JPS62115461A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve the photoconductive characteristics (electrophotographic characteristics) and environmental resistance of an electrophotographic sensitive body by forming a laminate consisting of amorphous silicon and microcrystalline silicon as the photoconductive layer. CONSTITUTION:A blocking layer 102 of muC-Si and a photoconductive layer 103 are laminated on an electrically conductive support 101. The blocking layer 102 contains at least one among C, N and O and at least one kind of atom selected among the group III and V atoms in the periodic table and at least one kind of atom in the layer 102 forms an ununiform concn. distribution in the thickness direction. The photoconductive layer 103 is formed by laminating a muC-Si layer 104, th3 1st a-Si layer 105 and the 2nd a-Si layer 106. The layer 106 contains at least one among C, O and N and at least one among C, O and N in the layer 106 forms an ununiform concn. distribution in the thickness direction so that the concn. is made higher on the surface side.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an electrophotographic photoreceptor having excellent charging characteristics, photosensitivity characteristics, environmental resistance, and the like.

[Prior art and its problems] Conventionally, inorganic materials such as CdS, Zn○, Se, 5e-Te, or amorphous silicon, or poly-N-vinylcarbazole (PVCz) have been used as materials for forming the photoconductive layer of electrophotographic photoreceptors. ) 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 process is 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 the photoconductive properties arise due to residual snow, etc., and therefore, the service life is short and practicality is low.

Furthermore, ZnO is susceptible to oxidation and reduction and is significantly affected by the environmental atmosphere, so there is a problem in that it has low reliability in use.

Furthermore, organic photoconductive materials such as PVCz and TNF are suspected of being carcinogenic, and in addition to posing health problems for the human body, organic materials have poor 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
It is actively being applied to IT batteries, film transistors, and image sensors. As part of this application of a-8i, attempts have been made to use a-8i as a photoconductive material for electrophotographic photoreceptors, and photoreceptors using a-8i are collected because they are non-polluting materials. It has the advantages of not requiring any treatment, having higher spectral sensitivity in the visible light region than other materials, and having high surface hardness and low 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, a layered structure is created in which a blocking 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-3i is usually formed by a glow discharge decomposition method using silane gas, but at this time, a-3i is
Hydrogen is incorporated into 3i11, 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-8i 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. In addition, if the hydrogen content in the a-3i anisotropy is large, depending on the film formation conditions, (S
Those having bonding structures such as iH2)n and s r 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-3i reduces the optical bandgap and its resistance, but increases photosensitivity to long wavelength light. 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 Get-14 and decomposing it by glow discharge to generate pus with a narrow optical band gap. System gas and GeH
Since the optimum substrate temperature differs between + and +, the produced film has many structural defects and cannot obtain good photoconductive properties. Further, waste gas treatment is complicated because GeH+ waste gas becomes a toxic gas when oxidized. Therefore, such technology is not practical.

The present invention has been made in view of the above circumstances, and provides an electrophotographic photoreceptor that has excellent charging ability, low residual potential, high sensitivity over a wide wavelength range, and excellent environmental resistance. The purpose is to

[Means for Solving the Problems] The electrophotographic photoreceptor according to the present invention includes a conductive support, a blocking layer formed on the conductive support, and a photoreceptor formed on the blocking layer. In the electrophotographic photoreceptor having a conductive layer, the blocking layer contains at least one kind of atom selected from carbon, nitrogen, and oxygen, and at least one kind of atom selected from Groups 1 and 2 of the periodic table. The photoconductive layer is formed of microcrystalline silicon containing at least one kind of atoms forming a non-uniform concentration distribution in the layer thickness direction, even if the selected atoms are not included, and the photoconductive layer is a microcrystalline silicon layer; 1st
an amorphous silicon layer containing at least one kind of atom selected from carbon, nitrogen, and oxygen;
It is characterized by being composed of a laminate including a second amorphous silicon layer in which at least one kind of atoms selected from nitrogen and oxygen forms a concentration distribution in the layer thickness direction.

The present inventor has developed an electrophotographic photoreceptor according to the present invention in order to overcome the drawbacks of the prior art described above and to develop an electrophotographic photoreceptor that has both excellent photoconductive properties (N-photographic properties) and environmental resistance. As a result of various experimental studies, they found that this objective could be achieved by making part or all of the photoconductive layer consist of microcrystalline as a seed, or by making it a laminate of amorphous silicon and microcrystalline silicon. This invention was completed after coming up with the idea that this could be done.

This invention will be specifically explained below.

The blocking layer of the electrophotographic photoreceptor of the present invention may be made of amorphous silicon (hereinafter referred to as a-3i) or microcrystalline silicon (hereinafter referred to as μC-8i) as a semiconductor.
) is used.

μC-8i 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-8i shows a crystal diffraction pattern with a 2θ of around 27 to 28.5°.

In addition, polycrystalline silicon has a dark resistance of 10BΩ.
α, whereas μC-8i has a dark resistance of 10Ω·α or more. This μC-8i is formed by agglomeration of microcrystals having a grain size of approximately several tens of angstroms or more.

A blocking layer with such μC-S+ is a
Similarly to -3i, it can be produced by depositing μC-8i on a conductive support using silane gas as a raw material using a high frequency glow discharge decomposition method. In this case, if the temperature of the support is set higher than in the case of forming a-3i, and the high frequency power is also set higher than in the case of forming a-3i, it becomes easier to form μC-8i. In addition, by increasing the support temperature and high frequency power, the flow rate of raw material gas such as silane gas can be increased, and as a result,
The film formation speed can be increased.

In addition, by using gas obtained by diluting the raw material gas SiH+ and high-order silane gas such as 5i2Hs with hydrogen,
μC-8i can be formed with higher efficiency.

FIG. 1 is a diagram showing an apparatus for manufacturing an electrophotographic photoreceptor according to the present invention. For example, the gas cylinders 1 and 2°3.4 contain SiH+ and B2 H6, respectively.

Source gases such as H2 and CH4 are contained. The gas in these gas cylinders 1, 2, 3, 4 is supplied to a mixer 8 via a valve 6 and piping 7 for flow rate adjustment. 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, so that 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 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
．． From 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, and the heater 15 heats the drum base 14 to a constant temperature, and at the same time, a high frequency current is supplied between the electrode 13 and the drum base 14 by the high frequency 'R'rA16, and the temperature is increased between the two. to form a glow discharge. As a result, μC-8i is deposited on the drum base 14. In addition, N20. NH3, NO
2, N2.

By using CH4, C2H4,02 gas, etc.
These atoms can be included in μC-8i.

In this way, the electrophotographic photoreceptor according to the present invention has a conventional a
Similar to those using -3i, it can be manufactured using closed system manufacturing equipment, so it is safe for the human body. Furthermore, this electrophotographic photoreceptor has excellent heat resistance, moisture resistance, and abrasion resistance, so it has the advantage of having a long lifespan with little deterioration even after repeated use over a long period of time. Furthermore, since a long wavelength sensitizing gas such as GeH4 is not required, there is no need to provide waste gas treatment equipment, and industrial productivity is extremely high.

It is preferable that μC-S + 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
-8i optical energy gap Ea is a-3i optical energy gap Ea (1,65 to 1.70e
V) is small compared to V). In other words, the optical energy gear □ of μC-8i changes depending on the crystal grain size and crystallinity of μC-8i microcrystals, and as the crystal grain size and crystallinity increase, the optical energy gap decreases. , approaches the optical energy gap of crystalline silicon, 1.1 eV. By the way, the μC-8i layer and the a-8i layer absorb light with a larger energy than this optical energy gap, and transmit light with a smaller energy. For this reason, a-8i
absorbs only visible light energy, but μC-8i, which has a smaller optical energy gap than a-3i, can even absorb near-infrared light, which has a longer wavelength and lower energy than visible light. Therefore, μC-8i has high photosensitivity over a wide wavelength range.

μC-8i having such characteristics is suitable as a photoreceptor material for a laser printer using a semiconductor laser as a light source. When a-8i is used as a photoreceptor for a laser printer, the light wavelength of the semiconductor laser is 790 nm.
Since the wavelength range is longer than the wavelength region in which the wavelength is highly sensitive, the sensitivity of the photoreceptor becomes insufficient. Therefore, it is necessary to apply a laser intensity to the photoreceptor that exceeds the capability of the semiconductor laser, which poses a practical problem. On the other hand, when the photoreceptor is formed with μC-8i,
Since the high-sensitivity region extends to the near-infrared region, it is possible to obtain a photoreceptor for semiconductor laser printers with extremely excellent photosensitivity characteristics.

In order to further improve the photoconductive properties of μC-8i, which has excellent photosensitivity characteristics like a mouth, μC
-8i preferably contains hydrogen.

For example, when hydrogen is doped into μC-8il by a glow discharge decomposition method, a silane-based raw material gas such as SiH4 and 5t2Hs and a carrier gas such as hydrogen are introduced into a reaction vessel and a glow discharge is performed. Or, S i F4
A mixed gas of silicon halide such as and 3iCI4 and hydrogen gas may be used, or a silane-based gas and
The reaction may be performed using a mixed gas with silicon halide. Furthermore, the μC-5i 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-8i preferably has a thickness of 1 to 80 μm, and more preferably 5 to 50 μm.

Substantially the entire region 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-8i. The chargeability is higher in the laminate, and the photosensitivity is higher in the long wavelength region of the infrared region, although it depends on their volume ratio (but 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-8i, or may be made of a mixture or a laminate.

Preferably, μC-8i is doped with at least one type of atom selected from nitrogen N, carbon C, and oxygen O. Thereby, the dark resistance of μC-5i can be increased and the photoconductive properties can be improved.

These atoms precipitate at the grain boundaries of μC-8i and act as terminators for silicon dangling bonds,
It is believed that the density of states existing in the forbidden cloth between the bands is reduced, thereby increasing the dark resistance.

Preferably, a blocking layer is provided between the conductive support and the photoconductive layer. This blocking layer suppresses the flow of charge between the conductive support and the photoconductive layer, thereby increasing the charge retention function on the surface of the photoconductive member and increasing the charging ability of the photoconductive member. . In the Carlson method, when the surface of the photoreceptor is positively charged, the blocking 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 blocking 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 blocking layer. The blocking layer may be formed using μC-8i or a-3
It is also possible to use i to construct a blocking layer.

In order to make μC-8i and a-3i p-type, it is necessary to dope them with atoms belonging to Group Ⅰ of the periodic table, such as boron B1 aluminum AI, gallium Ga, indium In, and thallium T1. Preferably μC-3i
In order to make the layer n-type, atoms belonging to group V of the periodic table, such as nitrogen N, phosphorus P, arsenic As1 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 light guide layer 1i.

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

Since μC-8i 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 forming the surface layer include Si3N4, SiO2, 5iC1AFO
3, a-8'N:Ella-3iO:Hs and a-8i
There are inorganic compounds such as C:H and organic materials such as polyvinyl chloride and polyamide.

As described above, a photoconductive member applied to an electrophotographic photoreceptor includes a blocking layer formed on a support, a photoconductive layer formed on this blocking layer, and a surface layer formed on this photoconductive layer. The structure is not limited to one in which a charge transfer layer (CTL) is formed on a support, and a functionally separated structure in which a charge transfer layer (CTL) is formed on the charge transfer layer and a charge generation layer (CGL) is formed on the charge transfer layer is also possible. In this case, a blocking layer may be provided between the charge transfer layer and the support. The charge generation layer generates carriers upon irradiation with light. This charge generation layer is
Part or all of the layer is made of .mu.C-8i or a-8i, preferably with a thickness of 0.1 to 10 .mu.m. The charge transfer 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 need to have a long life, high mobility, and high transportability. The charge transport layer can be formed of μC-8i. In order to increase the dark resistance and improve the charging ability, it is preferable to light-dope atoms 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 transfer layer and a charge generation layer, one or more of C, N, and O atoms may be contained. If the charge transport layer is too thin or too thick, it will not function satisfactorily. Therefore, the thickness of the charge transport layer is preferably 3 to 80 μm.

By providing a blocking layer, even in a functionally separated photoreceptor having a charge transfer layer and a charge generation layer, its charge retention function and charging ability can be improved. Note that whether the blocking layer is p-type or n-type is determined depending on its charging characteristics. This blocking layer is made of μC-3i.

The feature of the invention according to this application is that the blocking layer contains at least one kind of atom selected from carbon, nitrogen, and oxygen, and at least one kind of atom selected from Groups Ⅰ and Ⅲ of the periodic table; The photoconductive layer is formed of microcrystalline silicon in which at least one of the selected atoms forms a non-uniform concentration distribution in the layer thickness direction, and the photoconductive layer includes the microcrystalline silicon layer and the first amorphous silicon layer. , a second layer containing at least one kind of atom selected from carbon, nitrogen, and oxygen, in which the at least one kind of atom selected from carbon, nitrogen, and oxygen forms a nonuniform concentration distribution in the layer thickness direction. It consists of a laminate with an amorphous silicon layer.

[Example 2] Next, the structure of the layers of an electrophotographic photoreceptor embodying the present invention will be described with reference to FIGS. 2 and 3.

In the electrophotographic photoreceptor shown in FIG. 2, a blocking 1102 made of μC-8i and a photoconductive layer 103 are laminated on a conductive support 101 made of aluminum. Blocking 11102 includes at least one type of atom selected from carbon, nitrogen, and oxygen, and m-th atom of the periodic table.
The layer contains at least one type of atom selected from Group 1 and Group 1V, and at least one of the selected atoms forms a non-uniform concentration distribution in the layer thickness direction.

The photoconductive layer 103 includes a μC-8i layer 104 and a first 8-
The 3i layer 105 and the second a-3i layer 106 are stacked, and the second a-8i layer 106 contains at least one or more atoms of C, O, and N atoms. Furthermore,
C10 contained in this second a-8i layer 106
, N atoms have a non-uniform concentration distribution in the layer thickness direction such that the concentration is higher on the support side. Note that a surface layer 107 is laminated on the second a-8i layer 106.

According to the electrophotographic photoreceptor of the present invention, the photoconductive layer 103 includes, in order from the support 101, the μC-81 layer 104, the photoconductive first a-8i layer 1105, and the second a-3i layer 106.
They are stacked in this order.

According to the structure of the electrophotographic photoreceptor, when the electrophotographic photoreceptor is irradiated with light near visible light, the first a-3i layer 105 absorbs the light, and the light is not completely absorbed here. The microcrystalline silicon μc-s 1 layer 104 absorbs the light. Furthermore, when light with a wavelength around near infrared rays is irradiated, the first a-3i layer 105 absorbs only several tens of percent, and the μC-8i layer 104 can absorb the rest.

When only a-8i is used as a photoconductive layer, it has high sensitivity near visible light, but the photosensitivity drops rapidly to light with a wavelength near infrared, which is normally used in laser printers, so the image capacitance is low. However, there are disadvantages in that image defects such as unevenness in image density distribution due to blemishes, spots, capri, and buffering occur. However, according to the electrophotographic photoreceptor of the present application, as described above, since it is provided with the μC-8i layer 104, it is possible to absorb light in a wide range of wavelengths, and as a result, it is possible to obtain clear images. can.

When the electrophotographic photoreceptor is charged, the second a-8i
The layer 106 retains a charge on its free surface side, and then when irradiated with light, the first a-3i layer 105 and the μc
-81 layer 104 and optical carriers are generated. The generated optical carriers are instantaneously transported and neutralize the charges held on the free surface side of the second amorphous silicon 1ii1106. In this case, the photoconductive layer is the first a-3i layer 105
and μC-8i layer 104, charging ability is improved and high contrast can be obtained.

The second a-3i layer 106 contains at least one of C, O, and N atoms, but the concentration distribution of this contained material is nonuniform in the layer pressure direction. In this case, peeling of the layer or occurrence of cracks can be prevented, and furthermore,
Since trapping of the carrier is prevented, blurring or blurring of the image can be prevented. If the concentration distribution of the inclusions is constant in the layer pressure direction and a relatively large optical bandgap width is formed in this layer, there will be a problem of poor adhesion between these two layers after film formation. There is. As a result, the adhesion between the two layers is poor and peeling or cracking occurs. Or, because the characteristics of the two layers are different, carriers may be trapped between the eyebrows, causing the image to blur or flow.

Also in the blocking layer 102, the concentration distribution of the inclusions contained therein is formed non-uniformly in the layer pressure direction.
It is possible to prevent layer peeling or cracking at the interface with 4, as well as carrier trapping.

The content of C, O, and N atoms contained in the blocking layer 102 is preferably 1 to 20 atomic %, and the content of atoms belonging to Group Ⅰ or Group V of the periodic table is 1×10
' to 5 atomic % is preferable.

The thickness of the blocking layer is preferably 100 μm to 10 μm, more preferably 0.1 μm to 3 μm.
is preferred.

According to this invention, it is highly sensitive to light with wavelengths from visible light to near infrared rays, so it is highly sensitive to long wavelength light, and can be used as a photoreceptor for laser printers. A photoreceptor with high resolution, high cost, and excellent charging ability can be provided.

FIG. 3 shows another layer structure of the electrophotographic photoreceptor according to the present invention. In the layer structure shown in FIG. 3, compared to the layer structure shown in FIG. 2, the microcrystalline silicon layer 104 and the first a-8i layer 105 are exchanged.

That is, the photoconductive layers 117) a-8 iti 105 and tlc-8 i are sequentially coated on the photoconductive layer 103 from the support 101 side.
The layers are laminated in this order: R104, and then the second a-8i layer 106. In this case, the same effect as the layered structure shown in FIG. 2 described above can be obtained.

Furthermore, in the second a-8i, 111106, uirC,O
.

At least one N atom has a non-uniform concentration distribution in the layer thickness direction such that the concentration is higher on the support side. Therefore, when the photoconductive layer 103 is irradiated with light, charges of the same polarity as the charged electrode and charges of the opposite polarity are generated in the photoconductive layer, and the charges of the same polarity flow toward the charged side, On the other hand, charges of opposite polarity flow toward the support, but by forming a concentration, it is possible to allow the flow of charges of opposite polarity and maintain the charge retention function.

Next, embodiments of the invention will be described.

An AI drum (diameter: 80 mm, length: 350 mm) serving as a conductive substrate was degreased with trichlene, washed and dried, and then loaded into a reaction vessel. The surface of this drum is subjected to acid treatment, alkali treatment, sand plasty treatment, or sand treatment as necessary to prevent interference. Drum base 10
1 is heated and maintained at approximately 320°C. Then, SiH+
82 Hs gas, 45% CH4 gas, and 600% H2 gas with a flow rate ratio of 3 x 10'' to the gas flow rate were mixed and supplied to the reaction vessel.Then, the inside of the reaction vessel was evacuated using a mechanical booster pump and a rotary pump. The reaction pressure was adjusted to 1 TOr (torr).700 W (watt) was applied to the electrode while rotating the base 14 by the motor 18.
between the electrode and the drum base by applying high frequency power of
5i) 14° B2 H6 and CH4 plasma was generated (glow discharge) to form a film. During film formation, the flow rates of 82 Hs and CH4 gas were gradually reduced to 20% Cl-14 gas and 104% B2 H6 gas. Under these conditions, film formation was continued for about 30 minutes, and a film with a thickness of 0 was formed on the support 101.
．． μC-8 with a grain size of 4μm, a crystallinity of 40%, and a crystallinity of 70%.
A blocking layer 102 of i was formed.

After the blocking layer was formed, the inflow of 82 H6 and CH4 gases was stopped, and film formation was continued at 5 o'clock to form μC-8il104 having a thickness of 15 μm, a crystal grain size of 30 μm, and a crystallinity of 60%. Next, H2 gas was supplied at 100% and B2 Hs gas at a flow rate ratio of 10-6 with respect to the SIH+ gas flow rate, and a reaction pressure of 0.6 Torr and 100 W of high frequency power was applied to generate a glow discharge. let Film formation was continued under these conditions for 1 hour to form the first a-3i layer 105 with a thickness of 3 μm. Next, a flow layer of CH4 gas was supplied at 1% of the SiH+ gas flow rate, and then, the flow rate of CH4 gas was gradually increased to 500% by continuing to gradually increase the supply amount of Cl-14 to the SiH4 gas flow rate. It increased to During this time, film formation was carried out for 40 minutes to form a 3 μm thick second a-8i layer 106 and a 2 μm thick surface layer 107 (shown in FIG. 2).

±1'' - In this comparative example, a photoreceptor consisting of only the a-3i layer was formed. In this case, the blocking layer 102 is S i H4
B2 H6 gas was supplied to the gas stream at a flow rate ratio of 10°3, reaction pressure was 0.5 Torr, and high frequency power of 150 W was applied to form a film for 10 minutes. The photoconductive layer was formed under the same conditions as the first a-8i layer 105 of Example 1, that is, the H2 gas was 10096 ml for the S i H4 gas flow rate;
B2 H6 gas was supplied at a flow rate ratio of 10-6, the reaction pressure was O, '6 Torr, and high frequency power of 100 W was applied.
The film was formed for an hour. After forming the photoconductive layer, C)-14 was supplied at a flow rate of 500% to the SiH + gas flow chamber, and a reaction pressure of 0.6 Torr and high frequency power of 100 W was applied to generate a glow discharge. A surface layer was formed by forming a film for 5 minutes. In this case, the thickness of the blocking layer was 0.5 μm, the thickness of the photoconductive layer was 12 μm, and the thickness of the surface layer was 0.1 μm.

A comparative experiment was conducted on the photoreceptors of Example 1 and Comparative Example 1 formed as described above. When a voltage of 6.5 KV (kilovolts) was applied to each photoreceptor, the surface potential of Example 1 was 500 V, and the retention rate for 15 seconds was 65%. On the other hand,
The surface potential of the comparative example was 400V, and the retention rate was 30%.

Further, as shown in the graph of FIG. 4, the photosensitivity of each photoreceptor to wavelength was measured. In this Figure 4, the horizontal axis shows the wavelength of light (nm), and the vertical axis shows the sensitivity (Cm/era).
We measured the sensitivity at multiple wavelengths. In this graph, the solid line indicates the measurement results of Actual Example 1, and the broken line indicates the measurement results of Comparative Example 1. As is clear from this graph, according to this Example 1, good sensitivity could be obtained for light in the long wavelength region of about 700 to 800 nm.

Next, each photoreceptor was attached to a laser printer, an image was formed by the laser printer, and the images were compared. In this case, in Example 1, a clear image with high resolution and high contrast was obtained.

On the other hand, in the case of Comparative Example 1, image density unevenness caused by fogging or interference fringes occurred.

Example 2 In Example 1, when forming the a-3i layer 106, the second a-8i layer 106 was formed by varying the flow rate ratio of CH4 gas to the SiH+ gas flow rate. For other points, the film was formed under the same conditions as in Example 1.
The concentration distribution of the added concentration was formed in the direction of the layer thickness. Second
The relationship between the layer thickness in the a-3i layer 106 and the flow rate ratio of CH4 gas to SiH+ gas flow rate is shown in the fifth to thirteenth
As shown in the figure. In Figures 5 to 13, the horizontal axis shows the gas flow rate ratio, and the vertical axis shows the layer thickness, the solid line shows the flow rate of gas containing at least one of C10 and N atoms, and the broken line shows the periodic table. It shows the flow rate of a gas containing at least one type of group 1 or group V atoms. In either case, the concentration of atoms contained in each gas is non-uniform in the thickness direction of the layer. This example 2
In this case, the same effect as in Example 1 could be obtained.

"Husband 1" - In the case of this example, CH4 used in Example 2
An electrophotographic photoreceptor was formed using N2 gas instead of gas. That is, when forming the second a-3i layer 106, nitrogen N was added, and the concentration of nitrogen N was distributed in the layer thickness direction. In the case of Example 3 as well, the same effects as in Example 1 could be obtained.

In Friend 11 Ball Example 4, light guide i! layer 103 as first a-3i layer 1
05, uc-8i layer 104, second a-8il! 110
They are stacked on the blocking 11102 in the order of 6.

An Ai drum (diameter: 80 mm, length: 350 mm) serving as a conductive substrate was degreased with trichlene, washed and dried, and then loaded into a reaction vessel. The surface of this drum is subjected to acid treatment, alkali treatment, or sandblasting treatment as necessary to prevent interference. The drum substrate is heated and held at approximately 320°C. Next, 821-1s gas with a flow rate ratio of 5×10”, which is the highest in the SiH+ gas flow, is
% N2 gas and 700% H2 gas were mixed and supplied to the reaction vessel. After that, the inside of the reaction vessel is evacuated using a mechanical booster pump and a rotary pump, and the pressure is reduced to 0.
．． Adjusted to 1 Torr. While the base 14 was rotated by the motor 18, a high frequency power of 500 W (watts) was applied to the electrode to form a film. During film formation, the flow rate of the 82 Hs gas was gradually reduced to a flow rate ratio of 5 x 10'. Under these conditions, film formation was carried out for about 1 hour, and a blocking layer 102 of μC-8+ having a crystal grain size of 30% and a crystallinity of 60% was formed on the support 101.

After forming the blocking layer 102, Ar gas was added at 150% and 82 Hs gas was added at 3xl with respect to the SiH4 gas flow rate.
The reaction pressure was 0.4 Torr, 10
High frequency power of 0 W is applied to generate glow discharge. Open film formation was continued for about 1 hour under these conditions to form the first a-8i layer 105 with a thickness of 3 μm.

After the first a-8i layer 105 has been formed, H2 gas is supplied at a flow rate ratio of 8 times the flow rate of SiH+ gas, the reaction pressure is 1.0 Torr, and high frequency power of 400 W is applied to cause glow discharge. cause to occur. Film formation was continued under these conditions for 5 hours.
An r layer 104 was formed.

Subsequently, for 5i)-14 gas flow suspension, add N2 gas to 5
0%, Ar gas was supplied at a mixing ratio of 1001%, the reaction pressure was 0.5 Torr, and high frequency power of 200 W was applied.
2. Gradually increase the gas flow m up to 500% to obtain a film thickness of 2,
A second a-8i layer 106 of 5 μm was formed.

L Flame 11 In this comparative example, the blocking layer, photoconductive layer, and surface layer were formed only from a-3i. The blocking layer is SiH
4 gas flow rate, N2 gas was supplied at 100% and B2 Hs gas was supplied at a flow rate ratio of 10°3, reaction pressure was 0.4 Torr, and high frequency power of 150 W was applied to generate glow discharge. Open film formation was continued under these conditions for about 30 minutes, and the film thickness was 2 μm.
A blocking layer was formed. The photoconductive layer was formed under the same conditions as the first amorphous silicon layer 105 of Example 2, that is, Ar gas was 150% and 8 in.
2H6 gas was supplied at a flow m ratio of 3X10-s, the reaction pressure was 0.4 Torr, and a high frequency power of 100 W was applied to generate about 5
The film formation is continued intermittently to form a layer with a thickness of 15 μm. Furthermore,
Supply N2 gas at 500% of the SiH+ gas flow rate,
A reaction pressure of 0.7 Torr and a high frequency power of 300 W were applied, and film formation was continued for about 5 minutes to form a surface protective layer of 0.1 μm.

A comparative experiment was conducted on the electrophotographic photoreceptors of Example 4 and Comparative Example 2 formed as described above. When a voltage of 6.5 KV (kilovolts) was applied to each electrophotographic photoreceptor, the surface potential of Example 4 was 550 ■, and the retention rate for 15 seconds was 60%.
Met. On the other hand, the surface potential of Comparative Example 2 was 400 V, and the retention rate was 30%.

When the sensitivity according to the wavelength of light was measured, the same results as in Example 1 were obtained, as shown in FIG. 4 described above.

Furthermore, when the electrophotographic photoreceptors of Example 4 and Comparative Example 2 were used in a copying machine and a laser printer, the same results as in Example 1 were obtained. That is, in the comparative example, fogging and interference fringes occurred in the image, but in the photoreceptor according to Example 4, there was no image defect and a good image could be obtained. Further, as a result of a continuous use test of 100,000 sheets, Example 4 did not cause any abnormality or change in the image, but Comparative Example 4 started to have image blurring after approximately 20,000 sheets.

叉m In the above-mentioned Example 4, when forming the μC-81 layer 104, the flow rate ratio of CH4 gas to the SiH+ gas flow rate was further supplied by 0.3%. The other layers were formed under the same conditions as in Example 4. 6. To the electrophotographic photoreceptor of Example 5.
When a voltage of 5 KV was applied, the surface potential was improved by 20% compared to Example 4, and when the electrophotographic photoreceptor of Example 5 was used in an actual device, a better image than that of Example 4 could be obtained. Ta.

In Example 4, when forming the μC-8i layer 104, S
i The flow rate ratio of N2 gas to H4 gas flow rate is 1.5
%. The other layers were formed under the same conditions as in Example 4. 6.5KV to the electrophotographic photoreceptor of Example 6
When a voltage of 25% was applied, the surface potential was found to be 25
%, and a better image than in Example 4 could be obtained.

! In Example 4, when forming the μc-s 1 layer 104,
A ratio of B2 Hs2 to SiH4 of 10-7 was provided. The other layers were formed under the same conditions as in Example 4. According to the electrophotographic photoreceptor of Example 7, the long wavelength sensitivity is improved by 15% than that of Example 4, and when the electrophotographic photoreceptor of Example 7 is used in an actual device, a better image than that of Example 4 can be obtained. I was able to get

Example 8 In Example 4, CH4 gas was supplied instead of N2 gas, and CH4 was varied from 10% to 300%. When the electrophotographic photoreceptor according to Example 8 is used in an actual device,
As in Example 4, a good image could be obtained.

In Example 4, when forming the second a-8i layer 106, the flow ratio of N2 gas to the SiH4 gas flow rate was varied variously as shown in FIGS. 5 to 13. A second a-8i layer 106 was formed. For other points, the film was formed under the same conditions as in Example 4, and nitrogen N was added once to form a distribution in the layer thickness direction. When the electrophotographic photoreceptor according to Example 9 was used in an actual device, good images could be obtained as in Example 4.

In LLLL Nail Example 8, the second a-3i layer 106 was formed by varying the flow rate ratio of CH4 gas to SiH+ gas flow rate as shown in FIGS. 5 to 13. The film was formed under the same conditions as in Example 4 in other respects, and a concentration gradient of nitrogen N was formed in the direction of the layer thickness. When the electrophotographic photoreceptor according to Example 10 was used in an actual device, good images could be obtained as in Example 4.

[Effects of the Invention] According to the present invention, electrophotography 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 photoreceptor can be obtained.

[Brief explanation of drawings]

FIG. 1 is a diagram showing an apparatus for manufacturing an 8N photographic photoreceptor according to the present invention, FIGS. 2 and 3 are cross-sectional views showing an electrophotographic photoreceptor according to an embodiment of the invention, and FIG. 5 to 13 are graphs showing the relationship between the layer thickness and the C and OIN gas flow rates when forming layers. 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, 101; support, 10
2: blocking layer, 103: photoconductive layer, 106: surface layer. Applicant's Representative Patent Attorney Takehiko Suzue Figure 1 Figure 2 Figure 3 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 1 Figure 12 Figure 13 Figure 1 Display of the case Patent Application No. 60-256067 2, Name of the invention Electronic photoreceptor 3, Relationship with the case of the person making the amendment Patent applicant 5, Spontaneous - Vehicle pressure 6, Subject of the amendment .
7. Contents of amendment (1) The scope of claims is amended as shown in the attached sheet. (2) In the specification, "Group ■" is corrected to "Group V" on page 8, line 11, page 21, line 7, and page 22, line 9, respectively. . (3) In the specification, on page 9, line 6, the word "species" is corrected to "main". (4) In the specification, on page 23, line 20, "buffer fringes" is corrected to "interference fringes." (5) In the specification, "layer pressure" is corrected to "layer thickness" on page 24, line 19, page 25, line 3, and member 25, line 12, respectively. (6) In the specification, on page 22, line 19, and page 27, line 2, the words "support" are corrected to "surface." (In the specification, on page 40, line 4, the word "bluff" is corrected to "graph.") 2. Claims (1) An electrically conductive support, In an electrophotographic photoreceptor, the electrophotographic photoreceptor has a blocking layer formed on the blocking layer and a photoconductive layer formed on the blocking layer,
The blocking layer contains at least one type of atom selected from carbon, nitrogen, and oxygen, and at least one type of atom selected from Groups IV and V of the periodic table, and at least one of the selected atoms The photoconductive layer is made of microcrystalline silicon in which atoms form a non-uniform concentration distribution in the layer thickness direction. a microcrystalline silicon layer, a first amorphous silicon layer, and at least one kind of atom selected from carbon, triad, and oxygen; the at least one kind of atom selected from carbon, nitrogen, and oxygen has a layer thickness; An electrophotographic photoreceptor comprising a laminate of W and two amorphous silicon layers forming a non-uniform concentration distribution in the direction. (2) Carbon contained in the blocking layer, 4(
The concentration distribution of at least one atom selected from element and oxygen, and at least one atom selected from Groups I and V of the Periodic Table, is such that the concentration on the conductive support side is (3 ) The photoconductive layer is applied from the conductive support side. The electrophotographic photosensitive material according to claim 1 or 2, characterized in that a microcrystalline silicon layer, a first amorphous silicon layer, and a second amorphous silicon layer are laminated in this order. body. (4) The photoconductive layer is applied from the conductive support side. The electrophotographic photosensitive material according to claim 1 or 2, characterized in that the first amorphous silicon layer, the microcrystalline silicon layer, and the second amorphous silicon layer are laminated in this order. body. (5) The concentration of at least one type of atom selected from carbon, nitrogen, and oxygen added to the second amorphous silicon layer of the photoconductive layer is formed such that the concentration on the conductive support side is low. An electrophotographic photoreceptor according to claim 3 or 4, characterized in that: (6) Each layer of the photoconductive layer contains at least one type of atom selected from atoms belonging to Group 1 or Group V of the Periodic Table. The electrophotographic photoreceptor according to any one of Item 5.

Claims (6)

[Claims] (1) In an electrophotographic photoreceptor having a conductive support, a blocking layer formed on the conductive support, and a photoconductive layer formed on the blocking layer, the blocking layer comprises: At least one atom selected from carbon, nitrogen and oxygen, and Group III and Group III of the periodic table.
The photoconductive material is formed of microcrystalline silicon containing at least one type of atom selected from Group IV, and at least one of the selected atoms forms a non-uniform concentration distribution in the layer thickness direction. The layer includes a microcrystalline silicon layer, a first amorphous silicon layer, and at least one type of atom selected from carbon, nitrogen, and oxygen, and the at least one type of atom selected from carbon, nitrogen, and oxygen is in the layer. An electrophotographic photoreceptor comprising a laminate including a second amorphous silicon layer forming a non-uniform concentration distribution in the thickness direction. (2) At least one atom selected from carbon, nitrogen, and oxygen and at least one atom selected from Groups III and IV of the Periodic Table contained in the blocking layer. The electrophotographic photoreceptor according to claim 2 or 3, wherein the concentration distribution is such that the concentration on the conductive support side is higher. (3) A patent claim characterized in that the photoconductive layer is laminated in the order of a microcrystalline silicon layer, a first amorphous silicon layer, and a second amorphous silicon layer from the conductive support side. The electrophotographic photoreceptor according to item 1 or 2. (4) A patent claim characterized in that the photoconductive layer is laminated in the order of a first amorphous silicon layer, a microcrystalline silicon layer, and a second amorphous silicon layer from the conductive support side. The electrophotographic photoreceptor according to item 1 or 2. (5) The concentration of at least one type of atom selected from carbon, nitrogen, and oxygen added to the second amorphous silicon layer of the photoconductive layer is such that the concentration on the conductive support side is low. Characteristic Claim No. 3
The electrophotographic photoreceptor according to item 1 or 4. (6) Each layer of the photoconductive layer contains at least one type of atom selected from atoms belonging to Group III or Group V of the periodic table.
The electrophotographic photoreceptor according to any one of Items 1 to 5.