JPS62258468A - Photoreceptive member having improved image forming function - Google Patents

Abstract

PURPOSE:To maintain stable spectral sensitivity by setting the difference in refractive index between the surface layer consisting of an amorphous silicon material and photosensitive layer at a prescribed value or below to increase the concn. of nitrogen atoms toward a free surface side. CONSTITUTION:The nitrogen atoms are distributed in the surface layer to such a state as to leave the difference (DELTAn) to the negligible extent in the processing of image formation between the refractive index of the surface layer 204 and the refractive index of the photosensitive layer 203 at the boundary between the layer 204 and the layer 203 and to increase the distribution concn. of the nitrogen atoms beginning from the boundary toward the free surface 207 side of the surface layer. The reflection of light at the boundary 208 is considerably decreased and the problems arising from the relation of the surface layer with the photosensitive layer are solved. The always stable image having high quality is obtd. with the above-mentioned photoreceptive member without posing problems such as after-image and in sensitivity in the stage of using said member as an electrophotographic sensitive material for high-speed continuous image formation. The range of DELTAn is preferably DELTAn<=0.62.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a light-receiving member suitable for high-speed image forming systems such as high-speed copying systems, facsimile systems, and printer systems.

[Description of prior art]

Conventionally, various types of light-receiving members have been proposed for use in electrophotographic photoreceptors, etc., but among them, there are materials whose photosensitivity region is highly compatible with the emission wavelength region of the light source used for image formation. For example, JP-A-1) E54-86 has a high Vickers hardness and poses no practical problem of pollution.
Amorphous materials based on silicon atoms (Sl), so-called amorphous silicon (hereinafter referred to as ``a
It is written as 81 J. ) is attracting attention. And such a light receiving member is a-
8l, in a preferred state, a-8i (a-8i) containing at least one of a hydrogen atom (H) or a halogen atom (X)
Hereinafter, it will be expressed as [, -3t(n, x)J. ), in order to expand the design tolerance range, it is possible to prevent charge from being injected into the photosensitive layer when the photosensitive layer is subjected to charging treatment. As a layer that effectively blocks the photosensitive layer, and as a layer that further improves the moisture resistance, resistance to continuous repeated use, electrical pressure resistance, use environment characteristics, durability, etc. of the photosensitive layer and improves image quality.
In the laminated structure with the S l (Hr It is what it is.

By the way, regarding the surface layer, it is required to exhibit various functions as mentioned above, and various proposals have been made, and the preferred ones are oxygen atoms (0) and carbon atoms (C ) and nitrogen atoms (N) at a relatively high concentration.
(H,X) (hereinafter ra-8l(0,C,N)(H,X
) J. ) is known.

However, although the surface layer composed of a-s+ (0, C, N) (H, There are several challenges that preclude improvements in obtaining high-speed, high-quality images.

First, it is very difficult to mass-produce a surface layer with uniform thickness over the entire area with good productivity and stable quality, and therefore in many cases the surface layer is non-uniform. The result is a thick layer. In addition, a light-receiving member having such a surface layer is used repeatedly in any case, and in the case of electrophotographic copying, for example, due to rubbing with paper, toner, developing device, cleaner, etc. The surface is gradually abraded with local rubbing force depending on the location, and the surface layer may become uneven in layer thickness.

The problem of non-uniformity or non-uniformity in the thickness of the surface layer is that when there is an interface that causes reflection between the surface layer and the photosensitive layer, the reflectance varies depending on the location on the light-receiving member. This causes non-uniformity, which causes non-uniform sensitivity and uneven density in images. This is a serious problem especially in electrophotography.

Furthermore, since the surface layer is required to have high resistance in some respects, it may generate a residual potential when used repeatedly, especially when used repeatedly at high speeds. There is a problem in that the image quality deteriorates as the process is repeated. Furthermore, when used continuously for a long period of time, there is another problem in that the function of the surface layer as an image defect prevention layer deteriorates, resulting in the occurrence of image defects.

In addition, in the light receiving member having the above-mentioned surface layer,
Regardless of its preferred form, reflected light often occurs at the surface of the surface layer and also at the interface between the surface layer and the underlying photosensitive layer, in which case The reflectance of these reflected lights sometimes changes greatly depending on the wavelength of the irradiated light, the layer thickness of the surface layer, and the refractive index of the surface layer 5, and as a result, the color sensitivity of the photosensitive layer becomes uneven, resulting in There is a problem in that the image becomes uneven accordingly.

These various problems related to the surface layer could be ignored in some cases due to the lack of thin slicing in conventional high-speed copying systems, but in high-speed copying systems that use coherent light sources such as lasers. This problem is important in high-speed continuous image forming systems such as , facsimile systems, and glinter systems, and especially in digital high-speed continuous image systems, and a solution is required.

For these reasons, in order to solve the above problems,
From the viewpoint of matching the refractive indices of both layers at the interface between the surface layer and the photosensitive layer to eliminate light reflection at the interface, the composition of the surface layer at the interface is made to closely resemble or match the composition of the photosensitive layer. A method of widening the optical bandgap (Egopt) of the surface layer from the viewpoint of efficiently allowing light to enter the photosensitive layer, and a method that combines these methods have been proposed.

However, none of these approaches is sufficient to provide an optimal light-receiving member that satisfies the demands of high-speed continuous imaging systems, and there are problems that need to be resolved. That is, the main problems include afterimages and sensitivity problems, which are considered to be caused by photocarriers generated by absorption of light at the interface between the surface layer and the photosensitive layer.

On the other hand, as digital high-speed continuous image forming systems gradually become widespread, it has become a social demand to provide a light-receiving member that can fully meet the demands of the system and consistently perform its function as a light-receiving member. be.

[Purpose of the invention]

The present invention solves the above-mentioned problems with regard to a light-receiving member used in electrophotographic photoreceptors, etc., which does not cause problems even in high-speed continuous image forming systems, and which satisfies the above-mentioned requirements. The main purpose is to provide

Another object of the present invention is to provide a light-receiving member that maintains stable spectral sensitivity at all times and does not cause any problems regarding image retention or sensitivity even during high-speed continuous image formation. It is in.

[Structure of the invention]

The present inventors have solved the above-mentioned problems in the conventional light-receiving members used in electrophotographic photoreceptors, etc., and furthermore, in order to meet the above-mentioned demands, the present inventors have used various methods from various angles to achieve the above-mentioned object of the present invention. I did a lot of research.

That is, the present inventor believes that the above-mentioned problems with conventional light-receiving members used in electrophotographic photoreceptors, etc. are ultimately caused by the non-uniformity of the thickness of the surface layer caused by the manufacturing process and by repeated use. It was experimentally confirmed that the main causes were non-uniformity and light reflection at the interface between the surface layer and the photosensitive layer, and the key to solving these problems was not only the thickness of the surface layer but also the The study was conducted from the viewpoint that the surface layer is located at the interface with the photosensitive layer.

Incidentally, the present inventors have found that when the reflected light from the surface (free surface) of the surface layer interferes with the reflected light from the interface between the surface layer and the photosensitive layer, the thickness of the surface layer and the relationship between the surface layer and the photosensitive layer are It was confirmed that the above-mentioned phenomenon exists in relation to the refractive index of the material, the layer quality of the surface layer, and the photoconductivity.

That is, the refractive index of the surface layer is n, the layer thickness of the surface layer is d, the wavelength of the incident light is λ, and m and m' are integers (112, "
), then 2 n d = (m −' )λ
When , the reflected light is small, and when 2nd=m'λ, the reflected light is large.

Specifically, the surface layer is a-S i N (H,X)
When we consider the case where n = 2, when the incident light is from a semiconductor laser or the like with a wavelength of 800 ohm, when d is 1000λ, 3000X, or 5000^, there is almost no light reflection. , d is 2000
If there are 4oooX and 6000 people, the occurrence of light reflection will be as low as 30%.

Similarly, when the incident light has a wavelength of 550 ohm (6 values of visible light), d is 690X.

If d is 2060, 344o'';, the occurrence of light reflection is extremely small, but if d is 1380, 2750, 413
If it is 0λ..., the occurrence of light reflection will be about 30%.

As is clear from the above, in conventional light-receiving members, as the thickness of the surface layer increases, the reflectance increases and decreases accordingly. This change in reflectance (0%4+30%) causes the aforementioned image unevenness.

Based on the facts found in this way, the present inventors believe that it is possible to reduce or, if possible, eliminate light reflection at the interface between the surface layer and the photosensitive layer. If the layer thickness of the surface layer of the light-receiving member becomes uneven due to repeated use, the above-mentioned problems caused by the uneven state or non-uniformity of the layer thickness of the surface layer may occur. We have now obtained knowledge that can solve this problem, as well as the other problems mentioned above.

Based on this knowledge, the present inventor proposed that in order to reduce or eliminate the reflection of light at the interface between the surface layer and the photosensitive layer in a light-receiving member, the distribution state of the constituent components of the surface layer should be changed. I tried.

That is, the present inventors have developed a light-receiving member having a surface layer composed of a-3IN(H,X), in which the surface layer contains nitrogen atoms (N) at a relatively high concentration. H
, X), the following facts were found.

First, regarding the nitrogen atoms contained in the surface layer, a high concentration region is provided on the free surface side and a low concentration region is provided on the photosensitive layer side, so that the distribution concentration in the layer thickness direction changes discontinuously. Since the matching of the refractive index at the interface between the surface layer and the photosensitive layer is poor, in some cases, even spectral sensitivity unevenness occurs due to the poor matching of the refractive index within the surface layer.

Also, unlike the above case, in order to match the refractive index at the interface between the photosensitive layer and the surface layer and increase the amount of light incident on the photosensitive layer, the distribution of nitrogen atoms is reduced toward the photosensitive layer side, and the surface layer is When the distribution concentration of nitrogen atoms changes continuously so that the concentration of nitrogen atoms increases on the free surface side of the layer, the occurrence of light reflection at the interface between the surface layer and the photosensitive layer is different from the above case. Although the difference is somewhat reduced, an undesirable region with a narrow and heavy Egopt layer is formed in the interface region of the surface layer, and therefore photocarriers generated by light absorption in this region are restrained in this region, resulting in poor image quality. This results in a decrease in

In consideration of the facts thus revealed, the present inventors determined the distribution state of nitrogen atoms in the surface layer at the interface 208 between the surface layer 204 and the photosensitive layer 203, as schematically shown in FIG. A negligible rudder (Δn) is left between the refractive index (n) of the photosensitive layer 204 and the refractive index (n, ) of the photosensitive layer 203, and the free surface 207 of the surface layer starts at the interface. When the distribution concentration of nitrogen atoms increases toward the side, the occurrence of light reflection at the interface 208 is extremely reduced, and the various problems described above due to the relationship between the surface layer and the photosensitive layer are resolved. When used as an electrophotographic photoreceptor for high-speed continuous image formation, a light-receiving member having a surface layer that explodes and hides is stable at all times without causing the above-mentioned afterimage problems, sensitivity problems, etc. We obtained the knowledge that desirable high-quality images can be obtained by using this method.

The range of the difference (Δn) shown in FIG.
It was confirmed that n≦0.62, more preferably Δn≦0.4.

The present invention has been completed based on this confirmed fact, and provides a light-receiving member used for electrophotography, etc., which has at least a photosensitive layer and a surface layer on a support. is composed of an amorphous material having a silicon atom as a base material, containing a nitrogen atom, and optionally containing one or more selected from hydrogen atoms, halogen atoms, carbon atoms, and oxygen atoms, and where the nitrogen atoms are , leaving a negligible difference between the refractive index of the surface layer and the refractive index of the photosensitive layer at the interface between the surface layer and the photosensitive layer, starting at the interface and # The gist of this is that it is distributed in the surface layer so that the concentration increases toward the free surface side of the bulletin surface layer.

The above-mentioned experiments 1 to 3 conducted by the present inventors to determine the range of Δn shown in FIG. 2 are as described below.

Experiment 1 Relationship between the nitrogen atomic weight in the surface layer and the refractive index and optical bandgap width of the layer (1) Sample creation To measure the refractive index and optical bandgap width, the composition of silicon atoms and nitrogen atoms was changed. The resulting films were each deposited on a glass substrate (trade name: Corning 7059).

At this time, a known apparatus using a glow discharge method was used as a deposited layer forming apparatus.

The glass substrate is carried into the deposited film forming apparatus, placed and fixed on the holding means, and the system internal pressure (i-1OTor
The pressure was reduced to below r. At the same time, the glass substrate was heated by a substrate heater.

At this time, the glass substrate was maintained at a predetermined temperature by a temperature measuring means such as a thermocouple so that the manufacturing temperature would not change due to differences in the substrate.

When the temperature of the glass substrate became constant, the gas introduction pulp was opened, and the mass flow controller was set so that each raw material gas had the required flow rate. When the gas flow rate became stable, the power supply was turned on to generate a glow discharge in the deposition space and perform a film deposition operation.

Regarding the deposition time of the deposited film, the thickness of the deposited film to be formed is such that there are no errors due to light absorption during film formation, and there is no influence of the material of the substrate, and the wavelength dependence of the light absorption coefficient is determined. The thickness was adjusted so that it could be measured.

After a deposited film having the required composition was formed as described above, the discharge was turned off, the sealant was closed, the introduction of gas was stopped, and the substrate was cooled in a vacuum.

When the substrate temperature dropped to room temperature, the substrate with the formed deposited film was removed from the holding means and carried out of the system.

(2) Measurement The following measurements were performed on the sample deposited on the glass substrate in (1) above.

Measurement of refractive index In the preparation of the sample (1), Corning Co., Ltd. 7
An a-8iN film was deposited on 059 glass to a thickness of 1 μm.

A 7059 glass substrate with an a-8iN film deposited on its surface was set in a spectrophotometer (Model 330 manufactured by Hitachi, Ltd.), and the transmittance at each wavelength (400 nm to 2600 nm) was measured.

The results are schematically shown in FIG. 3(A).

The transmittance changes p-periodically due to interference.

The refractive index is determined at the minimum point (4) between the two points (B and C) where the transmittance is 100% in Figure 3 (4).

If the transmittance at the minimum point (point A) is T%, then the relationship expressed by the following equation (1) holds true between the transmittance and the refractive index.

Then, calculate the refractive index n of j)a-'91 using equation (1).

n: refractive index of a-31N film, nip: refractive index of 7059 glass (1,530) CB) Measurement of optical band gap (Egopt)a
-The 7059 glass on which the SiN film was deposited was set in a spectrophotometer (Hitachi Model 330), and each wavelength (30
The absorbance (the logarithm of the transmittance with the opposite sign) was measured with respect to 0 nm to 11000 nm).

The results are schematically shown in the third) figure.

The following equation (2) holds between the absorbance and the extinction coefficient of a-8iN.

However, [) = −log’f D: Absorbance e: 2.718281828- d: thickness of a-8iN layer α: extinction coefficient of a-8iN layer Then, calculate the extinction coefficient according to formula C2).

Further, the optical bandgap is determined from the intersection of the following equation (3) with the X axis.

Vabu = B (E-E)) ... Decoy ...
...(3) α: extinction coefficient, h: Norank constant, B: frequency of irradiation light, B: proportionality constant, E: energy of irradiation source, E: optical band gap, which schematically shows equation (3). and as shown in Figure 3 (C).

(3) Results The results of the measurement using (2) = (4) and (2) -CB) K are summarized in Figure 30.

In FIG. 30, the left vertical axis represents the optical bandgap (
Egopt ) (eV), and the right vertical axis is the refractive index (
n), and the horizontal axis represents the nitrogen atomic weight (N
/Si+N) (atomic%).

The following can be understood from FIG. 3a.

That is, in order to increase the degree of light reaching the photosensitive layer, the optical band gap (Egopt) of the surface layer should be as large as possible, but in the case of an amorphous material containing silicon atoms, In general, the refractive index (n) decreases as Egopt increases. The refractive index of the a-8i (H,X) photosensitive layer therein is approximately 3.
．． It is about 2 to 3.5.

Therefore, it can be seen that the refractive index matching at the interface between the photosensitive layer and the surface layer deteriorates as ggopt increases. However, if the refractive index is matched at the interface between the photosensitive layer and the surface layer, Egopt in the region of the surface layer on the photosensitive layer side will be small, and the light absorption rate in the surface layer will increase. In addition to reducing the amount of light incident on the photosensitive layer, photocarriers generated by light absorption in the photosensitive layer side region of the surface layer are restrained in that region, resulting in the problem of generation of residual potential.

Considering the above, from the relationship between the optical band gear lag, refractive index, and nitrogen atomic weight shown in FIG. 30, Δn in FIG.
When considering the upper limit of the part, it was found that the difference between the refractive index of the surface layer at the interface with the photosensitive layer and the refractive index of the photosensitive layer is preferably Δn≦0.62, preferably Δn≦0.62. It was found that Δn≦0.43.

Experiment 2 Relationship between the refractive index at the interface between the surface layer and the photosensitive layer and the difference in image density Ten aluminum cylinders each with diameters of 80 mm and 108 mm were prepared. For 10 aluminum cylinders with a diameter of 80i+xφ, the sample numbers are ff1l to 10,
For the 10 aluminum cylinders with a diameter of 108 mm, the sample numbers were 1lhll to 20. Regarding the aluminum cylinders ff11 to ff10 having a diameter of 80 mm, layers were formed on the surface of each cylinder in the following order: charge injection blocking layer/photosensitive layer/surface layer. In addition, for the aluminum cylinders I&Lll to 20 with a diameter of 108+otφ, a long wavelength light absorption layer/charge injection blocking layer/
Layers were formed in the order of photosensitive layer/surface layer.

The long wavelength light absorbing layer, charge injection blocking layer, and photosensitive layer were formed according to the conditions listed in Table A, and the conditions and procedures for forming these layers were the same. Moreover, the surface layer formation was performed according to the conditions described in Table B.

Table A Table B [However, in creating the surface layer, the composition ratio of the raw material gas was changed by controlling the flow rate of the raw material gas using a computer according to a predetermined flow rate curve using a mass flow controller. ] The difference in refractive index (Δn) at the interface between the photosensitive layer and the surface layer and the difference in image density (ΔD) were measured for each of Sample Arashi 1 to 20 having the predetermined layer configuration thus created.

The measured value of Δn was determined in the same manner as in Experiment 1 using a refractive index measurement sample prepared under the same conditions as the photosensitive layer forming conditions employed in Experiment 1 to measure the refractive index.

Measurement of ΔD was carried out using a Canon Co., Ltd. copier NP 7550 for sample sizes 1 to 10, and a Canon Co., Ltd. laser copier NP for sample sizes 11 to 20.
9030, and a standard grayscale chart manufactured by Eastman Kodak Company was used as a test chart.

The measurement results of Δn and ΔD for samples 1 to 20 are summarized in FIG. 4.

From the results shown in FIG. 4, it is clear that the difference Δn between the refractive index at the interface between the surface layer and the photosensitive layer and the refractive index of the photosensitive layer is preferably ≦0.
62, preferably ≦0.43, which confirms the value stated in Experiment 1.

Experiment 3 For the samples rlhl to 2o created in Experiment 2, in addition to the measurement of Δn in Experiment 2, the optical band gap difference (ΔEgopt) and sensitivity (d/@rg) between the surface layer and the photosensitive layer were measured. went.

The measurement of ΔEgopt was performed according to the method in Experiment 1, and the sensitivity was measured according to the sensitivity measurement method commonly employed in the relevant technical field.

The measurement results were summarized in a three-dimensional graph, and Δn, ΔEgo p and sensitivity values for each sample were read from the graph.

The results are summarized in Table 0 below. Note that the sensitivity is expressed as a relative sensitivity with the sensitivity of sample t1 and sample NfLll as 1, respectively. However, it goes without saying that whether it is sample-1 or sample-1, even if the sensitivity is set to 1, they are sufficiently usable in a normal speed copying system.

Table C Judging from the results shown in Table C and the results shown in Figure 4 above,
Δn is 0.62 or less, and ΔEgopt is 0.0.
If it is set to 1 or more, the image density difference will be 0.05 or less,
It is understood that it can sufficiently withstand the expression of a high level of texture and has an advantage in relative sensitivity.

The above is a -SiN (H,X) on the photosensitive floor.
A light-receiving member having a surface layer composed of If the concentration is distributed in the surface layer such that the concentration starts at the interface and increases toward the free surface side of the surface layer, leaving a difference of Δn≦0.62 between the This refers to the efficient and effective performance of desired functions in a high-speed continuous copying system.

The C-receiving member provided by the present invention has characteristics in its surface layer as described above, and other constituent layers including the support and the photosensitive layer may be optional depending on the purpose of use. It is up to you to choose.

Therefore, typical examples of the layer structure of the light-receiving member of the present invention will be described below, but the light-receiving member of the present invention is not limited thereto.

FIGS. 1A to 1C are diagrams schematically showing typical examples of the layer structure of the light-receiving member of the present invention for use in electrophotography.

In the example shown in FIG. 1(A), this I
It was installed in I.

In the example shown in FIG. 2(B), a long wavelength light absorption layer 105, a charge injection blocking layer 102, a photosensitive layer 103, and a surface layer 104 are provided in this order on a support 101. Long wavelength light absorption layer 105 and charge injection blocking layer 102
You can also change the order.

In the example shown in FIG. 1(C), a layer 106 having both a charge injection blocking layer and a long wavelength light absorption layer, a photosensitive layer 103, and a surface layer 104 are provided in this order on a support 101. .

26- The support 101 used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include Ni and Cr.

AI, Mo, Au, Nb, Tm, V, Ti, Pt,
Examples include metals such as Pb and alloys thereof, such as stainless steel.

Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, and polyimide, glass, ceramic, paper, etc. .

Preferably, at least one surface of these electrically insulating supports is conductively treated, and a light-receiving layer is provided on the conductively treated surface side.

For example, if it is glass, Ni is applied to its surface.

Cr, ^J, Mo, Au, Ir, Nb, Ta, V, TI
, Pi, Pd.

In,O,,8nO,,ITQ(In,O,-4-sn
Conductivity can be imparted by providing a thin film consisting of materials such as Ni, Cr, A/, Ag, Pb, Zn, etc. in the case of synthetic resin films such as polyester films.
Ni.

A thin film of a metal such as Au, Mo, Ir, Nb, Ta, V, TJ, Pi, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is treated with a linate treatment with the metal. imparts conductivity to The shape of the support is a plate with a smooth or uneven surface, an endless belt,
The thickness of the light-receiving member is appropriately determined so as to form a light-receiving member of the desired shape. However, if flexibility is required as a light-receiving member, it may be used as a support. It can be made as thin as possible within the range where its functions are fully demonstrated. However, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 1Oμ or more.

In the light-receiving member of the present invention, the support 101 and the photosensitive layer 1
The charge injection blocking layer 102 provided between the photosensitive layer 103 and the photosensitive layer 103 from the support side when the photosensitive layer 103 is subjected to charging treatment.
The charge injection blocking layer 102 is a layer provided to prevent charges from being injected into the a-sBH,
X), or polycrystalline silicon (rpoly-siJ
It is called. ), or so-called non-single-crystal silicon (hereinafter referred to as "Non-S"), such as materials containing both.
- Classified as 84. ], containing a p-type impurity or an n-type impurity, and at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms as necessary.

Examples of p-type impurities include atoms belonging to so-called group 1 of the periodic table (group Ⅰ atoms), and examples of n-type impurities include atoms belonging to so-called group V of the periodic table (group V atoms). .

Specifically, the Group Ⅰ atoms contained in the charge injection blocking layer include B (boron), AI (alunium)-G
Although a (gallium), IO (indium), TIJ (thallium), etc. can be used, B and Ga are particularly preferred. Also, specific examples of Group V atoms include P (phosphorus), As (arsenic), and sb (antimony).
, B1 (bismuth), etc. can be used, but particularly preferred are P and As.

The amount of Group 1 atoms or Group V atoms contained in the charge injection blocking layer is 3 to 5 x 10'a toml.
c ppm, preferably 50 to I x 10'a
tomlcppmzR suitably I x 10"~5 x
It is desirable to set it to 10' atomic ppm.

Furthermore, by containing at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms in the charge injection blocking layer, adhesion to the support or other layers is improved, and the optical band gap is improved. The effect of adjusting (Ngopt) is achieved. The amount of these atoms contained in the charge injection blocking layer 102 is preferably 0,
OO1~3QatomicX, preferably 0.002~2fS atomic%, optimally Q, QQ3~20 atomic%.

Furthermore, the layer thickness of the charge injection blocking layer of the light receiving member of the present invention is as follows:
Preferably 30λ to 10μ, more preferably.

By the way, as mentioned above, the charge injection blocking layer in the present invention comprises either a group (I) atom or a group V atom (M),
Non-81 (H
,X) (hereinafter referred to as "NonNon-8l,C,N)(
H,X). ], i.e., m-8m-8l, C,
N)(H,X) or poly-81M(0,C,N)(
There are various methods for forming a layer composed of poly-81 (0, C, N) (T (, For example, the following methods can be cited.

One method is to raise the substrate temperature to a high temperature, specifically 400℃.
In this method, the temperature is set at ~450° C., and a film is deposited on the substrate by plasma CVD.

Another method involves first forming an amorphous film on the surface of the substrate, that is, plasma CVD on the substrate at a substrate temperature of about 250°C.
In this method, a film is formed by a method, and the amorphous film is annealed to form a poly. The annealing treatment is performed by heating the substrate to 400 to 450° C. for about 20 minutes or by irradiating it with laser light for about 20 minutes.

The photosensitive layer of the light-receiving member of the present invention is a-8i (H).

X) or a-81 (containing Ga, 8n as necessary)
H,
X) Written as J. ], and has a light guiding property, and the M layer further contains at least one kind selected from group 1 atoms, group V atoms, and/or oxygen atoms, carbon atoms, and dependent atoms. It can be made to contain.

Specific examples of the halogen atom (X) contained in the photosensitive layer include fluorine, chlorine, odor, and iodine.
Particularly preferred are fluorine and chlorine. The amount of hydrogen atoms CH) or the amount of halogen atoms (X) contained in the photosensitive layer, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 1 to 40.
atomic%, more preferably 5-3Q atomic
It is desirable to set it to c%.

Further, the purpose of containing Group 1 atoms or Group V atoms in the photosensitive layer is to control the conductivity or amount of conduction of the photosensitive layer. As such Group II atoms and Group V atoms, the same atoms as those contained in the charge injection blocking layer described above can be used, but when they are contained in the photosensitive layer, they are included in the charge injection blocking layer. Contains a substance of opposite polarity to that contained in the charge injection blocking layer, or contains a substance of the same polarity as that contained in the charge injection blocking layer in an amount much smaller than that contained in the charge injection blocking layer. You can force it.

The amount of group
tomlc ppm, preferably 5×1O−1 to 5
×IQ” atomic ppm, optimally I
It is desirable to set it as 0-'' to 2 x 10'' atomic ppm.

The purpose of containing at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms in the photosensitive layer is to increase the dark resistance of the photosensitive layer and to improve the film quality of the photosensitive layer. be. The amount of these atoms contained in the photosensitive layer is preferably l x 10-'
~5Qajomic%, more preferably Id, 2X
10-' to 40 atomic%, optimally 3X
It is desirable to set it to 10-B to 3Q atomic%.

Furthermore, in the light-receiving member of the present invention, the layer thickness of the photosensitive layer is
This is one of the important factors to efficiently achieve the object of the present invention, and it is necessary to pay sufficient attention when designing the light-receiving member so that the desired characteristics are imparted to the light-receiving member. The thickness is preferably 3 to 100μ, more preferably 5 to 80μ, and suitably 7 to 50μ.

The surface layer 104 of the light-receiving member of the present invention has specific contents as described above, and is the % image point of the present invention.
A free surface 11n is provided on the photosensitive layer 103 described above.
107.

The surface layer 104 improves the characteristics normally required for a light-receiving member, such as moisture resistance, continuous edge reversing characteristics, electrical pressure resistance, usage environment characteristics, and durability, and also improves the characteristics of the free surface 107. In addition to reducing the reflection of incident light and increasing transmittance, it also reduces the absorption coefficient of light near the interface between the surface layer and the photosensitive layer, thereby significantly reducing the density of photocarriers generated there. It is something that plays.

When the light-receiving member of the present invention is applied as an electrophotographic photoreceptor, the surface layer 104 not only performs the above-mentioned functions, but also performs the same functions as conventional electrophotographic light-receiving members even in high-speed continuous image formation. It functions to prevent problems such as afterimages and sensitivity problems that are seen in .

The surface layer of the light-receiving member of the present invention has a nitrogen atom (N) and, if necessary, a hydrogen atom (H), a herogen atom (X), a carbon atom (C), and an oxygen atom (0). The layer contains one or more selected from the following, and in particular, nitrogen atoms are contained in the layer in a specific distribution as described above.

The amount of EjilRM molecules (N) contained in the surface layer in a specific distribution as described above is a value calculated from the formula: The minimum value of the distribution concentration in the layer direction is 0.5 a
atomic%, the maximum value is in the range of 95 atomic%, and can be arbitrarily selected within this range, but the average value of the distribution concentration is preferably 20 to 90 atomic%, more preferably 30 to 85 atomic%, optimally 40 to 3Q.
atomic%.

In addition, the amount of hydrogen atoms (H), the amount of herogen atoms (X) contained in the surface layer, and the amount of hydrogen atoms and herogen atoms (
The amount of H+X) is a value calculated from the formula: Preferably 1 to 70 atomic
%, more preferably 2-65 atomic%, optimally 5-60 alomic%.

In addition, carbon atoms (C) and/or oxygen atoms (
0], these atoms are distributed and contained in the nuclear layer in a specific state, as in the case of the nitrogen atoms. In that case, the amount of carbon atoms (C), the number of oxygen atoms (0), and the amount of carbon atoms + oxygen atoms (C+0)
The amount can be arbitrarily selected within the range of nitrogen atoms.

In the light-receiving member of the present invention, the layer thickness of the surface layer 104 is also an important factor for efficiently achieving the object of the present invention.
It is determined as appropriate depending on the desired purpose, but it is determined based on the mutual and organic relationship depending on the amount of constituent atoms contained in the surface layer or the characteristics required for the surface layer. Need to decide. Furthermore, it is also necessary to consider economic efficiency, including productivity and mass production.

For these reasons, the surface layer 104 of the light receiving member of the present invention
The layer thickness is preferably 0.003 to 30 μm, more preferably 0.004 to 20 μm, optimally 0.005 μm.
~101un.

The light-receiving member of the present invention has high photosensitivity in the entire visible light range, and is particularly excellent in photosensitivity characteristics on the long wavelength side, so it is particularly excellent in matching with a cow conductor laser, and has a high photoresponse. It exhibits excellent electrical, optical, photoconductive properties, electrical voltage resistance, and use environment characteristics.

In particular, when applied as a light-receiving member for electrophotography, there is no influence of residual potential on image formation even in high-speed electronic image forming systems, and its electrical properties are stable and high. It has high sensitivity and high 8N ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear eight-tones, and high resolution. Obtainable.

The constituent layers of the light-receiving member of the present invention can all be formed by a vacuum film deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blating method. These methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the light-receiving member to be manufactured. The glow discharge method or the sputtering method is preferable because it is relatively easy to control the conditions for manufacturing the member and hydrogen atoms can be easily introduced together with silicon atoms. be.

Further, the glow discharge method and the sputtering method may be used together in the same apparatus system.

Regarding the formation of the photosensitive layer, it is a-81 (H.

For example, in the glow discharge method, a raw material gas for supplying 81 that can supply silicon atoms (81) and/or a halogen atom (X ) A raw material gas for introduction is introduced into a deposition chamber whose interior can be reduced in pressure, a glow discharge is generated in the deposition chamber, and m-8i (H, A layer consisting of X) is formed.

In addition, in the case of the sputtering method, for example, in the case of the sputtering method, the K used to form the photosensitive layer consisting of m-8i()(, A gas of a silicon compound containing atoms may be introduced into the deposition chamber to form a plasma atmosphere of the gas.

When the photosensitive layer is made of a-8jGa (H,
A raw material gas for supplying Ge that can supply Ge) and a raw material gas for supplying hydrogen atoms (H) and/or halogen atoms (X) that can supply hydrogen atoms (H) and/or halogen atoms (X). , a gas is introduced at a desired pressure into a deposition chamber whose interior can be depressurized, a glow discharge is generated in the deposition chamber, and a
A layer composed of -5iGe (H,X) is formed.

K, which forms a photosensitive layer composed of a-8iGe (H, These steps are performed by sputtering in a desired gas atmosphere.

a-8IGa(H,X
) For example, when forming a photosensitive layer composed of Heat and evaporate by electron beam method (g, B, method) etc.
This can be done by passing the flying evaporates through a desired gas plasma atmosphere.

When the photosensitive layer is composed of a-818n (H+ Even if the above-mentioned a-81Ge(H.

When forming a layer consisting of This is done by making it contain.

a-81(H) using a glow discharge method, sputtering method, or ion blating method.

4l-X) A-81(Ge, 8n) () (, To form the photosensitive layer, a-8i(H,X) or a-81(Ge,
8n) (When forming the layer of T(, The starting material for introduction is the aforementioned a-81()(,X) or a
-81(Ge, 8n) (I(,

For example, using the glow discharge method, atoms (0, C.

A photosensitive layer composed of a-si(a,X) containing N) or a-8i(Ge) containing atoms (O#C+N).

K forming the photosensitive layer composed of 8n) (HlX) is
A photosensitive layer composed of the above-mentioned a-81(H,X) or a-
When forming a photosensitive layer composed of 81 (Ge, 8n) (H, -81(Ge, 8
n) (H,

The surface layer of the light-receiving member of the present invention is provided on the photosensitive layer of the member, and has a silicon atom as a host, contains nitride atoms (N), and optionally hydrogen atoms (H) and halogen atoms. (X), an amorphous material containing one or more selected from carbon atoms (C) and acid atoms (0), that is, 5IN (c, 0) (u, X), In-service g
i hydrogen atoms) leave a negligible difference between the refractive index of the surface layer and the refractive index of the photosensitive layer at the interface between the surface layer and the photosensitive layer, and at the interface. It is distributed in the surface layer such that the concentration increases from the beginning toward the free surface side of the surface layer.

The surface layer of the light-receiving member of the present invention is the same as the above-mentioned photosensitive layer, and is formed by a glow discharge method, a sputtering method, or an ion-blast ink method. is effective.

For example, when using the glow discharge method, silicon atoms (8i)
A raw material gas whose constituent atoms are , a raw material gas whose constituent atoms are nitrogen atoms (N), and, if necessary, hydrogen atoms (H), halogen atoms (X), carbon atoms (C), and oxygen atoms (0). The raw material gas for introducing one or more atoms selected from the following may be mixed in a predetermined ratio as the case may be. There is still a raw material gas whose constituent atoms are silicon atoms (Sl), a raw material gas whose constituent atoms are i1 elementary atoms (N) and hydrogen atoms (H), and if necessary, silicon atoms (X) and carbon atoms (C). A raw material gas for introducing one or more atoms selected from and oxygen atoms (0) can be mixed at a predetermined ratio as the case may be.

Alternatively, a raw material gas containing silicon atoms (8I) and hydrogen atoms (H) as constituent atoms, a raw material gas containing nitrogenous atoms (N) as constituent atoms, and halogen atoms (X) and carbon atoms (C) as necessary. A raw material gas for introducing one or more atoms selected from IR atoms (0) and acid IR atoms (0) can be used by optionally mixing them in a predetermined ratio. Alternatively, a raw material gas consisting of silicon atoms (Sl) and hydrogen atoms (H), nitrogen atoms (N) and halogen atoms (
A source gas containing X) as a constituent atom and, if necessary, a source gas for introducing carbon atoms (C) and/or oxygen atoms (0) can also be used in a predetermined ratio.

The above are just examples, and it goes without saying that in addition to these examples, the raw material gases to be used and the combinations of these raw material gases can be appropriately selected as desired.

When forming the surface layer of the light-receiving member of the present invention by sputtering, monocrystalline 1Ml1f& or polycrystalline 81Q8 or 81. N, Way 8, or Sl and 8
1. The sputtering may be carried out by using wafers containing a mixture of N as a target and sputtering them in various gas atmospheres.

For example, if you use 81 way eight as a target,
Raw material gas for introducing phoneme atoms (N) and, if necessary, one or more selected from hydrogen atoms (H), halogen atoms (X), carbon atoms (C), and oxygen atoms (0) are diluted with a diluting gas if necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the 81 way.

Another method is to use a single target made of a mixture of 8I and 5IaN4 in an atmosphere of diluent gas as a sputtering gas, or with hydrogen atoms (H)% halogen atoms (X), carbon atoms The surface layer can be formed by sputtering in a gas atmosphere containing one or more selected from (C) and oxygen atoms (0).

The raw material gas for supplying 81 used in forming the surface layer of the light-receiving member of the present invention as described above is "H4s 81*Hs+ t 8ImH8t81".
Gaseous or gasifiable hydrogenated silica (such as 4H10)
Silane M) can be mentioned, and 8JH,
,81,)I is preferred.

In addition, gases that can be effectively used as raw material gases for introducing nitrogen atoms (N) include examples in which N is a constituent atom or N and H are constituent atoms, nitrogen (Nt), ammonia, etc. (NHl), hydrazine (H,NNH,), hydrogen azide (HNs), ammonium azide (NH4Nm
), gaseous or gasifiable nitrogen, and nitrogen compounds such as nitrides and azides.

In addition to these, halogenated nitrogen compounds such as nitrogen trifluoride (PIN) and nitrogen tetrafluoride (FaNt) have the advantage of being able to introduce halogen atoms (X) in addition to nitrogen atoms (N). can be mentioned.

In addition, the raw material gas for water*mm children's use is hydrogen gas, HP, HCA! , HBr, HI, etc. (7genides, 8iH4,81, Hay 81a) I
Silicon hydride such as s l 814H10, or 81H
*F friend, SIH 1. , SiH, tJ Yuki.

81HCJ1, 8iHIBrl, 817(Br,
It is possible to use gaseous or gasifiable materials such as /N-logogen-substituted silicon hydride, etc., and when these raw material gases are used, they are extremely effective in terms of controlling electrical or photoelectric properties. This is effective because it allows the content of hydrogen atoms (6) in certain areas to be controlled in the container.

When the hydrogen halide or the halogen-substituted silicon hydride is used, hydrogen atoms (CH) are also introduced at the same time as the halogen atoms, which is particularly effective.

Further, as the raw material gas for introducing halogen atoms, there are many halogen compounds, such as evaporated halogen gas,
Gaseous or gasifiable halogen compounds such as halides, interhalogen compounds, and halogen-substituted silane derivatives are preferred. Specifically, fluorine, chlorine, bromine,
Iodine hegen gas, BrF, ClF, Cl
F5 +BrF6, BrFj, IFy, I(
/N O intergenic compounds such as J', IBr, and 8
1F,, 81. Examples include silicon halides such as F6, 8iC14, and 5IHr4. When using a silicon halide in a gaseous state or one that can be gasified as described above, the surface I@ composed of a-81 containing halogen atoms can be prepared without using a separate raw material gas for supplying Si. It is particularly effective because it can form

The raw material gases for introducing carbon atoms (C) include methane (CH4), ethyl (C,H,), and propane (CsH).
s), Robtano (n C4I(01), Pentane (
Saturated hydrocarbons with a carbon number of 1 to 5 such as CaH+m), ethylene (Cabs), propylene (C3He), butene 1
Ethylene hydrocarbons having 2 to 5 carbon atoms, such as (C4H1l), buty/-2 (C4HI), inbutylene (Cabs), and pentene (CwHIo), acetylene (Cl
am), methylacetylene (CaH2), butyne (04
Examples include acetylene hydrocarbons having 2 to 4 carbon atoms such as H@).

Furthermore, as for the raw material gas for introducing acid The constituent atoms are, for example, jinloxane (H, 81081
1(,),) Phosphoroxan (Hs S 1081HtO
8i Ha) e'l) Low grade odtfy can be mentioned.

Regardless of which method is used to form the surface layer of the light-receiving member of the present invention composed of a-8I N (Cl 0 ) (H*X) as described above, , carried out in accordance with the following conditions.

That is, the support temperature is usually 50 to 350°C, particularly preferably 50 to 300°C. The gas pressure inside the deposition chamber is normally 0. O1 to l Torr, particularly preferably 0.1 = 0.5 Torr. Further, the discharge power is usually 0.005 to 50 W/-, but more preferably o, oi to 36 w7c:nr.
.

Particularly preferably, it is 0.01 to 20 W/-.

〔Example〕

EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 In this example, a photoreceptor drum for electrophotography was manufactured using a halogen lamp as a light source and a filter for cutting long wavelength light in order to improve color sensitivity.

The base is an A7 cylinder (length L): 358
ffillI N diameter (r): 108 mm) was used.

A photosensitive layer and a surface layer were deposited on this Al substrate using the apparatus shown in FIG. 5 in the following manner.

First, the apparatus shown in FIG. 5 will be explained.

501 is a high frequency power supply, 502 matching boxes, 5
03 is an exhaust pump, 504 is a base rotation motor, 505
506 is a substrate, 506 is a heater for heating the substrate, 507 is a gas introduction pipe, 508 is a cathode electrode for high frequency introduction, 509 is a shield plate, 510 is a power source for the heater, 521 to 523, 5
41-543 are valves, 531-533 are mass 70-controllers, 551-553 are regulators, 56
1 is a cylinder for hydrogen gas (H2), 562 is a cylinder for silane gas (
81Ha) cylinder, and 563 a raw material gas cylinder for nitrogen atom introduction.

Using the apparatus shown in FIG. 5, the layer formation was carried out as follows.

All main valves of cylinders 561 to 563 were closed, all mass flow controllers and valves were opened, and the pressure inside the deposition apparatus was reduced to 10-' Torr using exhaust pump 503. At the same time, fi 50 is applied to the heater of 506.
5^l Substrate was heated to t-250'C and kept constant at 250°C. 521-523, 541-543, 551
Close the valves 553 and open the main valves of cylinders 561 to 563. Set the secondary pressure i of the valves with regulators 551 to 553 to 1.5 Kp/”cd.53
1 Nomasflocontro-5-'It-3008CCM
The valves 541 and 521 were opened in sequence to introduce H2 gas into the deposition apparatus.

Next, set the 582's 81H gas and the 532's mass flow controller setting to 2008CC'M, ■! stH gas was introduced into the deposition apparatus in the same manner as the gas introduction.

When the internal pressure inside the deposition apparatus stabilizes at Q, 4 Torr, turn on the high frequency power supply 501 and adjust the matching box 502 to generate a glow discharge between the 5o5 Al substrate and the cathode electrode 508. A-81:) (photosensitive layer) was deposited with a thickness of 25 μm using a power of 200 W. After depositing the a-8i:l (layer) in this way, the discharge was turned off and 563 NH3 gas was added to 533 The mass 70 controller was set and H was introduced into the deposition apparatus in the same manner as the introduction of gas.

After the internal pressure became stable, the high frequency power source was switched on and the high frequency power was set to 200 W. At this time, 0.5 μm
The gas flow rate was varied under the conditions shown in Table A-1 below so that a thick surface layer was formed and the nitrogen atoms in the surface layer had the distribution shown in FIG. 6(3).

Table A-1 Then, a 0.5 μm thick a-8IN:H layer was deposited, and after death, the discharge was stopped, all valves were closed, the heater was turned off, and after cooling to room temperature in a vacuum, a deposited film was formed on the nine substrates. The pressure was removed from the system.

The film formed in the manner described above was used on a Canon copier NP.
When I put it in a modified 7550 machine and printed out an image, I was able to get a good image with no image unevenness or image memory, even if I increased the process speed and outputted 100 sheets of A4 size paper per minute.

In addition, when we tested the durability by adding abrasive to the toner as an accelerated test under these conditions, we found that even after printing 1 million sheets of A4 size paper, changes in the thickness of the surface layer due to wear were observed, but image unevenness and No memory problems were observed at all.

Example 2 Using an A cylinder similar to that used in Example IK, a photosensitive layer was formed on the surface of the cylinder in the same manner as in Example 1, and then oxygen atoms and carbon atoms were A surface layer composed of a-8iN:H:0 having a thickness of 0.5 μm was formed by changing the gas flow rate under the conditions shown in Table A-2 below so as to obtain the distribution shown in Table A-2 below.

When an image was formed on the obtained light-receiving member in the same manner as in Example 1, good results were obtained as in Example 1.

Table A-2 Example 3 Using an Al cylinder similar to that used in Example 1, a photosensitive layer was formed on the surface of the cylinder in the same manner as in Example 1, and then oxygen atoms and carbon atoms were The gas flow rate was changed under the conditions shown in Table A-3 below so that the distribution shown in Figure 6(5) was obtained, and a-8i N with a thickness of 0.5 μm was obtained:
A surface layer composed of H:O was formed.

When an image was formed on the obtained light-receiving member in the same manner as in Example 1, good results were obtained as in Example 1.

Table A-3 Example 4 Using an Al cylinder similar to that used in Example 1, a photosensitive layer was formed on the surface of the cylinder in the same manner as in Example 1, and then oxygen atoms and carbon atoms were A surface layer composed of a-8IN:H:F having a thickness of 0.5 μm was formed by changing the gas flow rate under the conditions shown in Table A-4 below so as to obtain the distribution shown in Figure 6.

When an image was formed on the obtained light-receiving member in the same manner as in Example 1, good results were obtained as in Example IK.

Table A-4 Example 5 AI similar to that used in Example 1! Using a cylinder, a photosensitive layer was formed on the surface of the cylinder in the same manner as in Example 1, and then the distribution of oxygen atoms and carbon atoms was as shown in Table A-5 below. By changing the gas flow rate under the conditions shown, 0.5. /jm thickness a-8iN:H
A surface layer composed of :O:C was formed.

When an image was formed on the obtained light-receiving member in the same manner as in Example 1, good results were obtained as in Example 1.

Table A-5 Example 6 An Al cylinder similar to that used in Example IK was used, and a photosensitive layer was formed on the surface of the cylinder in the same manner as in Example 1. The surface layer composed of a-8IN:H:O:C with a thickness of 0.5 μm was formed by changing the gas flow rate under the conditions shown in Table A-6 below so that the distribution was as shown in Figure 6. Formed.

When an image was formed on the obtained light-receiving member in the same manner as in Example 1, good results were obtained as in Example 1.

Table A-6 Examples 7-17 AI similar to that used in Example 1! 1 cylinder
One cylinder was prepared, and a photosensitive layer was formed on the surface of each cylinder in the same manner as in Example 1. Next, elementary atoms were layered on each photosensitive layer in the form shown in FIGS. The amount of SiH, gas, NH3 gas and H2 gas was automatically adjusted by microcomputer control so that the surface layer was distributed 0.5 μm through gummy discharge.
Formed thickly.

When images were formed on the 11 types of light-receiving members obtained in the same manner as in Example 1, good results similar to those in Example 1 were obtained in all cases.

Examples 18 to 29' 12 Al cylinders similar to those used in Example 1 were used.
The Al layer was prepared under the layer forming conditions shown in Table B-1 below.
A charge injection blocking layer, a photosensitive layer, and then a surface layer were formed on each surface of the cylinder.

Note that the flow rate changes of H, stu, and HN gas during the formation of the first surface layer were controlled by a microcomputer so that the carbon atoms in the surface layer were distributed in the states shown in Figures 6 to η, respectively. Adjusted automatically.

When images were formed on the 12 types of light-receiving members obtained in the same manner as in Example 1, good results similar to those in Example 1 were obtained.

61 - Examples 30 to 41 The same Al cylinder as used in Example 1 was
This was prepared, and a charge injection blocking layer, a photosensitive layer, a photosensitive layer,
Next, a surface layer was formed.

In addition, H! during the formation of the surface layer! r S In2 and NH,
Changes in the gas flow rate were automatically adjusted by microcomputer control so that the carbon atoms in the surface layer were distributed as shown in Figures 6 to 7.

When images were formed on the 12 types of light-receiving members obtained in the same manner as in Example 1, good results similar to those in Example 1 were obtained.

Examples 42 to 53 Spot system 80 μm cow conductor laser (wavelength 7sonm)
) was used as a light source to create a photoreceptor drum for a laser beam printer.

As a base, AI cylinder (length 6): 358
12 cod (m+11° diameter (r): 80 cod) were prepared.

As a device, valves 624 to 62 are added to the device shown in FIG.
6, 644-646, mass 70 controller 634
~636, regulator 654~656, -nitrogen oxide (No) cylinder 664, hydrogen diluted diborane (B!H6
/Hri cylinder 665, Germay (GeH+) cylinder 66
The apparatus shown in FIG. 7 with the addition of 6 was used.

A long wavelength light absorbing layer and a charge injection blocking layer on the surface of each of the 12 cylinders using the apparatus shown in FIG.
The formation operations of the photosensitive layer and the surface layer were performed as follows.

First, by the same method as in Example 1, the pressure inside the deposition apparatus was reduced and the substrate was heated, and then H of Example 1 was applied.

In the same manner as the gas introduction, 300SCCM was added to the deposition apparatus.
H, gas, 200 SCCM SIH, gas, 15S
3000pp for CCM NO gas and SM H4 gas
B, H6 gas, GeH at a flow rate of 11005cc
, gas is introduced, and the internal pressure inside the deposition apparatus is Q, 5'for
Once it stabilizes at r, a glow discharge is generated and the high frequency power is applied to 200W to a thickness of 1μm! l-8iQe (H,
B, N, O) were deposited (formation of a long wavelength light absorption layer).

After that, 1-8
1 (H, B, N, O) was deposited to a thickness of 5 μm (formation of charge injection blocking layer).

Next, stop the NO gas, B, and H6 gas, and
A layer composed of a-81:H was deposited to a thickness of (formation of photosensitive layer).

After depositing the a-81:H layer, the discharge was turned off, and the surface layer in which nitrogen atoms were distributed in the shape shown in FIG. It was deposited thickly.

The 12 types of photoreceptor drums created in this way were manufactured by Canon N.
When evaluated by putting it into a P9030 laser copier and outputting an image, good results were given as in Example IK.

65-Examples 54 to 65 Twelve i-cylinders similar to those used in Example 1 were prepared, and an electrophotographic photosensitive drum having a layered structure having a photosensitive layer and a surface layer on the surface of each cylinder was prepared. It was created using the apparatus shown in Figure 5.

Regarding the photosensitive layer, carbon atoms were distributed within the layer in order to improve chargeability and sensitivity.

In addition, in forming the photosensitive layer, H,
Gas 300 SCCM, SIH, Gas 200 SCC
M.

The same operation as in Example 1 was performed except that CH, gas I SCCM was used, and 25 μml lc was deposited.

Subsequently, the surface layer was subjected to the same operation as in Example 1, so that nitrogen atoms were distributed in each surface layer in the form shown in Figures 6 to η, and there was no sudden change in internal pressure. As,
By microcomputer control, H, gas, 81H
, gas, NH, automatically adjusts the gas flow rate to 0.5μ
A surface layer of m thickness was deposited.

The 12 types of light-receiving members obtained were evaluated in the same manner as in Example 1, and as in Example 1, good results were given.

[Brief explanation of drawings]

Figures 1 (Al to (C)) are diagrams schematically showing typical examples of the layer structure of the light-receiving member of the present invention. Figure 2 shows the nitrogen atoms in the surface layer of the light-receiving member. FIG. 3 is a schematic diagram of rounding to explain the distribution state. Figures 3 (4) to (C) show the details of the refractive index measurement and optical band gap measurement of the sample deposited on the glass substrate in Experiment 1. Figure 3 (to) is a diagram summarizing the measurement results of the refractive index and optical band gap of samples deposited on a glass substrate in experiment IK. , is a diagram summarizing the measurement results of the difference in refractive index and the difference in image density at the interface between the photosensitive layer and the surface layer of the samples prepared in Experiment 2. FIG. 6 is an explanatory diagram of an apparatus used for producing the light-receiving member of the present invention. FIGS. It is an explanatory diagram of the distribution state of nitrogen atoms used in forming the layer. Regarding FIG. 1, 101...Support, 102... Charge injection blocking layer, 1
03... Photosensitive layer, 104... Surface layer, 105...
Long wavelength light absorption layer, regarding FIG. 2, 203... photosensitive layer, 204... surface layer, 207...
- Free surface, 208... Interface, Regarding Fig. 5, 501... High frequency power supply, 502... Matching box, 503... Exhaust pump, 504... Base rotation motor, 505... Base , 506... Heater for heating the substrate, 507... Gas introduction tube, 508... Cathode electrode, 509... Shield plate, 510... Power source for heater, 521-523, 541-543... Pulp, 531-533...Mass 70 control 5-15
51-553... Regulator, 561... Hydrogen gas cylinder, 562... Silane gas cylinder, 56
3... Gas cylinder for nitrogen atom introduction, in Fig. 7, 624-626, 644-646... Pulp, 63
4-636...mass flow controller, 654-6
56...Regulator, 664...-Cylinder for nitrogen oxide, 665...Cylinder for B2Ha/Hz, 66
6... Germanic gas cylinder. Patent issue Canon Co., Ltd. Figure 1 + f O o O <
Ajiku of Orchid Ward Q Method ← Q ′″′ Layer thickness from the interface of the citrus surface layer Position of the interface C (K) Layer thickness from the interface of the surface layer■ Position of the interface O - N content - N content Quantitative Procedural Amendment (Method) May 28, 1986 Michibu Uga, Commissioner of the Patent Office1, Indication of the Case Patent Application No. 92520 of 19852, Name of the Invention Improved Photoreception with Image Forming Function Member 3: Relationship with the person making the amendment Patent applicant address 3-30-2 Shimomaruko, Ota-ku, Tokyo Name
(100) Canon Co., Ltd. 4, Agent Address: 6, Kojimachi Green Building, 3-12-6 Kojimachi, Chiyoda-ku, Tokyo, Subject of amendment: Specification 7, Amendment contents: Specification originally attached to the application (no change in content) )

Claims (2)

[Claims] (1) In a light-receiving member having at least a photosensitive layer and a surface layer on a support, the surface layer is based on silicon atoms, contains nitrogen atoms, and optionally contains hydrogen atoms, halogen atoms, carbon atoms, and oxygen atoms. The nitrogen atom is composed of an amorphous material containing one or more selected from among the refractive index of the surface layer and the refractive index of the photosensitive layer at the interface between the surface layer and the photosensitive layer. is distributed in the surface layer such that the concentration starts at the interface and increases toward the free surface side of the surface layer, leaving a negligible difference between the two and Characteristic light-receiving member. (2) The light-receiving member according to claim (1), wherein the difference in refractive index (Δn) that can be ignored in the image forming process corresponds to Δn≦0.62.