JPS61295564A - 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 2 and a photoconductive layer 23. 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 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 of the barrier layer 22 and/or the proper region on the surface side of the photoconductive layer contains at least one kind of the element selected from carbon, oxygen and nitrogen. The element concn. changes from the boundary between the barrier layer and the conductive base and/or the surface of the photoconductive layer toward the inside. 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, Cd S s Z n Os S e , S e-
Inorganic materials such as T e or amorphous silicon or poly-N-vinylcarbazole (PVCz) or trinitrofluorene (TNF)
Organic materials such as 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-St)
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 this application of a-3t, attempts have been made to use a-St as a photoconductive material for electrophotographic photoreceptors, and photoreceptors using a-3t can be recycled as they are non-polluting materials. No processing required;
Compared to other materials, it has advantages such as high spectral sensitivity in the visible light region, high surface hardness, and excellent wear resistance and impact resistance.

This a-SL 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, a layered structure is created 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. It satisfies these demands.

By the way, a-3L is usually formed by a glow discharge decomposition method using silane gas, but at this time, a-3L 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-Si increases, but along with this, the photosensitivity to long wavelength light decreases. Therefore, it is difficult to use it in a laser beam printer equipped with a semiconductor laser, for example. Also, a-8i
If the hydrogen content in the film is high, depending on the film forming conditions,
(SiH) and those having a bonded n structure such as S t H2 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 the a-SL decreases, the optical bandgap decreases and its resistance decreases, but the photosensitivity to long 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.

Note that as a technique to increase sensitivity to long wavelength light, silane gas and germane G e H4 are mixed.

Glow discharge decomposition produces some films with a narrow optical bandgap, but in general, silane-based gases and G e H4 have different optimal substrate temperatures;
The produced film has many structural defects and cannot obtain good photoconductive properties. Furthermore, waste gas from G e Hi becomes toxic gas when oxidized, so waste gas treatment is also complicated. Therefore, such technology is not practical.

[Object of the Invention] The present invention has been 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 a 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. , an appropriate region of the barrier layer on the conductive support side and/or an appropriate region on the surface side of the photoconductive layer contains at least one element selected from carbon, oxygen, and nitrogen, and the concentration of this element is such that the barrier layer and the conductive layer have the same concentration. It is characterized by changing inward from the boundary with the photoconductive support and/or the surface of the photoconductive layer.

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 -3i) 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-St. In other words, all or some regions of the photoconductive layer are formed of microcrystalline silicon (μC-3T), but are they formed of a mixture of microcrystalline silicon and amorphous silicon (a-Si)? , or a laminate of microcrystalline silicon and amorphous silicon. In addition, in a functionally separated photoconductive member, μC is added to the charge generation layer.
-3i is used.

μC-5i is a-
Si and polycrystalline silicon (polycrystalline silicon)
clearly distinguished from That is, in X-ray diffraction Δl determination, since a-3i is amorphous, only a halo appears and no diffraction pattern can be observed, but μC-5t
shows a crystal diffraction pattern in which 2θ is around 27 to 28.5°. Furthermore, while polycrystalline silicon has a dark resistance of 10<6 >[Omega]., the St of .mu.C-5i is formed by an aggregation of microcrystals having a grain size of approximately several tens of angstroms or more.

A mixture of pc-3t and a-3t is a mixture of μC-6i crystal regions mixed in a-Si, and μC-5i and a
-Si exists in a similar volume ratio. Also,
The laminate of μC-3i and a-3i is mostly a-3
A layer consisting of i and a layer filled with μC-5i are laminated.

Similar to a-5i, a photoconductive layer containing μC-3i can be produced by depositing μC-3t on a conductive support using silane gas as a raw material using a high-frequency glow discharge decomposition method. can. In this case, if the temperature of the support is set higher than when forming a-5i and the high frequency power is also set higher than when forming a-Si, 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 Si 2 He as a raw material gas with hydrogen, μC-3i can be formed with higher efficiency.

FIG. 1 is a diagram showing an apparatus for manufacturing a photoconductive member according to the present invention. For example, the gas cylinders 1.2 and 3°4 contain SiH, BH, and H, 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. A rotating shaft 10 is attached to the bottom 11 of the reaction vessel 9 so as to be rotatable around the vertical direction, and a disk-shaped support 12 is attached to the upper end of the rotating shaft 10 with its surface perpendicular to the rotating shaft 10. It has been fixed. 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, and a heater 15 for heating the drum base is arranged inside the drum base 14. It is set up. A high frequency power source 16 is connected between the electrode 13 and the drum base 14, and the electrode 13
A high frequency current is supplied between the drum base 14 and the drum base 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 a suitable evacuation means such as a vacuum pump.

When manufacturing a photoreceptor using an 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 placed in 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-3i) is deposited on the drum base 14. Note that N2O, NH, NH, No, N2. C) (4° By using CH, O gas, etc., these elements can be tripled in μC-8i.

In this way, the photoconductive member according to the present invention is similar to the conventional a-
Similar to those using 3i, 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-3i contains 0.1 to 30 atomic percent 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 5i layer by a glow discharge decomposition method, a silane-based raw material gas such as SiH and 5i2He, and a carrier gas such as hydrogen are introduced into a reaction vessel and a glow discharge is performed. , S iF 4 and S
A mixed gas of silicon halide such as iC14 and hydrogen gas may be used, or a mixed gas of silane-based gas and silicon halide may be used. Furthermore,
The μC-8i layer can be formed not only by the glow discharge decomposition method but also by a physical method such as sputtering. Note that the photoconductive layer containing μC-3i has photoconductive properties,
It is preferable to have a film thickness of 1 to 8θ μm, and more preferably a film thickness of 5 to 50 μm.

Substantially the entire region of the photoconductive layer may be formed of μC-3t, or may be formed of a mixture or a laminate of a-8t and μC-3i. The charging ability is higher in the laminate, and the photosensitivity is higher in the long wavelength region of the infrared region, although it depends on the volume ratio, in the mixture, and in the visible light region, the two are almost the same.

Therefore, depending on the use of the photoreceptor, substantially all the regions may be made of μC-3i, or may be made of a mixture or a laminate.

It is preferable to dope μC-5t with at least one element selected from nitrogen, nitrogen, carbon, and oxygen. Thereby, the dark resistance of μC-5t can be increased and the photoconductive properties can be improved.

These elements precipitate at the grain boundaries of μC-3i 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 of nQ 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-5i.

In order to make μC-3i and a-3i p-type, it is necessary to dope them with elements belonging to Group Ⅰ of the periodic table, such as boron B, aluminum AI, gallium Ga, indium In, and thallium T1. Preferably μC-3i
In order to make the layer n-type, an element belonging to Group V of the periodic table, such as nitrogen N1 phosphorus P1 arsenic As, antimony S
It is preferable to dope with B, bismuth Bi, or the like.

This doping with p-type impurities or n-type 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 leading conductive 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. Examples of materials forming the surface layer include SiN, SiO, and SiC.

There are inorganic compounds such as AIO, a-3iN;H, a-SiO;Hs 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 L of 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. The charge generation layer is preferably made of microcrystalline silicon μC-3T 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-3t or μC-
3i may be formed. 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 O 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-3t or μC-3i.

The invention according to this application is characterized in that at least a part of the photoconductive layer is formed of μC-3t, and the barrier layer is formed of 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;
A photoconductive layer 23 is formed thereon. 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 is μC
-5i, and the barrier layer 22 is a-S containing hydrogen.
Consists of i. 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-3i is lightly doped with an element belonging to Group 3 or Group 5 of the periodic table (10 to 10-3 atomic percent). , the photoconductive layer 23 becomes an i-type (intrinsic) semiconductor, has a high dark resistance, and improves the S/N ratio and charging ability. Further, the photoconductive layer preferably has a thickness of 3 to 80 μm, more preferably 10 to 40 μm.

Further, a-8t constituting the barrier layer 22 is also doped with an element belonging to Group 3 or Group 5 of the periodic table, so that the barrier layer 22 is a p-type semiconductor or an n-type semiconductor. The content thereof is preferably 10 to 2 at%.

As a result, the resistance of the barrier layer 22 becomes low, and the 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.

a-3iN; H, a-5iCN; H, etc., c, o.

a-3 containing at least one element among N
It is formed by t. This protects the surface of the photoconductive layer and improves its environmental resistance, and also improves its charging ability due to its charge retention function. The gold content of C, O, and N is preferably 10 to 5 atomic percent. Furthermore, the film thickness of the surface layer 24 and the barrier layer 22 is 0.01 to 10μ.
It is preferably 0.1 to 2 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
Contains at least one element selected from C, 0, and N, and the concentration of the element decreases inward from the boundary between the barrier layer 22 and the support 21 and/or the surface of the photoconductive layer 23. It is characterized by the presence of C and O contained in the barrier layer 22.

The total amount of N is preferably 20 atomic % or less.

Further, in the photoconductive layer 23, it is preferable to perform light doping so that the photoconductivity does not decrease.

4(a) to (h) show the photoconductive layer 23 and the barrier layer 2.
C in 2, 0. The concentration distribution of the total amount of N is shown. In the pattern shown in Figure 4(a), the C, O, and N elements are
The barrier layer 22 decreases linearly inward from the boundary with the support, and in the pattern shown in FIG. 4(b), it decreases inward from the surface side of the photoconductive layer 23. . In addition, in FIGS. 4(c) and 4(d), the barrier layer 22
C, O, and N decrease toward the inner side from the boundary with the support 21 and the surface of the photoconductive layer 23. Other patterns are changing as well.

When the surface layer 24 is doped with C, O, and N, there is a concentration difference of C20°N between the photoconductive layer 23 and the surface layer 24, but the boundary between the photoconductive layer 23 and the surface layer 24 C toward the support 21 in a pattern as shown in FIG.
By gradually decreasing the concentration of 10 or N, rapid changes in the concentration of these elements are prevented and the concentration changes gently, so that the flow of carriers 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 density between 23 and 23 is reduced. Also at the boundary between the photoconductive layer 23 and the barrier layer 22, the concentration changes of these elements become gentle, and charges move smoothly.

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. Furthermore, by containing C, O, 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, and the flow of carriers is improved. moves with high efficiency. Moreover, when the barrier layer 22 and the surface layer 24 are doped with C, O, and N, the photoconductive layer 2
3, and these barrier layer 22 and surface layer 24, C40
Or the nitrogen rate changes rapidly.

However, by including C10 or N in these boundary regions as in the present invention, rapid changes in the 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.

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 was reduced to 3×10
-5 torr was reached and the drum temperature stabilized. Then 30
SiH gas with a flow rate of 03CCM, BH gas with a flow rate ratio of 5X10-4 to this S z H4 gas flow rate, 60S
CH4 gas of CCMB and argon gas of 200 SCCM 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. The pressure inside the reaction vessel at this time is 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. Thereafter, film formation was performed by setting the flow rate of S i H4 to 600 SCCM, the flow rate of hydrogen gas B HSiH to 2003 CCM, and the flow rate ratio of 2 B to 4 to 1X10. The reaction pressure was 1.5 torr and the high frequency power was 350 watts, making it possible to obtain a photoconductive layer of 30 μm. Then, after stopping all gases and purging for 15 minutes, the ioscCM SIHt, gas, and 400
A film was formed by flowing SCCM CH4 gas under the conditions of a reaction pressure of 0.7 torr and a 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 10 V for an exposure dose of 50 erg/cd, and a half-reduction 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 vacuum in the reaction vessel reached 5×10 torr and the drum temperature stabilized. Then 400S
CCM flow rate of SiH4 gas, flow rate specific force for this S t H4 gas flow rate 5 x 10-4 (7) B H
dregs, 1oosccM CH4 gas, and 200SCC
M of helium gas was mixed and supplied to the reaction vessel. 13
．． High frequency power of 200 Watts at 56 MHz was applied 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 O and 50 SCCM of CH4 gas was flowed for 5 minutes. Thereafter, the high frequency power was set to 200 W, and glow discharge was performed for 30 seconds. The reaction pressure was 0.85 Torr. Then, the high frequency power is set to 0, and the 5SCCM
of CH4 gas was flowed for 5 minutes. After that, the high frequency power is
00' watts and glow discharged for 20 seconds. The reaction pressure was 0.83 Torr. The thickness of the barrier layer 21 thus formed was 1.8 μm. Next, all gases were stopped and gas purging was performed for 15 minutes. Then, the flow rate of SiH4 was set to 650SCCH, the flow rate of M1 hydrogen gas was set to 3003CCM, and the flow rate of S iH4 was set to 3003CCM.
The film was formed by setting the flow rate ratio to iH4 to be 8X10-8. The reaction pressure was 1.7 torr and the radio frequency power was 400 watts, making it possible to obtain a photoconductive layer of 42 μm. Then turn off all gas and
After purging for 15 minutes, 11005CC of S i H4
Gas and 400 SCCM of N2 gas were flowed, and the reaction pressure was 0.
．． The film was formed under conditions of 7 torr and high frequency power of 200 watts. The thickness of the obtained surface layer was 1.8 μm. What about the photoreceptor film formed in this way? When an image was formed using a laser printer equipped with a semiconductor laser with an oscillation wavelength of 90 nm, it was possible to form a clear image with high resolution. In addition, the electrophotographic characteristics have a half-reduction exposure of 8.5
The erg/d was extremely good.

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

[Brief explanation of drawings]

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. (h) is C,0
, 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 representative Patent attorney Takehiko Suzue Figure 1 Figure 2 Figure 3 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. 1. A photoconductive member containing one type of element, the element concentration changing inward from the boundary between the barrier layer and the conductive support and/or the surface of the photoconductive layer. (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 4, 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 4, wherein the photoconductive layer is a laminated layer of a microcrystalline silicon layer and an amorphous silicon layer. Element.