type semiconductor or an n-type semiconductor. The content is preferably 10-3 to ↓00 atoms. As a result, the barrier layer 22 has a low resistance and its blocking ability is further improved.

As shown in FIG. 3, in a photoconductive member in which a surface layer 24 is formed on a photoconductive layer 23, this surface layer 24 is
a-3iC;H, a-3iO;H.

It is formed of a-3i containing at least one element among C10°N, such as a-5iN;H, a-3iCN;H, etc. This protects the surface of the photoconductive layer, improves environmental resistance, and improves charging ability. The content of C, O, and N is preferably 10 to 50 atomic %. Further, the thickness of the surface layer 24 and the barrier layer 22 is preferably 0.01 to 10 μm, more preferably 0.1 to 2 μm.

In this invention, a suitable region of the barrier layer 22 on the conductive support side and/or a suitable region on the surface side of the photoconductive layer 23 is
It is characterized by containing at least one element selected from C1O and N.

In the region on the conductive support side, it is preferable for the concentration of C, O, and N to be constant from the viewpoint of ease of film formation, but the concentration may gradually decrease from the support toward the photoconductive layer. Alternatively, this region may have a constant concentration in the barrier layer, and the concentration may gradually decrease from the barrier layer side to the surface layer side of the photoconductive layer. Further, in the surface side region, these elements may be locally present in the upper part of the photoconductive layer 23, or may be distributed such that the concentration thereof is non-uniform. In any case, the total amount of C, O, and N contained in the region on the surface side and the conductive support side is 20 at%
It is preferable that it is below. Further, in the photoconductive layer 23, it is preferable to perform light doping so that the photoconductivity does not decrease.

In this way, the barrier layer 21 is made p-type or n-type, and C, O,
By containing N, injection of electrons or holes from the support 21 to the photoconductive layer 23 can be prevented with high efficiency, and the charge retention function can be extremely improved. In addition, by including C, 0, and N in the photoconductive layer 23, the charge retention function is further improved, and the passage of carriers during light irradiation is not blocked, resulting in improved carrier flow and high carrier efficiency. Move with. In addition, the barrier layer 22 and the surface layer 24
When the photoconductive layer 23, the barrier layer 22, and the surface layer 24 are doped with C, O, or N, the concentration of C10 or N changes rapidly.

However, by including C20 or N in these boundary regions as in the present invention, rapid changes in concentration of these elements can be prevented and carrier flow at the boundaries can be made smooth. Due to these effects, the residual potential of the photoreceptor can be kept low during repeated use, and good electrophotographic properties can be obtained. Furthermore, during film formation, it is possible to prevent peeling of the film due to stress concentration between foreign substances, and also to prevent cracking due to distortion of internal stress of the film.

4(a) to (j) show the photoconductive layer 23 and the barrier layer 2.
2 shows the concentration distribution of the total amount of C, O, and N in No. 2. In the pattern shown in Figure 4(a), the C, 0, and N elements are
It exists at a constant concentration in the support side region of the barrier layer 22 and the surface side region of the photoconductive layer 23. On the other hand, in FIGS. 4(b) to 4(d), in the barrier layer 22, the barrier layer 22
In the photoconductive layer 23, a pattern in which the density gradually decreases from the boundary between the substrate 21 and the support 21 toward the inside (surface side), or a pattern in which the surface layer 24 and the light from the inside (the boundary with the conductive layer 23) to the inside (the support body 21
A decreasing pattern towards the side) is shown. In the other patterns shown in FIGS. 4(e) to (j), the concentrations of these elements change similarly. In addition, Fig. 4(a)
,(d).

Patterns other than the pattern shown in (f) are those of the photoconductive layer 23.
C, O only on either the surface side of the barrier layer 22 or the support side of the barrier layer 22.
, N.

When the surface layer 24 is doped with C, O, and N, there is a concentration difference of C10°N between the photoconductive layer 23 and the surface layer 24, but the boundary between the photoconductive layer 23 and the surface layer 24 0 toward the support 21 in a pattern as shown in FIG.
．． By gradually decreasing the concentration of 0 or N, rapid changes in the concentration of these elements are prevented and the concentration changes gently, so that the flow of charge at the boundary can be made smooth. In addition, in the barrier layer 22, the concentration of these elements decreases in the direction from the support 21 to the photoconductive layer 23, so the photoconductive layer does not contain C, O, and N or is lightly doped with these elements. The difference in agricultural degree between 23 and 23 will be reduced. Also at the boundary between the photoconductive layer 23 and the barrier layer 22, the concentration changes of these elements become gradual, and carriers move smoothly. Due to these effects, the residual potential of the photoreceptor can be kept low during repeated use, and good electrophotographic properties can be obtained.

Next, embodiments of the invention will be described.

Example 1 After cleaning and drying an Al drum serving as a conductive substrate, the inside of the reaction vessel was heated to 350° C. while being evacuated using a diffusion pump. After about 1 hour, the degree of vacuum inside the reaction vessel decreased to -
5 torr and the drum temperature stabilized at 3×10. Then S I H with a flow rate of 3005 CCM,
i gas, the flow rate ratio to this S I H4 gas flow rate is 5
BH gas of X10-', CH4 gas of 60 SCCMG, and argon gas of 2005 CCM were mixed and supplied to the reaction vessel. 200 at 13.56MHz
High frequency power of watts was applied to cause glow discharge, thereby forming a barrier layer 21. At this time, the pressure inside the reaction vessel was approximately 0.8
The resulting layer thickness was 1.2 μm. Next, all gases were turned off and a gas barge was performed for 15 minutes. After that, the flow rate of S i H4 was 6008CCM, the flow rate of hydrogen gas was 200SCCM, and the S t H of B2H6 was
The film was formed by setting the flowmeter ratio to 4 to 1X10-7. Reaction pressure is 1.5 Torr, high frequency power is 350 Torr.
This made it possible to obtain a photoconductive layer with a thickness of 30 μm. Then, after stopping all gases and purging for 15 minutes, 11005 CC of SiH4 gas and 40
A film was formed under conditions of flowing CH4 gas of 0 SCCM, reaction pressure of 0.7 torr, and high frequency power of 200 watts. The thickness of the surface layer obtained was 1.5 μm. When an image was formed on the photoreceptor thus formed using a laser printer equipped with a semiconductor laser with an oscillation wavelength of 790 nm, a clear image with high resolution could be formed. Furthermore, the electrophotographic properties were extremely good, with a surface potential of 550 V and a white background potential of 1 (lv) for an exposure dose of 50 erg/c, and a half-decrease exposure dose of 9 erg/cd.

Example 2 After cleaning and drying an Al drum serving as a conductive substrate, the inside of the reaction vessel was heated to 320° C. while being evacuated using a diffusion pump. After about 1 hour, the degree of vacuum inside the reaction vessel reached 5 x 10-
5 torr and the drum temperature stabilized. Then 400
SiH gas at a flow rate of 5 CCM, the flow rate ratio to this S t H4 gas flow rate or BI (gas, 100
SCCM of CH4 gas and 2008 CCM of helium gas were mixed and supplied to the reaction vessel. 13.56M H
A high frequency power of 200 watts was applied at z to cause glow discharge, and a film was formed for 1 minute at a reaction pressure of 0.9 torr. Next, the high frequency power was set to 0, and 50 SCCM of CH4 gas was flowed for 5 minutes. After that, increase the high frequency power to 200 watts and
Glow discharge was performed for 0 seconds. The reaction pressure was 0.85) liters. Next, the high frequency power is set to 0, and CH4 of 5SCCM is
The gas was passed for 5 minutes. Thereafter, the high frequency power was set to 200 W, and glow discharge was performed for 20 seconds. The reaction pressure is 0683
It was Toru. Barrier layer 21 obtained by forming a film in this way
The layer thickness was 1.8 μm. Next, all gases were turned off and a gas barge was performed for 15 minutes. After that, S.I.
H, i flow rate is 6503 CCM, hydrogen gas flow rate is 3
The film was formed by setting the flow rate ratio of 008CCM, B2H6 to SiH to be 8×10=. The reaction pressure was 1.7 torr and the high frequency power was 400 watts, which made it possible to obtain a 42 μm photoconductive layer. Then, after turning off all gases and purging for 15 minutes, the 110
05CC of S I H4 gas and 400SCCM of N2
Flowing gas, reaction pressure 0.7 Torr and high frequency power 200
The film was formed under the following conditions. The thickness of the obtained surface layer was 1.8 μm. When an image was formed on the photoreceptor thus formed using a laser printer equipped with a semiconductor laser with an oscillation wavelength of 790 nm, a clear image with high resolution could be formed. Furthermore, the electrophotographic custom-made product had an extremely good half-reduction exposure of 8.5 erg/cd.

[Effects of the Invention] According to the present invention, a photoconductive material with high resistance, excellent charging characteristics, high photosensitivity in the visible light and near-infrared light regions, easy manufacture, and high practicality. A sexual member can be obtained.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an apparatus for manufacturing a photoconductive member according to the present invention, FIGS. 2 and 3 are sectional views showing a photoconductive member according to an embodiment of the present invention, and FIGS. (j) is C, O
, N is a diagram showing the concentration distribution of N. . 1.2,3,4. Cylinder, 5; Pressure gauge, 6; Valve, 7
: Piping, 8; Mixer, 9; Reaction container, 10; Rotating shaft, 1
3; Electrode, 14; Drum base, 15: Heater, 16; High frequency power supply, 19; Gate valve, 21; Support, 22;
Barrier layer, 23; photoconductive layer, 24; surface layer. Applicant's agent Patent attorney Takehiko Suzue 1d Figure 1 Figure 2 Figure 3 Figure 4 Figure 4

Claims (6)

[Claims] (1) In a photoconductive member having a conductive support, a barrier layer formed on the conductive support, and a photoconductive layer formed on the barrier layer, the barrier layer is The photoconductive layer is formed of amorphous silicon containing hydrogen and an element belonging to Group III or V of the periodic table, and at least a portion of the photoconductive layer is formed of an element belonging to Group III or V of the periodic table.
A suitable region of the barrier layer on the conductive support side and/or a suitable region on the surface side of the photoconductive layer contains at least one selected from carbon, oxygen and nitrogen. A photoconductive member characterized by containing one kind of element. (2) The photoconductive member according to claim 1, wherein the appropriate area is all areas of the barrier layer and the photoconductive layer. (3) The photoconductive member according to claim 1, wherein the photoconductive layer contains hydrogen. (4) A surface layer made of amorphous silicon containing at least one element selected from carbon, oxygen, and nitrogen is formed on the photoconductive layer. The photoconductive member according to any one of items 3 to 3. (5) The photoconductive layer according to any one of claims 1 to 3, wherein the photoconductive layer includes a region of microcrystalline silicon and a region of amorphous silicon. Conductive member. (6) The photoconductive layer according to any one of claims 1 to 3, wherein a layer of microcrystalline silicon and a layer of amorphous silicon are laminated. Conductive member.