JPS61295570A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member having excellent electrostatic chargeableness, 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. The barrier layer 22 is formed of the amorphous silicon contg. hydrogen, the element belonging to the group III or V or periodic table and at least one kind of the element selected from carbon, oxygen and nitrogen. At least part of the photoconductive layer 23 is formed of microcrystalline silicon and the average grain size of the microcrystalline silicon changes in the layer thickness direction. 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,
This invention relates to a photoconductive part with excellent photosensitivity, environmental resistance, etc.

[Technical background of the invention and its problems] Conventionally, as materials for forming the photoconductive layer of an electrophotographic photoreceptor, inorganic materials such as CdS, ZnO, Se, 5e-Te, or amorphous silicon, or poly-N-vinylcarbazole have been used. (PVCz) or trinitrofluorene (T
Organic materials such as NF) are used. however,
These conventional photoconductive materials have various problems in terms of photoconductive properties or manufacturing, and these materials are used depending on the purpose of use, sacrificing the properties of the photoreceptor system to some extent.

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
Because of this, problems with photoconductive properties arise due to residual copies during repeated copying, resulting in a short lifespan and low practicality.

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 materials such as PVCz and TNF are suspected to be carcinogens and present human health concerns, while organic materials have poor thermal stability and wear resistance. The disadvantage is that it is low and has a short lifespan.

On the other hand, amorphous silicon (hereinafter abbreviated as a-Si)
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-3i, attempts have been made to use a-3i as a photoconductive material for electrophotographic photoreceptors, and photoreceptors using a-3i can be collected because 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 abrasion resistance and impact resistance.

This a-3i 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-3t is usually formed by a glow discharge decomposition method using silane gas, but at this time, a-3t is
Hydrogen is incorporated into the 3i 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-5t film increases, the optical bandgap increases and the resistance of a-3i 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. Also, a-Si
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 I 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, reducing the amount of hydrogen penetrating into a-8i reduces the optical band gap and its resistance, but increases photosensitivity to long wavelength light. However, if the amount of hydrogen -1-Tm is small, there will be less hydrogen to combine with silicon dangling bonds and reduce them. 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.

As a technique to increase the sensitivity to long wavelength light, there is a method of mixing silane gas and germane G e H,a and decomposing it by glow discharge to produce a film with a narrow optical bandgap. , eH The silane-based gas and 4 have different optimum substrate temperatures, so the produced film has many structural defects and cannot obtain good optical and conductive 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 not practical.

[LJ Characteristics of the Invention] This 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 the substrate. Our primary objective 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, and a photoconductive layer formed on the second side of the barrier layer. In the photoconductive member, the barrier layer is made of amorphous silicon containing hydrogen, an element belonging to Group I or Group V of the periodic table, and at least one element selected from carbon, oxygen, and nitrogen. The photoconductive layer is characterized in that at least a portion of the photoconductive layer is made of microcrystalline silicon, and that the average grain size of the microcrystalline silicon changes in the layer thickness direction.

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 -5i) 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-5t. That is, whether all or some regions of the photoconductive layer are formed of microcrystalline silicon (μC-5t) or a mixture of microcrystalline silicon and amorphous silicon (a-5i); 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.
-3t is used.

μC-3i has a
-3i and polycrystalline silicon (polycrystalline silicon). That is, in X-ray diffraction Al11 constant, since a-8i is amorphous, only a halo appears and no diffraction pattern can be observed, but μC
-3i indicates a crystal diffraction pattern in which 2θ is around 27 to 28.5°. Further, while polycrystalline silicon has a dark resistance of 10 6 Ω·cm, μC-3i has a dark resistance of 10 11 Ω·cm or more. This μC-3
i 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-Si is a mixture of μC-3i and a-Si, which is mixed in the crystal region of μC-5i or a-5i, and is mixed with μC-3i and a-Si.
-3i exists in a similar volume ratio. Also,
The laminate of μC-3i and a-3i is mostly a-5
a layer consisting of i;

! It refers to a structure in which layers filled with 1C-S i are laminated.

Similar to a-3t, such a photoconductive layer containing μC-3i is produced by depositing μC-5i on a conductive support using silane gas as a raw material using a high-frequency glow discharge decomposition method. I can do it. In this case, the temperature of the support is set higher than when forming a-3i,
If the high frequency power is also set higher than in the case of a-8i, μ
It becomes easier to form C-5i. In addition, by increasing the support temperature and high frequency power, the flow rate of a chemical gas such as silane gas can be increased, and as a result, the film formation rate can be increased. In addition, the raw material gas SiH
By using a gas obtained by diluting a high-order silane gas such as Si2H6 with hydrogen, μC-5i can be formed with even higher efficiency.

FIG. 1 is a diagram showing an apparatus for manufacturing a photoconductive member according to the present invention. Gas cylinder 1.2,3゜SiHB
HH 4 includes, for example, each of 4. Raw material gases such as 2B and 2°CH4 are 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. A pressure gauge 5 is installed in each cylinder, and while monitoring this pressure gauge 5, a valve 6 is activated: AK! By E, the flow rate and mixing ratio of each source gas to be supplied to the mixer Si can be adjusted. The gases mixed in the mixer 8 are supplied to a reaction vessel 9. Bottom 11 of reaction vessel 9
A rotary shaft 10 is attached to the rotary shaft 10 so as to be rotatable around the vertical direction, and a disk-shaped support 12 is fixed to the upper end of the rotary shaft 10 so as to be perpendicular to the rotary 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, 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,
A high frequency current is supplied between the electrode 13 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 vacuum 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 container 9, the gate valve 19 is opened and the inside of the reaction container 9 is heated approximately o, i+-.
Evacuate to a pressure below Torr. Next, the required reaction gases in the cylinders 1, 2, and 3.4 are mixed at a predetermined mixing ratio and introduced into the reaction vessel 9. In this case, the gas flow rate introduced into the reaction vessel 9 is such that the pressure inside the reaction vessel 9 is 0.
Set it so that it is 1 to 1 Torr. Next, motor 1
8 to rotate the drum base 14, and
The drum base 14 is heated to a constant temperature, and a high frequency current is supplied between the electrode 13 and the drum base 14 by the high frequency power source 16 to form a glow discharge between them. As a result, microcrystalline silicon (μC-3t) is deposited on the drum base 14. Note that N O, NH, NH, No , N , CH4 are present in the raw material gas.
By using CH, O gas, etc., these elements can be incorporated into μC-5i.

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-3t contains 0.1 to 30 atom % of hydrogen. As a result, the dark resistance and bright resistance become harmonious, and the photoconductive properties are improved. μC-
For doping of hydrogen into the 5i layer, for example, when using a glow discharge decomposition method, a silane-based raw material gas such as SiH4 and Si2H6 and a carrier gas such as hydrogen are introduced into a reaction vessel and a glow discharge is caused. or SiF4 and 5
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. Historically, the μC-3i 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-5i has photoconductive properties "2.
The film thickness is preferably 1 to 80 μm, and more preferably 5 to 50 μm.

Substantially all regions of the photoconductive layer may be formed of μC-3i, or may be formed of a mixture or a laminate of a-3i 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-3i, 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, and oxygen. Thereby, the dark resistance of μC-3i can be increased and the photoconductive properties can be improved.

These elements precipitate at the grain boundaries of μC-8i 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 p-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-3i, or may be formed using a-Si.

In order to make μC-5i and a-3i p-type, they must be doped with elements belonging to Group Ⅰ of the periodic table, such as boron B1 aluminum AI, gallium Ga-, indium In, and thallium T1. is preferable, μC-
In order to make the 5i layer p-type, it is preferable to dope it with an element belonging to Group V of the periodic table, such as nitride IN, phosphorus P5 arsenic As, antimony Sb, and bismuth Bi.

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-3i 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. Materials for forming the surface layer include St N , SiO, and SiC.

AI O, a-3iN; H, a-5iO; H.

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

Photoconductive members applied to electrophotographic photoreceptors include 1.
As mentioned above, the support is not limited to one in which a barrier layer is formed on the support, a photoconductive layer is formed on the barrier layer, and a surface layer is formed on the photoconductive layer. A charge transport layer (CTL) is formed on one layer of the charge transport layer, and a charge generation layer (CTL) is formed on the charge transport layer.
It can also be constructed in a functionally separated form in which a CG L) is formed. 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,
It is necessary for the carrier to have a long life, high mobility, and high transportability. The charge transport layer may be formed of a-8i or μC-3i. In order to increase the dark resistance and improve the charging ability, it is preferable to perform light doping with an element belonging to either Group Ⅰ or Group V of the periodic table. In addition, in order to further improve the charging ability and have the functions of both a charge transport layer and a charge generation layer, C,
It may contain one or more of the elements N and O. 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 that functions as a charge transport layer and an electric charge generation layer, it is possible to enhance the electric charge retention function and improve the charging ability. . 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 uC-3i.

A feature of the invention according to this application is that at least a portion of the photoconductive layer is formed of μC-3t, and the average grain size thereof varies in the layer thickness direction. Figures 2 and 3
FIG. 2 is a cross-sectional view of a photoconductive portion embodying the present invention. In FIG. A layer 23 is formed.

-h1 In FIG. 3, a barrier layer 22 is formed on a conductive support 21, and a photoconductive layer 23 and a surface layer 24 are laminated in this order on the barrier layer 22. Photoconductive layer 23
consists at least in part of μC-8i.

The barrier layer can be formed of μC-3i or a-3i. This barrier layer 22 is doped with an element belonging to Group Ⅰ or Group V of the periodic table, thereby making the barrier layer 22 a p-type or n-type semiconductor. The content m is preferably 10= to 10 atomic %. Further, when the barrier layer 22 contains at least one or more elements among C, O, and N in the range of 0.1 to 20 atoms, the charge blocking ability is further improved, so that the electrophotographic properties are improved. Above, preferred.

The photoconductive layer is mainly made of μC-5i, but μ
C-5i itself is somewhat n'Jl. For this reason, it is preferable to lightly dope (10-7 to 10-3 atomic %) the μC-3i layer with an element belonging to Group 1 of the periodic table. As a result, the photoconductive layer 23 becomes a type 1 (intrinsic) semiconductor, has a high dark resistance, and improves the S/N ratio and charging ability. Further, it is preferable that the photoconductive layer 23 contains at least one element selected from C, 0, and N in a range of 0.1 to 10 atomic %. This makes it possible to improve the charging ability. Further, the photoconductive layer preferably has a thickness of 3 to 80 μm, more preferably 10 to 40 μm.

It is preferable to include hydrogen in μC-5i in order to improve photoconductive properties. In this case, hydrogen is present in the amorphous silicon existing at the boundaries between microcrystalline silicon particles or surrounding the μC-3i particles, and is considered to be bonded to the S1 atom. This amount of hydrogen is usually 0.1 to 30 at%,
Preferably, it is 1 to 10 atomic %.

Further, the surface layer 24 formed on the photoconductive layer 23 is made of C
, O, and N, containing at least one element of a-3i. This protects the surface of the photoconductive layer, improves environmental resistance, and improves charging ability. This C,O.

The content of N is preferably 10 to 50 atomic %. Historically, the thickness of the surface layer 24 and the barrier layer 22 is 0.0.
The thickness is preferably 1 to 10 μm, more preferably 0.1 to 2 μm.

In this invention, μC forming the photoconductive layer 23 is
-3i is characterized in that the average grain size changes in the layer thickness direction. μC-5i has a slightly lower dark resistance than a-3t, and a light absorption coefficient that is small for visible light and large for infrared light. On the other hand, the larger the crystal grain size of μC-3i, the stronger the crystalline properties, that is, the properties specific to μCSi, and the smaller the crystal grain size, the stronger the amorphous properties, that is, the properties specific to a-3i. Become. For this reason, μ
By changing the crystallinity of C-5i in the layer thickness direction, the resistance of the photoconductive layer 23 is increased and the charging ability is increased to -1. High sensitivity can be achieved over a wide range up to the oscillation wavelength (around 7900 m). This results in
It becomes possible to use this photoconductive member in both PPC (plain paper copiers) and laser printers.

The average particle size of μC-5i is preferably varied within the range of 10 to 400 angstroms, and in order to further increase the dark resistance and enhance the photosensitivity, the average particle size is varied within the range of 20 to 100 angstroms. It is preferable to let The average particle size may be decreased in the layer thickness direction from the support 21 side toward the surface layer 24, or conversely may be increased. However, in the case of a pattern in which the average particle size is large on the support body 21 side and becomes smaller toward the surface, the long wavelength sensitivity becomes high, so it is particularly effective when used in a semiconductor laser printer. .

In order to form a film with the average particle size changed in this way, high-frequency glow discharge decomposition is performed using a mixed gas of silane gas such as S I H4 and hydrogen gas, and the flow rate of hydrogen gas is gradually increased. or the high frequency power.

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 x 10-
5 torr and the drum temperature stabilized. Next, 300
SCCM flow rate of SiH gas, the flow rate ratio to this SIH,4 gas flow rate is 5 × 10 B2H6 gas, 60S
CCM of CH4 gas and 2003 CCM of argon gas were mixed and supplied to the reaction vessel. Applying high frequency power of 200 watts at 13.56 MHz to generate a glow discharge,
A barrier layer 21 was formed. The pressure inside the reaction vessel at this time was approximately 0.8 torr, and the resulting layer thickness was 1.5 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 increased to 6003C.
CM, hydrogen gas flow rate 500SCCMSB2H6 S
The flow rate ratio to tH,i was set to 8X10-8, the reaction pressure was 1.5 Torr, and the high frequency power was 450
A film was formed for 15 minutes using a wattmeter. Next, the high frequency power was reduced to 0, the flow rate of hydrogen gas was lowered to 4008 CCM, and the hydrogen gas was allowed to flow together with other gases for 5 minutes. After the gas flow rate became stable, the high frequency power was set to 450 watts, and the film was formed for 15 minutes at a reaction pressure of 1.4 torr.

After that, the high frequency power was set to 0, and the flow rate of hydrogen gas was set to 400.
The temperature was lowered to 5 CCM and held for 5 minutes. When the flow rate became stable and the reaction pressure reached 1.4 torr, high frequency power of 450 watts was applied to form a film for 15 minutes. Next, the high frequency power was reduced to 0, the hydrogen gas was reduced to 30'OSCCM, and held for 5 minutes. After the flow rate became stable, a high frequency power of 450 watts was applied to form a film for 15 minutes. The reaction pressure at this time was 1.35 torr. After that, the high frequency power was set to 0, the hydrogen gas flow rate was lowered to 2003CCM, and the
Hold for minutes. Next, high frequency power was applied to form a film at a reaction pressure of 1.2 Torr for 30 minutes.

In the photoconductive layer thus obtained, the average grain size is calculated from the half-width of the peak of the (111) plane that appears at a diffraction angle of 28°3° by X-ray diffraction.
The layer thickness of one photoconductive layer, which was found to vary from the support side to the surface by 75.60 and 35.28 angstroms, was 25 μm. Then, after turning off all gases and purging for 15 minutes, the 11005CC S I
A surface layer was formed by flowing H4 gas and 400 SCCM of N2 gas under the conditions of a reaction pressure of 0.7 Torr and high frequency power of 200 Watts. When an image was formed on the photoreceptor with a film formed in this way using a laser printer equipped with a semiconductor laser with an emission wavelength of 790 nm, the resolution was high.
It was possible to form a clear image with no defects in density or fog.

Also, the electrophotographic characteristics have a half-reduction exposure of 8erg/ca? It was extremely good.

Example 2 After cleaning and drying an Al drum serving as a conductive substrate, the inside of the reaction vessel was heated to 300°C while being evacuated with a diffusion pump. After about 1 hour, the degree of vacuum inside the reaction vessel is 3X10
The temperature of the drum reached -51-degrees and stabilized. Then 3
SiH gas with a flow rate of 003 CCM, this S t Ht,
B2H6 gas with a flow rate ratio of 5 x 10 to the gas flow rate,
A mixture of 60 SCCM of N2 gas and 2003 CCM of argon gas was supplied to the reaction vessel. 13.56M
Glow emission by applying high frequency power of 200 watts at Hz7
The barrier layer 21 was formed by heating. The pressure inside the reaction vessel at this time was approximately 0.8 Torr, and the obtained layer thickness was 1.2 μm.
Met. Next, all gases were stopped and a gas purge was performed for 15 minutes. After that, increase the flow rate of S L H4 to 6
00SCCM, hydrogen gas flow rate 500SCCM, B2
The flow rate ratio of H, to S t H4 was set to 8×10 −8 , and the film was formed for 50 minutes at a reaction pressure of 1.5 torr and a high frequency power of 400 watts. Next, the high frequency power was set to O, the flow rate of hydrogen gas was lowered to 3003 CCM, and the hydrogen gas was allowed to flow together with other gases for 5 minutes. After the gas flow rate stabilized, the high frequency power was increased to 400 watts, and the reaction pressure was increased to 1.3 watts.
5) A film was formed for 30 minutes in a closed state.

After that, the high frequency power was set to 0, hydrogen gas was stopped, and argon gas was flowed at 500 SCCM instead. After the flow rate stabilized and the reaction pressure reached 1.5 Torr, high frequency power was applied at 400 W. A film was formed for 20 minutes. When the photoconductive layer thus obtained was subjected to X-ray diffraction, the average particle diameter was 60.32 angstroms starting from the support 21 side, and /1l11 could not be determined on the surface side.

The layer thickness of the photoconductive layer was 32 μm. When an image was formed on the photoreceptor with a film formed in this way using a laser printer equipped with a semiconductor laser with an emission wavelength of 790 nm, a clear image with high resolution and no defects in density or fog was formed. I was able to do that. The electrophotographic properties were also very good, with a half-decreased exposure at 790 nm of 9°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 drawings]

FIG. 1 is a diagram showing an apparatus for manufacturing a photoconductive member according to the present invention, and FIGS. 2 and 3 are sectional views showing a photoconductive member according to an embodiment of the present invention. 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 body, 22
; Barrier layer, 23: Photoconductive layer, 24; Surface layer. Applicant's agent Patent attorney Takehiko Suzue d Figure 1 Figure 2 Figure 3

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 , hydrogen, an element belonging to Group III or V of the periodic table, and at least one element selected from carbon, oxygen, and nitrogen;
A photoconductive member, wherein at least a portion of the photoconductive layer is formed of microcrystalline silicon, and the average grain size of the microcrystalline silicon changes in the layer thickness direction. (2) The photoconductive member according to claim 1, wherein the photoconductive layer contains hydrogen. (3) The photoconductive member according to claim 1 or 2, wherein the photoconductive layer contains an element belonging to Group III or Group V of the periodic table. (4) The photoconductive layer according to any one of claims 1 to 3, wherein the photoconductive layer contains at least one element selected from carbon, oxygen, and nitrogen. Conductive member. (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 a layer of microcrystalline silicon and a layer of amorphous silicon are laminated. Conductive member.