JP2668408B2 - Electrophotographic image forming member - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an electrophotographic image forming member using non-single-crystal silicon carbide such as amorphous silicon carbide and a method for producing the electrophotographic image forming member. Is.

In particular, the present invention relates to an electrophotographic image forming member comprising a non-single-crystal silicon carbide photoconductive layer and a non-single-crystal silicon carbide surface layer laminated on a support, and a method for producing the same.

[Conventional technology and problems to be solved]

An attempt to use non-single-crystal silicon carbide such as amorphous silicon carbide for an electrophotographic image forming member has been disclosed in
No. 119356, No. 56-24354, No. 60-203958
And JP-A-58-174954. In addition to those having a charge injection preventing layer, JP-A-57-122445, JP-A-60-115940,
60-242465, 60-235147, 61
-126557 is known. Further, those having a surface layer include those described in JP-A-60-115941 and JP-A-61-2758.
No. 46, No. 61-159657, No. 60-235153, No. 62-83753 and the like are known.

By the way, such conventional non-single-crystal silicon carbide is similar to hydrogenated amorphous silicon in high-frequency plasma CV.
It was generally deposited by the D method, and the deposition conditions were generally the same.

Such a non-single-crystal silicon carbide film deposited by the conventional technique has a hydrogen-related defect and a double bond between carbon atoms in the non-single-crystal silicon carbide film compared with the hydrogenated amorphous silicon film which has been sufficiently optimized in recent years. The reality is that there are more or less related defects. Furthermore, the carbon atoms in the non-single-crystal silicon carbide film may increase the tail state on the conduction band side and decrease the mobility of electrons depending on how they are contained, so that a photoconductive material having a high dark resistance may be used. However, in many cases, its application range is narrowed in terms of application to an electrophotographic image forming member. That is, the electrophotographic characteristics of a conventional electrophotographic image forming member using a non-single-crystal silicon carbide film are often examined for a light source including long-wavelength light such as a tungsten lamp. The photoexcited carriers generated by light absorption by the entire photoconductive layer have obtained general practical characteristics. Further, a charge generation layer is provided on at least one of the upper and lower sides of the non-single-crystal silicon carbide film, and carriers (charges) generated in the layer are injected into the non-single-crystal silicon carbide layer to form a latent image. In many cases. That is, the conventional electrophotographic image forming member using the conventional non-single-crystal silicon carbide film has a carrier range in which either the electron or the hole in the non-single-crystal silicon carbide layer has a sufficient carrier range as in the above-described example. In many cases, it was practically used by taking advantage of the fact that it has.

Such a conventional non-single-crystal silicon carbide film can satisfy sufficient practical use, for example, when it is used as a photoconductive layer of a photosensitive image forming member such as a general copying machine or a printer. Is. But OA
With the further increase in processing speed of related equipment,
In the current situation where even higher performance is required for the electrophotographic image forming member used in this case, the conventional one is not always satisfactory in all respects. is there.

For example, when non-single-crystal silicon carbide is applied to an image forming member of a high-speed electrophotographic apparatus, if charging and exposure are repeated many times, pinholes due to corona charging may occur and image defects may become a problem. Not a few.

Further, in such an apparatus, it has been desired to further improve a phenomenon called a ghost in which a previous image is superimposed on a next image.

In addition, in such an apparatus, the electrophotographic process for obtaining a high quality image is complicated, but at that time, the dark decay characteristic at the time of corona charging becomes a problem, and further improvement thereof is desired. By the way.

In addition, in the electrophotographic image forming process, processes such as corona charging-image exposure-development-transfer-cleaning are continuously repeated, but before the corona charging, the surface potential of the previous image pattern is erased. Then, a uniform exposure usually called a pre-exposure is performed.

However, in an electrophotographic imaging member having a non-single-crystal silicon carbide photoconductive layer obtained by a conventional method, a large amount of electrons and holes tend to be trapped in the photoconductive layer by this pre-exposure. It was The trapped electrons and holes are released from the trap during corona charging, and as a result, the surface potential decreases and dark decay after corona charging tends to increase, which is not preferable.

Further, the trapped electrons and holes can recombine with the photoexcited electrons and holes at the time of image exposure and cause a reduction in sensitivity.

When the conventional electrophotographic image forming member having a photoconductive layer made of non-single-crystal silicon carbide is applied to an image forming member of a high-speed and high-performance electrophotographic apparatus, the trapped electrons and holes The effect of can not be ignored.

In addition, when depositing a non-single crystal silicon carbide film by the conventionally proposed high frequency plasma CVD method, the deposition rate is 80 Å / s.
There is a problem that the electrical characteristics of the non-single-crystal silicon carbide film are sharply deteriorated at ec or more. Therefore, in order to improve the productivity, a method of obtaining a high-quality non-single-crystal silicon carbide film at a high deposition rate is desired. It is rare.

Furthermore, in addition to that, when a surface layer is laminated on a conventional non-single-crystal silicon carbide photoconductive layer and it is applied to an image forming member of a higher speed electrophotographic apparatus, it is compared with the case where the surface layer is not provided. Although the charging ability is increased, the so-called "falling" phenomenon of the surface potential is often observed, in which the surface potential gradually decreases as charging is repeated due to the high speed and the rotation cycle is shortened. It was This phenomenon causes a difference in the degree of “fall” between the previously irradiated part of the photoconductive layer and the previously unirradiated part,
Since it also leads to a bad effect on the image that ghosts appear strongly, a solution has been desired.

Furthermore, it is an effective means to provide a charge injection prevention layer for the purpose of preventing the injection of charges from the support side and further improving the charging characteristics. However, a photoconductive layer composed of conventional non-single-crystal silicon carbide is used. When a layer and a charge injection prevention layer are laminated and applied to an image forming member of a higher speed electrophotographic apparatus, pinholes are generated due to the high charging speed and the severer charging conditions. There is a problem that a bad effect such as easy occurrence is likely to occur.

[Object of the invention]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrophotographic image forming member in which a non-single-crystal silicon carbide film in which the problems of the prior art are solved is applied to a photoconductive layer and a surface layer.

Another object of the present invention is to provide a method for manufacturing an electrophotographic image forming member which can produce the electrophotographic image forming member with the above-mentioned problems solved with high productivity.

[Means for solving the problem]

In order to achieve the above object, the present invention provides an electrophotographic image forming member comprising at least a photoconductive layer and a surface layer laminated on a support, wherein the photoconductive layer contains 1 to 10 atomic% of hydrogen atoms. Non-single-crystal carbonization containing 5% by atom to 15% by atom of carbon atom and 0.01 to 0.05 of the stretching mode of C—H bond and the stretching mode of Si—H bond by infrared absorption spectrum It has a layer structure that does not include a graphite structure or contains 1% or less per unit volume of silicon, and the surface layer has 50 to 70 atomic% of hydrogen atoms and 20 to 40 atomic% of carbon atoms. % Of non-single-crystal silicon carbide, and has a layer structure not containing a graphite structure or containing 1% or less per unit volume.

[Configuration of the invention]

FIG. 1 shows the layer structure of the electrophotographic image forming member of the present invention.

FIG. 1-A is a view showing the basic layer structure of the present invention. The electrophotographic image forming member of the present invention is a support 10 from the bottom.
1. The photoconductive layer 103 made of non-single-crystal silicon carbide and the surface layer 104 made of non-single-crystal silicon carbide are arranged in this order.

FIG. 1B is a view showing a preferred embodiment of the present invention. In addition to FIG. 1A, the gap between the support 101 and the photoconductive layer 103 made of non-single-crystal silicon carbide is shown. In which a charge injection preventing layer 102 is provided.

The image forming member of the present invention contains 1 atom% to 10 atom% of hydrogen atoms and 5 atom% to 15 atom% of carbon atoms in the photoconductive layer.
The ratio of the C—H bond stretching mode and the Si—H bond stretching mode according to the infrared absorption spectrum is 0.01 to 0.05, and the graphite structure per unit volume has a characteristic of 1% or less. Using a layer made of non-single-crystal silicon carbide, the surface layer contains 50 to 70 atomic% hydrogen atoms, contains 20 to 40 atomic% carbon atoms, and has a graphite structure per unit volume. Non-single-crystal silicon carbide having a characteristic of 1% or less is used, which is laminated as shown in FIG.

Hereinafter, the configuration of the present invention will be specifically described step by step for each component.

Support The support used in the present invention may be either conductive or electrically insulating. As the conductive support,
For example, NiCr, stainless steel, A, Cr, Mo, Au, Nb, Ta, V, Ti, P
Metals such as t and Pb or alloys thereof are exemplified.

Examples of the electrically insulating support include synthetic resin films such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide, or sheets, glass, ceramic, and paper.
It is preferable that at least one surface of these electrically insulating supports is subjected to a conductive treatment, and a light-receiving layer is provided on the conductive-treated surface side.

For example, in the case of glass, NiCr, Al, Cr, M
Provide conductivity by providing a thin film composed of o, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, InO ₃ , ITO (In ₂ O ₃ + Sn), or synthetic resin such as polyester film For film, NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Tl, Pt
A thin film of such a metal is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, or the like, or the surface is laminated with the metal to impart conductivity to the surface.
The shape of the support may be a plate-shaped endless belt shape or a cylindrical shape having a smooth surface or an uneven surface, and the thickness thereof is appropriately determined so that a desired electrophotographic light-receiving member can be formed. When flexibility as an electrophotographic light-receiving member is required, it can be made as thin as possible within a range in which the function as a support is sufficiently exhibited. However, it is usually 10 μm or more in terms of mechanical strength and the like in manufacturing and handling the support.

Charge Injection Prevention Layer In the present invention, the structure shown in FIG. 1-A is essential, but a photoconductive layer composed of a support and non-single-crystal silicon carbide as indicated by 102 in FIG. 1-B is used. By providing a layer for preventing charge injection from the support between the layers, the electrophotographic properties can be further improved.

As such a charge injection prevention layer, a non-single-crystal silicon film such as amorphous silicon, a non-single-crystal silicon oxide film, a non-single-crystal silicon nitride film, a non-single-crystal silicon carbide film, or the like is doped with a valence electron controlling agent. Are suitable. Above all, those obtained by doping the non-single-crystal silicon carbide film of the present invention with a valence electron controlling agent show the best characteristics.

It is considered that the charge injection prevention layer used as such a preferable constituent element of the invention exhibits the following actions and effects. That is, in the electrophotographic image forming member of the present invention, since the number of defects in the non-single-crystal silicon carbide film is extremely small, the injection of charges from the support side through the defect levels is reduced, and the charging characteristics are improved. To do. In addition, when the corona charge is increased in order to apply to a higher-speed electrophotographic apparatus, in a conventional electrophotographic image forming member using a non-single-crystal silicon carbide film, charge injection via defect levels is not performed. Increase, which is accelerated by the corona charged electric field, and the injected charge gains excess energy. The injected charge having excess energy interacts with the defect or lattice to excite the charge trapped in the defect, and the charge in the band avalanchely increases. As a result, a very large current flows in the non-single-crystal silicon carbide film, and the phenomenon that pinholes locally occur is likely to occur.

On the other hand, since the non-single crystal silicon carbide film of the present invention is used as a photoconductive layer and is laminated with a charge injection preventing layer, the electrophotographic image forming member has very few defects in the photoconductive layer. Therefore, even when used in a high-speed electrophotographic apparatus, the pinhole is hardly generated. Furthermore, since the number of defects is small, in the non-single-crystal silicon carbide film of the present invention, silicon atoms and carbon atoms are firmly bonded to each other or to each other, and it is considered that pinholes are less likely to occur. .

As described above, the charge injection preventing layer, which is a preferred component of the present invention, is a non-single-crystal silicon film, a non-single-crystal silicon oxide film, a non-single-crystal silicon nitride film, a non-single-crystal silicon carbide film, and the like. It is formed by containing atoms functioning as. For example, when the charge injection preventing layer is used while being controlled to be p-type, it is sufficient that the layer contains an atom of Group III of the periodic table.
What is necessary is just to include the atom of Group V of a periodic table. These
Group III or Group V atoms are B, A as Group III atoms.
Atoms such as l, Ca, In, and Tl can be used, and atoms such as P, As, Sb, and Bi can be used as Group V atoms. The doping amount for controlling these valence electrons is effectively 200 atom ppm to 1000.
0 atomic ppm is preferred, and optimally 300 atomic ppm to 5000 atomic pp
m. The term “effective” here means the ratio of working as a donor or an acceptor. If both donor and acceptor are included, the difference is the effective doping amount. Further, in addition to these valence electron controlling agents, H atoms or halogen atoms such as F and Cl may be contained for the purpose of reducing the defect density and simultaneously improving the stability of the film.

The content of H and halogen atoms in the film is preferably 1 to 40 atomic% for H and 10 ppm to 5 atomic% for halogen, respectively.

The atoms constituting the charge injection prevention layer, that is, Si, O,
Atoms such as N, C, Group III atoms, Group V atoms, H, F, Cl, etc. are basically contained in a layer at a uniform concentration, but a certain concentration distribution depends on the purpose. It can also be used by changing the content in the layer so that

The charge injection preventing layer, which is a preferred component of the present invention, is basically provided directly on the support as shown in FIG. 1-B, but further improves the adhesion between the support and the support. It is also possible to additionally provide a layer to be formed, an antireflection layer for absorbing long-wavelength light, and the like, which are appropriately selected and provided according to the required characteristics of the electrophotographic photosensitive member.

Photoconductive Layer The photoconductive layer of the present invention has a basic mode in which it is provided on the support 101 as shown in FIG. 1-A103. The photoconductive layer 103 contains 1 atom% to 10 atom% of hydrogen atoms, 5 atom% to 15 atom% of carbon atom paper, and has a C—H bond stretching mode according to an infrared absorption spectrum and a Si—H bond. Is in the range of 0.01 to 0.05 and the graphite structure per unit volume is made of non-single-crystal silicon carbide having a characteristic of 1% or less.

The present invention examines in detail the light decay process of the surface potential, which is one of the most suitable means for evaluating the electrical characteristics of the electrophotographic image forming member, and as a photoconductive layer, It is based on the finding that the above-mentioned object of the present invention can be achieved by taking the essential constitution.

In the following, the results of a study of the light attenuation process of the photoconductive layer performed by the present inventors will be described, and the operation, effects, conditions to be provided, and the like of the photoconductive layer of the present invention will be described in further detail.

The light attenuation of the photoconductive layer is considered as follows in the case of positive charging, for example.

The primary photocurrent of holes flowing in the photoconductive layer is expressed as follows.

Where J _h is the current due to holes, L is the layer thickness of the photoconductive layer,
Is the average hole moving distance, F is the irradiation light amount, and e is the elementary charge.

The number of holes photo-excited in the layer is Suppose that

Here, η _h (x) is the number of holes at a certain position x in the layer, W _h is the range of holes (equal to μ _h τ _h E product, μ _h : mobility of holes, τ _h : lifetime of holes, E: electric field), ηo _h is the number of holes initially excited.

Then, the average moving distance up to x in the layer is It is.

Therefore, the current J _h due to holes is Becomes

Furthermore, the light absorption in the layer is F = F _o exp (−αx) (F
_o : irradiation light amount, α: extinction coefficient, x: a certain position), the photocurrent J _{h of the} hole is Becomes

Similarly, the current J _e due to electrons is It is expressed as

Here, We is an electron range (μ _e τ _h E product, μ _e : electron mobility, τ _e : electron lifetime, E: electric field).

Thus the total current J becomes J = J _e + J _h.

From the above, the light attenuation of the surface potential is (Where C is the capacitance of the layer, V is the surface potential, and t is time). (Where V _o is the initial surface potential).

FIGS. 2 (positive charge) and 3 (negative charge) show typical examples of typical light decay curves of an electrophotographic image forming member composed of a conventional non-single-crystal silicon carbide film. The measurement of light attenuation characteristics
For example PHOTOGRAPHIC SCIENCE AND ENGINEERING Volume
24, No. 5, Sept / Oct, 1980, page 251 and the like.

In the figure, the positive charge has a smaller light attenuation than the negative charge when the exposure wavelength is shorter. However, it is considered that light attenuation is excellent for light including long-wavelength light such as a tungsten lamp.

FIGS. 2 and 3 show the equations (1), (2), and (3).
As a result of investigation based on the equation, it was estimated that the product of the mobility of holes and the lifetime (hereinafter referred to as “μτ product”) was smaller than that of electrons.

On the other hand, an example of a typical light decay curve of the electrophotographic image forming member formed of the non-single crystal silicon carbide film of the present invention
FIG. 5 (positive charge) and FIG. 5 (negative charge).

FIG. 4 and FIG. 5 were examined based on the above equations (1), (2), and (3). The μτ product of holes was constituted by the conventional non-single-crystal silicon carbide film. It was found to be improved over the electrophotographic imaging member.

Conventionally, in non-single-crystal films such as amorphous silicon,
It is known that a hydrogen atom plays an important role as a compensating atom for dangling bonds of silicon. However, more than necessary hydrogen atoms break the bonds necessary to create a three-dimensional network between silicon atoms or between silicon atoms and carbon atoms, reducing the structural strength of the non-single-crystal film. There is something to do. Further, hydrogen atoms bonded to silicon atoms form bonding orbitals near the upper part of the valence band, and have a function of increasing the forbidden band width. However, a large amount of hydrogen atoms not only increases the forbidden band width, but also causes disorder of the band structure in the valence band, and decreases the mobility of holes in the valence band. Further, with the disorder of the band structure of the valence band, a defect level called a tail state increases from the valence band toward the forbidden band. These defect levels not only act as traps for holes but also act as recombination centers for electrons, which greatly affect the transport of photoexcited carriers.

Further, in the case of a non-single-crystal silicon carbide film, there is a special difficulty in containing carbon atoms in addition to the above points. The carbon atoms are, as is well known in organic chemistry, SP, S
Many hybrid orbits such as P ² and SP ³ can be taken. The carbon atom is usually most stable when it has a graphite structure. Therefore, the amount of defects in the non-single-crystal silicon carbide film depends on the orbit taken by the electrons in the carbon atoms. In order to reduce defects as much as possible, the carbon atoms in the non-single-crystal silicon carbide film must be formed so as to be four-coordinate (SP ³ ).

Also, since the bond energy between carbon and hydrogen atoms is larger than the bond energy between silicon and hydrogen atoms,
Usually, the ratio of hydrogen atoms remaining in a non-single-crystal silicon carbide film in a carbon-hydrogen bond state is large. For this reason, the bond between carbon and silicon was sometimes hindered.

Based on the above considerations, the proportion of constituent atoms of the non-single-crystal silicon carbide film, the bonding state of hydrogen atoms and the bonding state of carbon atoms were examined. As a result, the content of hydrogen atoms in the non-single-crystal silicon carbide film is preferably 1 atomic% to 10 atomic%,
3 to 7 atomic% was optimal.

As described above, if the hydrogen content is less than this range, the number of dangling bonds related to silicon atoms and carbon atoms increases, and the number of defects in the non-single-crystal silicon carbide film tends to increase. On the other hand, if it exceeds this range, defects on the valence band side increase, and the ratio of hydrogen atoms bonded to carbon atoms increases, which tends to make it difficult to form a three-dimensional network.

Furthermore, the bonded hydrogen atom in the non-single-crystal silicon carbide film is preferably a so-called Si-H bond in which one hydrogen atom is attached to a silicon atom, and a carbon atom is also one hydrogen atom is attached to a carbon atom. CH bonds are preferred. The ratio between the C—H bond expansion mode and the Si—H bond expansion mode in the infrared absorption spectrum is preferably in the range of 0.01 to 0.05. Within this range, hydrogen atoms can sufficiently compensate dangling bonds, and defects related to hydrogen atoms can be sufficiently reduced. The content of carbon atoms in the non-single crystal silicon carbide film is an important factor for achieving the object of the present invention. As described above, since carbon atoms can take many electron orbitals, defects are easily formed in a non-single-crystal silicon carbide film.

The present inventors have studied the carbon content in detail, and as a result, have found that it is necessary for carbon atoms to be uniformly dispersed in Si atoms without contact.
According to the percolation theory, its content is shown to be around 40 atomic%. However, at around 40 atomic%, clusters composed of carbon atoms were formed, so that the extremely good electrical characteristics as aimed at this time could not be obtained. As a result of intensive studies on this point, the present inventors have found that the optimum carbon content is 5 to 15 atomic%.

Further, it is necessary that the graphite structure, which greatly affects the electrical characteristics of the film, be 1% or less per unit volume. When the graphite structure increases, the dark resistance of the non-single-crystal silicon carbide film tends to decrease, and the charging ability of the electrophotographic image forming member tends to decrease. Then, the graphite structure tends to become a defect, the transport ability of photoexcited carriers is reduced, and the optical sensitivity of the electrophotographic image forming member tends to be deteriorated.

According to the inventors, the object of the present invention cannot be achieved even if any of the above ranges is deviated.

The photoconductive layer of the present invention as described in detail above can control p and n by doping according to the purpose. For example, when the photoconductive layer is to be controlled to be p-type, the layer may contain an atom of Group III of the periodic table. A group V atom may be contained. As group III or group V atoms, B, Al, Ga, In, and Tl can be used as group III atoms, and P, As, Sb, and Bi can be used as group V atoms. it can.
The doping amount of these valence electron controlling agents is effectively 0.
01 atomic ppm to 100 atomic ppm is preferred, and optimally 0.1 atomic pp
m to 10 atomic ppm.

Further, the photoconductive layer of the present invention, in addition to the above additives, for the purpose of controlling the light absorption characteristics or resistance value of the layer,
For the purpose of further reducing the defect density and at the same time further improving the stability of the film, halogen atoms such as F and Cl can be contained, respectively, for atoms such as O and N.

Surface Layer In the present invention, a surface layer such as 104 in FIG. 1 is provided on the photoconductive layer. The surface layer contains 50 atomic% of hydrogen atoms
It is composed of a non-single-crystal silicon carbide film containing up to 70 at%, containing 20 to 40 at% of carbon atoms, and having a graphite structure of 1% or less.

It is considered that such a surface layer used as a component of the present invention exerts the following actions and effects. That is, for example, on the photoconductive layer composed of non-single-crystal silicon carbide of the prior art, for example, a surface layer composed of non-single-crystal silicon carbide having a composition different from that of the photoconductive layer and having substantially no photoconductivity. In a laminated electrophotographic image forming member, a "falling" phenomenon of the surface potential due to defects in the vicinity of the surface of the photoconductive layer and in the surface layer may be observed. This "falling" phenomenon is caused by the phenomenon that charges are trapped near the interface between the photoconductive layer and the surface layer, modify the electric field distribution near the interface, and promote the injection of charges from the free surface. it is conceivable that. It is considered that such a “falling” phenomenon is related to a deep level in the forbidden band existing in the non-single-crystal silicon carbide film. The fall phenomenon of the electrophotographic image forming member caused by the `` deep level '' in the forbidden band in the non-single-crystal silicon carbide film is not a problem in a normal electrophotographic apparatus, but In a higher speed electrophotographic apparatus, the influence becomes more prominent.

On the other hand, in the electrophotographic imaging member having the photoconductive layer composed of the non-single-crystal silicon carbide and the surface layer according to the present invention, the defects in the photoconductive layer and the surface layer are extremely small, so that the speed of the formation can be increased. When it is applied to the electrophotographic apparatus, the "falling" phenomenon as seen in the prior art does not occur and good charging characteristics are exhibited. In addition, the surface layer composed of non-single-crystal silicon carbide can increase the structural flexibility by setting the hydrogen content in the range of 50 to 70 atomic% described above. The carbon atom weight is 20 to 40 atomic%
Since the graphite structure per unit volume is 1% or less, hydrogen atoms are sufficiently bonded to carbon atoms, and defects are small. As a result, since the number of deep defects near the interface between the photoconductive layer and the surface layer is reduced, it exhibits good characteristics and is suitable for an image forming member for a higher-speed electrophotographic apparatus.

The surface layer, which is a constituent element of the present invention, may contain halogen atoms such as F and Cl for the purpose of reducing the defect density and at the same time further improving the stability of the film, in addition to the above essential constituent elements. It is a thing. The content of the halogen atoms in the film is preferably in a range of 10 atomic ppm to 5 atomic%.

A method for forming a deposited film and a method for forming a deposited film suitable for depositing a non-single-crystal silicon carbide film that can achieve the object of the present invention will be described. The deposited film forming apparatus and method are unique to the present invention.

6 and 7 are a side sectional view and a plan sectional view of a deposited film forming apparatus suitable for manufacturing the non-single-crystal silicon carbide electrophotographic image forming member of the present invention.

The deposited film forming apparatus used in the present invention includes reactor vessels 601, 701 capable of reducing pressure, microwave introduction windows 602, 702 made of alumina ceramics, microwave waveguide 603, exhaust pipe 604,
704, cylindrical supports 605, 705 (in the case of a small support, dig a groove in the surface of the cylindrical support, adhere a small support to the groove to form a deposited film on the small support), heat the support Heaters 607, 707, gas introduction pipes (side gas pipes) 608, 708, gas introduction pipes (central gas pipe) 611, bias power supply 612 for applying DC, AC, and RF biases, and support body rotation motor 610 .
Although not shown, the gas introduction pipes 608, 611, and 708 are SiH
A cylinder of the raw material gas such as ₄ , CH ₄ , B ₂ H ₆ or the like is connected through a valve and a mass flow controller. The exhaust pipe 604 is connected to a diffusion pump (not shown).

The image forming member for electrophotography of the present invention is manufactured by using the above-described deposited film forming apparatus according to the following procedure.

Formation of Charge Injection Prevention Layer First, the cylindrical supports 605, 705 are set in the reactor vessels 601, 701, the support is rotated by the support rotating motor 610, and a vacuum of 10 ^-6 Torr or less is applied by a diffusion pump (not shown). Exhaust every time. Then, the temperature of the cylindrical support is controlled by the heaters 607 and 707 for heating the cylindrical support in a preferable temperature range of 200 ° C to 400 ° C. After the cylindrical supports 605, 705 have reached a predetermined temperature, a gas cylinder (not shown) introduces a charge injection prevention layer forming gas into the gas introduction pipes 608, 708 or 611, and the gas discharge nozzles 608 ', 708' discharge spaces 606, 706. Release into.
Next, the pressure in the discharge spaces 606 and 706 is adjusted to a predetermined value. After the internal pressure stabilizes, the microwave power supply (not shown)
Microwave energy is introduced into the discharge spaces 606 and 706 through the microwave introduction window. At this time, if necessary, a DC (D
C) or / and high frequency (RF) is applied. This state is maintained for a predetermined time, and the charge injection prevention layer is formed on the support. Thereafter, the introduction of the microwave energy and the raw material gas is temporarily stopped, and the process shifts to the formation of the photoconductive layer.

As the source gas used for forming the charge injection preventing layer, when the charge injection preventing layer is formed of a non-single-crystal silicon film, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , SiF ₄ , Si ₂ F ₆ etc. are used as the main source gas. When the charge injection prevention layer is formed of a silicon oxide film, a silicon nitride film, or a silicon carbide film, O ₂ , NO, NO ₂ , N ₂ O, CO, C is used for a silicon oxide film.
A gas such as O ₂ , a gas such as N ₂ , NH ₃ for a silicon nitride film, and a CH ₄ , C ₂ H ₆ , C
Gases such as ₃ H ₈ , C ₂ H ₄ , C ₃ H ₆ , C ₂ H ₂ , C ₆ H ₆ , CF _{4 and the} like are mixed with the silicon-based gas and used. In addition, as a doping gas for controlling valence electrons, a group III atom (when p-type) or a group V atom (n
A gas containing (in the case of forming a mold) may be added.

As group III atoms, atoms such as B, Al, Ga, In, and Tl can be used, and B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H
_{9, B 5 H 11, B} 6 H 10, B 6 H 12, boron hydride such as B ₆ H ₄ and the like. Other examples include AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , and TlCl ₃ .

As group V atoms, atoms such as P, As, Sb, and Bi can be used. Examples of the feed gas for the supply include phosphorus hydride such as PH ₃ and P ₂ H ₄ , and others such as AsH ₃ , SbH ₃ and BiH ₃ . H atoms and halogen atoms are automatically contained when each of the above gases contains these atoms, but when used in a relatively large amount, In the case of H atoms, H ₂ gas may be used as an additive gas, and as for halogen atoms, F ₂ , HF, HCl, Cl ₂ or the like may be used as an additive gas.

Formation of Photoconductive Layer After the formation of the charge injection preventing layer as described above, the formation of the photoconductive layer is continued in the same device.

When the photoconductive layer is formed, it is preferable that the carbon-containing gas mainly flows out from the gas introduction pipes 608 and 708, and the silicon-containing gas, hydrogen gas, and the valence control agent flow out from the gas introduction pipe 611. The carbon-containing gas should not be exposed to the plasma for a long time in the plasma, and should be deposited on the support in the shortest possible time. Because, when the decomposition of the carbon-containing gas in the plasma progresses and carbon atoms are present,
This is because carbon atoms are very reactive, and are considered to easily react with undecomposed carbon-containing gas or with deposited carbon atoms to bring a graphite structure into the deposited film.

On the other hand, the layer thickness is several tens μm like an electrophotographic image forming member.
Devices that also require high speed deposition from a productivity standpoint. In that case, it is necessary to give sufficient energy to the silicon source gas as the source. Also,
Further, in order to reduce defects in the deposited film and improve electric characteristics, it is necessary to add hydrogen gas. Hydrogen gas is not very useful for improving characteristics in the form of H ₂ , and is useful for improving characteristics when converted to hydrogen radicals. In addition, the more hydrogen radicals are present, the better the characteristics. Similarly, in the valence electron controlling agent, in order to effectively use the valence electron controlling agent, it is necessary to supply sufficient energy to the source gas for the valence electron controlling agent in the plasma.

For the above reasons, the present inventors have studied a new gas introduction method, and have found a gas introduction method suitable for forming a high-quality non-single-crystal silicon carbide film as described above.

The gas is introduced in this way, and 606,706 in the discharge space
Is adjusted to a predetermined pressure of 0.1 Torr or less. After the pressure in the discharge space is stabilized, a microwave power supply (not shown)
From the discharge space through the waveguide 603 and the microwave introduction window 602
Microwave energy is introduced into 606,706. Microwave energy introduces more than 1.1 times the energy required to saturate the deposition rate. Only by providing such microwave energy, sufficient energy can be provided to the source gas for forming the deposited film and the hydrogen gas.

Further, a direct current (DC) and / or a high frequency (RF) is applied to the gas introduction pipe 611 from the bias applying power source 612. The DC bias must make the gas introduction pipe 611 positive. When the gas introduction pipe is made negative, almost no current flows, and the effect of DC bias does not appear.

By applying a DC bias, the ions in the plasma are sufficiently energized and the redistribution of the deposited film on the support surface is promoted, so that the electrical characteristics of the deposited film are improved.

Also, even if an RF bias is applied instead of a DC bias, the DC
An effect similar to that of the bias appears. RF bias (for example,
13.56MHz) improves the stability of plasma discharge especially at pressures near 10 ^-3 Torr. In particular, the silicon-based gas introduced from the gas introduction pipe 611 necessary for forming the high-quality non-single-crystal silicon carbide film of the present invention is given sufficient energy, and the carbon-based gas introduced from the gas introduction pipes 608 and 708 is provided. It is important to apply the DC bias or the RF bias as described above in order to give an appropriate energy and to react as quickly as possible without excessively decomposing.

In order to deposit the high quality non-single-crystal silicon carbide film of the present invention, the pressure of the discharge spaces 606 and 706 is preferably 0.1 Torr.
Below, it is optimally set to 0.0005 to 0.01 Torr.

In addition, in order to deposit a high-quality non-single-crystal silicon carbide film of the present invention, the power of the bias applied to the gas introduction pipe 611 is preferably 1/5 to 1.5 times the microwave power introduced into the discharge spaces 606, 706. , More optimally 1/4 to 1
Good times. If the bias power is smaller than the above range,
No bias effect appears. When the bias power is larger than the above range, the number of defects in the deposited film is greatly increased. This means that there is a close relationship between the deposition rate of the non-single-crystal silicon carbide film, the gas phase reaction in the plasma, and the surface reaction on the support. It is thought to be due to the fact that it can be obtained only in a special range.

Since the material of the gas introduction pipe 611 to which a bias is applied is placed in a place where plasma is strong, it is very important to form a high-quality deposited film. In particular, the material is required to have a high melting point, to be difficult to be sputtered, and to have low reactivity with a source gas for forming a deposited film.

Suitable materials satisfying such conditions include stainless steel, nickel, molybdenum, tantalum, and platinum.

The source gases suitable for depositing the non-single-crystal silicon carbide film that can achieve the object of the present invention are as follows.

The raw material gas of _{silicon, SiH 4, Si 2 H 6} , Si 3 H 8, ... SiF
Silane-based gas such as ₄ , Si ₂ F ₆ ... Can be used.

CH ₄ , C ₂ H ₆ ,, C ₃ H ₈ , ... C ₂ H ₄ ,, C ₃ H ₆ ,
Gases such as… C ₂ H ₂ ,… C ₆ H ₆ , CF ₄ ,… can be used. Also,
The source gas containing both silicon and carbon is (CH ₃ ) ₄
Gases such as Si ... can be used.

The mixing ratio between the silicon-based source gas and the carbon-based source gas is preferably 10/5 to 100/1, and most preferably 10/2 to 100/5.

The above-mentioned various source gases can be used as a mixture of a plurality of types.

In the present invention, it is important to use the raw material gas and the hydrogen gas as a mixture in order to form a high quality non-single-crystal silicon carbide film.

As described above, in the present invention, valence electrons can be controlled by doping a non-single-crystal silicon carbide film. In this case, the source gas is a group III atom of the periodic table (p-type). Case) A gas containing a Group V atom (when it is made n-type) may be added.

As the group III atoms, atoms such as B, Al, Ga, In, and Tl can be used, and as a source gas for supplying them, B ₂ H ₆ , B
_{4 H 10, B 5 H 9} , B 5 H 11, B 6 H 10, B 6 H 12, boron hydride such as B ₆ H ₄ and the like.

In addition to these, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like can be mentioned.

As group V atoms, atoms such as P, As, Sb, and Bi can be used. Examples of the feed gas for the supply include phosphorus hydride such as PH ₃ and P ₂ H ₄ , and others such as AsH ₃ , SbH ₃ and BiH ₃ .

Furthermore, in the present invention, as described above,
Although atoms such as O, N, F, and Cl can be contained, as a gas for introducing these atoms, O ₂ , NO,
Gases such as NO ₂ , N ₂ O, CO, CO ₂ are N ₂ , N
Gases such as H ₃ are F atoms, SiF ₄ , Si ₂ F ₆ , F ₂ , CF
₄ , HF and the like, and for Cl atom, HCl, Cl ₂ , SiCl _{4 and the} like can be mentioned as preferable examples.

Formation of Surface Layer After forming the photoconductive layer as described above, the surface layer is continuously formed in the same apparatus. The surface layer is formed by flowing a predetermined gas by the same method and procedure as the formation of the photoconductive layer and causing discharge for a predetermined time under a predetermined pressure and a predetermined discharge power.

The surface layer composed of the non-single-crystal silicon carbide film suitable for the present invention has a carbon content of 20% in the non-single-crystal silicon carbide film.
The flow rate ratio of the carbon-containing source gas to the silicon-containing source gas is increased so as to be at least 40 atomic%, the support temperature is set to 20 ° C. to 150 ° C., and the flow rate of the hydrogen gas is set to It is formed by making it less than when the photoconductive layer made of crystalline silicon carbide is formed.

Source gases suitable for depositing a surface layer composed of non-single-crystal silicon carbide that can achieve the object of the present invention are as follows.

The raw material gas of _{silicon, SiH 4, Si 2 H 6} , Si 3 H 8, ... SiF
Silane-based gas such as ₄ , Si ₂ F ₆ ... Can be used.

CH ₄ , C ₂ H ₆ ,, C ₃ H ₈ , ... C ₂ H ₄ ,, C ₃ H ₆ ,
Gases such as… C ₂ H ₂ ,… C ₆ H ₆ , CF ₄ ,… can be used.

Also, as a source gas containing both silicon and carbon,
Gases such as (CH ₃ ) ₄ Si… can be used.

The raw material gas may be used as a mixture of a plurality of types. Further, in the present invention, it is necessary to mix and use the source gas and the hydrogen gas in order to form a high quality non-single-crystal silicon carbide film.

In the present invention, as described above, halogen atoms such as F and Cl can be contained in the surface layer. As a gas for introducing these atoms, for F atoms, SiF ₄ , S
i ₂ F ₆ , F ₂ , HF etc., and for Cl atom, HCl, Cl ₂ , SiCl
_{4 and the} like are each preferably used.

The electrophotographic image forming member of the present invention is manufactured as described above.

Hereinafter, the present invention will be described more specifically based on Experimental Examples and Examples, but the present invention is not limited thereto.

<Experimental Example 1 and Comparative Experimental Example 1> Microwave plasma CVD as shown in FIGS. 6 and 7
Using the device (2.45GHz) and following the procedure detailed above,
Several kinds of non-single-crystal silicon carbide films for photoconductive layers were formed under the conditions for forming a deposited film within the scope of the present invention and the conditions for forming a deposited film outside the scope of the present invention as shown in Table 1.

The non-single crystal silicon carbide film was formed on Corning 7059 glass and on a Si wafer. 7059 glass and Si wafer have a cylindrical shape A with an outer diameter of φ108 mm, a length of 360 mm and a thickness of 5 mm.
l Set a 1 inch x 2 inch groove in the cylinder (sample holder). The sample holder set with 7059 glass and Si wafer was set at the position 605 shown in FIG.

The measurement results of the characteristics of the film-formed sample are shown in Table 2.

The items for measuring and evaluating the above properties were as follows.

(1) In order to confirm the composition and structure of the film, the amount of H in the film (and the IR intensity ratio) was quantified in accordance with a conventional general method using a Si wafer sample and FIR (Nicolet 60SXB).

The quantification of the amount of C in the film was measured using XMA (X-650 manufactured by Hitachi).

The quantification of the amount of graphite in the film was measured as follows.

A silicon wafer on which a non-single-crystal silicon carbide film is deposited is processed by a laser Raman spectrophotometer.
tometer, NR-11 manufactured by JASCO JAPAN SPECTROSCOPIC CO. LTD
00) and the Raman spectrum was measured.

The percentage of graphite structure is related to the TO mode (Transverse Optical mode) of silicon 480 cm ^-1 ~ 520c
The peak area between m ^-1 is 100%, the total peak area of appearing between 1450cm ^-1 ~1710cm ^-1 related to graphite was calculated by comparing the peak area of the TO mode of the silicon.

(2) The PDS method (Photo thermal deflector) was applied to the sample on 7059 glass to evaluate the quality of the formed film.
Tail state was measured by ion spectroscopy). PDS
Law is SEMICONDUCTORS AND SEMIMETALS Volume 21, P83 1
984 ACADEMIC PRESS, INC.

The measured extinction coefficient is It is represented by

The expansion of the tail state becomes smaller as the characteristic energy Ec becomes smaller.

That is, it can be said that the smaller the characteristic energy Ec, the better the film. Sample N in Table 2
o.001 to 014 correspond to the sample numbers in Table 1.

Deposited film by the deposited film forming method of the present invention, that is, 1 atomic% to 10 atomic% of hydrogen atom, 5 atomic% to 15 atomic% of carbon atom, CH / SiH = 0.01 to 0.05, and graphite structure is 1% or less. It was confirmed that each of the non-single-crystal silicon carbide films (Sample No. 011, 012, 013, 014) satisfying the above conditions had a characteristic energy Ec lower than that of the comparative experimental example and had better film quality.

<Comparative Experimental Example 2> A high frequency (hereinafter abbreviated as "RF") (13.56 MHz) glow discharge decomposition method was used on a glass substrate under the conditions of Sample No. 015 in Table 3 using the same sample holder as in Experimental Example 1. Then, a non-single-crystal silicon carbide film was formed.

FIG. 8 shows an apparatus for manufacturing an image forming member for electrophotography by the conventional RF glow discharge decomposition method used in this comparative experimental example.

In the figure, reference numeral 803 denotes the same aluminum sample holder used in Experimental Example 1.

First, the exhaust valve 805 was opened, and the reaction container 801 was exhausted by a vacuum pump (not shown).

Next, when the reading of the vacuum gauge 804 became 1 × 10 ⁻³ Torr, the raw material gas was introduced into the reaction vessel 801 through the supply valve 807.

The temperature of the cylindrical sample holder 803 installed in the reaction container 801 was controlled by the heater 806.

After the preparation for film formation is completed as described above,
RF power is introduced from the RF power source, and a deposited film is formed on the 1inch × 2inch Corning 7059 glass set by digging a groove on a cylindrical Al cylinder under the film formation conditions shown in Table 3. It was Table 4 shows the results of the evaluation of the characteristics.

As shown in Table 4, when a non-single-crystal silicon carbide film is formed by the RF glow discharge decomposition method, H
It can be seen that the amount increases and the graphite structure also increases.

<Experimental Example 2 and Comparative Experimental Example 3> FIGS. 6 and 7 similar to Experimental Example 1 and Comparative Experimental Example 1 above.
Using a microwave plasma CVD device as shown in the figure,
A non-single-crystal silicon carbide film for the surface layer was deposited.

The non-single crystal silicon carbide film was formed on Corning 7059 glass and on a Si wafer. The 7059 glass and Si wafer were set by digging a groove of 1 inch × 2 inch in a cylindrical Al cylinder. A cylindrical Al cylinder on which 7059 glass and a Si wafer were set was set at a position 605 shown in FIG. The non-single-crystal silicon carbide film was formed under the conditions shown in Table 5.

The characteristics of those samples were measured in Experimental Example 1 and Comparative Experimental Example
The measurement was performed in the same manner as described above. Table 6 shows the measurement results.

Sample Nos. 101 to 107 in Table 6 are sample Nos.
It corresponds to. From Table 6, samples prepared by the method for forming a deposited film for a surface layer of the present invention (Sample Nos. 105 to 107)
In each case, the characteristic energy Ec was lower than those of the others, and it was confirmed that the films had better film quality.

<Example 1 and Comparative Example 1> A non-single-crystal silicon carbide film under the same conditions as those of Experimental Examples 1 and 2 and Comparative Experimental Examples 1 and 2 was used as a support, having a length of 360 mm, an outer diameter of 108 mm, and a thickness of 5 mm. An aluminum cylinder was used to produce an electrophotographic image forming member comprising a photoconductive layer and a surface layer.

The layer configuration of the electrophotographic image forming member is such that a photoconductive layer (first layer) 103 made of non-single-crystal silicon carbide and a non-single-crystal silicon carbide are formed on a support 101 as shown in FIG. 1A. The surface layer (second layer) 104 is configured.

Regarding the electrophotographic image forming member in this example, the layer thickness of the photoconductive layer 103 was 25 μm, and the layer thickness of the surface layer 104 was 0.5 μm.
And manufactured under the conditions shown in Tables 7 and 8.

The electrophotographic image forming member produced as described above is modified so that the charging ability, dark decay, photosensitivity and ghost can be evaluated, and at the same time, 90 sheets (A-4) can be copied per minute. Evaluation was made with a copier (Canon NP8570 modified) that was modified to increase speed. For the pre-exposure, light having a wavelength of 700 m was irradiated at 20 erg. The charging ability, dark decay, light sensitivity and ghost were evaluated as follows.

The electrophotographic image forming member changes as shown in FIG. 9 (a) by corona charging and light exposure. 0 and P ₁ is the surface potential Vs a rise of the surface potential by corona charging. Next, it moves to the image exposure section (P ₂ ). During this period, the surface potential is darkly attenuated to Vd. Image exposure is performed at P ₂ , and the surface potential decays to Ve at P ₃ .

In this embodiment, the charging ability is the constant corona current
Evaluated by Vd, dark decay is Vs when surface potential Vd is constant
-Vd evaluated. The light sensitivity is the exposure (wavelength) required to achieve a surface potential Ve of 10% of Vd when the surface potential Vd is constant.
(500 nm light).

Further, the ghost was evaluated as follows. FIG. 9 (b)
Shows the change of the surface potential when the electrophotographic image forming member having the surface potential of 0 is subjected to corona charging stepwise. The electrophotographic imaging member is charged a plurality of times as it rotates beneath the charger. FIG. 9 (b) shows 1
A first charging Vg ₁ and a second charging Vg ₂ are shown. The ghost was evaluated by Vg ₂ −Vg ₁ .

Table 9 shows the above evaluation results. In the table, all the relative comparisons are performed, but it is shown that the larger the numerical value, the better the chargeability, the smaller the numerical value of the dark decay is better, and the smaller the numerical values of the light decay and ghost are, the better. ing.

From the above, the microwave plasma CVD of the present invention on the support
It was confirmed that the electrophotographic image forming member (Sample No. 211, 212, 213, 214) provided with the photoconductive layer and the surface layer by the method was significantly improved as compared with the comparative example, and especially for high speed electrophotographic images. It was proved that it was optimal as a forming member.

In addition, a conventional electrophotographic image forming member (Sample No.
201 to 210, 215), the "falling" of the surface potential was observed, but the electrophotographic image forming member of the present invention (Sample No. 21).
1,212,213,214), no “fall” of the surface potential was observed.

<Example 2 and Comparative Example 2> Prevention of charge injection on the support 101 as shown in FIG. 1-B using a non-single-crystal silicon carbide film under the same conditions as in Experimental Examples 1 and 2 and Comparative Experimental Examples 1 and 2. Layer (first layer) 102, photoconductive layer (second layer) 1
03 and an electrophotographic image forming member comprising the surface layer (third layer) 104 were produced.

In the image forming member for electrophotography according to the present embodiment, the layer thickness of the charge injection preventing layer 102 is 3 μm, and the layer thickness of the photoconductive layer 103 is
25 μm, the thickness of the surface layer 104 was 0.5 μm, and Table 10 and 11
A deposited film was produced under the conditions shown in the table.

The electrophotographic image forming member produced as described above,
Copy machine modified in the same manner as in Example 1 (Canon NP8570
In the above section, the charging ability, dark decay, light sensitivity, and ghost were evaluated. Table 12 shows the results.

As described above, the electrophotographic image forming member (Sample No. 311, 312, 313, 314) provided with the photoconductive layer and the surface layer by the microwave plasma CVD method of the present invention on the charge injection preventing layer is much improved as compared with the comparative example. Was confirmed.

In addition, a conventional electrophotographic image forming member (Sample No. 30)
1 to 310, 315), "falling" of the surface potential was observed, but the electrophotographic image forming member of the present invention (Sample No. 311).
314), no “fall” of the surface potential was observed.

<Example 3 and Comparative Example 3> Using a non-single-crystal silicon carbide film under the same conditions as in Experimental Examples 1 and 2 and Comparative Experimental Example 1, a charge injection preventing layer (first layer) 102 An electrophotographic image forming member including a layer (second layer) 103 and a surface layer (third layer) 104 was prepared.

In the image forming member for electrophotography according to the present embodiment, the layer thickness of the charge injection preventing layer 102 is 3 μm, and the layer thickness of the photoconductive layer 103 is
The thickness of the surface layer 104 was 0.5 μm, and a deposited film was produced under the conditions shown in Table 13.

The electrophotographic image forming member produced as described above,
Copy machine modified in the same manner as in Example 1 (Canon NP8570
In the above section, the charging ability, dark decay, light sensitivity, and ghost were evaluated. Table 14 shows the results.

As described above, the electrophotographic image forming member (Sample No. 411, 412, 413, 414) in which the photoconductive layer and the surface layer by the microwave plasma CVD method of the present invention are provided on the charge injection preventing layer is significantly improved as compared with the comparative example. Was confirmed.

In addition, a conventional electrophotographic image forming member (Sample No. 40
1 to 410), the "falling" of the surface potential was observed, but the electrophotographic image forming member (Sample No. 411 to 4) of the present invention was observed.
In 14), no “fall” of the surface potential was observed.

Example 4 and Comparative Example 4 Using a non-single-crystal silicon carbide film under the same conditions as in Experimental Examples 1 and 2 and Comparative Experimental Example 1, a charge injection preventing layer (first layer) 102 and a photoconductive layer were formed on a support 101. An electrophotographic image forming member including a layer (second layer) 103 and a surface layer (third layer) 104 was prepared.

In the image forming member for electrophotography according to the present embodiment, the layer thickness of the charge injection preventing layer 102 is 3 μm, and the layer thickness of the photoconductive layer 103 is
The deposited film was manufactured under the conditions shown in Table 15 with a thickness of 25 μm and a thickness of the surface layer 104 of 0.5 μm.

The electrophotographic image forming member produced as described above,
The charging ability, dark decay, photosensitivity and ghost were evaluated using a copying machine (Canon NP8570 modified) which was modified in the same manner as in Example 1 and was modified to reverse the charging polarity. Result 16
It is shown in the table.

As described above, the electrophotographic image forming member (Sample No. 511, 512, 513, 514) provided with the photoconductive layer and the surface layer by the microwave plasma CVD method of the present invention on the charge injection preventing layer is significantly improved as compared with the comparative example. Was confirmed.

In addition, a conventional electrophotographic image forming member (Sample No. 50
1 to 510), the "falling" of the surface potential was observed, but the electrophotographic image forming member (Sample No. 511 to 5) of the present invention was observed.
In 14), no “fall” of the surface potential was observed.

<Example 5 and Comparative Example 5> Under the conditions shown in Table 17, a charge injection preventing layer (first layer) 102, a photoconductive layer (second layer) 103, and a surface layer (third layer) were formed on a support 101.
An electrophotographic image forming member consisting of layer 104) was prepared.

In the image forming member for electrophotography according to the present embodiment, the layer thickness of the charge injection preventing layer 102 is 3 μm, and the layer thickness of the photoconductive layer 103 is
The deposited film was manufactured under the conditions shown in Table 17 with a thickness of 25 μm and a thickness of the surface layer 104 of 0.5 μm.

The electrophotographic image forming member produced as described above,
Copy machine modified in the same manner as in Example 1 (Canon NP8570
In the above section, the charging ability, dark decay, light sensitivity, and ghost were evaluated. Table 18 shows the results.

As can be seen from Table 18, an electrophotographic image forming member provided with a photoconductive layer and a surface layer by the microwave plasma CVD method of the present invention on the charge injection preventing layer (Sample Nos. 605, 606, 607)
It was confirmed that was significantly improved as compared with the comparative example.

<Example 6 and Comparative Example 6> Using a plasma CVD method, a charge injection preventing layer (first layer) 102 and a photoconductive layer (second layer) 10 were formed on a support under the conditions shown in Table 19.
3 and an electrophotographic image forming member comprising the surface layer (third layer) 104.

In the electrophotographic image forming member in this embodiment, the thickness of the charge injection preventing layer 102 is 3 μm, the thickness of the non-single-crystal silicon carbide photoconductive layer 103 is 25 μm, and the thickness of the surface layer 104 is 0.5 μm.
μm, and a deposited film was produced under the conditions shown in Table 19.

The electrophotographic image forming member formed as described above,
Copy machine modified in the same manner as in Example 4 (Canon NP8570
In the above section, the charging ability, dark decay, light sensitivity, and ghost were evaluated. The results are shown in Table 20.

As described above, the electrophotographic image forming member (Sample No. 705, 706, 707) provided with the photoconductive layer and the surface layer by the microwave plasma CVD method of the present invention on the charge injection preventing layer was remarkably improved as compared with the others. Was confirmed.

According to the electrophotographic image forming member formed of the non-single-crystal silicon carbide of the present invention formed by the microwave plasma CVD method of the present invention, when this is used in a higher-speed electrophotographic apparatus Also, in regard to charging ability, dark decay, photosensitivity, ghost, and the like, characteristics far superior to those of an electrophotographic image forming member composed of conventional non-single-crystal silicon carbide can be obtained.

Further, according to the electrophotographic image forming member of the present invention in which the photoconductive layer and the surface layer are laminated, it is possible to further reduce the fall of the surface potential which occurs in a higher-speed electrophotographic apparatus.

[Brief description of the drawings]

FIG. 1 is a diagram showing a schematic cross section of an electrophotographic image forming member of the present invention. In the figure, 101 ... support, 102 ...
Charge injection preventing layer 103 photoconductive layer 104 surface layer 2 and 3 show microwave plasma according to the prior art.
3 shows a light decay curve of a surface potential with respect to time of an electrophotographic image forming member by a CVD method. 4 and 5 show a microwave plasma CV according to the present invention.
3 shows a light decay curve of the surface potential of an electrophotographic image forming member according to Method D. 6 and 7 show a microwave plasma according to the present invention.
FIG. 3 is a schematic explanatory view of a side cross-sectional view and a plan cross-sectional view of a deposition film forming apparatus using a CVD method. In the figure, 601, 701 ... Reactor vessel, 602, 702 ... Microwave introduction window, 603, 703 ... Waveguide, 604, 704 ... Exhaust pipe, 605, 705 ... Cylindrical support, 606, 706 ... Discharge space,
607,707 …… Supporter heating heater, 608,708 …… Gas introduction pipe, 609,709 …… Movement flange, 610,710 …… Rotating motor, 611,711 …… Gas introduction pipe, 612 ……
Bias power supply, 608 ', 708' ... Gas discharge nozzle. FIG. 8 shows a side sectional view of an apparatus for manufacturing an electrophotographic image forming member by a conventional RF glow discharge decomposition method in a comparative example. In the figure, 801 ... Reaction container, 802 ... Gas introduction pipe, 803 ... Cylindrical Al cylinder, 804 ... Vacuum gauge, 805
... exhaust valve, 806 ... heater, 807 ... source gas supply valve. 9 (a) and 9 (b) are schematic explanatory views of the evaluation method of the electrophotographic image forming member in the present invention.

 ───────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-85752 (JP, A) JP-A-63-123051 (JP, A) JP-A-1-133060 (JP, A) JP-A-1- 40837 (JP, A)

Claims (2)

(57) [Claims] 1. An electrophotographic image forming member comprising at least a photoconductive layer and a surface layer laminated on a support, wherein the photoconductive layer contains 1 to 10 atomic% of hydrogen atoms and carbon It is composed of non-single-crystal silicon carbide containing 5 to 15 atomic% of atoms and having a ratio of the C—H bond stretching mode and the Si—H bond stretching mode in the infrared absorption spectrum of 0.01 to 0.05. And a layer structure not containing a graphite structure or containing 1% or less per unit volume, wherein the surface layer contains 50 atom% to 70 atom% of hydrogen atoms and 20 atom% of carbon atoms.
Composed of non-single-crystal silicon carbide containing up to 40 atomic%,
An image forming member for electrophotography, which has a layered structure containing no graphite structure or containing 1% or less per unit volume. 2. The image forming member for electrophotography according to claim 1, further comprising a charge injection preventing layer between the support and the photoconductive layer.